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5.1 Nomenclature and Isomerism 5.6 Nomenclature of Cycloalkanes

5.2 Industrial Sources of Alkanes 5.7 Geometrical Isomerism in Alicyclic Compounds
5.3 Preparation of Alkanes 5.8 Chemical Properties of Cycloalkanes
5.4 Physical Properties EXERCISES
5.5 Chemical Properties SOLUTIONS

Compounds containing only two elements, carbon and hydrogens, are known as hydrocarbons. On the basis of
structure and properties, hydrocarbons are divided in two main classes, viz. aliphatic and aromatic. Aliphatic hydrocarbons
are further divided into different families, namely alkanes, alkenes, alkynes and their cyclic analogs (cycloalkanes,
cycloalkenes and cycloalkynes). The last type of hydrocarbons are also known as cyclic aliphatic or alicyclic compounds.

ALKANES
Alkanes are open-chain (acyclic) hydrocarbons comprising the homologous series with the general formula
CnH2n+2 where n is an integer. They have only single bonds and therefore said to be saturated. Because of their low
chemical activity, alkanes are also known as paraffins.

5.1 Nomenclature and Isomerism

According to IUPAC system of nomenclature, open chain aliphatic compounds are named as alkanes. The first
three members do not exhibit isomerism, all other members show chain or nuclear isomerism. The number of isomers
increases with the increase in the number of carbon atoms, e.g. butane has 2 isomers, pentane 3, hexane 5, heptane 9,
octane 18 and decane 75.
Conformations : Each carbon atom of alkanes is in sp3 state of hybridisation and all C – H and C – C bonds are
strong sigma (s) bonds. Since sigma bonded carbon atoms can rotate about the C – C bond, a chain of singly bonded
carbon atoms can be arranged in any zig-zag shape. Two such arrangements are shown for four consecutive carbon
atoms.

C
C C C
C
C C
C
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Such different arrangements of atoms that can be converted into one another by rotation about single bonds are called
conformations. Since conformations cannot be isolated, they are not isomers. Ethane can have infinite number of
conformations, the two extreme conformations are eclipsed* (with highest energy, hence least stable) and staggered*
(with lowest energy, hence most stable). The infinite number of intermediate conformations are called skew conformations.
To represent such conformations, we shall often use two kinds of three dimensional formulas : andiron or sawhorse
formulas (i) and Newman projections (ii).

H HH H
H H
H H
H C H
C
H
H or or
C H H C
H H H
H H
H H H
H H
(i) (ii) (i) (ii)

(a) Eclipsed (b) Staggered

The energy required to rotate the ethane molecule about the carbon-carbon bonds is called torsional energy and thus
the instability of the eclipsed conformation or any of the skew conformations is said to be due to torsional strain.
REMEMBER THAT

(i) like ethane, two extreme conformations of propane are eclipsed and staggered.
(ii) The relative stability order of the six important conformations of n-butane is
Anti > Gauche º Gauche > Eclipsed º Eclipsed > Fully eclipsed
(iii) The two conformations of cyclohexane are the boat or C-form and the chair or Z-form; the latter form is more stable than the boat
form by 44 kJ mol –1 .

1. How many types of carbon atoms are present in the hydrocarbon 3, 3, 5-trimethylhexane?
2. Write down the IUPAC name of the compound (CH3)2C (C2H5).C(CH3)(C2H5).CH(C2H5).CH3.
3. Draw the structures of the following groups, and give their more common names.
(a) the (1-methylethyl) group (b) the (2-methylpropyl) group
(c) the (1-methylpropyl) group (d) the (1,1-dimethylethyl) group
4. Draw the structures of the following compounds.
(a) 1,1-Dimethyl-2-(1,1,3-trimethylbutyl)cyclooctane. (b) 5-(1,2,2-trimethylpropyl)nonane
5. Comment on the calculated and experimental values of entropy of ethane.

5.2 Industrial Sources of Alkanes

The principal industrial source of alkanes is petroleum which is accompanied by natural gas. Natural gas
consists mainly of methane and progressively small amounts of ethane, propane and higher alkanes. The propane-butane
fraction obtained from natural gas is used as domestic fuel under the name of LPG (Liquefied Petroleum Gas). Petroleum is
separated by fractional distillation into various fractions. The use of each fraction chiefly depends upon its volatility or
viscosity. The non-volatile fraction, residue or coke obtained from paraffin-base petroleum consists of complex hydrocarbons
having a high carbon-to-hydrogen ratio, it is used as a fuel or in the manufacture of carbon electrodes for the electrochemical
industries.
The second potential source of alkanes is coal which is converted into useful petroleum products through
hydrogenation.

* There is an energy barrier of 2.8 kcal/mol for the interconversion of staggered and eclipsed conformations. This value is not high, even
at room temperature the fraction of collisions with sufficient energy is large enough to overcome the energy barrier of 2.8 kcal/mol.
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5.3 Preparation of Alkanes

5.3.1 Hydrogenation of Alkenes and Alkynes

(For details, consult chapter on alkenes)
Pt, Pd or Ni
CH 3 CH = CH 2 + H2 ¾¾¾¾¾® CH 3 CH 2 CH 3
Propene Propane

Ni
CH º CH + 2H 2 ¾¾® CH 3 - CH 3
REMEMBER THAT

(i) The reaction temperature varies from room temperature to 200–300°. Hydrogenation of alkene using Ni catalyst at 200–300°C is
known as Sabatier-Senderens reduction.
(ii) Raney nickel* is highly active and can be used at ordinary temperatures.
(iii) Other catalysts used during hydrogenation are PtO 2 (Adam's catalyst) and [(Ph 3P) 3 RhCl] – Wilkinson's catalyst.

5.3.2 Reduction of Alkyl Halides

(a) Reduction of alkyl halides by electron-transfer from metal (Zn).

Zn + H + , Zn + OH -
RX ¾¾¾¾¾¾¾¾¾¾¾® RH
or Zn - Cu couple + C 2 H 5 OH

Remember, here reduction is not done by nascent hydrogen. The metal transfers the electron to the alkyl halide
generating carbanion which, being a very strong base, abstracts a proton from the acid or any potential proton donor
including solvent like ethanol.

Zn : ¾¾® Zn 2 + + 2 e –
® R . + XQ
R - X + e – ¾¾
.
® R :Q
R + e – ¾¾
R :Q + H + ¾¾
®R -H

(b) Reduction with hydride donors like lithium aluminium hydride (LiAlH4) or sodium borohydride (NaBH4).

4RX + LiAlH 4 ¾¾
® 4RX + LiX + AlX 3 (X ¹ F)
REMEMBER THAT

(i) Reduction takes place in four independent steps, each involving a nucleophilic displacement by hydride ions (H : Q ) given by
LiAlH 4 .
(ii) LiAlH4 reduces 1° and 2° alkyl halides, while NaBH4 reduces only 2° and 3° alkyl halides.

(c) Reduction by tri-n-butyl tinhydride or triphenyl tinhydride.

RX + (n-C4 H 9 )3 SnH ¾¾
® RH + ( n-C 4 H 9 )3 SnX
(d) Reduction via organometallic compounds.
dry ether H O
(i) RX + 2Li ¾¾¾¾¾
® R - Li + ¾¾¾
2 ® RH + LiOH
( - LiX) Alkyllithium

dry ether H O
(ii) ® R - (Mg + X) ¾¾¾
RX + Mg ¾¾¾¾¾ 2 ® RH + Mg(X)OH

Grignard reagent

* Raney nickel is prepared by treating Ni–Al alloy with NaOH, Al dissolves in NaOH leaving behind nickel in finely divided form.
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Note that organometallics have basic carbanionic site and hence can easily abstract proton from water, dil. acid
or alcohol.
Due to carbanionic character of the alkyl group of the Grignard reagent, latter may be considered as a magnesium
salt of the extremely weak acid, R–H. Thus the reaction of RMgX with water is simply the displacement of the weaker acid,
R–H from its salt by the stronger acid (HOH).
RMgX + HOH ¾¾
® RH + Mg(OH)X
Stronger Weaker
acid acid

1. How will you prepare C2H5D from C2H5Br?

dry ether
2. CH 3 CH 2 CH 2 Cl + Mg ¾¾¾¾¾
® CH 3 CH 2 CH 2 MgCl or (CH 3 )2 CHMgCl
3. Pick up the stronger and weaker acids in the following reaction :

C2 H 5 MgBr + NH 3 ¾¾
® C2 H 6 + Mg(NH 2 )X

(e) Alkyl iodides undergo reduction on heating with hydriodic acid at high temperature in presence of red
phosphorus.
red P, 150° C
RI + HI ¾¾¾¾¾¾
® RH + I 2
Iodine is removed as PI3 (2P + 3I2 ——® 2PI3).

5.3.3 Reduction of functional groups containing oxygen with HI and red phosphorus
e.g. ROH to RH, RCHO to RCH3, R2CO to R2CH2, RCOOH to RCH3.
red P
CH 3 OH + 2HI ¾¾¾® CH 4 + H 2 O + I 2
150ºC

red P
CH 3 CHO + 4HI ¾¾¾® CH 3 CH 3 + H 2 O + I 2
150ºC

red P
CH 3 COOH + 6HI ¾¾¾® CH 3 CH 3 + 2H 2 O + I 2
200ºC

CH 3 COCl + 6HI ¾¾
® CH 3 CH 3 + H 2 O + HCl + 3I 2
Phosphorus and iodine react to form PI3 which again produces hydriodic acid.
Aldehydes and ketones can also be reduced to hydrocarbons by Clemmensen reduction (reagent : Zn-Hg/conc.
HCl) and Wolf-Kishner reduction (reagent : NH2NH2/C2H5ONa at 180°).
Zn -Hg
CH 3 CHO ¾¾¾¾® CH 3 CH 3 + H 2 O
HCl

CH3 H2NNH2 CH3 C2H5ONa CH3

C=O C = NNH2 CH2
180ºC
CH3 CH3 CH3
In Mozingo reduction : The carbonyl group is converted into its dithioacetal using ethanedithiol which is then
hydrogenated over Raney nickel.
R CH2SH + –
Et2O BF 3 R SCH2 H2 / Ni R HSCH2
C=O + C CH2 +
R CH2SH R SCH2 R HSCH2

Primary and secondary alcohols can also be converted to alkanes through fosylates.
TsCl LiAlH
RCH 2 OH ¾¾¾® RCH2 OTs ¾¾¾¾ 4
® RCH 3
|¾¾¾¾
LiAlD 4
® RCH2 D
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5.3.4 Hydroboration of Alkanes

B H 3 CH COOH or
RCH = CH 2 ¾¾¾®
2 6 (R - CH 2 - CH 2 - )3 B ¾¾¾¾¾¾¾ ® 3RCH 2 CH 3
CH 3 CH 2 COOH
Trialkylborane

5.3.5 Decarboxylation of carboxylic acids

heat
RCOONa + NaOH(CaO) ¾¾¾
® RH + Na 2 CO 3
Soda lime

Yield of alkanes is low in case of higher alkanes, e.g.

heat
C 2 H 5 COONa + NaOH(CaO) ¾¾¾
® C 2 H 6 + CH 4 + H 2
This reaction involves carbanion as the intermediate, hence nucleophilic substitution is also possible during
decaroxylation.

NaOH + CaO
Cl COOH ¾¾¾¾¾¾
® + Na2CO3
heat

5.3.6 Coupling of alkyl halides with organometallic compounds

(i) Wurtz reaction. The two alkyl groups can be coupled by reacting an ethereal solution of RBr, RCl or RI with Na or
K. Yields of product are best for 1° (60%) and poorest for 3° (10%) alkyl halides.
dry ether
2C 2 H 5 Cl + 2Na ¾¾¾¾¾
® C 2 H 5 C 2 H 5 + 2NaCl

Cl

+ 2 Na ¾ dry ether
¾ ¾ ¾¾ ® + NaCl + NaBr

Br

dry ether + 2 NaBr

BrCH 2 CH 2 CH 2 Br + 2Na ¾¾¾¾¾
®

(a) The yield is good in case of symmetrical alkanes (alkanes having even number of carbon atoms) i.e. when the
two alkyl halides are same, otherwise cross products will be formed.
Na
CH 3 Br + C2 H 5 Br ¾¾¾¾¾
® CH 3 CH 3 + C 2 H 5 C2 H 5 + CH 3 C2 H 5
dry ether

It is very difficult to separate the mixture of hydrocarbons.

(b) Other hydrocarbons are also formed as by-products, e.g.
Na, dry ether
2C 2 H 5 Br ¾¾¾¾¾¾
® C 2 H 5 C 2 H 5 + C 2 H 6 + C2 H 4
Mechanism of Wurtz reaction
Ionic mechanism. It operates when the reaction is carried out in solution.
.
® R - Na + + NaX
RX + 2Na ¾¾
S 2
R - + RX ¾¾¾
N ® R - R + X-

Formation of by-products, viz. alkene is due to disporportionation reaction, i.e. one molecule gains hydrogen at the
expense of the other.

– –
CH3—CH 2 + H— CH 2— CH 2 —X CH3— CH 3 + CH 2 = CH 2 + X
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Free radical mechanism. It operates when the reaction is carried out in vapour phase.

. .
RX + Na ¾¾
® R + NaX

. .
R + R ¾¾
® R -R

.
Disproportionation in free radicals, e.g. C 2 H 5
. .
C2 H 5 + C2 H 5 ¾¾
® C2 H6 + C2 H 4

(ii) Frankland reaction

heat
R - I + Zn + I - R ¾¾¾
® R - R + ZnI 2

(iii) Corey-House synthesis

R
|
Li CuX R'X
R-X ¾¾® R - Li ¾¾¾® R - CuLi ¾¾¾
® R -R'
(1° , 2° or 3° ) Alkyllithium Lithium (only 1° )
dialkylcuprate*

CH(CH3 )2
| CH CH Cl
Li CH -CuI
3 )2 ¾¾® ¾¾
(CH® ¾¾¾
(CH® (CH ) CH - CuLi ¾¾¾¾¾® - CH 2 2- -CH
3 2
(CH3 )2(CH
CHCl CHCl (CH )
3 ) 2 CH3-2Li ¾¾¾
® Li
3 )2 CH3 -2 C uLi ¾¾¾¾¾®(CH
(CH3 )32)CH
2 CH - CH CH33
2 - Methylbutane

(a) Grignard reagents can be used in place of alkyllithium.

(b) R' can be same or different from R, but the former should be primary.

5.3.7 Kolbe's electrolytic method

electrolysis
RCOO - Na + ¾¾¾¾¾® R - R + CO 2 + NaOH + H 2
14 4244 3 14 4244 3
At anode At cathode

. . 1
At cathode : Na + + e – ¾¾
® Na ; Na + H 2 O ¾¾
® NaOH + H 2
2
.. . .
- -e
. . : ¾¾® RCO O
At anode : RCO O . . : ¾¾
® R + CO 2

. . Coupling
R + R ¾¾¾¾¾ ®R -R

5.3.8 Methane can be prepared from aluminium carbide

Al 4 C 3 + 12H 2 O ¾¾
® 4Al(OH)3 + 3CH 4

5.4 Physical Properties

(i) C1–C4 are gases, C5–C17 are liquids and higher are solids.
(ii) As in other homologous series, boiling points of n-alkanes increase nearly 20-30° with the increase of each CH2
unit. In case of isomeric alkanes, boiling points decrease with the increase in the branching of the chain. The
higher boiling points of n-alkanes among isomeric alkanes is because of their large surface area which leads to
large vander Waals attractive forces. With the increase in branch, the molecule tends to become spherical due to
which surface area decreases and thus the vander Waals forces become weaker.

* Lithium dialkylcuprate is also known as Gilman reagent.

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(iii) The increase in melting point is not regular, an alkane with even number of carbon atoms melts at a higher
temperature than that with the higher homologue having an odd number of carbon atoms. This is because of the
zig-zag shape of the chains due to which the terminal carbon atoms of the alkane with odd number of carbon
atoms will lie on the same side while the terminal carbon atoms of the alkane with even number of carbon atoms
will be on the opposite sides. Thus alkanes with even number of carbon atoms pack better into a solid structure,
hence they melt at higher temperatures than the odd numbered alkanes which do not pack so well.
H H H H H
H H H
H C C H
H C C
C C C C H
C
H H
H H H H H H H
H
Structure of n-pentane (an odd numbered Structure of n-butane (an even numbered
alkane). Note the two end C atoms are lying on alkane). Note the two end C atoms are lying on
the same side leading to loose packing the opposite ends allowing closer packing
Branching of the chain also affects the alkanes' melting point. A branched alkane generally melts at a higher
temperature than the n-alkane with the same number of carbon atoms. Branching of an alkane gives it a more
compact three-dimensional structure which packs more easily into a solid structure and thus increases the
melting point.
(iv) The relative density increases with the size of the alkanes and tends to approach a constant value of 0.8 with
C16H34. Remember that nearly all organic compounds are less dense than water, as they consist mainly of C and
H. In general, for a compound to be denser than water, it must contain a heavy atom like Br or I or several atoms
like Cl.

1. Arrange the following compounds in order of decreasing boiling point.

(a) Octane, hexane, and decane
(b) n-Octane, 3,3-dimethylhexane, and 2,2,3,3-tetramethylbutane
2. Arrange the above compounds in order of decreasing melting point.

Relative stabilities of isomeric alkanes : Like most other organic compounds, alkanes burn readily in air. This
combination with oxygen is known as combustion and is quite exothermic. All hydrocarbons yield carbon dioxide and
water as the final products, e.g.

CH 4 + 2O 2 ¾¾
® CO 2 + 2H 2 O DH 0 = -212.8 kcal. ( -890 kJ)
The heat released on complete combustion of one mole of a substance is called its heat of combustion. A low
value of heat of combustion indicates the low heat content or enthalpy and thus higher stability of the molecule. Heat of
combustion is used for assessing the relative stability of isomeric alkanes. For example,

Octane 2-Methylheptane 2,2-Dimethylhexane 2,2,3,3-Tetramethylbutane

0
DH (kJ/mol.) 5471 5466 5458 5452
(kcal/mol.) 1307.5 1306.3 1304.6 1303

Thus here, 2,2,3,3-tetramethylbutane, the most highly branched isomer, is the most stable and octane, the
unbranched isomer is the least stable. The small differences in stability between branched and unbranched alkanes
depend on induced dipole-induced dipole attractive forces. We know that branching causes spherical shape which leads
to decreased forces of attraction between molecules (intermolecular forces).
Simultaneously, branching causes induced dipole-induced dipole attractions within a molecule which leads to
increased intramolecular attractive forces causing stability of the molecule. Thus branching increases intramolecular attractive
forces leading to increased stability.
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5.5 Chemical Properties

Since alkanes have completely non-polar C–C bonds and nearly non-polar C–H bonds, these are highly stable
to most of the common reagents at room temperature. However, they undergo substitution reactions involving free radical
chain mechanism in the presence of UV, at higher temperature or in the presence of certain free-radical initiators such as
peroxides etc.

5.5.1 Substitution reactions

(i) Halogenation.

UV
R - H + X 2 ¾¾¾¾
® R - X + HX
or heat

Cl Cl Cl Cl
For example, CH 4 ¾¾¾
2® CH3 Cl ¾¾¾
2® CH 2 Cl 2 ¾¾¾
2 ® CHCl
3 ¾¾¾
2® CCl 4
Methane Methyl chloride Methylene chloride Chloroform Carbon tetrachloride
REMEMBER :

(i) When equimolar amounts of CH4 and chlorine are taken, a mixture of the four possible products is formed.
(ii) The yield of methyl chloride can highly be improved by using a large excess of methane. Due to great difference between the boiling
points of methane (–161.5°C) and methyl chloride (–24°C), the two can be separated easily.
(iii) Reactivity of X2 : F2 > Cl 2 > Br 2 > I2 .
(iv) Bromination takes place somewhat less readily than chlorination.
(v) Iodination is a reversible reaction, since HI, formed as a by-product, is a strong reducing agent and reduces alkyl iodides back to
alkane. Hence, iodination can be done only in presence of a strong oxidising agent like iodic acid, nitric acid or HgO which destroys
the hydriodic acid.

5HI + HIO 3 ¾¾
® 3I2 + 3H 2 O
Iodides are more conveniently prepared by treating the chloro- or bromo-derivative with sodium iodide dissolved in methanol or
acetone (Conant Finkelstein reaction).
acetone
RCl + NaI ¾¾¾¾® RI + NaCl ¯
Soluble in acetone Insoluble in acetone

(vi) Fluorine, being the most reactive, reacts so viogorously even in the dark and at room temperature that it may lead to explosion and
cleavage of the C–C as well as C–H bonds. Thus fluorination when required, is carried out by
(a ) using fluorine diluted with an inert gas.
(b) or by using inorganic fluorides (e.g. HgF2 ) on bromo or iodo derivatives.

2C2 H 5 Br + HgF2 ¾¾
® 2C 2 H 5 F + HgBr2
(vii) Reactivity of hydrogen atoms : 3° > 2° > 1° > CH4 .

Halogenation of higher alkanes : Consider the following examples.

2 Cl
(i) CH 3 CH 2 CH 3 ¾¾¾¾¾® CH 3 CH 2 CH 2 Cl + CH 3 CH(Cl)CH 3
light, 25°C
Propane n- Propyl chloride (45%) Isopropyl chloride (55%)

2 Cl
(ii) CH 3 CH 2 CH 2 CH 3 ¾¾¾¾¾® CH 3 CH 2 CH 2 CH 2 Cl + CH 3 CH 2 CH(Cl)CH 3
light, 25° C
n- Butane 1- Chlorobutane (28%) 2 - Chlorobutane (72%)

CH3 CH3 CH3

| Cl 2 | |
(iii) CH 3 - CH - CH 3 ¾¾¾¾¾® CH 3 - CH - CH 2 Cl + CH 3 - C - CH 3
light, 25°C |
2 - Methylpropane 1- Chloro - 2 - methyl -
(Isobutane) propane (Isobutyl Cl
chloride) 64% 2 - Chloro - 2 - methylpropane
( tert - Butyl chloride) 36%

2 Br
(iv) CH 3 CH 2 CH 3 ¾¾¾¾¾® CH 3 CH 2 CH 2 Br + CH 3 CH(Br)CH 3
light, 127°C
Propane n- Propyl bromide (3%) Isopropyl bromide (97%)
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2 Br
(v) CH 3 CH 2 CH 2 CH3 ¾¾¾¾¾® CH 3 CH 2 CH2 CH2 Br + CH 3 CH 2 CH(Br)CH 3
light, 127°C
n- Butane 1- Bromobutane (2%) 2 - Bromobutane (98%)

CH3 CH3 CH3

| Br2 | |
(vi) CH 3 - CH - CH 3 ¾¾¾¾¾® CH 3 - CH - CH 2 Br + CH 3 - C - CH 3
light, 127°C |
Isobutane trace
Br
> 99%

From the above reactions, it is observed that chlorination gives mixture in which no isomer greatly predominates,
while bromination gives mixture in which one isomer predominates greatly (97-99%). Three factors determine the relative
yields of the isomeric products.
(i) Probability factor. This factor is based on the number of each kind of H atom in the molecule. For example, in
CH3CH2CH2CH3 there are six equivalent 1° H's and four equivalent 2° H's. The probability of abstracting 1° H's
to 2° H's is 6 to 4 i.e. 3 to 2.
(ii) Reactivity of hydrogen. The order of reactivity of H is 3° > 2° > 1°.
For example, the relative rates per hydrogen atom is found to be
3° (5.0) > 2° (3.8) > 1° (1.0) For chlorination at 25°C
3° (1600) > 2° (82) > 1° (1) For bromination at 127°C
(iii) Reactivity of halogen free radical. The more reactive chlorine free radical is less selective and more influenced by
the probability factor. On the other hand, the less reactive Br is more selective and less influenced by the
probability factor (Reactivity-selectivity principle).

1. Predict the porportions for bromination at 127° of the following compounds; relative reactivity ratio for 3°, 2° and 1° hydrogens
during bromination is 1600 : 82 : 1.
(a) isobutane (b) 2-methylbutane
(c) 2,3-dimethylbutane (d) n-pentane

Mechanism of halogenation : Halogenation takes place via free radical formation according to following steps :
heat or light .
(i) Cl2 2Cl } Chain initiation

. .
(ii) Cl + CH4 ¾¾® CH 3 + HCl
. Chain-propagation
.
(iii) CH3 + Cl2 ¾¾® CH3 Cl + Cl
Steps (ii) and (iii) are repeated again and again until finally chain is terminated by either of the reactions.

(iv) . .
Cl + Cl ¾¾® Cl2
. .
or CH3 + CH 3 ¾¾® CH3CH3 Chain-termination

or . .
CH3 + Cl ¾¾® CH3 Cl
NOTE THAT

(i) Each photon of light cleaves one chlorine molecule to two chlorine atoms.
(ii) Each chloride atom (or free radical) starts a chain and on an average, each chain consists of 5000 repititions of chain-propagating
cycle.
(iii) Under one set of conditions, nearly 10000 molecules of CH3Cl are formed for every quantum (photon) of light absorbed.
(iv) Presence of even a small amount of inhibitors (e.g. oxygen) slows down or stops a reaction by reacting with the intermediate free
radicals, e.g.
. .
CH 3 + O2 ¾¾ ® CH 3 - O - O
. .
The CH3 OO radical is mch reactive than the CH3 radical and hence can't propagate the chain. When all the oxygen molecules
present have reacted with methyl radicals, the reaction takes its usual path.
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Relative reactivities of halogens towards methane : The observed relative order (F2 > Cl2 > Br2 > I2) can be
explained with the values of DH (since Eact has been measured only for a few of these reactions) for the three steps of
halogenation for the four halogens.

Three steps of halogenation Value of DH for each step with the four halogens
F Cl Br I
.
(i) X 2 ¾¾
® 2X +38 +58 +46 +36

(ii) X . + CH 4 ¾¾ .
® CH 3 + HX –32 +1 +16 +33

(iii) CH 3 . + X 2 ¾¾
® CH 3 X + X
. –70 –26 –24 –20

Recall that in case of diatomic molecules (X2), Eact = DH. Thus chlorine with the largest Eact should dissociate
most slowly, while iodine having smallest Eact should dissociate most rapidly. Since this does not agree with the observed
order of reactivity (F2 > Cl2 > Br2 > I2), dissociation step (i) can't be the rate-determining step of halogenation.
Now consider, step (iii) which is exothermic in all cases. Further, the value of DH with chlorine, bromine and
iodine has nearly the same value, their Eact should be small and these should react faster and nearly with the same rate.
Hence this step also cannot be the cause of the observed relative reactivities.
Now consider, step (ii), note that the values of DH is spread over a wide range.
(a) The value of DH for bromine (+16 kCal) indicates that the Eact of their reaction must be at least 16 kCal which in
practice is found to be 18 kCal.
(b) The smaller value of DH (+1 kCal) for chlorine indicates that the Eact of this reaction could have a smaller value,
which is found to be 4 kCal. The large difference in Eact values with chlorine and bromine indicates that fraction of
collisions of chlorine and methane possessing sufficient energy is much larger than that of bromine and methane. In
other words, fruitless collisions are very high in case of bromine and methane as compared to chlorine and
methane and thus the chain in bromination becomes much shorter than in clorination. Thus, it can be concluded
that although at a given temperature, bromine atoms are formed more rapidly than chlorine atoms because of lower
Eact of step (i), overall bromination is slower than chlorination because of the shorter chain length which in turn
is due to larger Eact of step (ii) with bromine.
(c) For an endothermic reaction of an iodine atoms, Eact should be atleast 33 kCal. To achieve this large value, iodine
atoms should collide with an enormous number of methane molecules (nearly 10 13 at 275°C). However, no
iodine atom lasts this long, but it recombines with another iodine atom to form iodine molecules. Thus iodination
proceeds at a negligible rate. Thus although iodine atoms are easily formed, their inability to abstract hydrogen
from CH4 prevents iodination.
(d) The Eact for the highly exothermic fluorination, step (ii), is not expected to be larger than for the endothermic
chlorination step (ii), in practice the value is found to be 1 kCal thus permitting longer chains than for chlorination.
Further, due to weak F–F bond, fluorine atoms are formed faster than chlorine atoms, leading to more chains. Thus
due to more chains and longer chains, fluorination is extremely endothermic with a DH of –102 kCal.
In short, we have observed that of the two propagating steps (ii) and (iii), step (ii) is more difficult than (iii). Thus,
it is the rate of the formation of methyl radical [step (ii)] that determines the rate of halogenation. The relative reactivity of
X2 towards CH4 is due to difference in the value of DH in step (ii) which in turn is due to difference in the bond energy of
the H–X bond. In other words, reactivity of a halogen towards CH4 depends upon the strength of the bond which that
halogen forms with hydrogen.
Reactivity of alkanes (Ease of abstraction of hydrogen atom) Snce the rate determining step in halogenation is
abstraction of hydrogen by a halogen atom, i.e. the formation of alkyl radical, halogenation of alkanes follows order of
stability of free radicals, i.e.
.
3° > 2° > 1° > C H 3 (Order of stability of radicals)
The above order of stability of radicals is due to ease of their formation from the corresponding alkane which in
turn is due to difference in the avlue of DH.
. .
CH 3 - H ¾¾
® CH 3 + H
Methyl
DH = 104 kcal
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. .
CH 3 CH 2 - H ¾¾
® CH 3 CH 2 + H
Ethyl (1°)
DH = 98 kcal

. .
CH 3 CH 2 CH2 - H ¾¾
® CH3 CH 2 CH 2 + H DH = 98 kcal
Propyl (1°)

. .
CH 3 CHCH 3 ¾¾
® CH 3 CHCH 3 + H
| Isopropyl (2°) DH = 95 kcal
H

CH3 CH3
| |
.
CH 3 CCH3 ¾¾
® CH 3 CCH
. 3 +H DH = 92 kcal
|
tert - Butyl
H
.
Thus the amount of energy required to form the various classes of radicals decreases in the order : CH3 > 1° >
.
2° > 3°, i.e. it is easiest to form 3° radical and it is most difficult to form CH3 . We can also interpret this in an alternative way
"the ease of abstraction of hydrogen atoms from hydrocarbons follows the sequence 3° > 2° > 1° > CH4 which should also
be the ease of formation of free radicals." Now we know that the more stable the free radical, the more easily it is formed. Thus
the order of stability and ease of formation of free radicals is
.
3° > 2° > 1° > CH3
The above order of stability is in accordance with the stability of free radicals on the basis of delocalisation of
odd electron.
Allyl, benzyl > 3° > 2° > 1° > methyl, vinyl (Order of stability of various free radicals)
No rearrangement in free radicals. Unlike carbocation, a less stable free radical does not rearrange to the more
stable free radical. This can be proved by the photochemical chlorination of the deuterium-labelled isobutane, I. In this
experiment, the DCl : HCl ratio was found to be equal to the tert-butyl chloride : deuterated isobutyl chloride, clearly
indicating that every abstraction of a tert-hydrogen (deuterium) gave a molecule of tert-butyl chloride, and every abstraction
of a primary hydrogen gave a molecule of deuterated isobutyl chloride.

CH3 CH3
Cl2
D—Cl + CH3—C—CH3 CH3—C—CH3
(3° radical)
CH3 Cl
Cl2
CH3—C—CH3

D CH3 CH3
I Cl2
H— Cl + CH3—C—CH2 CH3—C—CH2Cl

D D
(1° radical)

This leads to the conclusion that the 1° radical formed in the second reaction does not rearrange to the more
stable 3° radical by migration of hydrogen atom or alkyl group. However, less stable radical carrying halogen atom can
rearrange to the more stable radical by migration of halogen, e.g.

Br
| . .
CH 3 -CH -C H 2 ¾¾
® CH 3- C H - CH 2 Br
(1° radical) (2° radical)

CH3 CH3
.
| .|
CH 3 - C Cl CH 2 ¾¾
® CH 3 - C - CH 2 Cl
(1° radical) (3° radical)
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1. Account for the fact that the chain-initiating step in thermal chlorination of CH 4 is
heat . heat . .
Cl 2 ¾¾¾ ® 2Cl and not CH 4 ¾¾¾ ® CH 3 + H
2. Draw the reactants, transition state and products for the following reaction, indicating state of hybridisation at each stage.
. .
Cl + CH 4 ¾¾
® CH 3 + HCl
3. Predict the product obtained by chlorination of tert- butyl bromide.

(i) Transition state for halogenation. The rate determining step of halogenation of alkanes proceeds in the following
way :

2
sp
3 . . sp
— C — H + .X — C ---- H ---- X — C. + H — X

Reactants Transition state Products

(C and X both have
partial radical character)

We have observed that the differences in reactivity towards halogen atoms are mainly due to differences in Eact,
the lower is the Eact of formation of a free radical, the more stable it is. This in turn means that the more stable the
radical, the more stable is the transition state leading to its formation. The transition states formed during
chlorination and bromination differ from each other.
1. Amount of cleavage of the C—H bond of alkanes is less in chlorination.
2. Free radical character of carbon is less in chlorination and more in bromination. More* fully developed is
the radical character in the transition state, more effective with be the delocalization of the odd electon and
more will be the stability of the radical. Thus difference in stability between 1°, 2° and 3° radicals and hence
reactivity of H's (3° > 2° > 1°) becomes more important in bromination than in chlorination.
3. It is formed earlier in chlorination than in bromination.
4. Transition state of chlorination resembles more with reactants, while that of bromination resembles more
with products.
(ii) Nitration.

NO 2
|
400 - 500° C
CH 3 CH 2 CH 3 + HNO 3 ¾¾¾¾¾® CH 3 CH 2 CH 2 NO 2 + CH 3 CHCH 3 + CH3 CH 2 NO 2 + CH3 NO 2
(vapour phase) 1- Nitorpropane 2 - Nitropropane Nitroethane Nitromethane

Vapour phase nitration causes chain fission. Liquid phase nitration is possible for alkanes having 6 or more
carbon atoms
(iii) Sulphonation. in case of n-alkanes, sulphonation is possible in alkanes having 6 or more carbon atoms, while
branched chain alkanes having less than 6 carbon atoms can also be sulphonated.
or Oleum
(CH3 )3 CH+ H 2SO 4 ¾¾¾¾¾
® (CH3 )3 CSO 3H
Isobutane (fuming) tert - Butyl sulphonic acid

5.5.2 Combustion or Complete oxidation

CH 4 + 2O 2 (excess) ¾¾
® CO 2 + 2H 2 O + 212.8 kcal

In general, æ 3n + 1 ö
C n H2 n + 2 + ç ÷ O 2 ¾¾
® nCO 2 + (n + 1)H2 O + Heat
è 2 ø

* In short, the declocalization of an odd electron, or accommodation of a positve or negative charage will take place more effectively when
the transition state is more fully developed, i.e. when the reagent is less reactive.
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The value of n and thus the nature of alkane can be ascertained by the following relation.
Volume of hydrocarbon 2
=
Volume of oxygen 3n + 1

Complete combustion of alkanes is the source of energy for the internal combustion engine. Although the complete
mechanism of combustion of alkanes is not fully developed, the reaction is a free radical chain raction.
To make gasoline engine more efficient, compression ratio of the fuel -air mixture was made higher, which,
sometimes produced knocking (objectionable metallic sound) instead of smooth explosion; knocking in turn reduces the
power of engine. Knocking depends upon the nature of the hydrocarbon and it falls off in the following order.
n-Alkanes > branched alkanes > alkenes > arenes
The relative antiknock tendency of a fuel is indicated by its octane number. An arbitraty scale has been set up
with n-heptane which knocks very badly, being given an octane number of zero, and 2, 2, 4- trimethylpentane (iso-octane),
being given the octane number of 100.

CH3 CH3
| |
CH 3 CH 2 CH 2 CH 2 CH 2 CH 2 CH 3 CH 3 - C - CH 2 - CH - CH3
n - Heptane |
(Octane number = 0) CH3
2,2,4 -Trimethylpentane
(Octane number =100)

Thus octane number of a gasoline is defined as the percentage of iso-octane present in a mixture of iso-octane and n-
heptane which matches the fuel (gasoline) in knocking; higher the octane number of a gasoline better is its quality. Regular
gasolines have an octane number of 74, gasolines having lower value than 74 are known as third grade gasoline, while
those having more than 74 octane number are known as premium gasolines. Compounds having more than 100 and even
less than 0 octane numbers are known ; e.g. n-nonane has an octane number of -45, while triptane (2, 2, 3-trimethylbutane)
has an octane number of 125. Gasoline with 100 or more octane number are used as fuel in aeroplanes (aviation gasoline).
Octane number of straight -run gasoline (gasoline, obtained by direct distillation of petroleum) can be improved
by the addition of compounds having higher octane number, viz. arenes, alkenes and branched chain alkanes. These
compounds in turn are produced from petroleum hydrocarbons by catalytic cracking, catalytic reforming and alkylation of
alkanes by alkenes. Octane number of a fuel is greatly improved by adding a small amount of tetraethyl lead, (C2H5)4Pb.
Gasoline, so obtained is known as ethyl gasolne or loaded gasoline. Tetraethyl lead (TEL) is believed to produce tiny particles
of lead oxides on whose surface certain reaction chains are broken.
In addition to CO2 and H2O, gasoline engine discharges include certain pollution-causing substances like
carbon monoxide, unburnt hydrocarbons, oxides of nitrogen and various lead compounds. This problem has been solved
by installing converters in automobile engines. Converters clean up exhaust emissions by catalytic oxidation of
hydrocarbons and carbon monoxide and by breaking oxides of nitrogen into nitrogen and oxygen. However, oxidation
catalysts used in converters contain platinum which is poisoned by lead. For overcoming this problem, use of unleaded
petrol is made compulsory. Absence of TEL in gasoline brought back the problem of knocking, which is solved in two
ways.
(i) By lowering the compression ratio in the newly built automobile engines.
(ii) By increasing octane number by the addition of arenes, alkenes and branched alkanes.
As octane number is used to describe the knocking property of gasoline, cetane number is used for measuring
the knocking character of diesel, used as fuel in diesel engines, Cetane (n-hexadecane) ignites very readily and is given a
cetane number of 100, while a-methylnaphthalene which ignites very sluggishly is given cetane number zero.

CH3

CH3(CH2)14CH3
Hexadecane (Cetane)
a-Methylnaphthalene
(Cetane number = 100)
(Cetane number = 0)

It must be noted that the discharge of CO2 from gasoline engines is also one of the compounds responsible for
causing green house effect. Gases accumulated in the atmosphere absorb and trap infrared light radiated outward from the
earth and convert it into heat, increasing temperature of the earth which in due course of time could cause drastic climatic
changes. Principal green house gases are carbon dioxide, chlorofluorocarbons (commonly known as CFCs) and methane.
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Other oxidation reactions of alkanes are
Cu tubes
(i) 2CH4 + 3O 2 (limited) ¾¾
® 2CO + 4H2 O (ii) CH + O ¾¾¾¾¾¾¾ ® CH 3 OH
1442432 100 atm, 200°C
1:1
CH 4 + O 2 (limited) ¾¾
® C + 2H 2 O
(Carbon black)

heated MoO alk.KMnO

(iii) CH 4 + O 2 ¾¾¾¾¾¾ ® HCHO + H 2 O (iv) (CH3 )3 CH + [O] ¾¾¾¾¾¾
4 ® (CH ) COH
3 3
Alkane with 3° C tert -Butanol

5.5.3 Pyrolysis
Decomposition of a compound by heat in absence of oxygen is known as pyrolysis. Pyrolysis of alkanes, especially
when applied to petroleum, is known as cracking, Here larger alkanes are converted into smaller alkanes, alkenes and
some hydrogen.
400 - 600° C 400 - 600°C
CH 2 = CH2 + CH4 ¬¾¾¾¾¾ CH3 CH2 CH3 ¾¾¾¾¾® CH 3 CH = CH 2 + H2
Ethene Methane Propane Propene
Of the four types of cracking (thermal cracking, steam cracking, hydrocracking and catalytic cracking), the last
one is most important. Here higher boiling petroleum fractions (gas oil) are heated in presence of finely divided silica-
alumina catalyst at 450-550°C and under slight pressure. Catalytic cracking not only converts larger molecules into
smaller ones thus increases the yield of gasoline, but it also improves the quality of gasoline by forming highly branched
alkanes and alkenes.

5.5.4 Alkylation
CH 3 CH3 CH 3 CH 3
| | | |
HF or
CH 3 - C - H + H2 C = C - CH 3 ¾¾¾® CH 3 - C - CH 2 - CH - CH 3
| Isobutene H2 SO 4 |
CH 3 CH 3
Isobutane 2,2,4 - Trimethylpentane (Isooctane)

5.5.5 Reforming, catalytic reforming or aromatisation

(Conversion of alkanes and cycloalkanes into aromatic compounds)

Cr2O3/Al2O3
600°C (–3H2)

n-Hexane Benzene

Cr2O3/Al2O3
600°C

n-Heptane Methylcyclohexane Toluene

Reforming, carried out in presence of hydrogen, is known as hydroforming and in presence of platinum as
platforming.

5.5.6 Isomeration
CH 3
anhy. AlCl 3 ,HCl |
CH 3 CH 2 CH 2 CH 3 ¾¾¾¾¾¾¾® CH 3 - CH - CH 3
n - Butane 200° C/ 35 atm Isobutane
Pyrolysis, alkylation, isomerisation and reforming are usd for increasing the octane number of gasoline

5.5.7 Insertion of methylene (carbene)

Singlet carbene (generated by the irradiation of ketene) can insert randomly into a s C–H bond of an alkane ; e.g.

® HCH2 CH 2 CH 2 CH 2 CH 2 CH 3 + CH 3CHCH 2 CH 2 CH 3 + CH 3 CH 2 CHCH2 CH 3

CH 3 CH 2 CH2 CH 2 CH 3 + H 2 C : ¾¾
n-Hexane(48%) | |
n - Pentane
CH2 H CH2 H
2-Methylpentane(35%) 3-Methylpentane (17%)
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231
NOTE

CH2, marked black are coming from carbene.

Remember that methylene is one of the most reactive and least selective species in organic chemistry.

CYCLOALKANES

Alicyclic (aliphatic cyclic) are those carbocyclic or homocyclic componds whose chemical properties are similar
to that of aliphatic compounds. The saturated hydrocarbons of this family are known as cycloalkanes and are designated
by the general formula CnH2n.

5.6 Nomenclature of Cycloalkanes

For convenience, alicyclic compounds are often shown by the topological formulation (line formula) and hence
structures of these compounds are drawn as a regular polygon whose each corner depicts a CH2 (methylene) group unless
some other group is indicated. Thus saturated hydrocarbons, i.e cycloalkanes are also named as polymethylenes, the
number of methylene groups is indicted by the prefix tri- , tetra- penta- etc. before the word methylene. According to IUPAC
system, these are named as cycloalkanes. Thus
CH2
or
H2C CH2
Common name Trimethylene Tetramethylene Hexamethylene
IUPAC name Cyclopropane Cyclobutane Cyclohexane

Substituents on the ring and unsaturation in the ring are named according to IUPAC formula, For example,
CH3 OH OH
OH 1 1
1 1 2 2
6 2 2 5
5 3 3
4
4 3 4
Cl
3-Chloromethylcyclohexane 1, 2-Cyclohexanediol 1, 3-Cyclopentadiene 3-Cyclohexenol
Bicyclic compound are named according to following rules :
(i) The compound is named as a bicyclo alkane corresponding to the total number of carbon atoms constituting
various rings (side chain carbon atoms should not be considered)
(ii) The number of carbon atoms in each of
3° carbon
the three bridges joining the two tertiary H
carbon atoms, known as bridge-heads, C
is written in brackets in descending
order. Bridge H2C CH2 Bridge
Prefix bicyclo indicate two rings, the having CH 2 having
word heptane indicates that the 2 carbon H2C CH2 2 carbon
compound has seven carbon atoms in
various rings first numeral 2 indicates C
that there are two carbon atoms between H 3° carbon
the two bridge heads, similar is the case
with the second numeral 2, while the Bridge having
numeral 1 indicates that there is only one carbon
one carbon between two bridge heads. Bicyclo [2.2.1] heptane or Norborane
(iii) For substituted bicyclic compounds, numbering is done from a bridge head of the longest bridge, continued to
the next longest bridge and then to the shortest bridge. For example,

7 1 2 5 7
4 6
8 8
3 3
1
6 5 4 Cl 2 9
3-Methylbicyclo [3.2.1] octane 3-Chloro-7-methylibicyclo [4.3.0] non-7-ene
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If two rings are joined by a quaternary carbon at the apex, then they are prefixed by the word spiro. The
numbering starts from the atom next to the spiro atom and proceeds through the smaller ring first, e.g.

Spiro atom 9 10 1 2
5 1
8
3 5
4 2 7 6 4 3
H3C
Spiro (2.2) pentane 7-Methylspiro (5.4) decane

Certain polcyclic hydrocarbons having strange and wonderful shapes have been synthesized. These are generally
given common names, sometimes indicating their shapes e.g. cubane (having shape of a cube), basketane (having shape
of a basket).

1. Draw tropological structural formula for (i) 3- propylcyclopentene, (ii) cyclopent-3-enol, (iii) bicyclo (3.2.1) octane (iv) bicyclo
(3.1.0) hexane, (v) 1-methyl-2-propenylcyclopentane, (vi) cis-1-chloro-2-bromocyclobutane.
2. Write the IUPAC name of the following compounds :

(i) (ii) (iii)

H3C Cl
(iv) Cl (v) (vi)

3. Use the solid-dot topological convention to indicate the cis-trans isomers for (i) 1,1,2-trimethylcyclopropane,
(ii) 1,3-dimethylcyclobutane, (iii) 1,2,4-trimethylcyclohexane, and (iv) 1-methyl-2-propenylcyclopentane.
4. (a) Draw the structural formula and stereochemical designation of the isomeric dimethylcyclohexane.
(b) Draw the structure and give the molecular formula for cyclododecane.

5.7 Geometrical Isomerism in Alicyclic Compounds

The inability of atoms in rings to rotate completely about their bonds leads to cis-trans (geometrical) isomerism in
alicyclic compounds. A cycloalkane has two distinct faces. If two substituents point towards the same face, they are cis; if
they point towards opposite faces, they are trans, e.g. 1, 2 -dimethylcyclopropane.
Me Me
Me Me
or or

H H H H

cis-1, 2-Dimethylcyclopropane

H Me

H Me
or or

Me H
Me H

trans-1, 2-Dimethylcyclopropane
In topological notation, the solid dot denotes an H projecting towards the viewer.
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5.8 Chemical Properties of Cycloalkanes

Chemically, cycloalkanes behave both like alkanes and alkenes.

All cycloalkanes, except cyclopropane, undergo halogenation in presence of diffused day light; cyclopropane
under these conditions undergo addition reactions indicating that the three-membered ring is highly unstable. Actually,
tendency of forming addition compounds decreases with increase in size of ring, i.e.
Cyclopropane > Cyclobutane > Cyclopentane > Cyclohexane
Addition reactions of cycloalkanes indicate that the stability of the ring increases as the ring becomes larger,
i.e. increasing stability of the various cycloalkanes upto cyclohexane follows the order :
Cyclopropane < Cyclobutane < Cyclopentane
Relative stability of alicyclic compounds is due to different amount of strain in the various rings. Different amount
of strain is due to deviation (d) form the normal bond angle of 109°28’
109°28'- a
d=
2
where a is the bond angle which is 60°, 90° and 108° in cyclopropane, cyclobutane and cyclopentane respectively.
Thus cyclopropane has the maximum strain and thus it will be least stable while cyclopentane with less strain is the most
stable among these three cycloalkanes. Strain theory, commonly known as Baeyer strain theory, explains the relative
stability of the first three cycloalkanes.

Example 1 :
Give IUPAC name of the following alkane.

Solution :
9
1 10
8
2
5 7
3
4 6
3,7-Diethyl-2,2,8-trimethyldecane

Example 2 :
Draw the eclipsed and staggered conformations of H2O2, NH2OH and CH3OH.
Solution :
H H H
O—O O—O (H2O2 )
H

H H H H
N—O N—O (NH2OH)
H H
H
H H H |
H |
| O (CH3OH)
C———O C
|
H H H
Staggered conformations Eclipsed conformations
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Example 3 :
Predict the proportions of isomeric products from chlorination at room temperature of (a) isobutane,
(b) 2-methylbutane, (c) 2, 3-dimethylbutane and (d) n-pentane. Relative reactivities of 3°, 2° and 1° H's for chlorination
is 5. 0 : 3. 8 : 1.0.
Solution :
CH3 CH3 CH3
Cl2
(a) CH3CHCH3 ——® CH3CHCH2Cl + CH3C(Cl)CH3
Isobutane Isobutyl chloride tert-Butyl chloride
I II
Relative proportions of the two products can be calculated as below :

Product Type and No. of Relative Weighted % Yield

formed H atoms involved reactivity reactivity
æ 9ö
I 1° (9 in No.) 1 9×1=9 çè ÷ø × 100 = 64%
14

æ 5ö
II 3° (1 in No.) 5.0 1×5=5 çè ÷ø × 100 = 36%
14

CH3 CH2Cl
CH3—CH—CH2—CH2Cl + CH3—CH—CH2CH3
CH3 1-Chloro-3-methylbutane 1-Chloro-2-methylbutane
Cl2 (I) (II)
(b) CH3—CH—CH2CH3
2-Methylbutane CH3 Cl CH3
(It has six 1°, three 1°C + CH3—CH—CHCH3 + CH3—C—CH2CH3
and two 2° H’s)
2-Chloro-3-methylbutane Cl
2-Chloro-2-methylbutane
(III) (IV)

Calculation of % formed of each product.

Name of Type and No. of Relative Weighted % Yield

product H’s involved reactivity reactivity
3
I 1°¢ (three in No.) 1 3×1=3 × 100 = 14%
21.6
6
II 1° (six in No.) 1 6×1=6 × 100 = 28%
21.6
7.6
III 2° (two in No.) 3.8 2 × 3.8 = 7.6 × 100 = 35%
21.6
5
IV 3° (one in No.) 5.0 1×5=5 × 100 = 23%
21.6

CH3 CH3 CH3 CH3 CH3 CH3

Cl2
(c) CH3—CH—CH—CH3 ——® CH3—CH—CH—CH2Cl + CH3—C—–CHCH3
2, 3-Dimethylbutane (I) Cl
(II)

(It has twelve 1° H’s and two 3° H’s)

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235

Name of Type and No. of Relative Weighted % Yield

product H’s involved reactivity reactivity

æ 12 ö
I 1° (12 in No.) 1 12 × 1 = 12 çè ÷ø × 100 = 55%
22

æ 10 ö
II 3° (2 in No.) 5 2 × 5 = 10 çè ÷ø × 100 = 45%
22

Cl Cl
Cl2
(d) CH3CH 2CH 2CH2CH 3 ——® CH3CH 2CH 2CH 2CH 2Cl + CH3CH2CH 2CHCH 3 + CH3CH2CH 2CHCH 2CH 3
n-Pentane I II III

(It has six 1° H’s. four 2° H’s and two 2° H’s)

Name of Type and No. of Weighted % Yield

product H’s involved reactivity

æ 6 ö
I 1° (Six in No.) 6×1=6 çè ÷ × 100 = 21%
28.8 ø

æ 15.2 ö
II 2° (Four in No.) 4 × 3.8 = 15.2 çè ÷ × 100 = 53%
28.8 ø

æ 7.6 ö
III 2°¢ (Two in No.) 2 × 3.8 = 7.6 çè ÷ × 100 = 26%
28.8 ø

Example 4 :
Chlorine atom can react with CH4 in the following two ways :
. . .
HCl + CH 3 ¬¾
¾ CH 4 + Cl ¾¾
® CH 3 Cl + H
Are both steps possible? Explain your answer.

Solution :
Let us write down the two possible reactions with their DH and Eact values.

.
Cl . + CH3—H —— ® H—Cl + CH3 D H = + 1 kCal
(104) (103)

Eact = 4 kCal
Cl . + CH3—H —— ® CH 3—Cl + H . D H = + 20 kCal
(104) (84)

Eact ³ 20 kCal
Thus due to difference in Eact, we can say that the first reaction should be the only reaction that takes place.
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EXERCISE 5.1 (MCQ - ONE option correct)

1. Following two structures represent 13. If the Eact for a forward reaction is given
. . DH = + 1 kCal, Eact = 4 kCal
CH 3 - H + Cl ¾¾
® CH 3 + H - Cl
C the Eact for the backward reaction will be
C C C C C (a) 1 kcal (b) 4 kcal
C C C (c) –4 kcal (d) 3 kcal
C 14. Which of the following statement is false?
(a) Energy of activation for an endothermic reaction can't be
(a) geometrical isomers (b) chain isomers less than the value of DH
(c) enantiomers (d) conformers (b) Reactions involving the union of two free radicals has no
2. Which conformation of ethane is more prevalent at high Eact
temperature? (c) Whole of energy liberated during formation of a bond is
(a) staggered (b) eclipsed available for the cleavage of bond
(c) skew (d) all are equal. (d) Energy of activation for the cleavage of Cl–Cl bond to Cl• is
3. Which of the following can exist in different conformations ? equal to the bond energy of the Cl–Cl bond.
(a) H2O 2 (b) CH3OH 15. Reactivity of chlorine and bromine towards methane at 275°C
(c) NH2OH (d) All the three. differ by a factor of nearly
4. The possible number of conformations in CH3OH is (a) 10 2 (b) 10 3
(a) 1 (b) 2 (c) 10 4 (d) > 105
(c) 8 (d) ¥ 16. Predict the nature of A in the following reaction :
5. Which is the correct representation for the reduction of alkyl 1 eq Br2
halide by Zn and dil. HCl? A
hv
+ 2+ -
(a) R - X + Zn + H ¾¾
® R - H + Zn +X Br
Br
(b) R - X + 2[H] ¾¾ ® R - H + HX
(c) Both of the above (a) (b)
(d) None of the two
6. Boiling points of C2H6 and C3H8 ; C2H5OH and C3H7OH ;
CH3NH2 and C2H5NH2 generally differ by Br
Br
(a) 5-10°C (b) 10-20°C
(c) 20-30°C (d) no definite range (c) (d)
Br
7. The strongest known acid is
(a) H2CrO4 (b) HNO3 17. Chlorination of methane involves following steps :
(c) HF–SbF5 (d) FSO3H–SbF5 .
(i) Cl - Cl ¾¾
® 2Cl
8. Mixture of n-alkanes and branched alkanes can be separated by
(a) steam distillation . .
(ii) CH 4 + Cl ¾¾
® CH 3 + HCl
(b) fractional distillation . .
(c) urea inclusion complex formation (iii) CH 3 + Cl 2 ¾¾ ® CH 3 Cl + Cl
(d) fractional crystallisation. Which of the following steps is rate determining?
9. Pick up the correct statement regarding reactivity of CH4 and (a) step (i) (b) step (ii)
C2H6 towards chlorination. (c) step (iii) (d) steps (ii) and (iii) both
(a) CH4 is more reactive than C2H6 18. The use of leaded petrol in engines fitted with converters is
(b) C2H6 is more reactive than CH4 objectionable mainly because
(c) Both are equal reactive (a) it is costlier
(d) (a) and (b) are correct. (b) it gives less mileage
10. Halogenation of alkanes is an example of (c) it causes more pollution
(a) substitution (b) oxidation (d) its lead content poisons the catalyst used in converters
(c) both (a) and (b) (d) elimination. 19. 20 ml of methane are burnt with 50 ml of oxygen, the volume of
11. When isobutane is treated with bromine at 127°C, the product the gas left after cooling to room temperature will be
formed is (a) 80 ml (b) 60 ml
(a) a mixture of isobutyl bromide and tert-butyl bromide (c) 30 ml (d) 20 ml
(b) a mixture of sec-butyl bromide and tert- butyl bromide 20. The most stable of meso HOOC - CH- CH- COOH in strong
(c) a mixture of isobutyl bromide, sec- butyl bromide and tert- | |
butyl bromide as the major product Me Me
(d) almost 100% tert-butyl bromide. basic medium is
12. The relative rate for chlorination of a hydrocarbon per hydrogen (a) Anti form (b) Gauche form
atom is found to be 5.0 : 3.8 : 1.0 for tert-, sec- and pri-hydrogen (c) Fully eclipsed form (d) Partially eclipsed form
atoms. What changes can be brought about with change in
(1) x
temperature? 21. CH3 - CH2 - CH3 ¾¾¾® CH 3 - CH 2 - CH 2 - Br
(2) y
(a) The relative rates do not change at all with rise in (3) z
temperature
(b) The relative rates further widen with increase in temperature x, y, z are respectively :
(c) The relative rates can shrink even to 1 : 1 : 1 with rise in (a) Br2/hn, conc. H2SO4, ThO2/D
temperature (b) Cl2/hn, alc. KOH/D, HBr/R2O2
–
(d) Selectivity of a reagent for its attack on a site does not (c) Cl2/hn, ter-BuO /D, HBr (dark)
change with temperature. (d) F2/hn, Al2O3/D, NBS
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22. The reaction of 1-bromo-3-chlorocyclobutane with metallic 30. Pick up the dissimilar structure
sodiuim in dioxane under refluxed condition gives
(a)
(a) Cl Cl
(b)

(b) Br Cl (c)

(d)
(c) Br Br 31. The simplest chiral alkane will have how many carbon atoms?
(a) 4 (b) 6
(c) 7 (d) 8
32. The highest boiling point is expected for
(d) (a) isooctane
(b) n-octane
(c) 2, 2, 3, 3-tetramethylbutane
23. Which of the following compound has twice the number of primary
(d) n-Butane
hydrogens as the number of secondary hydrogens?
33. The reaction conditions leading to the best yield of C2H5Cl are
(a) (CH3)2CClCH(CH3) 2
(b) (CH3) 3C.CH2.C(CH3) 3 UV light
(a) C 2 H 6 (excess) + Cl 2 ¾¾¾¾®
(c) (C2H5)2C(CH3)CH2CH3
(d) (C2H5) 2CHCH2CH2CH(CH3) 2 (b)
dark
C 2 H 6 + Cl 2 ¾¾¾¾¾®
24. Methane can be chlorinated by room temp.
(i) treating with chlorine in presence of UV light UV light
(ii) heating with chlorine in presence of tetraethyl lead (c) C 2 H 6 + Cl 2 (excess) ¾¾¾¾®
(iii) treating with tert-butyl hypochlorite in presence of UV light dark, heat
(a) only (i) method (b) only (i) and (ii) methods (d) C 2 H 6 + Cl 2 ¾¾¾¾¾
®
34. Which of the following will have least hindered rotation about C–
(c) (i) and (iii) methods (d) (i), (ii) as well as (iii) method. C bond?
25. In the following reaction (a) Ethane (b) Ethylene
Me (c) Acetylene (d) Hexachloroethane
35. Isomers which can be interconverted through rotation around a
D Cl NaSH(1 eq.) single bond are
¾¾¾¾¾¾ ® Major product
H Br DMSO (a) enantiomers (b) diastereomers
(c) conformers (d) positional isomers
Ph 36. When cyclohexane is poured on water, if floats because
Which option has the correct features for reaction mechanism, (a) cyclohexane is in boat form
leaving group & stereochemistry ? (b) cyclohexane is in chair form
– – (c) cyclohexane is in crown form
(a) SN2/ Cl / inversion (b)
SN2/ Br / inversion
(d) cyclohexane is less dense than water.
– –
(c) SN1/ Br / racemisation (d) E2/ Br / anti-elimination 37. Photobromination of 2-methylpropane gives a mixture of 1-
bromo-2-methylpropane and 2-bromo-2-methylpropane in the
26. An alkyl bromide, RBr of molecular weight 151 is the exclusive
product of bromination of which hydrocarbon? ratio of 9 : 1. This can be explained on the basis that
(a) 2, 2,-Dimethylhexane (b) 2, 2, 3-Trimethylheptane (a) bromine is highly reactive
(c) 2, 2-Dimethylpropane (d) Dodecane (b) reactivity order for 3°, 2° and 1° hydrogen during
27. Chlorination of an equimolar mixture of neopentane and ethane bromination is 5.0 : 3.8 : 1 respectively
gives neopentyl chloride and ethyl chloride in the ratio of 2.3 : 1. (c) reactivity of bromine is governed by probability factor
The reactivity ratio of 1° hydrogen atoms of the neopentane and (d) the above statement is false.
ethane will be
CH3
(a) same (b) 1.15 : 1
(c) 2:1 (d) 1.70 : 1
38. H3C Cl2, hv N (isomeric products);
28. During bromination of methane, addition of HBr will
(a) speed up bromination
(b) slow down bromination CH3
(c) produce no effect on bromination
fractional distillation
(d) change the mechanism of bromination C 5 H11Cl ¾¾¾¾¾¾¾¾¾ ® M (isomeric products)
29. When n-pentane and diazomethane mixture is irradiated with Identify N and M
UV light, three compounds are formed (a) 6, 4 (b) 6, 6
CH3 CH 2 CH2 CH2 CH 2 CH3 (CH3 )2 CHCH 2 CH2 CH 3 (c) 4, 4 (d) 3, 3
I II 39. When fluorine reacts with 2-methylpropane in presence of light
(C2 H 5 )2 CHCH 3 gives 14% tert-butyl fluoride and 86% isobutylfluoride. What
III
will be the ratio of relative reactivity of a tertiary hydrogen to
Which of the compound given above will be formed as major
primary hydrogen ?
product?
(a) I (b) II (a) 0.682 (b) 1.46
(c) III (d) all equal (c) 6.14 (d) 0.813
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EXERCISE 5.2
DIRECTIONS for Q. 1 to Q. 12 : Multiple choice questions with DIRECTIONS for Q. 13 to Q. 23 : Read the following passages and
one or more than one correct option(s). answer the questions that follows :

1. Which of the following statements are not correct for alkanes?

(a) All C – H and C – C bonds have a length of 1.112Å and PASSAGE 1
1.54Å respectively At certain temperature, the % of monochlorinated products
(b) All bond angles are tetrahedral having a value of 109.5'. obtained for the following reactions are given :
(c) The C–C chain is linear and not zigzag Cl /hn
(d) All alkanes exhibit isomerism CH3 - CH2 - CH2 - CH3 ¾¾¾¾
2 ®
2. Which of the following reactions can be used to prepare methane?
(a) Clemmensen reduction CH3 - CH2 - CH2 - CH2 - Cl+ CH 3 - CH - CH2 - CH3
(b) Wurtz reaction (28.30%) |
Cl (71.70%)
(c) Catalytic hydrogenation of methyl iodine
(d) Reduction of methyl idodide by using a zinc copper couple
3. Methane is obtained when CH 3 CH3
(a) sodium acetate is heated with soda lime | Cl2 /hn
|
CH3 - CH - CH3 ¾¾¾¾® CH3 - C - CH3 + CH3 - CH - CH 2 - Cl
(b) iodomethane is reduced | |
(c) aluminium carbide reacts with water Cl CH3
(d) potassium acetate is electrolysed (33.33%) (66.66%)
4. Which of the following will give three monobromo derivatives?
(a) CH 3 CH 2 CH 2 CH 2 CH 2 CH 3 For all questions assume reactivity ratio to be same as in the
above reactions.
(b) CH 3 CH 2 CH 2 - CH(CH 3 )CH 3 The propagation step of monochlorination of alkane involves
(c) CH 3 - CH 2 - C(CH 3 )2 CH 3 formation of the radical intermediate.
g g
(d) CH 3 CH(CH 3 )CH(CH 3 )CH 3 R - H + Cl ¾¾ ® R + H - Cl
5. Alkenes undergo The energy profile for the formation of free radical is described
(a) substitution reactions (b) addition reactions as
(c) ozonolysis (d) none of these
6. Methane can be prepared by
(a) Wurtz reaction (b) Decarboxylation
(c) Hydrogenation reaction Potential (X)
(d) Alkyl magnesium bromide Energy (P)
7. Only two isomeric monochloro derivatives are possible for : (Q)
(a) n-butane (b) 2, 4-dimethylpentane
(c) benzene (d) 2-methylpropane (R)
8. Which is/are true statements/reactions?
Reaction
(a) ® CH 4 (b) CaC 2 + H 2 O ¾¾
Al 4 C 3 + H 2 O ¾¾ ® C2H2 for the compound (X)
(c) Mg 2 C3 + H 2 O ¾¾
® CH 3 C = CH Me
(d) Holme signal uses mixture of Ca3P2 and CaC2

9. O
Me Me
This change can be carried out using :
[X]
(a) NH2NH2, glycol/OH– (b) Sn(Hg)/conc. HCl
(c) P/HI (d) NH3/LiAlH4 13. For the compound (X), the following statement is true for the
10. CH4 gas is also called/content of : monochlorination via intermediate (Q)
(a) CNG (b) Marsh gas (a) 2-different products both optically active.
(c) water gas (d) producer gas (b) 2-different products one active and other inactive.
11. Methane will be produced in which of the following reaction ? (c) 2-different products and are distereomers of each other.
H O LAH (d) Only one product is obtained
(a) Be2 C ¾¾¾
2 ® (b) CH3 OH ¾¾¾® 14. Which of the following is incorrect for the monochlorination of
Na (X)?
CH3 - Cl ¾¾¾¾ ® H2 O
(c) EtOH Al 4 C3 ¾¾¾®
(d) (a) Via intermediate (P), only one product is obtained
12. Compound which can not be synthesized by Wurtz reaction (b) Via intermediate (R), two products are obtained which are
using one type of halide only ? enantiomers
(c) All products obtained are optically inactive
(d) The % distribution of product formed via intermediate (P)
is 19.86%
(a) 15. Excluding stereochemistry which of the following is false for all
the products obtained by monochlorination of (X).
(a) Product obtained by the most stable free radical
intermediate is the major product of the reaction.
(b) (b) 50.33% of the product is formed by intermediate Q formed
in the reaction.
(c) Three different types of products are obtained.
(d) All three types of products are having prochiral carbon
(c) (d) atom.
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PASSAGE 2 Instructions for Q. 24 & 26 : Following questions are Multiple
Answer the following questions based on given reaction. Matching type Questions :

24. Column I Column II

O (A) CH3 CH3 (a) Wurtz reaction
¾¾¾¾¾¾¾®
2 Products
hn
(monochlorination) (B) CH3CH2CH3 (b) Frankland reaction
(C) (CH3) 3CCH3 (c) Corey House reaction
16. Total number of theoretically products (including stereo) are 25. Column I Column II
(a) 4 (b) 5 (A) Lowest alkane (a) CNG
(c) 8 (d) 10 (B) A higher straight (b) Possess lowest octane
17. How many products are resolvable ? chain alkene number
(a) 2 (b) 4 (C) Gasoline (c) Aromatic hydrocarbons
(c) 5 (d) 6 (D) Sodium plumbite (d) Doctor sweetening solution
18. How many fractions are present on fractional distillation ? 26. Column-I Column-II
(a) 4 (b) 5 (A) Decarboxylation of (a) Methane
(c) 6 (d) 8 RCOONa
(B) Wurtz reaction (b) Ethyne
PASSAGE 3 (C) Corey House reaction (c) n-Butane
Kolbe’s electrolysis can be represented as (D) Dehydrohalogenation (d) 2-Methylpropane
Cathode Å +2e–
–
2Na 2Na Instructions for Q. 27 to 33 : Following questions are Assertion and
2RCOONa 2Na + 2H2O ® H2­+2NaOH Reasoning Type Questions :
A Anode
2RCOO
– (i) –2e–
2R
. Note : Each question contains STATEMENT-1 (Assertion) and
Å (ii) –2CO2 STATEMENT-2 (Reason). Each question has 4 choices (a), (b), (c)
and (d) out of which ONLY ONE is correct.
R g + R g ¾¾
®R - R (a) Statement-1 is True, Statement-2 is True; Statement-2 is a correct
explanation for Statement-1.
19. During the electrolysis of sodium ethanoate, the gas liberated at (b) Statement-1 is True, Statement-2 is True; Statement-2 is NOT a
cathode is : correct explanation for Statement-1.
(a) H2 (b) CO 2 (c) Statement -1 is True, Statement-2 is False.
(c) CH4 (d) CH3 – CH3
(d) Statement -1 is False, Statement-2 is True.
20. During the electrolysis pH of electrolyte .................. progressively
(e) Statement -1 is False, Statement-2 is False.
(a) increases (b) decreases
(c) remains same (d) can not be predicted
21. In Kolbe’s electrolysis, if A is sodium propanoate, then 27. Statement 1 : Cyclopropane has the highest heat of combustion
hydrocarbon formed is : per methylene group
(a) CH3 – CH3 (b) CH2 = CH2 Statement 2 : Its potential energy is raised by angle strain.
(c) CH3 – CH2 – CH2 – CH3 (d) A mixture of 1, 2 and 3 28. Statement 1 : Iodination of alkane is slow and reversible in
nature
Statement 2 : Iodination of alkane is performed in the presence
PASSAGE 4 of strong an oxidising agent like HIO 3, which consumes the
An acyclic hydrocarbon P, having molecular formula C6H10, gave by-product HI and recycles into reactants I2.
acetone as the only organic product through the 29. Statement 1 : When n-butane is heated in the presence of AlCl3/
following sequence of reaction, in which Q is an intermediate organic HCl it will be converted into propane
compound.
Statement 2 : In the presence of AlCl3/HCl if any alkane having
more than four carbon is heated than isomerisation is held to
give isomer of reactant alkane.
30. Statement 1 : Branched alkanes have lower boiling point than
their unbranched isomers.
Statement 2 : Branched alkanes has relatively small surface
area, so less London’s dispersion force act among molecules.
22. The structure of compound P is 31. Statement 1 : Alkanes float on the surface of water.
(a) Statement 2 : Density of alkanes is in the range of 0.6 – 0.9 g/
(b) ml, which is lower than water.
32. Statement 1 : 2-chlorobutane on dehydrochlorination gives 2-
butene (cis + trans) as a major product rather than 1-butene
(c) Statement 2 : 2-Butene is thermodynamically more stable than
1-butane.
33. Statement 1 : 2-Bromobutane on reaction with sodium ethoxide
in ethanol gives 1-butene as a major product.
Statement 2 : 1-Butene is more stable than 2 -butene.
(d)
Instructions for Q. 34 to 41 : Following questions are Integer Type
23. The structure of the compound Q is Questions :

Cl
(a) (b) 34. ¾¾¾
2®
(A) number of monochloro derivatives
hn
formed. (excluding stereoisomers)
35. Total number of trichloroderivatives of the compound (excluding

stereoisomers) will be .
(c) (d)
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36. Number of monochloro derivatives (excluding stereoisomers), 38. How many stereoisomers are possible for dichlorocyclobutane?
dichloro derivatives and trichloro derivatives of cyclopentane 39. How ma ny enantiomeric pairs are possible in
are n1, n2 and n3 then (n1 + n2)/n3 is equal to bromochlorocyclopentane?
37. How many isomers (including geometrical and optical) are 70. How many meso isomers are possible in diiodcyclopentane?
possible for bromochlorocyclobutane? 41. On conversion into the Grignard reagent followed by treatment
with water, how many alkyl bromides would yield isopentane?

EXERCISE 5.3 (Subjective Problems)

1. Write IUPAC name of the following compounds : 13 . Predi ct the pe rce nta ge of i somers formed duri ng
monochlorination of
(a ) 2, 2-dimethylbutane
(b) isohexane and
(c) 2, 2, 4-trimethylpentane
(a) (b) Relative order of rea cti vity i s 3 ° (5.0 ), 2 ° (3.8 ) a nd
1° (1.0)
14 . Chlorination of propane gives four products (A, B, C and D) of
the formula C3 H6 Cl 2 . A, B, C and D on further chlorination
gives one, two, three and three trichloro derivatives respectively.
Assign structures to A, B, C and D.
15 . Explain the following :
(c) (d) (a ) Alkanes are inert
(b) Pyrolysis of alkanes leads to cleavage of C–C bonds rather
than C–H bonds
(c) Although combustion of alkanes is a strongly exothermic
process, it occurs only at high temperatures.
16 . Identify A to G
(e) (i) CH 3 CH 2 CH 2 CH 2 Br + [(CH 3 )3 C -]2 CuLi ¾¾®A
Cl
. Cl 2
(ii) CH 3 .CHBrCH 3 ¾¾¾ ® B ¾¾ ® C ¾¾¾ ®D

(iii) RCl Li H2O

(E) ether
F G
(f)
Na

2. Draw line formula for 2, 7-Dimethyloctane

(i) 2, 2, 3, 3-Tetramethylpentane 17 . Draw structural formula of
(ii) 2-Chloro-2, 4, 4-trimethylheptane (i) Cyclopentylacetylene
(iii) 5-(1', 2'-dimethylpropyl)-6-methyldodecane. (ii) 3-Chloro-1, 1-dimethylcycloheptane
3. Write the structural formula and give IUPAC names for the (ii) cis-1-Bromo-2-methylcyclopentane
possible monobromo derivatives of isopentane. (iv) Bicyclo [2.2.1] hepta-2, 5-diene
4. Give the structure and IUPAC name of alkane or alkanes having (v) 1-Chlorobicyclo [2.2.2] octane
molecular weight 86. 18 . Two isomeric hydrocarbons, A and B have the molecular
5. Derive the structural formula and IUPAC names for all dichloro formula C6 H12 . These do not react with hydrogen but react
derivatives of propane. with chlorine in sunlight to give the monochloro derivatives of
6. Arrange the following alkanes in order of their increasing boiling the formula C6 H11 Cl. Compound A gives only one product,
points : while B gives several different products. Assign structures to
(i) n-Pentane (ii) n-Heptane A and B.
(iii) 2-Methylhexane (iv) 2-Methylheptane 19 . A rocket is filled with a petroleum fuel of composition n-C14 H30
(v) 3, 3-Dimethylpentane and density 0.764 g/mL and liquid oxygen.
7. Write equations for the preparation of n-butane from (a ) Determine the weight of oxygen required for complete
(i) n-butyl bromide (ii) sec-butyl bromide combustion of every litre of the petroleum fuel.
(iii) ethyl chloride (b) Determine the amount of heat evolved in the combustion
8. Give the simplest and easiest possible way for synthesising of one l itre of t he fuel , a ssuming that ea ch
(i) monodeuteratedethane –CH2 – and each –CH3 group evolve 157 kcal/mol and
(ii) 1, 2-dideuteratedethane 186 kcal/mol respectively.
(iii) 1, 1-dideuteratedethane (c) Determine the weight of hydrogen required for producing
9. How will you carry out following synthesis in the minimum same heat as one litre of petroleum fuel and the necessary
steps?
oxygen. Given DHH = –104 kcal/mol. Assuming that
(i) propane to 2, 3-dimethylbutane 2
(ii) propane to 2-methylpentane formation of H2 is the only reaction that takes place in the
(iii) propane to neopentane rocket fuel.
10 . 2-Methyl propane can be synthesis ed fro m three-c arbon 20 . A solution containing 4.12 mg of an unknown alcohol (ROH) is
compounds by two alternate ways, which of the two is superior. added to a solution of methylmagnesium iodide and 1.56 mL
11 . Arrange the following compounds in order of decreasing ease of a gas were collected at STP. Determine the molecular weight
of abstraction of hydrogen atom : of ROH.
(a ) CH2 = CH2 (b) CH2 = CHCH3 21 . 1.79 mg of an alcohol of mol. wt. 90 gave 1.34 mL of the gas
(c) C6 H 5 CH 3 measured at NTP. Det ermine the number of
12 . Name the first four simplest alkanes that give a single product –OH groups in the compound.
on methylene insertion.
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241

EXERCISE 5.1
1 (d) 6 (c) 11 (d) 16 (c) 21 (b) 26 (c) 31 (c) 36 (d)
2 (b) 7 (d) 12 (c) 17 (b) 22 (d) 27 (b) 32 (b) 37 (d)
3 (d) 8 (c) 13 (d) 18 (d) 23 (c) 28 (b) 33 (a) 38 (a)
4 (d) 9 (b) 14 (c) 19 (c) 24 (d) 29 (a) 34 (a) 39 (b)
5 (a) 10 (c) 15 (d) 20 (a) 25 (b) 30 (c) 35 (c)

1. The two structures are the zig zag structures of a compound – –

having five carbon atoms in a straight chain. 20. (a) In strong basic medium OOC – CH – CH – COO will be
2. The eclipsed-like conformations become more prevalent with
increase in temperature. Me Me
3. A compound can exist in different conformations only when it stable in its anti form to minimise repulsion.
has three consecutive single bonds. - HCl
4. Due to restricted rotation, about a single bond, infinite number 21. (b) CH3 - CH2 - CH3 ¾¾
® CH3 - CH- CH3 ¾¾¾¾¾®
alc. DKOH
of arrangements are possible ; the two extreme cases are known |
Cl
as eclipsed and staggered.
5. Reduction of alkyl halides by Zn and HCl takes place by elec- HBr,.R O
tron-transfer mechanism and not through nascent hydrogen, as CH3 - CH = CH 2 ¾¾¾¾¾®
2 2 CH3 - CH 2 - CH 2 - Br
believed earlier. 22. (d) Since bromides are more reactive than chlorides in Wurtz
6. Boiling points of two lower homologues generally differ by 20– reaction, therefore, Wurtz reaction occurs on the side of Br
30°C. atom i.e.,
7. FSO3H—SbF5, also known as magic acid, is the strongest known
acid. It easily reacts even with alkanes forming a variety of
- NaBr
products. Cl Br + Na ¾¾¾¾ ®
8. n-Alkanes and branched alkanes have close boiling points, hence
they can’t be separated by fractional distillation. If a mixture
of isomeric alkanes is treated with urea preferably in presence
of a little CH3OH, only n-alkanes form urea inclusion com- – Na
Cl ¾¾¾¾®
plexes which crystallise out leaving behind branched chain ( - NaCl)
alkanes. These complexes are decomposed by treating with
water when urea dissolves leaving behind n-alkane. Bicyclo[1.1.0]butane
9. Hydrogen atoms of methane, fall into a special class, and are
less reactive than the 1° hydrogen atoms of other alkanes.
10. Halogenation (a common substitution reaction), is an oxidative 2° 1°
process in which C has lost its shared electrons to some extent CH2CH3
1° 2° | 2° 1° No. of 1° H’s = 12
to the newly introduced halogen (C—X). CH3CH2—C—CH2CH3
11. Bromine is less reactive than chlorine and hence more selective, 23. No. of 2° H’s = 6
|
leading to the formation of the product corresponding to 3° free CH3
radical, i.e. tert-butyl bromide. 1°
12. At very high temperatures, virtually every collision has enough 24. Chlorination of methane is a free radical reaction and hence it
energy for abstraction of even 1° hydrogens. It is generally true can be initiated by any factor that can produce chlorine free
that as the temperature is raised a given reagent becomes less radical.
selective in the position of its attack ; conversely, as the tem-
Cl—Cl ——® Cl . + Cl .
(a) UV
perature is lowered it becomes more selective.
13. Eact (backward) = Eact (forward| – DHforward = 4 – 1 = 3 kcal. CH4 + Cl ——® CH 3. + HCl
.
14. Bond-breaking and bond-making are not perfectly synchronized, CH . + Cl—Cl ——® CH Cl + Cl.
3 3
and thus the energy liberated by the one process is not com-
(C 2H5) 4Pb ——® 4CH3CH2. + Pb .
heat
(b)
pletely available for the other.
15. Chlorine atoms are 375000 times as reactive as bromine atoms CH 3CH 2 + Cl—Cl ——® CH3CH 2Cl + Cl .
.
towards methane under given conditions. This difference is CH4 + Cl . ——® CH 3. + HCl
due to difference in Eact which is 4 kcal for chlorine and 18 kcal CH . + Cl—Cl ——® CH Cl + Cl.
3 3
for bromine.
(c) UV . .
16. Bromine is less reactive and hence highly selective leading to the (CH 3)3COCl ——® (CH3)3 CO + Cl
replacement of tert-hydrogen atom hence the product A and B CH4 + (CH 3)3CO . —— ® CH3. + (CH 3)3COH
will not formed. In presence of light substitution reaction takes . .
CH 3 + (CH 3)3COCl —— ® CH 3Cl + (CH3) 3CO
place rather than addition.
17. Of the two propagating steps, Eact of the first step is high and 26. An alkyl bromide (RBr) can be the exclusive bromination prod-
hence it is difficult to accomplish. uct of a hydrocarbon whose all hydrogen atoms are equivalent.
18. Lead poisons the platinum used in converters to oxidise The molecular weight of the alkyl group (R–) is 151 – 80 = 71
pollutants like hydrocarbons, carbon monoxide and nitrogen and thus alkane should have molecular weight of 71 + 1 = 72,
oxides and thus these pollutants will be released as such in the thus it should be a pentane, which is found to be neopentane,
atmosphere causing pollution. (CH3)4C, whose all 12 hydrogen atoms are identical.
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27. Neopentane, (CH3)4C has 12 primary hydrogen atoms, while However, if excess of C2H6 is used, the yield of C 2H5Cl is
ethane, CH3CH3 has 6. Further the ratio of products formed is greatly improved since the chances of a Cl. colliding with C2H6
2.3 : 1 ; thus the reactivity ratio should be 1.15 : 1. molecule rather than with a chlorinated derivative are enhanced.
28. Addition of HBr, during bromination of methane will produce 34. Ethylene has restricted rotation, acetylene no rotation, hexachlo-
following reaction, which is roethane has more rotation than ethylene but less than ethane
CH3. + HBr ——® CH4 + Br. because of greater size of the substituent (chlorine) than in
the reverse of one of the chain-carrying steps, hence, conse- ethane (substituent is H).
quently bromination will slow down. 35. Conformers are isomers obtained due to rotation around C—C
29. Since methylene is highly reactive, here probability factor is single bond.
important. Thus, n-hexane will be the major product because 36. A substance lighter than water will float on water.
n-pentane has six 1° hydrogen atoms. 37. Br. is less reactive, hence it is more selective, and therefore 2-
1° 2° 2° 2° 1° :CH bromo-2-methylpropane will be major product. The relative
2
CH3CH2CH2CH2CH3 ——® HCH2CH2CH2CH2CH2CH3 ratio of the products 1-bromo-2-methylpropane and 2-
30. Note that all compounds are derivatives of hexane, and in (a), bromo-2-methylpropane will be 0.56 : 99.4.
(b) and (d) the two methyl groups are separated by one — 39. (b) Suppose relative reactivity for 3° H is x
CH2— group, while in (c) the two methyl groups are present on and suppose relative reactivity for 1° H is y.
adjacent carbon atoms. So with the given information
31. In a chiral alkane, the four substituents on C should be differ- 9y x
ent, so the simplest alkane will have H, CH3, C2H5 and C3H7 as = 0.86 = 0.14
9y + x 9y + x
substituents.
32. Branching decreases surface area of the molecule. Thus among 9y x
normal and branched chain isomers, normal alkane will have So =
highest boiling point. 0.86 0.14
33. When equimolar amounts of C2H6 and Cl2 react, a mixture of x 9 ´ 0.14
all possible mono- and poly-chloro products will be formed. Hence, = = 1.46
y 0.86

EXERCISE 5.2
1 (c, d) 2 (c, d) 3 (a, b, c) 4 (a, c)
>1 CORRECT
5 (a, b, c) 6 (b, d) 7 (a, d) 8 (a, b, c, d)
OPTION
9 (a, b, c) 10 (a, b) 11 (a, c, d) 12 (b, c, b)
PASSAGE 1 13 ( c) 14 (b) 15 (a)
PASSAGE 2 16 ( c) 17 (d) 18 (b)
PASSAGE 3 19 ( a) 20 (a) 21 (d)
PASSAGE 4 22 ( d) 23 (b)
24 (A) - a, b ; (B) - a, b ; (C) -c
MATCHING
TYPE 25 (A) - a ; (B) - b ; (C) - c, d; (D) - d
QUESTIONS
26 (A) - a,c,d; (B) - c,d; (C) - d; (D)-b
27 (a) 28 (b) 29 (d) 30 (a)
A/R
31 (a) 32 (a) 33 (e)
34 6 35 4 36 1 37 7
INTEGER
38 5 39 4 40 2 41 4
11. (a, c, d) Be2C + 4H2 O ® CH4 + 2Be(OH)2 Sol. (13-15)
.
Me CH2 CH3
Na
CH3 - Cl ¾¾¾¾
® CH 4 Me Me
.
EtOH
+ +
Al 4C3 + 12H2O ® 3CH4 + 4Al(OH)3 Me Me . CH3 CH3 CH3 CH3
[X]
12. (b, c, d) Me
[X] (R) 3° Free radical (P) 1° Free radical (Q) 2° Free radical

CH2 – Cl CH3
Me Me Cl
H

Cl CH3 CH3 CH3 CH3

Me +
Dia + Dia
Me Me CH3
H
Cl
Me
Cl CH3 CH3
 www.crackjee.xyz
243
9 36. 1
9×1=9 1° product = ´ 100 = 19.86% Cl Cl Cl
45.3 Cl Cl
22.8 Cl
6 × 3.8 = 22.8 2° product = ´ 100 = 50.33%
45.3 n1 = ; n2 = and
,
13.5
3 × 4.5 = 13.5 3° product = ´ 100 = 29.80% Cl
45.3 and
45.3 Cl Cl Cl Cl Cl Cl
13. (c) 14. (b) 15. (a) Cl
Cl Cl
Cl n3 =
Cl , , ,
Cl Cl Cl Cl
16. (c) =8 37. 7
Cl
Seven possible isomers are
2 1 1 4 Br
Cl
Cl

17. (d) =6 1-Bromo-1-chlorocyclobutane

Cl (Stereoisomerism not possible)
2 4
Cl Plane of
Cl Et Et Br symmetry Br
Cl
18. (b) =5
Cl Cl Cl
Cl 1-Bromo-3-chlorocyclobutane
1 1 1 1 1 (Both are optically inactive)
22. (d) 23. (b)
CH3 CH3 O Cl Br Br Cl Cl Br Br Cl
diH2SO 4/HgSO4
CH3 C C CH CH3 C C CH3

CH3 CH3 cis-(+), cis -(–)- trans-(+), trans -(–)-

1-Bromo-2-chlorocyclobutane
(P)
38. 5
CH3 OH 1, 3-Dichlorocyclobutane can exist in cis and trans forms. trans-
NaBH4/dil acid 1, 2-Dichlorocyclobutane can exist in (+)– and (–)-forms.
CH3 C CH CH3 However, cis-1, 2-Dichlorocyclobutane has a plane of symme-
try and hence it can exist as meso isomer.
CH3 39. 4
Br Br Br Br
Conc.H2SO4 Cl Cl Cl Cl
(–H2O)

cis, racemic trans, racemic

CH3
CH3 1-Bromo-2-cyclopentane
O3/Zn/H2O Br Br Br Br
CH3 C O CH3 C C CH3 (major)

CH3
(Q) Cl Cl Cl Cl
26. A - (a, c, d); B - (c, d); C - (d); D - (b) cis, racemic trans, racemic
29. When n-butane is heated in the presence of AlCl3/HCl it will be
1-Bromo-3-cyclopentane
converted into isobutane. In the presence of AlCl3/HCl if any
alkane having more than four carbon is heated than isomerisation 40. 2
is held to give isomer of reactant alkane. I
33. 2-bromobutane on reaction with sodium ethoxide in ethanol I I I
gives 2-butene as a major product.
–
EtO
meso-1, 2-Diiodocyclopentane meso-1, 3-Diiodocyclopentane
H – CH – CH (CH3) – Br EtOH + CH = CH + Br - 41. 4
| All alkyl bromides having carbon skeleton of isopentane (2-
CH3 CH3 methylbutane (CH3)2CHCH2CH3) will give isopentane via
This is according to saytzeff’s rule i.e. the predominant product Grignard reagent.
is the most substituted alkene, i.e. are carrying the largest CH3 CH3
number of alkyl substituents of hydrogen is eliminated
preferentially from the carbon atom joined to the least number BrCH2CHCH 2CH 3 CH3CBrCH2CH3
of hydrogen atoms. CH 3 Br CH3
2-butene is more stable than 1-butene due to presence of large
number of hyperconjugating structures in 2-butene. CH 3CH CHCH 3 CH3CHCH 2CH2Br
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EXERCISE 5.3

(i) Now let us take a chain of 5 carbon atoms, then the CH3
2 group may be placed either on C2 or C3 to give two differ-
2 1 ent monomethylpentanes.
3
1. (a) 1 3 (b) 4 CH3 CH3
2, 2-Dimethylpropane 5 1 2 3 4 5
6 C—C—C—C—C CH3CHCH2CH2CH3 CH3CH2CHCH2CH3
2, 3-Dimethylhexane 2-Methylpentane, (II) 3-Methylpentane, (III)

(ii) Now let us take a chain of 4 carbon atoms, then the two
7 remaining carbon atoms can be present either as a CH3CH2
8 3
6 2 4 or two CH3 groups. However, introduction of CH3CH2
3 on any of the four carbon atoms will give either of the
(c) 5 (d) 1
5
2 4 2, 2, 4, 4-Tetramethylpentane above three isomer, i.e. no new alkane will be formed.
1
CH2CH3
6-Ethyl-2-methyloctane
1 2 3 4
C—C—C—C CH3CH2CH2CH2CH2CH3 CH3CHCH2CH3
2' n-Hexane, (I) 3-Methylpentane, (III)
2 4 1' Hence the two carbon atoms should be present as two CH3
1 3
5
groups ; and that too not on the end carbon atoms. Hence two
(e) 6 CH3 groups can be attached exclusively on C 2 or C3 to give one
8
7
dimethylbutane or one CH3 group on C2 and other on C3 to
5-(1'-methylethyl)-3-methyloctane give another dimethylbutane.
CH3 CH3 CH3
1 2 3 4
10 8 6 4 2
9 7 5 3 1
C—C—C—C CH3—C—CH2CH3 CH3—CH—CHCH3
CH3
(f) 1'
2, 2-Dimethylbutane, (IV) 2, 3-Dimethylbutane, (V)
2'
3' So, on the whole C6H14 can exist in five isomeric forms. Simi-
5-(2'-methylpropyl) decane larly, we can derive the possible number of isomers of any
alkane.
4
5. Two chlorine can be placed on the same carbon atom and also
2
2. (i) 1 3 5 on different carbon atoms, the possible different structures
obtained are

Cl Cl Cl
2 4 6
(ii) 3 5 7 Cl—CHCH2CH3 CH3—C—CH3
1
Cl
1, 1-Dichloropropane 2, 2-Dichloropropane
2 4 6 8 10 12
3 5 7 9 11
1 ClCH2CHClCH3 ClCH2CH2CH2Cl
(iii) 1' 3'
2'
1, 2-Dichloropropane 1, 3-Dichloropropane
6. Order of increasing boiling points :
3. Isopentane has four types of hydrogen atoms, so four
monobromo derivatives are possible. n -Pentane < 3, 3-Dimethylpentane < 2-Methylhexane
(C 5 ) (C7 ) (C7 )
1 CH2Cl 1 Cl < n-Heptane < 2-Methylheptane
2 4 4 (C7 ) (C8 )
2
3 3
n-Pentane has lowest boiling point because it has least number
1-Chloro-2-methyl- 2-Chloro-2-methyl-
butane butane of carbon atoms, while 2-methylheptane has maximum number
of carbon atoms (C8), so it should have highest boiling point.
Of the three hydrocarbons, each having seven carbon atoms, n-
3 1 heptane has the longest chain and thus has the highest boiling
4 2
3 1 point, 3, 3-dimethylpentane is more branched, hence has the
CH2Cl
Cl 4 2 smallest surface area and so the lowest boiling point among the
2-Chloro-3-methyl- 1-Chloro-3-methyl- three C7 compounds.
butane butane Mg
7. (i) CH3CH 2CH 2CH2Br ——® CH3CH2CH2CH2MgBr
4. An alkane (CnH2n+2) of molecular weight 86 should have mo-
n-Butyl bromide
lecular formula of C6H14 ; so one suitable alkane should be n-
HO
hexane, CH3CH2CH2CH2CH2CH3 (I), having a chain of six 2
——® CH3CH 2CH2CH3
carbon atoms. n-Butane
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245
13. (a) 2, 2-Dimethylbutane has nine 1°, two 2° and three 1°¢
CH3 CH3 hydrogen atoms. So it will form three products.
Mg
CH3CH2CHBr ——® CH3CH2CHMgBr Name of Weight reactivity % Yield
(ii)
product No. of H’s × (Weighted
sec-Butyl bromide
Relative reactivity react. × 100)
HO 9
——®
2
CH3CH2CH2CH3 1-Chloro 9×1=9 × 100 = 46
19.6
n-Butane

Li CuCl
7.6
(iii) CH3CH2Cl ——® CH3CH2Li ——® 3-Chloro 2 × 3.8 = 7.6 × 100 = 39
19.6
Ethyl chloride
3
CH CH Cl 4-Chloro 3×1=3 × 100 = 15
(CH3CH2)2CuLi ————®
3 2
CH3CH2CH2CH3 19.6
n-Butane 1°
Mg D2O
CH3
8. (i) CH3CH 2Br ———® CH3CH2MgBr ——® CH3CH2D 1° 2° 2°' 1°'
ether
(b) Isohexane, CH3—CH—CH2—CH2—CH3 has five types
Pt
(ii) CH 2 = CH 2 + D2 ——® CH2DCH 2D 3°

UV
of hydrogen atoms, namely six 1°, one 3°, two 2°, two 2°¢
(iii) CH4 + CD2N2 CH3CD2H + N2
——® and three 1°¢. Thus the corresponding monochloro deriva-
9. (i) CH3CH2CH3 to (CH3) 2CHCH(CH 3)2 . tive will be in the ratio of 21, 17, 26, 26 and 10% respec-
syn-Alkanes can be easily prepared by Wurtz reaction tively.
Br , 127°C Na
(c) 2, 2, 4-Trimethylpentane has four types of hydrogen at-
CH3CH 2CH 3 ————®
2
(CH 3)2CHBr ——® (CH 3)2CHCH(CH 3) 2 oms, the % product corresponding will be 33, 28, 18 and
ether
Note : Bromination of propane is preferred over chlorination because 22%.
the ratio of isopropyl to n-propyl halide is 96 : 4 in bromination and 1° 1°'
56 : 44 in chlorination. CH3 CH3
1° 2° 1°'
(ii) CH3CH2CH3 to (CH3)2CHCH2CH2CH3 CH3—C—CH2—CH—CH3
Unsymmetrical higher alkanes are best prepared by Corey- 3°
House synthesis. CH3
1°
Cl , UV
CH3CH2CH3 ———®
2
CH3CH2CH2Cl + (CH3)2CHCl 14. The four dichloro derivatives are
1° 1° 1° 2°
CH(CH3)2 CH3CCl2CH3 ClCH2CH2CH2Cl
Li, ether
(CH3)2CHCl ———® (CH3)2CHLi
CuI
——® (CH3)2CH—CuLi (i), A (ii), B
1° 2° 1°' 1° 2° 1°'
CH CH CH Cl CH3CH2CHCl2 CH 3CHClCH 2Cl
—————–®
3 2 2 (CH 3)2CHCH2CH2CH 3
(iii), C (iv), D
(iii) Propane to neopentane, (CH3)2C(CH3)2. Note that two
15. (a) A reactive site in a molecule generally has at least one of
more methyl groups are introduced which can easily be the following features : (i) one or more unshared pair of
done by Corey synthesis. electrons, (ii) a polar bond, (iii) an electron deficient atom,
Br2 (i) Li (iv) an atom with an expandable octet. Alkanes have none
CH3CH2CH3 ——® CH3CHBrCH3 ———®
(ii) CuI of these features, hence these are inert.
(iii) CH3I (b) The C—C bond has a lower average bond energy (DH = +
347 kJ mol–1) than the C—H bond (DH = + 415 kJ mol–1).
(i) Li, (ii) CuI
(CH3)2CHCH3 —————® (CH3)2C(CH3)2 (c) The reaction is very slow at moderate temperatures be-
( iii) CH3I cause of a very high activation energy.
10. (a) CH 3CH 2CH 2X + [(CH 3)2CH–]2–CuLi 16. (i) (CH3)3CCH2CH2CH2CH3
(A)
¾ ¾® (CH3)2CHCH2CH2CH3
Cl. . rearrangement
(b) (CH3)2CHX + [CH 3CH 2CH2–] 2–CuLi (ii) CH3CHBrCH3 ——® CH3CHBrCH2 ——————® (migration of Br)
¾ ¾® CH3CH 2CH 2CH(CH3)2 (B) 1° radical

Dialkylcopper lithium in two cases is prepared from . Cl2

CH3CHCH2Br ——® CH3CHClCH2Br
(CH3)2CHLi and CH3CH2CH2Li respectively ; however
2° radical (c) (D)
method (a) is superior as it uses 1° halide (Corey-House
synthesis). Note that although alkyl free radicals do not rearrange by mi-
gration of hydrogen or alkyl, they rearrange by migration of
11. More is the stability of a free radical formed, more will be the
halogen.
ease of its formation (or abstraction of hydrogen to give free
(iii) Since 2, 7-dimethyloctane is formed by Wurtz reaction,
radical) ; thus the ease of abstraction of hydrogen follows the the RCl must be symmetrical molecule i.e.
order (CH3)2CHCH2CH2Cl. Thus compounds E to (G) may
CH2 = CHCH2—H, C6H5CH2—H > CH2 = CH—H be as below :
Allylic hydrogen Benzylic hydrogen Vinylic hydro- Li
gen (CH3)2CHCH2CH2X ——® (CH3)2CHCH2CH2Li
12. An alkane having identical hydrogen atoms will give only one (E) (F)
product on methylene insertion. The first four such alkanes are H2O
——® (CH 3)2CHCH 2CH3
CH4, CH3CH3 , (CH3)4C and (CH3)3C—C(CH3)3.
Isopentane (G)
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(b) The molecular formula of the fuel n–C14H30 indicates that
C º CH
it has twelve —CH2— and two CH3— groups, thus the
total amount of heat evolved on the combustion of 1 mol
17. (i) (ii) of the fuel
= (12 × 157) + (2 × 186) = 2256 kcal/mol
Cl
764
\ Heat evolved by 1 litre or moles of fuel
H H 198
(iii) (iv)
764
Br CH3 = × 2256 = 8710 kcal
198
(c) Given, H + H ——® H2, DH = – 104 kcal/mol
Thus 104 kcal of heat is evolved by 1 mole of H2
(v) 1 ´ 8710
8710 kcal of heat will be evolved by
Cl 104
A thickened line indicates a bond coming out of the plane of the = 84 mol of H2 = 168 g H2
paper. 20. We know that

Cl Vol. of gas in mL Wt. of substance in mg

No. of mmol = = Mol. wt. in mg/mmol
22.4 mL/mmol
Cl2
¾ ¾¾ ¾® 1.56 mL
18. Sunlight Here, No. of mmol of alcohol =
22.4 mL/mmol
Cyclohexane, A
Wt. of ROH in mg
\ Mol. wt. of ROH in mg/mmol =
CH3 CH2Cl CH3 No. of mmol
Cl
Cl2 4.12 mg
¾ ¾¾ ¾® + = = 59 mg/mmol
Sunlight (1.56/22.4) mmol
Methylcyclopentane Since, alcohol (ROH) contains one —OH group
\ CnH2n+1(OH) = 59
CH3 CH3 12n + (2n + 1) 1 + 16 + 1 = 59
Cl 14n + 18 = 59
+ +
n»3
\ ROH is C3H7OH.
Cl 1.79 mg
19. (a) Density of the petroleum fuel = 0.764 g/mL 21. No. of mmol of alcohol = » 0.02
90 mg/mmol
\ Weight of 1 litre of petroleum fuel = 764 g
764 g 1.34 mL
\ No. of moles of the fuel = No. of mmol of alcohol = » 0.06 m mol
198 g/mol 22.4 mL/mmol
0.02 mmol of an alcohol gives 0.06 mmol of H2
(Mol. wt. of fuel = 198)
1 mmol of alcohol gives 3 mmol of H2
Now writing the combustion reaction
or 1 mole of alcohol gives 3 moles of H2
43 \ Alcohol contains 3 —OH groups which is further confirmed by
n-C 14H30 + O ——® 14CO2 + 15H2O
2 2 its molecular weight.
764 43 For trihydric alcohol,
\ Amount of O2 required by 1 litre of fuel = ´ CnH2n–1 (OH)3 = 90
198 2 12n + (2n – 1)(1) + 51 = 90
764 43 14n + 50 = 90
or Wt. of O2 required by 1 litre of fuel = ´ ´ 32
198 2 n»3
= 2650 g
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ALKENES 6.8 Illustrative Examples on Alkenes

6.1 Relative Stability of Alkenes ALKYNES OR ACETYLENES
6.2 Stability of Cycloalkenes 6.9 Preparation of Alkynes
6.3 Preparation of Alkenes 6.10 Physical Properties
6.4 Physical Properties 6.11 Chemical Properties
6.5 Chemical properties 6.12 Illustrative Examples on Alkynes
DIENES 6.13 Characteristics of Alkanes, Alkenes and Alkynes
6.6 1,3-Butadiene EXERCISES
6.7 Degree of Unsaturation SOLUTIONS

ALKENES

Alkenes are open-chain hydrocarbons having carbon-carbon double bonds, C=C. They have the general formula
CnH2n and are also called alkylenes or olefins. The fist three members are commonly named by their common names,
namely ethylene, propylene and butylenes; higher alkenes are named by their IUPAC names, viz.

2 4 2 5 3 1

3 6 4 2
1 1 3

2-Butene 2-Methylpropene 5, 5-Dimethyl-2-hexene

OH
3
2 4 4 2
3 1
1
2 1 3
4 5
Cl 6 OH
3-Buten-2-ol
1-Chloro-2-butene (Note that - ol takes priority over -ene) 2-Cyclohexenol

Alkenyl groups : Like alkyl groups (alkane – H), there are three commonly encountered alkenyl groups which
are given special (trivial) names.

3 2 1 3 2 1
CH 2 = CH— C H 2 = CH - CH 2 - C H3 - C H = C H –
Vinyl Allyl Pr openyl
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Isomerism : Alkenes show chain (1-butene and isobutene), position (butene –1 and butene-2), functional (propene
and cyclopropane) and geometrical isomerism.

CH3CH2CH = CH2 and (CH3)2C = CH2 ; CH3CH2CH = CH2 and CH3CH = CHCH3 ; CH3CH = CH2
Butene-1 Isobutene Butene-1 Butene-2 Propene Cyclopropane

Chain isomers Position isomers Functional isomers

Geometrical isomerism : The p bond of alkenes prevents free rotation, i.e there is hindered rotation about the
carbon-carbon bond, therefore an alkene having two different substituents on each doubly bonded carbon, i.e. alkenes of
the type abC = Cab can exist in two different geometric isomers. For example,

a a a b H3C CH3 H CH3

C C C C C C C C
b b b a H H H3C H
cis trans cis-2-Butene trans-2-Butene

NOTE :

(i) In the cycloalkenes the trans isomers are unstable unless the ring contains at least eight carbon atoms
(ii) Geometric (cis-trans) isomers are stereoisomers because they differ only in the spatial arrangement of the groups.
(iii) Geometrical isomers are diastereomers (stereoisomers which are not enantiomers are called diastereomers) and
thus have different physical properties (m. p., b.p. etc.).
(iv) In modern nomenclature the terms cis and trans are being replaced by the letters Z (when the higher-priority
substituents on each carbon are on the same side of the double bond) and E (when the higher-priority substituents
are on opposite sides).
(v) The priority orders among some common atoms and groups are given below :
(a) I, Br, Cl, S, F, O, N, C, D, H
(b) I, Br, Cl, SO3H, F, OCOR, OR, OH, NO2, NR2, NHCOR, NHR, NH2, CCl3, COCl, COOR, COOH, CONH2,
COR, CHO, CH2OH, CN, C6H5, CR3, CHR2, CH2R, CH3, D and H.

1. Give IUPAC name of the following compounds:

(i) (ii) (iii)

(iv) (v) (vi)

OH

2. Draw structural formula of

(i) trans-2-methyl-3-heptene (ii) Z-2-chloro-2-butene
(iii) E-1-Iodo-2-pentene (iv) Z-1, 3-pentadiene.
3. Write structural formulas for trisubstituted alkenes of the formula C6H12.
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249

6.1 Relative Stability of Alkenes

Stabilities of a compund can be compared by converting different compounds to a common product and comparing
the amounts of heat given off. The smaller value of heat given off indicates smaller heat content (enthalpy) and hence
larger stability of the molecule. Two types of heat of reactions are used for comparing the stability of alkenes.
1. Heat of combustion : It is the amount of heat evolved during the complete burning of one mole of the alkene with
oxygen to form CO2 and H2O. However, heats of combustion are large numbers, and there is a small difference in
values of the two or more isomers, which is measured with difficulty.
2. Heat of hydrogenation : It is the amount of heat evolved when one molecule of an alkene is hydrogenated in
presenc eof a platinum catalyst forming corresponding alkane. Hydrogenation is mildly exothermic, evolving
about 20 to 30 kcal (80 to 120 kJ) of heat per mole of hydrogen consumed.

CH3 CH3
| |
Pt
CH3 CHCH = CH 2 + H 2 ¾¾® CH 3 CHCH 2 CH 3 DH0 = –30.3 kcal / mol. (–127 kj/mol.)
3 - Methyl -1- butene

CH3 CH3
| Pt |
CH3 CH2 C = CH2 + H2 ¾¾® CH3 CH2 CHCH3 DH0 = –28.5 kcal / mol. (–119 kj/mol.)
2 -Methyl -1- butene

CH3 CH3
| Pt |
CH3 C = CHCH 3 + H2 ¾¾® CH3 CHCH2 CH3 DH0 = –26.9 kcal / mol. (–113 kj/mol.)
2 - Methyl - 2- butene

Since all the three compounds form the same alkane (2-methylbutane), so the energy of the product for each of the
three reactions is same. Hence different heats of hydrogenation for the three reactions must be due to different heat
contents of the three reactants. The reactant having least heat of hydrogenation is the most stable because it has least
energy (enthalpy), while the reactant having maximum heat of hydrogenation is the least stable because it has greatest
energy (enthlpy). Thus the stability order of the above three alkenes is

CH3 CH 3 CH 3
| | |
CH 3 C = CHCH 3 > CH 3 CH 2 C = CH 2 > CH 3CHCH = CH 2

Heat of hydrogenation can't be used for measuring relative stabilities of isomeric alkenes which yields different
products on hydrogenation. For example, 2-methylpropene can't be compared directly with the isomeric butenes like 1-
butene, cis- and trans-2-butene because hydrogenation of 2-methylpropene gives 2-methylpropane (isobutane) while the
three isomeric butenes give n-butane.

CH 3 CH3
| Pt |
CH 3 C = CH 2 + H 2 ¾¾® CH 3 CHCH 3
2 - Methylpropene Isobutane

H
CH 3 CH 2 CH = CH2 , CH 3 CH = CHCH 3 ¾¾¾
2
® CH 3 CH 2 CH 2 CH 3
Pt
1- butene 2 - butenes n -Butane

Since butane and isobutane do not have the same enthalpy, a direct comparison of heat of hydrogenation is not
possible.

Studies of numerous alkenes reveal that the stabilities of alkenes is related to the number of alkyl groups bonded
to the two sp2 carbons. The greater the number of alkyl groups attached to the two sp2 carbon atoms (i.e. the more highly
substituted the carbon atoms of the double bond), the greater is the stability of the alkene. In other words, fewer the number of
H's present on the sp2 carbons, more is the stability of the alkene.
Thus the relative order of stabilities of the different alkenes is
R 2 C = CR 2 > R 2 C = CHR > RCH = CHR > RCH = CH 2
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Further in dialkylsubstituted alkenes, the trans-isomer is more stable than the cis-isomer because in the trans-
isomer, the large substituents are farther apart and thus exert less steric strain than in the correspond cis-isomer.

H3C H H3C CH3

C=C > C=C
H CH3 H H
trans- cis-

Two alkyl groups are on different sp 2 C's

Three factors are responsible for the stabilizing effect of alkyl groups on a double bond.
(i) Hyperconjugation : More the possibility of hyperconjugation in an alkene, higher will be its stability.
(ii) Steric repulsion between bulky groups makes the isomer relatively less stable than the other.
(iii) In highly substituted alkene, bulky alkyl groups are more away from each other (120° separation) than in the
isomer which have fewer alkyl groups on the sp2 carbon because here two alkyl groups are separated by the
tetrahedral bond angle of about 109.5°. For example

(CH3 )2 C = CHCH3 > (CH 3 )2 CHCH = CH 2

H
H3 C H H
120° C=C H3C C=C
H3 C CH3 109.5° C H
H3C
H
The two methyl groups are The two methyl groups
are separated by 109.5°

Thus the relative stability of the following alkenes can be summed up as below.

CH3 CH3
CH3 H CH3 CH3 CH3
H3C – C = C – CH3 > (CH3)2C = CHCH3 > C=C > C = CH2 > C=C
H CH3 CH3 H H
(12 H-C hyper- (9 H-C hyper- (trans -least steric strain) (cis-steric strain)
conjugated bonds) conjugated bonds)
(all the three have 6 H-C hyperconjugative bonds)

> CH3CH = CH2

(3 H-C hyper. bonds)

In general, the stability order of substituted ethylenes is :

Tetrasubstituted > Trisubstituted > trans-Disubstituted > gem-Disubstituted > cis-Disubstituted.
Actually, there are contradictory views regarding the relative stability of cis-disubstituted and gem-disubstituted
ethylenes.

6.2 Stability of Cycloalkenes

The presence of a ring system in cycloalkene affects in two ways : (i) a small ring produces ring strain and thus
imparts unstability, and (ii) presence of a trans-double bond is not possible in smaller rings, while in larger rings although
the trans- double bond exists, yet it is less stable than the cis- isomer (difference from open chain alkenes).
Cyclopropene is not stable because here a great strain is created when the usual angle of 120º (in alkenes) is
converted (compressed) to 60º (present in cycloalkenes).
Alkenes with fewer than eight carbon atoms do not form trans-isomer at room temperature because the two alkyl
groups on a trans double bond are so far apart that several carbon atoms are needed to complete the ring.
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H CH3 H CH2 H2C H

C C C
C C C
H CH3 H CH2 H CH2
cis- Butene-2 cis- Cyclobutene trans- Cyclobutene
(not possible)
The two connecting –CH2
moieties are very far away

Although trans- cycloheptene can be isolated at room temperature, it is not quite stable. trans-Cyclooctene is stable
at room temperature and the higher homologues containing at least 10 carbon atoms are quite stable in their trans- form. The
stability of the trans- cycloalkenes can be summed up in the form of Bredt rule "a bridged bicyclic compound can't have a
double bond at a bridge-head position unless one of the rings contains at least eight carbon atoms."

1. Tell which member of each pair is more stable?

(a) 2-methyl-1-butene or 3-methyl-1-butene (b) 2-methyl-1-butene or 2-methyl-2-butene
(c) 2, 3-dimethyl-1-butene or 2, 3-dimethyl-2-butene (d) cis- cyclooctene or trans- cyclooctene
2. Which of the following compounds is most stable?
3, 4-dimethyl-2-hexene, 2, 3-dimethyl-2-hexene, 4, 5-dimethyl-2-hexene.
3. (a) How many alkenes could you treat with H2/Pt in order to prepare methylcyclopentane?
(b) Which alkene is the most stable?
(c) Which alkene has the smallest heat of hydrogenation?
4. Give three alkenes containing six carbon atoms that form the same product whether they react with HBr in the presence of peroxides
or with HBr in the absence of peroxides.
5. Arrange the following alkenes in order of decreasing stability:
1-pentene, (E)-2-pentene, (Z)-2-pentene and 2-methyl-2-butene

6.3 Preparation of Alkenes

Common methods used for preparing alkenes involve elimination of atoms or groups from two adjacent carbons
( b- elimination)

6.3.1 By Dehydrohalogenation of Alkyl Halides

Dehydrohalogenation, elimination of a hydrogen and a halogen atom from an alkyl halide, can take place by the
E2 and E1 mechanisms. The second-order elimination (E2) is almost always better for synthetic purposes because the E1
has many competing reactions, one being rearrangement of the carbon skeleton.

E2 Mechanism
An E2 reaction gives excellent yield when bulky secondary and tertiary alkyl halides that are poor SN2 substrates
(in case of primary alkyl halide, a bulky base must be used to get good result) are treated with a strong base, like C2H5ONa
in C2H5OH, potassium tert-butoxide in tert-butyl alcohol or dimethyl sulphoxide, or potassium hydroxide in ethanol. In
the last case the reactive base is the ethoxide ion formed by the following equilibrium :
– –
OH + C 2H5OH H2O + C 2H5O
The E2 reaction is a concerted, one-step reaction, i.e. the proton and the halide ion are removed in the same step
without forming any intermediate
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–
H
B: a
b –
–C—C– C=C + B : H + :X
X
Mechanism of E2 reaction
Since the E2 reaction is initiated by removing the proton from a b-carbon, it is sometimes called b-elimination.
Further since the atoms (H and X) are removed from the two adjacent carbons, E2 reaction is also called 1,2-elimination
reaction.
Orientation of the double bond in the product : When the alkyl halide has two structurally different b-carbons
from which a proton can be removed, two elimination products are possible. For example,
Br
|
CH 3 - CH - CH 2 CH 3 + Base ¾¾
® CH 3 CH = CHCH 3 + CH 2 = CHCH 2 CH 3
But - 2 - ene But -1- ene
which one is the major product, depends upon several factors.
(i) Nature of base : If we use a small base, such as ethoxide ion or hydroxide ion, the major product of the reaction
will be the more stable, i.e. more highly substituted alkene (Zaitsev rule). This product is known as Zaistev or
Saytzeff product.
Br
| C H O-
CH3 CH 2 - C - CH3 ¾¾¾¾¾
2 5
® CH 3 CH = C - CH3 + CH3 CH2 - C = CH 2
| C 2H5 OH | |
CH3 CH3 CH3
(71%) (29%)
If we use a bulky base, such as tert-butoxide, triethylamine, diisopropylamine, 2,6-dimethylpyridine, etc., the
major product will be the least highly substituted product, called the Hofmann product.
Least hindered H
Br
| —
( CH ) CO
CH3 CH2 C CH3 ¾ ¾ ¾
3 ¾
3 ¾¾ ® CH CH
3 C CH 3 CH 3 CH 2 C CH 2
| ( CH3 ) 3 COH | |
CH3 CH3 CH3
Saytzeff product ( 28%) Hofmann product (72%)

Here the bulky tert-butoxide ion easily abstracts the less hindered proton forming less substituted alkene as the
major product.
(ii) Nature of halogen in alkyl halides : Although the major product of the E2 dehydrohalogenation of RCl, RBr,
and RI is normally the more substituted alkene, the major product of the E2 dehydrohalogenation of RF is the
less substituted alkene.
F
|
CH OH
CH 3 C HCH 2 CH 2 CH 3 + CH 3 O - ¾¾¾¾
3
® CH 3 CH = CHCH 2 CH 3 + CH 2 = CHCH 2 CH 2 CH 3
2 - Pentene (E and Z) (30%) 1- Pentene (70%)
This is due to the fact that among halide ions the fluoride ion is the strongest base and thus the poorest leaving
group. So when the base begins to remove a proton from the alkyl fluoride, the poor leaving character of the
fluoride ion delays its removal with the result a transition state resembling to a carbanion is formed (which is not
the case in other halides because Cl –, Br – and I– are good leaving groups). Thus when a carbanion type of
situation arises, naturally a stable carbanion will be formed easily (1° > 2° > 3°). Thus now let us study the two
possible transition states during above reaction.
d– d–
OCH3 OCH3

H H

CH2CHCH2 CH2CH3 CH3CHCHCH2CH3

d– d–
F F
Transition state leading to 1-pentene, Transition state leading to 2-pentene,
1° carbanion (more stable) 2° carbanion (less stable)

Because the transition state leading to 1-pentene is more stable, 1-pentene is formed more rapidly and thus
constitutes the major product.
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(iii) Alkyl halide containing double bond. In case the alkyl halide has a double bond or a benzene ring, a conjugated
alkene will be the major product which may or may not be the Saytzeff product.
Cl
|
OH -
CH 2 = CHCH 2CHCHCH 3 ¾¾¾® CH 2 = CHCH = CH CHCH 3 + CH 2 = CHCH 2 CH = C CH 3
| | |
CH3 CH3 CH3
Monosubstituted alkene Trisubstituted alkene
(Major product , conjugated system) (Minor)

Thus an E2 reaction is said to be regioselective because one of the constitutional isomers is formed in major
amount than the other.
In addition to being regioselective, dehydrohalogenation of alkyl halides is stereoselective and favours the
formation of the more stable stereoisomer. Usually, the trans (or E) alkene is formed in greater amounts than its cis (or Z)
stereoisomer. Elimination reactions of cycloalkyl halides lead to cis cycloalkenes when the ring has fewer than 11 carbons.
As the ring becomes larger, it can accommodate either a cis or a trans double bond, and thus large - ring cycloalkyl halides
give mixtures of cis and trans cycloalkenes.

Br H H H
H
CH3CH2OK
+ H
CH3CH2OH

Bromocyclodecene cis-Cyclodecene trans -cyclodecene

(85%) (15%)

E1 Mechanism
First order dehydrohalogenation usually takes place in a good ionizing solvent (such as an alcohol or water),
without a strong nucleophile or base. The substrate is usually a secondary or tertiary alkyl halide. The reaction involves
two steps, the first step is rate determining and hence the increase in concentration of the base which is involved in the
second fast step has no effect on the rate of the reaction.
CH3 CH3
+ –
CH3 — C – Br CH3 — C + Br

CH3 CH3

CH3 CH3
+ fast +
CH3 — C CH3 — C + H 3O

CH2 CH2
..
H2O : H
(i) When two products are possible, the major product is the Saytzeff product.
(ii) Because the rate determining step involves the removal of halide ion and formation of a carbocation, the rate of
E1 reaction depends on both the ease with which the leaving group leaves and the stability of the carbocation
formed. Stability of the common carbocations is:
3° benzylic > 3° allylic > 2° benzylic > 2° allylic > 3° > 1° benzylic » 1° allylic » 2° > 1° > vinyl
(iii) Since carbocations are formed as intermediates, E1 dehydrohalogenations are prone to rearrangement.

1. Give the major elimination product obtained from an E2 reaction of each of the following alkyl halides with OH –.

Cl F CH 3
| | |
(a) CH 3 CHCH 2 CH = CH 2 (b) CH 3 C HCH2 CH 3 (c) CH 3 CHCHCH 2 CH 3
|
F
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2. Which alkyl halide should be more reactive in an E2 reaction?

Br Br Br Br
| | | |
(a) CH 3 CH 2 CH 2 CHCH3 or CH 3 CH 2 CHCH 2 CH 3 (b) CH 3 CHCHCH 2 CH 3 or CH 3 CHCH 2CHCH 3
| |
CH 3 CH 3

3. For each of the following reactions, indicate whether elimination will occur via an E2 or and E1 reaction. Give the major product in
each case.

Br CH 3
| |
OCH 3- H O
(a) CH 3 CH 2 CHCH 3 ¾¾¾¾
® (b) CH 3 CCH 3 ¾¾¾
2 ®
DMSO |
Cl

F
| CH CH OH
CH OH (CH 3 )3 CCHCH 3 ¾¾¾¾¾¾
3 2 ®
(c) CH 3 CH 2 C HCH 3 ¾¾¾¾
3 ® (d)
|
Br
CH CH OH
(e) (CH 3 )3 CCHCH 3 ¾¾¾¾¾¾
3 2 ®
| DMSO
Br

6.3.2 By Dehydration of Alcohols

Dehydration of alcohols is done with Bronsted acids (proton donors) like sulphuric acid and phosphoric acid in
the laboratory, and with Lewis acids such as alumina in industries.

OH
| heat + –
CH 3 CH2 CHCH 3 H 2 SO 4 CH 3 CH CHCH 3 H3 O HSO4

Dehydration is reversible and in most cases the equilibrium constant is not large. In fact the reverse reaction
(hydration of alkenes) is a method for converting alkenes to alcohols. The reversibility of the reaction can be prevented by
removing the alkene by distillation as soon as it is formed (recall that alkenes have much lower boiling point than the
corresponding alcohol because the alcohol is hydrogen bonded). Like dehydrohalogenation of alkyl halides, alcohols
undergo dehydration in two ways E1 and E2 reactions.
Acid catalysed dehydration of secondary or tertiary alcohols : An E1 reaction : The first step in the dehydration
of alcohols is protonation which converts OH– (a poor leaving group) to H2O (a good leaving group).
.. +
:O H :OH2
| fast | –
Step 1 : CH3CHCH3 + H — OSO3H CH3CHCH3 + OSO3H

+
:OH2
| slow + ..
Step 2 : CH 3 C H CH3 CH 3 CH CH 3 H2 O :

+ fast
Step 3 : CH3 CH CH 2 CH 3 CH CH 2 B:H
|
H

B:
(i) Note that the overall role of the acid (H2SO4) is catalytic as it is regenerated in the reaction. The reaction is
exothermic.
(ii) The base B: used for removing proton may be any base present in the reaction mixture, i.e. –OSO3H, H2O or
(CH3)2CHOH in the present case.
(iii) The carbocation may rearrange to the more stable one to form rearranged final product. Sometimes, ring expansion
may occur (relief of strain) and thus higher cyclic compound will be formed. Ring expansion is observed when
positive charge is on carbon next to ring; and ring contraction is observed when positive charge is on ring carbon
atom.
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CH3 CH3
+
CH CH
OH ring expansion
+
H2S O4, heat

2° carbocation 2° carbocation

H
CH3 CH3 CH3
+ +
+
rearrangement –H

3° carbocation

(iv) Since 3° carbocations are formed most easily, followed by 2° carbocation and then 1°, the ease of dehydration
follows the order :
Type of alcohol R3COH > R2CHOH > RCH2OH
Dehydration condition 5% H2SO 4 at 50°C 75% H2SO 4 at 100°C 95% H2SO 4 at 170°C
(v) Dehydration of secondary and tertiary alcohols is an E1 reaction.
Acid-catalysed dehydration of primary alcohols : An E2 reaction. Since primary carbocations are not highly
stable, they are believed to undergo dehydration in an E2 manner. Here also the first step is protonation which loses H2O (a
good leaving group) with the simultaneous attack by a Lewis base, present in the reaction mixture, at the b-hydrogen atom.
.. H
Step I : CH 3 CH2 O
. .H H OSO3 H CH 3 CH 2 O
. .H OSO3 H

H
| a H +
Step II : CH2 CH 2
Simultaneous attack
O H ¾ ¾ ¾ ¾ ¾ ¾ ¾ ¾ ¾ ¾® CH2 CH 2 H2 O B H
B: b of : B, and removal of H

In case of dehydration of primary alcohols, ether is also obtained due to a competing reaction.

.. H ..
CH 3 CH2 O
. .H CH3 CH2 OH ¾¾® CH 3 CH 2 O CH2 CH3 H2 O
+ H
–H
CH3CH2OCH2CH3

Dehydration of alcohols by phosphoryl oxychloride in presence of pyridine : Dehydration of alcohols with

acids involves relatively harsh conditions (acid and heat) and gives low yield of the desired product due to formation of
carbocation as intermediate. These shortcomings can be avoided by carrying dehydration of alcohol in the presence of
phosphoryl oxychloride (POCl3) and pyridine.

OH
|
3 POCl
CH 3 CH 2 CHCH 3 ¾¾¾¾¾® CH 3 CH = CHCH 3
pyridine, 0° C

CH3 O CH3 O
.. . +. N
CH3 – CH – .OH + P CH3 – CH – O – P
. –
Cl Cl (–Cl)
Cl H Cl Cl

CH3 O CH3
.. N |
CH2 – CH – .O. – P CH 2 = CH OPOCl 2
(E2 reaction) +
N
H Cl Cl H
–
Remember that OPOCl 2 is
a good leaving group
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(i) The mildly basic reaction conditions prevailing during the reaction favours E2 reaction, and hence no carbocation
is formed.
(ii) Formation of HCl is avoided by using pyridine.
Alcohol dehydration, like alkyl halides, are regioselective (formation of one constitutional isomer in major amount
than the other) as well as stereoselective (formation of one stereoisomer in major amount than the other).

H2S O4 CH3 CH2CH3 CH3 H

CH3CH2CHCH2CH3 C=C + C=C
heat
H H H CH2CH3
OH
cis -2-pentene trans -2-pentene
(minor ) (major )

6.3.3 By Dehalogenation of vicinal Dihalides

(a) By treating vic-dibromide with a solution of NaI in acetone.
| | –
E2
C C I ¾¾
¾® C C IBr Br
| |
Br Br

I - Br + I - ¾¾
® I 2 + Br -
(b) By treating vic-dibromide with a mixture of zinc dust in acetic acid (or ethanol)
| |
CH COOH
C C Zn ¾ ¾ ¾
3
¾¾
¾® C C ZnBr2
| | Or
Br Br C2 H5 OH

Other electropositive metals like Na, Ca and Mg can also cause debromination of vic-dibromides. The reaction
follows E2 path and it is stereoselective as well as stereospecific meso form gives trans- alkene and d- and e-forms give cis-
alkene.
Since vic-dihalides are themselves generally prepared from alkenes, the method is of little use as a general
preparative reaction. However, halogen addition on alkene followed by dehalogenation is useful (i) for the purification of
alkenes and (ii) in protecting the double bond.

1. Like dehydration of a primary alcohol, n-butanol when treated with conc. H2SO 4 undergoes dehydration by E2 reaction, and
expected to form butene-1, yet butene-2 (expected product due to E1 reaction) is the main product in this reaction. Explain.
2. Give the major product formed when each of the following alcohol is heated in presence of conc. H 2SO 4.

OH CH2OH
|
(a) CH 3 CH 2 CH 2 CHC(CH 3 )3 (b)

OH

CHCH2CH3

(c) CH 3 CH 2 CH 2 CH 2 CH 2 OH (d)

3. Propose mechanism for each of the following reactions.

OH

H2 S O4
Br
(a) (b) HBr
heat
OH
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4. Predict the order of reactivity of dehydrohalogenation of ethyl bormide, n- propyl bromide, isobutyl bromide and neopentyl bromide.
5. Give structures of alknenes likely to be formed from dehydrobromination, by a strong base, of
(i) 2-bromo-2-methylbutane (ii) 2-bromo-2, 3-dimethylbutane
(iii) 1-bromo-2, 2-dimethylpropane (iv) 3-Bromo-2, 3-dimethylpentane.
6. Name the alkyl halide that would yield each of the following pure alkene upon dehydrohalogenation by a strong base
(i) 2-pentene (ii) 2-methyl-2-butene (iii) 2-methyl-1-butene.
7. Arrange the following in their decreasing dipole moment
CH3CH = CH2, CH2 = CHCl, CH3CH=CHCl
8. Predict the products formed by the dehydration of
(i) (CH3)2C(OH)CH(CH3) 2 (ii) CH3CH2CH2CH2OH (iii) (CH3)3C.CHOH.CH 3
(iv) (CH3)3C. CH2OH

6.3.4 Partial Reduction of Alkynes

R H R R
Li or Na H2 /Pd
C C RC –
– CR C C
NH3 Lindlar
H R catalyst H H
anti-(trans-) Alkene syn-(cis-) Alkene

Detailed discussion of reduction of alkynes is given in the chapter on alkynes.

6.3.5 Electrolysis of Aqueous Solution of Sodium or Potassium Salts of the Saturated Carboxylic
Acids (Kolbe method)

CH2COOK electrolysis CH2

+ 2CO2 + 2KOH + H 2
CH2COOK CH2

At cathode At anode

6.3.6 Pyrolysis of Quaternary Ammonium Hydroxide (Hofmann elimination)

When tetralkyl ammonium hydroxides are heated, an alkene is formed along with a tertiary amine.

CH3 +
b a | a b g
CH 3 CH 2 N CH 2 CH 2 C H 3 heat
OH ¾ ¾ ¾® CH 2 CH2 (CH 3 )2 NCH 2 CH 2 CH3 H2 O
|
CH3

NOTE THAT :

(i) Here proton is abstracted from the b-carbon atom.

(ii) Here the least substituted alkene is the main product (Hofmann rule) which is opposite to that of Saytzeff rule. Note
that in the above example, ethylene is the main product instead of propene. This is due to the fact that the strongly
electronegative (–N+R3) group induces positive charge on all the neighbouring atoms which render b-hydrogen
atom acidic. Now if electron releasing alkyl group is present on the b-carbon atom, it will reduce its acidic character
+ a b
and hence its abstraction, as in the case of N - C H2 - C H2 —¬ CH3 group, become less prominent.
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6.3.7 Cope Elimination

Amine oxides are obtained in good yield by the oxidation of tertiary amines either with H2O2 or a peroxyacid.
Because of positive charge on nitrogen, the amine oxides when heated undergo cope elimination to form alkenes (similarity
with Hofmann elimination of quarternary ammonium salts).
CH3 CH 3
| |
H2 O 2 heat
® CH 3 CH 2 CH N + (CH 3 )2 ¾¾¾
CH 3 CH 2 CHN(CH 3 )2 ¾¾¾¾ ® CH 3 CH = CHCH 3 + (CH 3 )2 NOH
|
O-
Cope elimination occurs under milder conditions than Hofmann elimination. Cope elimination generally gives
the same orientation as Hofmann elimination (i.e. Hofmann product). The reaction occurs with syn-stereochemistry.

6.3.8 Wittig Reaction

For details, consult reactions of aldehydes and ketones.
R R
C = O + Ph3P = CHR' C = CHR' + Ph 3P = O
R R

e.g., = O + Ph 3P = CHCH 3 = CHCH3 + Ph3P = O

6.4 Physical Properties

(i) The first four members (C1–C4) are gases, C5–C17 are liquids while the higher ones are solids.
(ii) They are insoluble in water, but quite soluble in non-polar solvents. They are less dense than water.
(iii) Like alkanes, the boiling points rise with increasing carbon number (20 –30° per CH2 added) and again branching
lowers the boiling point.
(iv) Dipole moment. Since the loosely held p electrons of the double bond are easily displaced, alkenes are weakly
polar and hence have larger dipole moments than alkanes (non-polar), e.g. dipole moments of propene and
butene-1 are 0.35 D and 0.37 D respectively. In case of geometrical isomers, cis-isomer has relatively higher
dipole moment than the corresponding trans-isomer which may have zero dipole moment in case of symmetrical
compound, viz. trans-2-butene.
C2H5 H CH3 H CH3 H

C C C

C C C
H H CH3 H H CH3
1-Butene (µ = 0.37 D) cis-2-Butene trans-2-Butene
(Note that polarity is (µ = A small value) (µ = 0)
developed only in one bond)

NOTE THAT :

(a) In cis- 2- butene, polarity and hence dipole moment in the two bonds are equal and in the same direction while
in the trans-2-butene dipole moments of the two groups are equal in magnitude but opposite in direction, hence
they cancel each other giving net zero dipole moment.
(b) Permanent dipole moment in cis- but-2-ene causes dipole-dipole attractions (which is absent in the trans-but-2-
ene) which leads to increased intermolecular attractions and hence higher boiling point than the trans, although
both isomers have similar vander Waals attractive forces.
(c) Melting points of the cis- and trans-alkenes do follow opposite trend, i.e. cis-isomer has lower m.p. than the trans-
because in trans-isomer molecules are held tightly in crystal lattice due to its molecular symmetry.
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6.5 Chemical properties

Due to the presence of loosely held p electrons, alkens undergo addition reactions.
X Y

C=C + XY C C

NOTE THAT

(i) p-bond (a reactive bond) is converted into s bond (relatively less reactive bond).
(ii) During addition reactions, strain is relieved, i.e. bond angle (120°) is converted into tetrahedral bond angle of
109°28¢
Addition on alkenes may be initiated by an electrophile or a free radical, both of which remain in search of
electrons or electron respectively.

X Y X
–
+ + Y
C=C + X C C C C (Electriphilic addition)

X Y X
• • X:Y •
C=C + X C C C C + X (Free radical addition)

Alkenes having strongly electron-withdrawing group on one of the doubly bonded carbon atoms polarize the
electrons in such a way that the b-carbon becomes electron deficient and hence react with the nucleophile (nucleophilic
addition), e.g.
Y Y X
| - | |
- X+
H2 C = CHCN + Y ¾¾
® H2 C - C HCN ¾¾¾
® H 2 C - CHCN (Nucleophilic addition)
Although most of addition reactions of alkenes follow two-step path, certain (rare) addition reactions take place
via one-step path. For example, hydrogenation of alkenes using hydrazine in conjunction with H2O2, O2 or [K3Fe(CN)6].
Here the active reducing agent is cis-diimide.

C C
C=C
C C + N2
+ H H
H H
N N H H
N=N
cis-Diimide Transition state cis-Product

However, the most common addition reactions of alkenes are electrophilic.

6.5.1 Addition of Hydrogen (Catalytic hydrogenation)

Alkenes react with hydrogen in the presence of a catalyst to yield the corresponding saturated alkane.

catalyst
C = C + H2 –C–C– ; DH = Heat of hydrogenation
H H
Hydrogenation is, although, an exothermic proces, it proceeds at a negligible rate in the absence of a catalyst, even
at elevated temperatures. Thus it is evident that the function of a catalyst is to lower the energy of activation and the reaction
can proceed rapidly at room temperature. A catalyst lowers the Eact by causing the reaction to take place by a different
mechanism.Platinum and palladium are the most common catalysts, palladium is normally used as a very fine powder
supported on an inert material like charcoal (Pd/C) to maximise surface area. Platinum is normally used as PtO2; commonly
known as Adam's catalyst. Other catalysts used during catalytic hydrogenation are nickel, rhodium and ruthenium. Unlike
most other organic reactions, catalytic hydrogenation is a heterogeneous process, i.e. the reaction does not occur in a
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homogeneous solution but takes place on the surface of insoluble catalyst particles. In practice the alkene is dissolved in an
alcohol, an alkane, or acetic acid; a small amount of the metal catalyst (insoluble in any solvent) is added and the container
is shaken or sitrred. Hydrogenation takes place at the surface of the metal catalyst, where the liquid solution of the alkene
comes into contact with hydrogen and the catalyst. The adsorption of H2 over a catalyst is a chemical reaction in which
unpaired electrons on the surface of the metal pair with the electrons of hydrogen and bind the hydrogen to the surface. The
collision of an alkene with the surface bearing absorbed hydrogen causes adsorption of the alkene as well. A stepwise
transfer of hydrogen atoms takes place producing an alkane which leaves the catalyst surface. As a consequence both
hydrogen atoms usually add from the same side of the double bond that is complexed with the catalyst (syn addition).
If H2 and D2 are mixed in the presence of a catalyst, the two isotopes quickly scramble to produce a random
mixture of HD, H2 and D2 (no scrambling occurs in the absence of the catalyst).
Soluble homogeneous catalysts, such as Wilkinson's catalsyt.
Ph3P PPh3
Rh
Cl PPh3
C = C + H2 –C–C–
(Wilkinson's catalyst)
H H
Wilkinson's catalyst is not chiral, but its triphenylphosphine (PPh3) ligands can be replaced by chiral ligands to
give chiral catalysts that are capable of converting optically inactive starting materials to optically active products (chirally
catalyzed hydrogenation reactions). Such a process is called asymmetric induction or enantioselective synthesis. For
example,
H CH3
Ru(BINAP)Cl2
OH + H2
OH
R (» 96%)

Ph Ph
P Cl
Ru(BINAP)Cl2 = Ru
P Cl
Ph
Ph

Here the catalyst is chiral because of sterically hindered restricted rotation around the carbon-carbon single bond.
Enantioselective synthesis is particularly important in the pharmaceutical industry, because in several drugs
only one enantiomer of a chiral drug is found to have the desired effect.
Stereochemistry of hydrogen addition : When hydrogen adds to an alkene, both hydrogen atoms add to the
same side of the double bond which makes the addition of H2 a syn addition reaction.

H H
Pt
C=C +H–H C–C

Syn -addition of H 2

If addition of hydrogen to an alkene forms a product with two chirality centers, only two of the four possible
stereoisomers are obtained because only syn addition can occur. The particular pair of stereoisomers that is formed
depends on whether the reactant is cis or trans alkene. Syn addition of hydrogen to a cis alkene forms only the erythro pair
of enantiomers.
In case the two chirality centers have the same set of substituents, the two structures obtained will be same and
hence a single compound (meso isomer) will be formed instead of the pair of erythro enantiomers.

CH3 CH3
CH3CH2 CH3 H2, Pt H D D H
C=C +
H D D H
D D
CH2CH3 CH2CH3
cis-2,3-Dideuteriopent-2-ene erythro enantiomers
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261

CH3 CH3
CH3 CH3 H2, Pt H D D H
C=C
H D D H
D D
CH3 CH3
cis-2,3-Dideuteriobut-2-ene erythro meso isomer

Syn addition of hydrogen to a trans alkene forms only the threo pair of enantiomers.

CH3 CH3
CH3 R H2, Pt H D D H
C=C
D H H D
D D
R R
tran-Alkene threo isomers (R = CH3 or other alkyl)

Addition of hydrogen on cycloalkene

H2, Pt
H H + H3C CHMe2
H3C CHMe2 CH3 CHMe2 H H
1-Isopropyl-2-methylcyclopentene cis- cis-
Enantiomers

H2 , Pt
H H
D D D D
1,2-Dideuteriocyclopentene meso

Recall that cycloalkenes with fewer than eight carbon atoms can exist only in the cis configuration because they
do not have enough carbons to incorporate a trans double bond. Therefore, it is not necessary to use the 'cis' designation
with their names.

Another interesting stereochemical feature of catalytic hydrogenation is its stereoselectivity (a reaction in which
a single starting material can give two or more stereoisomeric products, one of which is either exclusive or major product
than the other). Catalytic hydrogenation of a-pinene is a stereoselective reaction. syn- Addition of hydrogen can theoretically
lead to either cis- pinane or trans- pinane depending on which face of the double bond accepts the hydrogen atoms. However,
the actual product is only cis- pinane, no trans- isomer is formed.
Thus addition of hydrogen on a-pinene is 100 percent stereoselective. The reason being the fact that catalytic
hydrogenation is extremely sensitive to the steric environment around the double bond and often approaches only the less
hindered face of the double bond forming a single product.

1. Indicate the direction of the net dipole moments for cis-2, 3-dichloro-2-butene and cis-1, 2-dibromo-1, 2-dichloroethene. Compare
their dipole moments with that of cis-1, 2-dichloroethene.
2. Predict the nature of products formed by the catalytic hydrogenation of each of the following reactions.
(a) cis-Pent-2-ene (b) cis-Hex-2-ene (c) trans-Pent-2-ene (d) trans-Hex-2-ene
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Transfer hydrogenation
Here hydrogen required for hydrogenation is supplied by some well-known stable compounds like cyclohexene
or hydrazine.

Pd
2R2C = CR2 + 2R2CH – CHR2 +
100ºC

Pd
2R 2 C = CR 2 + H 2 N - NH 2 ¾¾¾¾® 2R 2 CH - CH R 2 + N 2
100ºC
The driving force in such cases is higher stability of the compound formed after transferring hydrogen. For
example, benzene is more stable than cyclohexene due to aromatic ring and N2 is more stable than hydrazine due to strongly
bonded nitrogen atoms in N2.

6.5.2 Addition of Halogens

Treatment of alkenes with chlorine or bromine yields 1, 2- dihalogenated alkanes (vicinal dihalides).

CH 3 CH = CH 2 + Br2 ¾¾
® CH3 CHBrCH 2 Br
1,2 - Dibromopropane

The reaction is carried out simply by mixing the two reactants usually in an inert solvent like CCl 4, CHCl3 and
dichloromethane which dissolve both reactants. The reaction takes place rapidly at room temperature or below; in fact
high temperature, exposure to light and presence of excess of halogens should be avoided because these conditions may
lead to substitution reaction.
(i) Addition of bromine is extremely useful for detecting the presence of carbon-carbon multiple bond. Rapid
decolorization of a bromine solution (red) is characteristic of compounds containing C–C multiple bonds. Use of
bromine is preferred over chlorine owing to its ease of handling (as it is a liquid while chlorine is a gas) and
coloured nature. F2 and I2 are not used as reagents, because fluorine reacts explosively with alkenes, while
addition of I2 to form vicinal diiodide is thermodynamically unfavourable because vicinal diiodides are unstable
at room temperature, decomposing back to alkene and I2.
(ii) The least reactive iodine (F2 > Cl2 > Br2 > I2) can be added by the use of its compounds like ICl, IBr etc.

Mechanism of addition of halogens

It is similar to mechanism involving addition of protic acids. However, here a cyclic halonium ion is formed in
the first step instead of the usual carbocation.

Br+
1st step –
C C + Br—Br C C + Br

Cyclic bromonium* ion

+
Br Br
– 2nd step
C C + X C C

X
Here X– = Br– (from Br 2), OH– (from H2O) or other nucleophile added from outside.
Evidence for the formation of bromonium ion comes from the stereospecific addition of bromine to isomeric 2-
butenes. Thus cis-2-butene exclusively forms racemic -2, 3-dibromobutane and the trans-2-butene results in the exclusive
formation of meso-2, 3-dibromobutane. This leads to the conclusion that addition of bromine to 2-butenes involves (anti)-
addition, i.e. the two bromine atoms are attached to opposite faces (anti) of the double bond. This is possible only when
cyclic bromonium ion is formed as an intermediate.

* Unlike a normal carbocation, all atoms in a cyclic halonium ion have filled octets. High reactivity of the ion is due to three membered ring
and presence of positive charge on an electronegative halogen atom.
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CH3
H
CH3 H Br
H Br H
CH3 Br H
a
Br— Br CH3 H CH3
Br CH3

b II
H H
CH3
a
CH3 Br
b H CH3
cis-2-Butene I CH3
cis-Bromonium ion
Br Br H
Br H Br
H CH3 CH3
III
II and III are enantiomers
(rac-2, 3-Dibromobutane)
Addition of bromine to cis-2-butene via a cyclic bromonium ion. Opposite-side attacks [(a) and (b)] are equally likely, and give
enantiomers in equal amounts.
Since addition of Br2 to the cis-alkene forms a pair of threo isomers, the two isomers II and III represent enantiomeric
pair.
Br
CH3
H
CH3 H Br
H Å
r
B
CH3 H H Br
c
Br—Br CH3 H CH3 CH3
Br
V
d
CH3 CH3
H
c
–
H Br
d H
trans-2-Butene IV CH3 CH3
trans-Bromonium ion
Br Br H
Br
Br H
CH3 H CH3
VI
V and VI are same
(meso -2, 3-Dibromobutane)
Addition of bromine to trans-2- butene via a cyclic bromonium ion. Opposite-side attacks [(c) and (d)] give the same product.
In case of erythro isomers, if the four substituents are same, the two isomers (V and VI) are identical and
constitute meso compound.
Addition of Br2 to a cyclic alkene results in the formation of only the pair of enantiomers in which two bromine
atoms are added on opposite sides of the ring.

Br2
CCl4
+
Br H H Br
H H H Br Br H

enantiomeric pair
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1. Write the product of 1-butene with I–Cl.

2. Write down the major product obtained from the reaction of bromine with 1-butene if the reaction were carried out in each of the
following solvents separately.
(a) Dichloromethane (b) water (c) Methanol (d) Ethanol

6.5.3 Addition of Hydrogen Halides

Hydrogen halides add on carbon-carbon double bond forming alkyl halides, e.g.

C C + HX C C

H X
(HCl, HBr or HI) Alkyl halide

Reaction is carried out by passing dry hydrogen halide directly into the alkene or by treating the two reactants
in presence of moderately polar solvent like acetic acid which will dissolve both the polar HX and the non-polar alkene.
Aqueous solutions of hydrogen halides are not generally used because it may lead to addition of water on alkene. Order of reactivity
among hydrogen halides is
HI* > HBr > HCl > HF (Relative reactivity of HX)
Addition of hydrogen halides on unsymmetrical alkenes(e.g. CH3CH=CH2, CH2= CHCl, CH3CH2CH=CH2
etc.) may led to two products, but actually only one product is exclusively or predominantly formed. For example,
HI
CH 3 CH = CH 2 ¾¾® CH3 .CHICH3 + CH 3 CH2 CH 2 I
Pr opene Isopropyl iodide n- Propyl iodide (Not formed)

KI
(CH3 )2 C = CH 2 ¾¾¾
® (CH 3 )2 CICH 3 + (CH 3 )2 CH.CH 2 I
Isobutene H 3 PO 4 tert - Butyl iodide (Not formed)

Such reactions which, from the standard point of orientation, give exclusively or nearly exclusively one of several possible
isomeric products are called regioselective (Latin regio-direction).
In such cases, addition is governed by Markownikoff's rule. "In the addition of HX to an alkene, the H attaches to
the carbon with fewer alkyl substituents and th X attaches to the carbon with more alkyl substituents." When both ends of
the double bond have the same degree of substitution, a mixture of two products is formed.

CH 3 CH 2 CH = CHCH 3 + HI ¾¾
® CH3 CH 2 CHICH 2 CH3 + CH 3 CH 2 CH 2 CHICH3
2 -Pentene 3 - Iodopentane ( » 50%) 2 -iodopentane ( »50%)
Mechanism of addition of hydrogen halides on carbon-carbon double bond. It is similar to the general mechanism of
electrophilic addition of acidic reagents to carbon-carbon double bonds.
Br - Å Å
(i) CH 3 CH CH3 ¾ ¾¾® CH 3 CH CH 3 CH3 CH = CH 2 + H + ¾¾® CH 3 CH2 CH 2
Br A 2° carbocation Less stable 1 ° carbocation
Isopropyl bromide (More stable) (Not for med)

(ii) Similarly, for the addition of HBr on isobutene.

Å
Br H+
(CH3 )2 CBr.CH 3 ¾ ¾¾® (CH3 )2 CCH3 (CH 3 ) 2 C = CH 2 ¾ ¾¾® (CH 3 )2 CH CH 2
tert - Butyl bromide 3° carbocation 1 ° carbocation
(More stable) ( Less stable)
Thus, orientation in electrophilic addition in determined by the relative rates of formation of the carbocation
which is same as their relative order of stability
3° > 2° >1° > CH3+ (Rate of formation of carbocations)
Thus now Markownikoffs rule can be defined as " electrophilic addition to a carbon-carbon double bond involves the
intermediate formation of the more stable carbocation (reaction intermediate)". The rate of formation of a carbocation in
electrophilic addition depends upon its stability can be proved by the stability of the transition state leading to carbocation.

* HI is usually generated in the reaction mixture by treating potassium iodide with phosphoric acid.
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C C + H:X C C C C + :X

X H H
Transition state

Presence of electron-releasing groups tend to disperse the partial positive charge developing on carbon of the
transition state leading to its greater stability. Recall that stabilization of transition state lowers Eact and permits a faster
reaction.
Thus the sability of a carbocation determines not only the orientation of addition to an alkene (i.e the nature of
the product), but also the relative reactivities of different alkenes.

Reactivity of alkenes towards HX

(CH3 )2 C = CH 2 > CH3 CH = CHCH3 , CH 3 CH 2 CH = CH 2 > CH 3 CH = CH 2 > CH 2 = CH 2> CH 2 = CHCl
I II III IV V VI
(a) Alkene I is most reactive because here the most stable (3°) carbocation is formed as an intermediate.
(b) Alkenes II, III and IV form 2° carbocations, hence they have intermediate reactivity.
(c) Alkenes V and VI form 1° carbocation but the carbocation from VI will be less stable due to the presence of
electron-attracting Cl which intensifies the positive charge on the carbon atom of the transition state.
+ +
CH 2 CH 3 CH 2 CH2 Cl
more stable less stable

HBr
F3 CCH = CH 2 ¾¾¾
® F3 CCH 2 CH 2 Br + F3 CCHCH 3
anti -Markovnikov's product |
(Major) Br
(Minor)

This is due to the presence of electron-withdrawing nature of the – CF3 group which causes the 2° carbocation I
to be less stable than II (a 1° carbocation)
+ +
F3 C -¬ C H - CH 3 F3 C -¬ CH 2 - C H 2
I (2°) II (1°), more stable

In certain reactions, Markownikoff's addition product is also accompanied by unexpected product, rather the
latter product predominates. This is found in those alkenes where the structure of carbocation, formed at the first step,
permits rearrangement to the more stable carbocation. For example, addition of HI on 3, 3-dimethyl-1- butene gives not
only the expected Markownikoff's product (3-iodo-2, 2-dimethylbutane), but also unexpected product, 2-iodo-2, 3-
dimethylbutane.

CH3 CH3 CH3

+ + –
H I
CH3 —C—CH = CH2 CH3 —C—CHCH3 CH3—C—–CHCH3

CH3 CH3 CH3 I

3, 3-Dimethyl-1-butene 2° Carbocation 3-Iodo-2, 2-dimethylbutane

–
1, 2-CH3 shift

CH3 CH3
–
I
CH3—C—CH—CH2 CH3—C —CH — CH3

CH3 I CH3
3° Carbocation 2-Iodo-2, 3-dimethylbutane
(More stable) (Unexpected but major product)
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Addition of hydrogen bromide on C =C in presence of peroxide, anti Markownikoff's addition or Peroxide
effect. Addition of hydrogen bromide (not HCl and HI) in presence of peroxides takes place contrary to Markownikoff's
rule. For instance, addition of hydrogen bromide to propene in presence of peroxide gives 1-bromopropane (n-propyl
bromide) rather than 2-bromopropane (isopropyl bromide).

Br
|
HBr HBr
CH3 - CH - CH 3 ¬¾¾
¾ CH 3 CH = CH 2 ¾¾¾
® CH 3 - CH 2 CH 2 Br
(Not formed) peroxide peroxide 1- Bromopropane

This reversal of the orientation of addition caused by the presence of peroxides is known as peroxide effect.
Further, Kharasch and Mayo found that if peroxide formation is carefylly excluded during the reaction or
certain inhibitors (e.g hydroquinone, diphenylamine, etc.) are added, the addition of HBr to alkenes follows Markownikoffs
rule.

Br Br
| |
HBr HBr, peroxide,
CH 3 CHCH 3 ¬¾¾¾¾
¾ CH 3 CH = CH 2 ¾¾¾¾¾¾¾
® CH 3 CHCH 3
2 - Bromopropane no peroxide hydroquinone 2 - Bromopropane

Mechanism of peroxide effect. The anti-Markownikoffs addition (peroxide effect) is explained on the basis of
the fact that in the presence of peroxides addition takes place via free radical mechanism rather than ionic mechanism in
Markownikoff's addition. Peroxides are compounds containing the weak –O–O– linkage; they initiate the free radical
formation and thus addition of HBr involves the following general steps of free radical reactions.

. ü
Step 1. RO - OR ¾¾ ® 2RO ï DH0 = –15 kcal
Chain - initiating steps
. .ý
RO + H : Br ¾¾
® ROH + Br ïþ

ü
. . ï
Step 2. Br + CH 3 CH = CH 2 ¾¾
® CH 3CHCH 2 Br or CH 3 CHBrCH 2 ý Chain - propagation DH0 = –3 kcal
A2° radical A1°radical ï steps
(more stable) (less stable,not formed)þ

. .
CH3 CHCH 2 Br + H : Br ¾¾
® CH 3 CH 2 CH 2 Br + Br
DH0 = –6 kcal
More stable 2° radical 1- Bromopropane

. .
Formation of the more stable 2° free radical (CH 3 CHCH 2 Br) rather 1° free radical CH 3 CHBr CH 2 can again be
explained on the basis of sability of their corresponding transition states.

CH3—CH CH2 CH3—CH CH2

Br Br

Transition state leading to 2° Transition state leading to 1°

radical, less crowded and radical, more crowded and
hence more favourable hence less favourable

NOTE THAT

(i) anti-Markownikoffs addition is caused not only by the presence of peroxides but also by irradiation with light of
. .
a Wavelength known to dissociate HBr into H and Br atoms (radicals).
(ii) HF, HCl and HI do not exhibit peroxide effect because of their relative bond strength (HF > HCl > HBr > HI). Thus
H—F and H—Cl bonds are too strong to break into free radicals, while H—I bond although dissociates easily
into iodine radicals, they being bigger in size are not much reactive but recombine together to form iodine
molecule.
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267
Alternatively, the reaction of an alkyl radical with HCl is strongly endothermic, so the free-radical chain reaction
is not effective for the addition of HCl.
.
Cl – C – C + H – Cl Cl – C – C – H + Cl . D H° = + 10 kcal

Similarly, the reaction of an iodine atom with an alkene is strongly endothermic and the free-radical addition of
HI is not observed.
.
C = C + I. I–C–C D H° = + 13 kcal

Thus only HBr has just the right reactivity for each step of the free-radical chain reaction to take place.
Stereochemistry of addition of hydrogen halides (Additions involving a carbocation or a free radical intermediate)
If two chirality centers are created as the result of an addition reaction through a carbocation or a radical
intermediate, four stereoisomers can be obtained as products.

C2H5 C2H5 C2H5 C2H5

C2H5 C2H5 H3C H H CH3 H3C H H CH3
HCl
C=C + + +
H3C CH3 H3C Cl Cl CH3 Cl CH3 H3C Cl
C2H5 C2H5 C2H5 C2H5
cis-3,4-Dimethyl-3-hexene
I II III IV
3-Chloro-3,4-dimethylhexane (Four stereoisomeric products)

However, I and II are identical and represent meso compound.

The four stereoisomers are obtained due to attack of Cl– ion on the carbocation (formed in the first step by the
addition of H+ on alkene) from above or below. In short, the two atoms of the reagent (H and Cl) can add from above-above,
above-below, below-above, or below-below. When the two atoms add to the same side or opposite sides of the double
bond, the addition is called syn addition and anti addition respectively. Because the four stereoisomers obtained by the cis
or trans alkene are identical, the reaction is not stereospecific.

6.5.4 Addition of Sulphuric Acid

This is also proton initiated electrophilic addition and takes place in accordance with Markownikoff's rule
forming alkyl hydrogen sulphate (ROSO3H)

OSO 3 H
|
cold
CH 3 CH = CH2 + HOSO 2 OH (80%) ¾¾¾
® CH 3 CHCH 3
Isopropyl hydrogen sulphate

Since alkyl hydrogen sulphates are soluble in sulphuric acid, a clear solution is obtained.
Like alkyl sulphonates which are esters of sulphonic acids, alkyl hydrogen sulphates are esters of sulphuric
acid and hence undergo hydrolysis when heated with water leading to the formation of alcohol and sulphuric acid. Alkyl
hydrogen sulphates, when heated alone, regenerate alkenes.

OSO 3 H OH
| |
heat H 2 O,heat
H2 SO 4 + CH 3 CH = CH2 ¬¾¾¾ CH 3 - CHCH 3 ¾¾¾¾¾
® CH 3CHCH 3 + H 2 SO 4
Pr opene Isopropyl hydrogen sulphate Isopropyl alcohol

Thus reaction of alkene with sulphuric acid is used in the preparation of alcohols but since the addition of
sulphuric acid follows Markownikoff's rule, certain alcohols can't be prepared by this method, for example, isopropyl
alcohol can be prepared but not n-propyl ; tert-butyl alcohol can be prepared but isobutyl alcohol not.
The fact that alkenes dissolve in cold concentrated alcohol to form alkyl hydrogen sulphate, which on heating
regenerates the parent alkene, is used in the purification and separation of alkenes from alkane (alkanes are insoluble in
sulphuric acid).
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1. Predict the possible products formed by the addition of HBr on

(i) 3– methyl-1-butene (ii) 3, 3-dimethyl -1-butene
2. Convert propene to (i) CH3CHDCH2D and (ii) CH3CHDCH3
3. Which of the following carbocations would you expect to rearrange?
CH3 CH3 CH3
+
+
(a) (b) (c)
+

+
CH2

(d) (e) +
(f)
+

4. What will be the major product in each of the following reaction?

H O
(a) CH 3 CH = CH 2 + 2NaI + HBr ¾¾
® (b) CH 3 CH = CHCH 3 + HCl ¾¾¾
2 ®

CH OH
(c) CH 3 CH = CHCH 3 + HBr ¾¾¾¾
3 ®
5. Which of the following reaction is highly regioselective?
CH3

+ HBr or + HBr

6. Which member of each pair is more reactive toward addition of HBr?

(a) 1-Propene or 2-methylpropene (b) Cyclohexene of 1-methylcyclohexene (c) 1-Butene or 1,3-butadiene
7. Propose mechanism for the following transformation.

CH2CH3
+ HBr
Br
8. (a) When Z-3-methyl-3-hexene undergoes hydroboration-oxidation, two isomeric products are formed. What is the relationship
between these isomers?
(b) Write the hydroboration-oxidation product(s) of the E-isomer of the above problem. Give the relationship between the products
formed from the Z- and E-isomers.
9. When HBr addsacrossthedoublebond of 1, 2-dimethylcyclopentene, theproduct isamixtureof the cis- and trans- isomers. Explain
why this addition is not stereospecific?
10. Show how the following transformations are accomplished?
OH OH
(a) (b) (c) CH3
CH3
OH
OH
11. Hydrolysis of alkyl hydrogen sulphates belong to which class of reactions ? Predict the mechanism or mechanisms for hydrolysis
of ethyl hydrogen sulphate and tert-butyl hydrogen sulphate.

6.5.5 Addition of Water (Acid -catalyzed hydration)

Water adds directly to the more reactive alkenes in presence of a strongly acidic catalyst forming alcohols.
Addition occurs according to Markownikoff's rule.

..
OH2Å OH
+ | |
H+ H 2 O: -H+
CH 3 CH = CH 2 ¾¾¾ ® CH 3 CHCH 3 ¾¾¾® CH 3 CHCH 3 ¾¾¾® CH3CHCH 3 + H+
For dehydrating alcohols, a conc. dehydrating acid like H2SO4 or H3PO4 is used to drive the equilibrium in
favour of alkene. Hydration of an alkene, on the other hand, is done by adding excess water to drive the equilibrium in
favour of alcohol.
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6.5.6 Addition of Hypohalous Acids (HOCl, HOBr or halogen + H2O)

This reaction is similar to that of the addition of halogen in the presence of water, where we get haloalcohols
(also known as halohydrins).
Halohydrin formation does not take place by direct reaction of an alkene with HOCl or HOBr; rather the addition
is done indirectly by reaction of the alkene with either Cl2 or Br2 in presence of water.

2 Cl
CH 2 = CH 2 ¾¾¾ ® CH 2 OHCH 2 Cl
H2 O
When halogenation is done with no solvent or with an inert solvent like CCl4 or CHCl3, only the halide ion (from
halogen) is available as a nucleophile to attack the halonium ion forming dihalide as the final product. But when an alkene
reacts with a halogen in presence of a nucleophilic solvent like water, although there are two nucleophiles X – and H2O, but
H2O being the solvent is present in large amount than Br–, hence it will preferentially attack the halonium ion forming
halohydrin as the final product.
+
Cl
H2O + H2O +
CH2 – CH2 ClCH2CH2OH2 ClCH2CH2OH + H3O
Since the mechanism involves a halonium ion, the stereochemistry of addition is anti. For example, addition of
bromine water to cyclopentene gives trans-2-bromocyclopentanol.
H

Br2 Br
H2O
+ enantiomer
H
OH
Cyclopentene trans-2-Bromocyclopentanol

Further, halohydrin formation follows Markownikov's rule (the electrophilic end, the chlorine atom, adds to the
less highly substituted carbon of the double bond and nucleophilic end, the hydroxyl group, adds to the more highly
substituted carbon of the double bond.
OH
|
CH 3 CH = CH 2 + Cl 2 + H 2 O ¾¾
® CH 3 CHCH 2 Cl + HCl
The Markovnikov orientation is explained by the stability of the transition state, formed by the attack of nucleophile
on the halonium ion.

+ + +
Cl Cl Cl
H2O d+ d+
CH3CH – CH2 CH3CH – CH2 or CH3CH – CH2

d+ d+
:OH2 :OH2
More stable transition state Less stable transition state
(partial 2º cation) (partial 1º cation)

H2O +
CH3CH CH2Cl CH3CH CH2Cl + H3O
+
OH2 OH

However, only few alkenes are soluble in water and thus bromohydrin formation is often carried out in a solvent
such as aqueous dimethyl sulphoxide, CH3SOCH3 (DMSO), using N-bromosuccinimide (NBS) as a source of bromine. NBS
is a stable, easily handled compound that decomposes slowly in water to yield Br2 at a controlled rate.

O OH
NBr
O CH2Br
CH3SOCH3 / H2 O
(76%)
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6.5.7 Dimerization
Isobutene, when heated with sulphuric acid, phosphoric acid or HF undergoes dimerization forming a mixture
of two alkenes each having 8 carbon atoms. Hydrogenation of either of these alkenes produces the same alkane, 2, 2, 4-
trimethylpentane, commonly known as iso-octane.

CH 3 CH 3 CH 3 CH 3 CH 3
| | | | |
H 2 SO 4 ,80° C
CH 3- C = CH 2 ¾¾¾¾¾¾
® CH 3 - C - CH 2 - C = CH 2 + CH 3- C - CH = C - CH 3
| |
CH 3 CH3
2, 4, 4 - Trimethyl -1-pentene 2, 4, 4-Trimthyl-2-pentene
(major)

CH 3 CH 3
| |
H 2 /Ni
¾¾¾¾
® CH3 - C - CH 2 - CH - CH 3
|
CH 3
2,2,4 -Trimethylpentane (Isooctane)

Note that this is in not an industrial method for the preparation of isooctane.
Mechanism : Since reaction is catalysted by acids, it is on electrophilic addition and proceeds as below :

CH3 CH 3
| |
H+ (CH ) C = CH
CH 3 - C = CH 2 ¾¾¾
® CH 3 - C - CH3 ¾¾¾¾¾¾¾
3 2 2
®
(Step 1) Å (Step 2)
3° carbocation

CH3 CH 3 CH 3 CH 3 CH3 CH 3
| | HSO -4 | | | |
CH 3 - C - CH 2 - C - CH 3 ¾¾¾¾¾¾¾¾
® CH 2 = C - CH2 - C - CH3 + CH 3 - C = CH - C - CH3
Å | ( - H 2 SO 4 )(Step 3) | |
CH 3 CH 3 CH 3
Dimeric 3 ° carbocation (major) A (minor) B

Under suitable conditions, the dimeric 3° carbocation may further take a fresh molecule of isobutene to form
trimeric 3° carbocation and so on, leading to the formation of a polymer.
The unexpected product ratio, i.e. formation of A as major product is because of less steric hindrance. The
expected Saytzeff product B is sterically hindered because the bulky tert-butyl group is cis to a methyl group.
Dimerization of alkenes can't be carried out by acid catalysts like HCl, HBr, or HI because the conjugate bases of
these acids i.e. Cl–, Br–, and I– are good nucleophiles and hence will attack the carbocation in preference to the alkene
leading to addition of HX on the alkene instead of dimerisation.

1. Predict the nature of the products :

ether – 5°C, CCl4

(i) + HBr (ii) + Br2

Pt
+ H2 H2O
(iii) (iv) + Br 2

CH3
2. (a) Write down the intermediate dimeric carbocation formed during dimerization of propene.
(b) Write the structural formula for the major trimeric alkene formed from iosbutene.
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6.5.8 Alkylation
Branched chain alkanes (especially those which contain 3° hydrogen atom) add across a double bond in the
presence of an acidic catalyst to form higher alkanes, e.g.

CH 3 CH3 CH3 CH 3
| | | |
conc. H 2 SO 4
® CH3 - C - CH 2 - C - CH 3
CH 3 - C = CH 2 + H - C - CH 3 ¾¾¾¾¾¾
| or HF, 0 -10° C | |
Isobutene
CH 3 H CH 3
Isobutane 2,2,4 - Trimethylpentane

This reaction is used to prepare isooctane on industrial scale.

Mechanism : Mechanism is similar to that of
dimerization upto step -2 leading to the formation of CH3 CH3 CH3 CH3
a carbocation having eight carbon atoms. In step 3,
the carbocation abstracts a hydrogen atom with its CH3 —C—CH2—C—CH3 CH3—C—CH2—C—CH3
pair of electrons (i. e. a hydride ion) from alkane
molecule to form isooctane and a stable (3°) tert - CH3 H CH3
+ Step 3
butyl cation. This reaction shows that 2, 2, 4-Trimethylpentane
(i) a carbocation is extremely acidic in nature, and H
(ii) inertness of alkanes is greatly exaggerated since +
alkanes can react quite readily, with a strong acid, +
CH3—C—CH3 CH3—C—CH3
and that too in a heterolytic manner. Remember that
1, 2-shift accompanying the rearrangement of CH3 CH3
carbocations is commonly encountered, however,
this type of hydride transfer was intramolecular Isobutane tert-Butyl cation
(within a molecule), here it is intermolecular (between
two molecules).

6.5.9 Hydration by Oxymercuration - Demercuration

Many alkenes do not easily undergo hydration in aqueous acid. Some alkenes are nearly insoluble in aqueous
acid, and others undergo side reactions like polymerization or charring under these strongly acidic conditions. In some
cases, the overall equilibrium favours the alkene rather than the alcohol. Oxymercuration - demercuration works with
many alkenes that do not easily undergo direct hydration. Alkenes react with mercuric acetate in presence of water to form
hydroxymercurial compounds (oxymercuration) which on reduction give alcohols (demercuration).
H O NaBH
CH 3 CH = CH 2 + Hg(OAc)2 ¾¾¾
2 ® CH CH - CH
3 2
4
¾¾¾¾ ® CH 3 CH - CH 3 + AcOH + Hg
| | |
OH HgOAc OH
This way of hydration has following advantages over direct hydration.
(a) The process is fast (completed within minutes) and convenient (the alkene is added at room temperature to an
aqueous solution of mercuric acetate diluted with the solvent, tetrahydrofuran).
(b) The reaction takes place under mild conditions and gives excellent results (> 90%).
(c) The organomercurial intermediate compound is not isolated but is simply reduced in situ by sodium borohydride.
(d) No free carbocation is formed, so no question of rearrangement.
Mechanism : Oxymercuration-demercuration is highly regioselective and yields alcohols corresponding to Markovnikoff's
addition of water. The first step (oxymercuration) is initiated by the dissociation of mercuric acetate to form the electrophile,
+
H gOAc .

O O O O
|| || || ||
CH 3 C O Hg O C CH 3 CH 3 C O H g O C CH3
Hg(OAc)2 OAc HgOAc

Mercuric acetate may act as an electrophile as such because of presence of electrons in 5 d orbital of Hg. The
electrophile attacks on the double bond to form a cyclic mercurium ion as intermediate which is indicated by the absence
of formation of products corresponding to rearranged carbocation. The cyclic mercurium ion reacts with water (solvent) to
give an organomercurial alcohol.
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Attack by water on the mercurinium ion comes from the opposite side of the ring, and at the more highly
substituted carbon, thus the hydroxyl group and the mercury atoms are added on opposite sides (anti addition).

O Ac

Hg d+ CH3 HgOAc CH3 HgOAc

.. | | | |
CH3 CH3 + d+ H 2O : H
HgOAc H3 C C C H H3 C C C H
C=C H3C – C – C – H
| | | |
CH3 H +OH CH3 OH CH3
CH3 CH3 2
2-Methyl-2-butene In unsymmetrical mercurinium
ion more substituted C has
positive charge (3° carbocation)

Mercury is removed in the second step (demercuration) by sodium borohydride, a reducing agent.

CH 3 HgOAc
| |
4H 3 C - C - C - H + NaBH 4 + 4OH - ¾¾
® 4(CH 3 )2 C - CH 2 + Hg
| | | |
OH CH3 OH CH 3
2 - Methyl - 2 - butanol
(Markovnikov product)

Alkoxymercuration-demercuration
When mercuration take place in presence of alcohol (solvent), the alcohol serves as a nucleophile to form
alkoxymercurial compound (alkoxymercuration) which as in the above reaction can be reduced (deoxymercuration) with
NaBH4 to form ether as the final product.
R R' R R'
R R' '' | | | |
R OH NaBH4
C= C Hg( OAc)2 ¾ ¾ ¾
¾® R C C H ¾ ¾ ¾ ¾® R C C H
R H | | |
OR'' HgOAc OR ''

1. Predict the major products in each of the following reactions :

(a) 1-Methylcyclohexane + aqueous mercuric acetate (b) 1-Methylcyclohexene + mercuric acetate in presence of ethanol
(c) the product from part (b) is treated with NaBH4
2. From which alkenes the following alcohols have been prepared?
OH
OH
(a) (b)

3. Give steps involved in the conversion of 1-iodo-2-methylcyclopentane to 1-methylcyclopentanol.

6.5.10 Hydroboration or Hydroboronation

Hydroboration involves addition of a B – H bond of borane (BH3) to an alkene to yield organoborane intermediates,
RBH2, R2BH and R3B. Since BH3 has three hydrogens, addition occurs in three steps forming R3B as the final product.
CH = CH CH = CH
CH 2 = CH 2 + BH 3 ¾¾
® CH 3 CH2 BH 2 ¾¾¾¾¾
2 2
®(CH 3 CH2 )2 BH ¾¾¾¾¾
2 2
® (CH 3 CH 2 )3 B
Monomer of Triethylborane
diborane
(i) The reaction procedure is simple and convenient leading to excellent yield.
(ii) Hydroboration is carried out in ether, viz. tetrahydrofuran or diglyme (diethylene glycol methyl ether).
Commercially diborane is available in tetrahydrofuran solution, where it exists as the monomer in the form of
acid-base complex with the solvent.
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H H
– +
:O

:
H—B + H—B— O

H H
Borane Tetrahydrofuran Borane-tetrahydrofuran complex
(Acid) (Base)

(iii) Alkylboranes are important intermediates for the synthesis of alcohols and alkanes. These are not isolated and
converted in situ to the corresponding product.
Preparation of alcohols : Alkylboranes formed by hydroboration of alkenes can be easily oxidised by alkaline hydrogen
peroxide in which boron is replaced by –OH forming alcohol as the final product

THF OH -
3CH 2 = CH 2 + BH 3 ¾¾¾® (CH3 CH 2 )3 B+ 3H 2 O 2 ¾¾¾® 3CH 3 CH 2 OH + B(OH)3
Triethylborane Ethyl alcohol Boric acid

Thus in hydroboration-oxidation reaction three moles of alkene react with one mole of BH3 to form three moles of
alcohol. (hydration of alkenes) Hydration of alkenes through hydroboration is highly regioselective as we will observe in
the following examples that the alcohol formed correponds to anti-Markownikoff's addition of water (opposite to
oxymercuration-demercuration and by direct acid-catalysed hydration).
(i) (BH 3 )2
CH 3 CH = CH 2 ¾¾¾¾¾¾¾
- ® CH 3 CH 2 CH 2 OH lim
(ii) H 2 O 2 , OH dx ® 0
n - Propyl alcohol

CH 3 - CH = C(CH 3 )2 ¾¾
® CH 3 CH - CH(CH 3 )2
2 - Methyl - 2 - butene |
OH
3 - Methyl - 2 - butanol

CH 3 CH 3
| (i) (BH 3 )2 |
CH 3 - C - CH = CH 2 ¾¾¾¾¾¾¾ ® CH 3 - C - CH 2 - CH 2 OH
| (ii) H O /OH - 2 2 |
CH 3 CH 3
3, 3 - Dimethyl -1- butanol (1°)

Formation of 1° alcohol indicates that rearrangement does not occur in hydroboration leading to the fact that
carbocations are not formed as intermediates.
Preparation of alkanes : Alkylboranes are readily cleaved to alkanes on boiling with acetic or propanoic acid.
C H COOH
(CH 3 CH2 CH 2 )3 B ¾¾¾¾¾¾
2 5
® 3CH 3 CH 2 CH 3
Propane

Thus hydroboration-acid hydrolysis provides a valuable method for reducing a double bond.
Mechanism of hydroboration : Because of vacant orbital on boron, borane may be regarded as an electrophile and thus
attacks p electrons of the alkene; positive charge on the alkene develops on that carbon atom which is best able to support
it. Moreover, steric hindrance favours addition of boron to the less hindered carbon of the double bond.
2° carbon 1° carbon
CH3 —CH CH2
CH3—CH CH2 + BH3 CH3— CH CH2 CH3CH2CH2BH2
H BH2
H—BH2
Four centred transition state

Because of the four-centre mechanism, hydroboration is a cis-addition i.e., boron and hydrogen add across the
double bond on the same side of the molecule. During the oxidation step, the boron is replaced by an –OH with the same
stereochemistry, overall resulting in syn non-Markovnikov addition of water. Thus 1-methylcyclopentene on hydroboration-
oxidation yields trans-2-methylcyclopentanol. Further, a racemic mixture is expected because a chiral product is formed
from achiral reagents. Alkylboranes behave like borane and react further with excess of alkene forming di-and tri-
alkylboranes. The rate of hydroboration decreases with the increase in the number of alkyl substituents on the double
bond.
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1. Convert CH3CH = CH2 to CH3CH2CH2D.

2. What product would you obtain from the reaction of 1-ethylcyclopentene with
(a) BH3 followed by H2O2, OH– (b) Hg(OAc)2 followed by NaBH4
3. Predict the starting material for preparing following alcohol by hydration method so that a quantitative yield can be obtained.
CH3
|
CH 3 CH 2 CHCHCH 2 CH 3
|
OH
4. What product will be formed from hydroboration-oxidation of 1-methylcyclopentene with deuterated borane, BD 3? Show both the
stereochemistry and regiochemistry of the product.
5. What alkenes might be used for preparing the following alcohols by hydroboration-oxidation?

(a) (CH3)2CH CH2CH2OH (b) (CH 3 )2 CHCHCH 3 (c) CH2OH

|
OH

6.5.11 Epioxidation and anti-Hydroxylation of Alkenes

Alkenes when treated with a peroxyacid form epoxides, also called oxiranes; commonly used peroxyacids are
peroxyacetic acid, peroxybenzoic acid, and m-chloroperoxybenzoic acid.
.
O O O
|| . ||
RCH CH 2 R C O O H ¾¾® R CH CH2 R C O H
Recall that an oxygen-oxygen bond is weak and easily broken. The oxygen atom of the OH group (marked by
asterisk) accepts a pair of electrons from the p bond of the alkene. Thus epoxidation is an example of electrophilic addition,
where peroxy acid act as an electrophile and alkene acts as a nucleophile. The mechanism is analogous to the mechanism
for the addition of bromine to a double bond. In short, epoxidation is a concerted process where several bonds are broken
and several are formed at the same time through a cyclic transition state.
(i) Since the epoxidation takes place in one step, the epoxide retains the stereochemistry of the alkene (an example
of stereospecific reaction).
(ii) If the solution is not too acidic, epoxides are easily isolated as stable products, if the acid used is strong, epoxides
are converted to glycols.
(iii) If the acid used is weakly acidic (e.g. peroxybenzoic acid in CCl4), epoxides are the final products. However, if
peracetic acid in strongly acidic water solution is used, epoxides are protonated and finally converted to trans-
glycol.
(iv) Presence of electron-releasing groups on the doubly bonded carbon atom increases the electron density of the
double bond and hence increases the rate of epoxidation. Thus, if a diene is treated with limited amount of
peroxy acid, the most substituted double bond will be epoxidized.

O O O
+ RCOOH + RCOH

one equivalent

6.5.12 syn-Hydroxylation of Alkenes

An alkene can be oxidised to cis-1,2-glycols either by potassium permanganate in a cold basic solution or by
osmium tetroxide, also called osmic acid.
OH OH
| |
KMnO 4 , OH - , H 2O
CH 3 CH = CHCH 3 ¾¾¾¾¾¾¾¾¾
® CH 3 CH - CHCH 3
cold
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275
The solution must be basic and reaction must be carried out at room temperature or below, in case the solution
is acidic or it is heated, the diol will be further oxidised.
OH OH
| |
OsO 4 / NaHSO 3 (or Na 2 SO 3 ), H 2 O
CH 3 CH = CHCH 3 ¾¾¾¾¾¾¾¾¾¾¾¾¾¾
® CH 3 CH - CHCH 3
or OsO 4 , H 2 O 2

Since both Mn and Os are in highly positive oxidation state (+7 and +8, respectively), they attract electrons and
the reactions occur to form cyclic intermediates. Further since the two carbon-oxygen bonds are formed simultaneously
with the cyclic ester, the hydroxyl groups appear to the same face of the double bond (syn-hydroxylation). Therefore, such
oxidations are highly stereoselective.

H H
+ –
OH
O O H H + MnO 2
O O
Mn Mn OH
HO
O O_ O O_ cis -1,2-cyclopentanediol

O O O OH
O
NaHS O3, H2 O
Os Os
or H2 O2
O O O O OH
cis -1,2-cyclohexanediol

Hydrogen peroxide hydrolyzes the osmate ester and reoxidizes osmium to osmium tetroxide
Of the two reagents used for syn-hydroxylation, osmium tetroxide gives the higher yields. However, the reagent
is expensive, highly toxic and volatile.

6.5.13 Oxidative Cleavage of Alkenes.

(i) Oxidation with hot alkaline permanganate, acidic permanganate or acidic dichromate or potassium periodate (NaIO4) in
presence of catalytic amounts of KMnO4. Aldehydes, ketones, carboxylic acids and carbon dioxide are formed.
(a) The terminal CH2 group (=CH2) of alkenes is completely oxidised to CO2 and H2O.
(b) A doubly bonded carbon atom having an alkyl group (=CHCH3) is oxidised to aldehyde which is further
oxidised to carboxylic acid.
(c) A doubly bonded carbon atom having two alkyl groups (=CR2) is oxidised to ketone.
CH3 CH 2 COOH
(i)KMnO 4 ,OH - ­
CH 3 CH 2 CH = CH2 ¾¾¾¾¾¾¾
® CH 3 CH 2 C HO + CO2 + H 2O
+
(ii) H

(i) KMnO , OH -
4
(CH 3 )2 C = CHCH 3 ¾¾¾¾¾¾¾®(CH 3 )2 C = O + CH 3 COOH
(ii)H +

CH3
– O
KMnO4 /OH
+
H COOH
1-Methylcyclohexene

(ii) Oxidation with potassium periodate or lead tetra-acetate (mild oxidising agents). This is similar to the above oxidation
except that here aldehyde, if formed, is not further oxidised to acid.
NaIO
CH 3 CH = CH 2 ¾¾¾¾
4
® CH 3 CHO + CH 2 O
or Pb(OAc)4

NaIO
CH 3 CH = C(CH 3 )2 ¾¾¾¾
4 ® CH CHO + O = C(CH )
3 3 2
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1. Write down the products in each of the following reactions; mentioning the stereochemistry in each case.
O O
+
CCl4 H3O
(a) + C6H5C – OOH (b) + CH3 – C – OOH

H O H O
+
CCl4 H3O
(c) + C6H5C – OOH (d) + CH3 – C – OOH
H H
2. Predict the major product of the following reactions, including stereochemistry.
(a) Cyclohexene + peroxyacetic acid in water (b) Methylenecyclohexane + OsO4, NaHSO3
(c) cis-2-Pentene + OsO4 / H2O2 (d) cis-2-Pentene + peroxyacetic acid in water
(e) trans-2-Pentene + OsO4 / H2O2 (f) trans-2-Pentene + peroxyacetic acid in water
3. Z-2-Pentene when treated with OsO 4 in pyridine followed by treatment with NaHSO3 in water gives a diol that is optically inactive
and can't be resolved, while similar reaction with E-2-butene gives a diol that is optically inactive but can be resolved into
enantiomers. Explain.
4. Give the products formed in each case :
(a) Cyclopentene is oxidised with osmium tetroxide.
(b) trans-Butene-2 is oxidised with dilute alkaline cold KMnO 4 solution
(c) Maleic acid is oxidised with performic acid
5. Identify A, B and C in the following set :
–
hot Cold MnO 4
B+C – A
MnO 4

(iii) Oxidative cleavage by ozone (ozonolysis). Ozonolysis is carried out in two stages. At first stage ozone is added by
passing ozone gas into a solution of the alkene in some inert solvent like CCl4 to form unstable compound called
initial ozonide (Primary ozonide or molozonide) which rearranges spontaneously to stable ozonide. In the
second stage, highly explosive ozonide is hydrolysed in situ with water in presence of a reducing agent such as
zinc or dimethyl sulphide to form carbonyl compounds (reductive ozonolysis).
O
O3 H2O/Zn dust
C C C C C C C O + O C

O O O O
O Ozonide
Molozonide

(i)O
3
In short, CH 3 CH 2 CH = C(CH 3 )2 ¾¾¾® CH 3 CH 2 CHO + O = C(CH 3 )2
(ii)H2 O/Zn
The function of a reducing agent is to prevent the oxidation of aldehydes to carboxylic acids.
If the ozonide is cleaved in the presence of an oxidizing agent (e.g. H2O2), the products formed will be ketones
and/or carboxylic acids (oxidative ozonolysis).
Knowing the number and structure of carbonyl compouns, the structure of the parent alkene can be easily
worked out. For this first write down the structural formulae of the products. Remove oxygen atoms of the
ketonic or aldehydic groups and then join the two carbonyl carbon atoms of the two products by a double bond.
These can be judged by the following examples :

3 (i)O
(a) CH 3 CH 2 CH 2 CHO + OHC.CH 3 ¬¾¾¾¾¾¾ CH 3 CH 2 CH 2 CH = CHCH 3
(ii) H 2 O/ Zn
Butanal Ethanal 2 - Hexene

3 O
(b) CH 3 CH2 CHO+ OC(CH3 )2 ¬¾¾¾¾¾ ¾ CH 3 CH2 CH = C(CH 3 )2
(ii) H O/ Zn 2
Pr opanal Pr opanone 2 - Methyl-2-pentene
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277

OO
(i) O3
(c)
(ii) H2O/Zn

CH 3
|
(d) 2CH 3 COCH 3 + OHC.CH 2 COCH 3 ¬¾
¾ (CH 3 )2 C = CH.CH 2 .C = C(CH 3 ) 2

(e) OHC . (CH2)4CHO

CH 3
|
(f) CH 3 COCH 2 CHO + 2HCHO ¬¾
¾ H 2 C = CH.CH 2 C = CH 2

6.5.14 1, 2-Diol Cleavage

1, 2-Diols are oxidatively cleaved by reaction with periodic acid to yield carbonyl compounds.
OH OH
HIO4
C–C H2O, THF
C=O + O=C

CH3
O
OH CH3
HIO4
H2O, THF
OH H
O
H
6-Oxoheptanal

HIO4
H2O, THF
2 O
OH OH Cyclopentanone

Cleavage of alkenes through hydroxylation with OsO 4 followed by diol cleavage with HIO4 is an excellent
alternative to direct alkene cleavage with KMnO4 or ozone.

6.5.15 Substitution Reactions

Due to the presence of alkyl group in higher alkenes, higher alkenes undergo substitution reactions, under
suitable conditions, at allylic position. For example, propene when heated with chlorine at high temperatures (500 –
600°C) gives 3-choro-1-propene commonly known as allyl chloride (bromine behaves similarly), recall that addition of
halogens to alkenes takes place at low temperature and in presence of inert solvent like carbon tetrachloride.

Cl Cl
| |
Cl /CCl 2 Cl
CH 3 C H - CH 2 ¬¾¾¾¾
2 4¾ CH CH = CH ¾¾¾¾¾
3 2 ® CH 2 ClCH = CH 2
low temp.500 - 600° C
1,2 - Dichloropropane 3 - chloro-1-propene

Halogenations of alkenes similar to like free-radical substitution of alkanes, in alkenes halogenation always takes
place at the allylic position, (- * CH 2 - CH = CH 2 ) marked by asterisk. This is due to ease of abstraction of allylic hydrogen
atom. The relative ease of abstraction of hydrogen atoms corresponds to the following order :
Allylic H atom > 3° > 2° >1°>CH4 > Vinylic
The same order is also found to be the relative order of stability of the various free radicals.
.
Allylic free radical > 3° > 2° >1°>CH3 > Vinylic
Higher stability of ally radical is due to resonance.
Mechanism of allylic chlorination.
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278

Cl
. . Cl 2 .
CH 3 - CH = CH2 ¾¾¾ ® CH 2 - CH = CH 2 ¾¾¾ ® ClCH 2 - CH = CH 2 + Cl
Allyl radical Allyl chloride
Note that due to resonance the two terminal carbon atoms may have radical character
. .
C H 2 - CH = CH 2 ¨ CH 2 = CH - CH 2 or CH 2 L CH L CH 2
144424443
.
This becomes important in unsymmetrically substituted allylic radical because in such cases two products are
formed in the final product
. é . . .
Cl ù Cl
RCH 2 CH = CH 2 ¾¾¾ ® êR C H - CH = CH 2 ¬® RCH = CH - C H 2 ú ¾¾¾ ® RCH - CH = CH 2 + RCH = CHCH 2 Cl
|
ë û
Cl
Allylic product Rearranged product

The question arises why chlorine radical only abstracts hydrogen, when it can also add to double bond to form
new free radical which can give addition product in the following way.
.
Cl . Cl2
CH3— CH = CH2 CH3—CH—CH2Cl CH3CHClCH2Cl
high temp. I
However, the above reaction does not take place at high temperature because at high temperature the radical I is
reconverted into the starting material. Moreover, the radical I relatively being less stable than the allyl radical will require
halogen molecule immediately; while the allyl radical, being more stable, can wait for the halogen molecule to react. Thus
allylic halogenation can take place at higher temperature and in low halogen concentration.
Allylic bromination is best carried out by N-bromosuccinimide (NBS) because it allows a radical substitution
reaction to be carried out without using a relatively high concentration of Br2 that could add to the double bond. Homolytic
cleavage of the N–Br bond generates the bromine radical needed to initiate the radical reaction. Light or heat can be used
to promote the reaction. The solvent used is generally CH2Cl2.

O Br O

hv or heat
+ N – Br + N–H
CH2Cl2

O O
NBS Succinimide

NBS . .
CH 3 CH 2 CH = CH 2 ¾¾¾ ® [CH 3 C HCH = CH 2 ¬¾® CH 3 CH = CH C H 2 ]

Br
|
Br2
¾¾¾
® CH 3CHCH = CH 2 + CH 3 CH = CHCH 2 Br
3 - Bromo -1- butene 1- Bromo - 2 - butene

Allylic bromination by means of N-bromosuccinimide is known as Wohl-Ziegler reaction.

6.5.16 Polymerization
The process of joining together of many small molecules to form very large molecule is known as polymerization, the
comound formed is known as polymer and the simple compound from which polymer is made is called monomer.
Formation of polyethylene is a simple and most common example of polymerization. Ethylene when heated under
pressue in presence of oxygen undergoes polymerization to form polyethylene, a common plastic material used in packaging.
2 O , heat
nCH 2 = CH 2 ¾¾¾¾®
pressure
- ( - CH 2 - CH 2 - CH 2 - CH 2 - ) - n

Polymerization of substituted ethylenes gives plastics of widely differing physical properties

peroxide –
nCH2 = CH – CH2 – CH –

X X n
where X = Cl, CN, COOCH3, CH3, C6H5 etc. depending upon the nature of the group X. For example, vinyl chloride (when
X = Cl, i.e. CH2 = CHCl) polymerizes to polyvinyl chloride (PVC) used in industry for making plastics, pipes, records etc.
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Most of the polymerization of alkenes occurs by chain mechanism and, depnding upon the reaction conditions,
may be classified into three categories free-radical, cationic and anionic.
Cationic polymerization
Alkenes that easily form carbocations are good candidates for cationic polymerization. The reaction is similar to
electrophilic additions on an alkene. It is initiated by acidic catalysts like H2SO4, BF3, AlCl3, HF, etc. Polymerization of
isobutylene in presence of H2SO4, and styrene in presence of BF3 are common examples.
Free-radical polymerization
Many alkenes undergo free-radical polymerization, when they are heated with radical initiators. For example,
styrene polymerizes to polystyrene when it is heated to 100°C in presence of a peroxide.
heat .
RO - OR ¾¾¾ ® 2RO

C6H5 C6H5 C6H5 C6H5

| . | | |
OR C6 H5 CH = CH 2
H 2C = CH ¾¾¾® RO - CH 2 - CH ¾¾¾¾¾¾¾ ® RO - CH2 - C H - CH 2 - CH
.
.

The chain reaction stops, either by coupling of two chains or by reaction with an impurity (e.g. O2).
Ethylene also polymerizes by free-radical polymerization. Because, the free radical intermediates are less stable,
so stronger reaction conditions are required, i.e. by heating to about 200°C under a pressure of about 3000 atm. The
product formed is called low-density polyethylene, and is the material used in polyethylene bags.
Anionic polymerization
Like cationic polymerisation, anionic polymerization depends on the presence of a stabilizing group. Thus the
presence of a strong electron-withdrawing group (e.g. carbonyl, cyano, nitro, etc.) on one of the doubly bonded carbon atom
increases the stability of the carbanion. Hence methyl a-cyanoacrylate (containing two powerful electron-withdrawing
groups) undergoes anionic polymerization in presence of a trace of a base because the intermediate carbanion is very stable.
CN – CN
–
HOCH2 – C
OH H2 C = C(CN)COOC2 H5
CH2 = C ..
COOC2H5 COOC2H 5
Methyl a - cyanoacrylate
(Acts as super glue)

COOC2H5
CN
HOCH2 – C – CH2– C Polymer (Solid)
COOC2H5
CN

1. An alkene undergoes ozonolysis to form two moles of 1, 4-butandial. Deduce its structure.
2. Complete the following :

high temperature
(a) + Br2 (b) CH 3 (CH 2 )3 CH 2 CH 2 CH = CH 2 + NBS ¾¾
®

(c) Designate different types of hydrogen atoms present in the compound CH 3CH = CHCH2CH2CH(CH3)2, and arrange them
in the decreasing order of their reactivity with bromine atom (Br.).
3. Predict the nature of all possible products formed in the following reaction :

14 (i) NBS
CH 3 - CH = CH 2 ¾¾¾¾¾¾¾¾¾
®
(ii) O 3 , (iii) H 2 O/Zn
4. tert-Butyl hypochlorite (tert-BuOCl) causes allylic chlorination. What products are formed by treating butene-1 and butene-2 with
this reagent ?
5. When cyclohexanol is dehydrated to cyclohexene, a gummy green substance forms on the bottom of the flask. Explain.
6. When a thin film of methyl a-cyanoacrylate is applied between two metal pieces of a metal, they become non-detachable. Explain.
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6.5.17 Addition of Carbenes

Carbenes are uncharged, reactive intermediates that have a carbon atom with two bonds and two nonbonding
electrons. Like borane (BH 3), methylene (the simplest member of carbenes) is a potent electrophile because it has an
unfilled octet. It adds to the electron rich p bond of an alkene to form a cyclopropane.

C=C + : CH2 C—C

CH2
Methylene is obtained by heating dizaomethane (thermolysis) or by irradiating it with light of a wavelength that
it can absorb (photolysis). However, use of diazomethane for preparing cyclopropane derivatives has two difficulties.
(a) It is extremely toxic and explosive.
(b) Methylene (obtained from diazomethane) is so reactive that it inserts into C=C bonds as well as C–H bonds, thus
forming several side products.
H3C H – + H3C H H3C H
:CH2–N º N:, hv
C=C C – C + C=C
H H H H H CH2–H
C
H2

H– CH 2– CH2 H H3C H
+ C=C + C=C
H H H–CH 2 H
However, cyclopropanes can best be prepared by Simmons-Smith reaction which involves the use of iodomethyl
zinc iodide. Iodomethyl zinc iodide is prepared by adding methylene iodide to the zinc-copper couple. This type of reagent
is called a carbenoid because it reacts much like a carbene, but it does not actually contain a divalent carbon.

CH 2 I 2 + Zn (Cu) ¾¾
® ICH 2 ZnI
Iodomethyl zinc iodide
(Simmon-Smith reagent)

CH2I 2
Zn, CuCl

Addition of dihalocarbenes
Dihalocarbenes can be synthesized by the a-elimination of HX from haloform. Note that the H atom of HCX3 is
acidic due to the presence of three electronegative elements on carbon; hence haloform when treated with a base undergoes
a-elimination (removal of H and halogen from the same carbon atom) to form dihalocarbenes.*
+
+ - –H – slow –
HCBr3 + K OH : CBr3 : CBr2 + Br
Tribromomethanide Dibromocarbene
anion

The cycloaddition products of dihalocarbenes retain the geometry of the alkene.

H H H H
CHBr3
C=C C C
NaOH, H2O
CH3 CH3 CH3 CH3
C
Br Br

H C6H5 CHCl3
H C6H5
C=C
NaOH, H2O
C6H5 H C6H5 H

Cl Cl
Since only a single stereoisomer (cis- or trans-) is formed as product, reaction is said to be stereospecific.

* Dihalocarbene carbon atom is sp 2 hybridised (similarity to carbocations).

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6.5.18 Nucleophilic Additions

Alkenes having electron withdrawing group easily undergo nucleophilic additions rather than electrophilic.
Actually, electron-withdrawing group deactivates the carbon-carbon double bond towards electrophilic additions but at
the same time makes it more susceptible to nucleophilic attack by stabilizing the intermediate carbanion by dispersing the
negative charge. Common examples are the additions on a, b-unsaturated nitriles, aldehydes, ketones and esters.
–
C2H5O – C 2H 5OH
CH2 = CH–C º N [C2H5OCH2–CH–C º N C2H5OCH2–CH = C = N ] C2H5OCH2–CH2–C º N
Other examples of nucleophilic additions are
..
(i) R 2 NH + CH2 = CHCN ¾¾
® R 2 NCH 2 CH 2 CN

H H
–
OC2H5 – –
(ii) CH2 = CH—CH = O CH2—CH = C—O C2H5OCH2—CH—C = O

OC2H5

C2 H5 OH
C2H5OCH2CH = CHOH + C2H5OCH2CH2CHO

O O
NCH2CH2C CH2CH2CN
NaOH
(iii) + CH2 = CHCN
NCH2CH2C CH2CH2CN

6.5.19 Isomerization
An alkene may be converted into other by heating at high temperature or preferably at a low temperature in the
presence of a catalyst like anhydrous aluminium chloride. Either of the following occurs during isomerization.
(i) A double bond migrates from the terminal position forming more substituted alkene, e.g.
heat
CH 3 CH2 CH 2 CH = CH 2 ¾¾¾
® CH 3 CH 2CH = CHCH 3
Pentene -1 AlCl3 Pentene - 2
(ii) A methyl group may shift from an allylic position, again forming more substituted alkene, e.g
heat
CH 3 CH2 CH = CH 2 ¾¾¾
® (CH 3 )2 CH = CH 2
Butene -1 AlCl 3 Isobutene

1. Give reaction(s) involved in the conversion of each of the following reactions.

H

Br
(a) trans-2-Butene to trans-1,2-dimethylcyclopropane (b) Cyclopentene to

2. What products would you expect from each of the following reactions?
CHCl
3 CH I
(a) trans-2-Butene ¾¾¾¾
Me COK
® (b) cis-2-Butene ¾¾¾¾
2 2®
3 Zn(Cu)
3. Give various steps involved in the following reactions,
CH 3
AlCl |
(a) CH3CH 2 CH 2CH = CH 2 ¾¾¾®
3 CH3CH 2CH = CHCH3 (b) CH 3 CH 2 CH = CH 2 ¾¾
® CH 2 = C - CH 3
200 -300°
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Summary for stereochemical aspect of additions on alkenes
Reagent Name of alkene Stereochemical addition Product formed
1. H2/Catalyst cis-alkene syn meso-
trans-alkene racemic-
2. X2 cis-Butene-2 anti racemic-2,3-Dibromobutane
trans-Butene-2 meso-2,3-Dibromobutane
3. HOCl cis-Butene-2 anti racemic-3-Chlorobutanol-2
trans-Butene-2 meso-3-Chlorobutanol-2
4. Cold alk. KMnO4 Maleic acid (cis-isomer) syn meso-Tartaric acid
or OsO4 Fumaric acid (trans-isomer) racemic-Tartaric acid
5. Peracids Maleic acid anti racemic-Tartaric acid
Fumaric acid meso-Tartaric acid
6. Singlet carbene cis-Butene-2 syn cis-1,2-Dimethylcyclopropane
trans-Butene-2 trans-1,2-Dimethylcyclopropane
7. Triplet carbene cis-Butene-2 or Non-stereoselective Mixture of cis- and trans-
trans-Butene-2 1,2-Dimethylcyclopropane

DIENES
Hydrocarbons containing two, three, four and several double bonds in a molecule are called dienes, trienes,
tetraenes and polyenes respectively. Dienes have the general formula, CnH2n – 2 and are isomeric with alkynes. Depending
upon the relative positions of double bonds, dienes are divided into three classes.
(i) Dienes having two double bonds on the same carbon atom are known as cumulative dienes. Such system is
found in allenes, cumulenes, ketenes etc.
CH 2 = CH = CH 2 CH 3 - CH = C = CH - CH 3
1,2 - propadiene 2, 3 -Pentadiene
(Allene) ( sym - Dimethylallene)

(ii) Dienes having alternate arragement of sngle and double bonds are called conjugated dienes, e.g.
CH 3
|
CH 2 = CH - CH = CH 2 CH 2 = C - CH = CH 2
1, 3 - Butadiene 2 - Methyl -1, 3 - butadiene (Isoprene)

(iii) Dienes having isolated double bonds, i.e. two double bonds separated by at least one sp3 hybridised carbon, are
known as isolated double bonds.
CH 3
|
CH 2 = CH - CH 2 - CH 2 - CH = CH 2 CH 2 = CH - CH - CH = CH 2
1, 5 - Hexadiene (diallyl) 3 - methyl -1, 4 - pentadiene

Among the three types, conjugated dienes are the most important. They differ from simple alkenes in three ways.
(a) They are more stable and hence the preferred products of elimination.
(b) They undergo 1, 4-addition, both electrophilic and free radical.
(c) They are more reactive toward free-radical additions.

6.6 1, 3-Butadiene

1,3-Butadiene (a conjugated diene) is the most important diene. Commercially, it is prepared by the cracking of
hydrocarbons. It is purely a synthetic compound and has several worth-noting features.
(i) Its all carbon atoms are sp2 hybridised.
(ii) It is highly stable as compared to compound having two isolated or two cumulative double bonds. High stability
is indicated by its low heat of hydrogenation (57.1 kCal) than the isolated diene (60 kCal). Difference of 60 kCal and
57.1 kCal represents resonance energy (2.9 kCal) of the molecule; the three resonating structures are drawn below.
+ - + -
CH 2 = CH - CH = CH 2 ¬¾® CH 2 - CH - CH = CH 2 ¬¾
® CH 2 - CH = CH - CH 2
(iii) 1, 3-Butadiene is thermodynamically more stable than isolated alkenes but its chemical reactivity is more than
that of alkenes because it involves the formation of highly stable allylic type of intermediate.
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1. Electrophilic additions : 1, 3-Butadiene readily undergoes catalytic hydrogenation and electrophilic addition
reactions with halogens (e.g. Br2) and hydrogen halides (e.g. HCl) to form two types of products : in one the two
atoms of the reagent add on C1 and C2 (1, 2-addition), while in other the two atoms add on C1 and C4 (1, 4-
addition); usually the 1, 4-addition product predominates.

H2/ Cat.
CH3—CH2— CH = CH2 + CH3—CH = CH—CH3
1-Butene (1, 2-addition) 2-Butene (1, 4-addition)

HCl
CH2 = CH— CH = CH2 CH3—CHCl—CH = CH2 + CH3—CH = CH—CH2Cl
1, 3-Butadiene 3-Chloro-1-butene 1-Chloro-2-butene

Br2
CH2Br—CHBr—CH = CH2 + CH2Br—CH = CH—CH2Br
3, 4-Dibromo-1-butene 1, 4-Dibromo-2-butene

The formation of two products, viz. 1, 2-addition and 1, 4-addition product is explained on the basis of the
stability of the intermediate carbocation.

Br
1 2 3 4 Å |
CH 2 = CH - CH - CH2 CH 2 - CH - CH = CH2
1, 3 - Butadine (1st step) Unstable 1° carbocation
(not formed)

(1st step)

Å Å
BrCH2 - CH - CH = CH 2 BrCH2 - CH = CH - CH2
Allylic carbocation (highly
stable, due to resonance)
–
–
Br (2nd step) Br (2nd step)

BrCH 2 - CH - CH = CH2 BrCH2 - CH = CH - CH2Br

|
Br
3, 4 - Dibromo - 1- butene 1,, 4 - Dibromo - 2- butene
(1, 2 - addition) (1, 4 - addition)

Relative proportion of 1, 2- and 1, 4-addition products depends upon reaction temperature. Reaction at a low
temperature (–80°C) gives a mixture contaning 80% of the 1, 2-product and 20% of the 1,4-product; while
reaction at a higher temperature (40°C) gives a mixture containing 20% 1, 2- and 80% 1, 4-product. The fact that
the 1, 4-compound predominates at room temperature indicates that it is more stable than the 1, 2-product.
Stability of the 1, 4-product is due to more substituted alkene.
Predominance of the 1, 2-product at –80°C indicates that this compound is formed faster than the 1, 4-product
(i.e. its predominance is due to its faster rate of formation, hence the 1, 2-product can said to be a kinetically or rate
controlled product). With increase in temperature, although the proportion of the two products formed at initial
stage remains the same, conversion of the 1, 2-product to 1, 4-product takes place faster to reach an equilibrium
state whose exact composition depends upon the value of temperature. Since at high temperatures, more stable
1, 4-product predominates which is actually due to conversion of the 1, 2-product to the 1, 4-product, we can say
that the 1, 4-product is thermodynamically or equilibrium controlled product.
2. Free radical additions : Conjugated dienes also undergo free radical addition reactions forming a mixture of 1,
2- and 1, 4-addition products. It is interesting to note that conjugated dienes are more stable than isolated
alkenes, even then they are more reactive to free-radical attack than the isolated alkenes. This is because of the
fact that the allyl radical formed in the first propagation step is more stable and requires a lower activation
energy than the alkyl free radical from the isolated alkenes.
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For example, addition of BrCCl3 to 1, 3-butadiene in presence of peroxides takes place in the following way :
.
Peroxide ¾¾
® Free radical (Rad )
. .
Rad + BrCCl3 ¾¾® Rad - Br + CCl 3
.
CCl3
CH2 = CH—CH = CH2 Cl3C—CH2—CH CH CH2
.
Allylic free radical
Br
BrCCl3
Cl3C— CH2— CH—CH = CH2 + Cl3C—CH2— CH = CH—CH2Br
1, 2-Addition product 1, 4-Addition product

3. [4 + 2] Cycloaddition : Addition of two unsaturated compounds, one havng four carbon atoms and other two, to
form cyclic products are known as [4 + 2] cycloadditions. Best known example is addition of 1, 3-butadiene (a 4-
carbon unit) to ethylene (a 2-C unit) to form cyclohexene (Diel's-Alder reaction).

Butadiene Ethylene Cyclohexene

(a diene) (a dienophile) (an adduct)
It should be noted that in Diel's-Alder reaction, 1, 3-butadiene reacts only in the s-cis form.
4. Chemical reduction : The enhanced chemical reactivity of conjugated alkenes relative to isolated double bonds
is reflected in the reduction of butadiene with sodium and alcohol to form butene-2 (1, 4-addition product)
which although has a double bond is not reduced further.
Na/C H OH Na/C H OH
H 2 C = CH - CH = CH 2 ¾¾¾¾¾¾
2 5
® H 3 C - CH = CH - CH 3 ¾¾¾¾¾¾
2 5
® No reduction
Butene - 2
. 2e
2Na ¾¾
® 2Na + 2e; H 2 C = CH - CH = CH 2 ¾¾®
– –
– – – –
H2C = CH— CH—CH2 H2C—CH = CH—CH2 º H2C CH CH—CH2

+ – –
2H 2e
H3C— CH = CH—CH3 H3C—CH—CH—CH3
Butene-2 highly unstable (hence not formed)

The enhanced reactivity of conjugated alkenes is again due to the formation of resonance stabilized allylic
carbanion as intermediate.
5. Polymerization : Like substituted ethylenes, conjugated dienes also undergo polymerization. For example, 1, 3-
butadiene when heated with metallic sodium under the influence of heat, light or peroxide forms a rubber like
polymer known as buna-N.
Na
nCH 2 = CH - CH = CH 2 ¾¾¾
® - ( -CH 2 - CH = CH - CH 2 -) - n
Buna N
Monomers are joined largely by 1, 4-linkages and to some extent by 1, 2-linkages.

6.7 Degree of Unsaturation

The number of pairs of hydrogen atoms required by the molecular formula of an unsaturated compound to be
converted into corresponding alkane is called degree of unsaturation. Mathematically,
2n1 + 2 - n2
Degree of unsaturation =
2
where, n1 is the number of carbon atoms and n2 is the number of hydrogen atoms.
1° unsaturation indicates the presence of one C=C bond or one ring.
2° unsaturation indicates the presence of two C=C bonds, or one CºC bond, or one C=C bond and one ring, or two rings.
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Degree of unsaturation with hetero atoms
Heteroatoms are any atoms other than carbon and hydrogen. The rules for calculating elements of unsaturation
in hydrocarbons can be extended to include heteroatoms.
Halogens : A halogen simply substitutes for a hydrogen atom in the molecular formula. Thus in calculating the degree of
unsaturation, simply count halogens as hydrogen atoms. Thus C4H5Br3 is equal to C4H8 it means the halogen derivative
has two degree of unsaturation.
Oxygen : An oxygen atom can be added to the chain without changing the number of hydrogen atoms or carbon atoms.
Thus in calculating the degree of unsaturation, ignore the oxygen atoms.
Nitrogen : A nitrogen atom can take the place of carbon atom in the chain. However, nitrogen is trivalent, having only one
additional hydrogen atom, compared with two hydrogens for each additional carbon atom. Thus in computing the degree
of unsaturation, count nitrogen as half a carbon atom. For example, in a compound of the formula C4H9N means C4.5H9
whose corresponding alkene would be C4.5H(4.5 × 2) + 2 or C4.5H9 + 2; thus the formula C4H9N has one degree of unsaturation.

1. Predict the product of the reaction :

alc. KOH
(i) (CH 3 )2 CH - CHCl - CH 2 - CH = CH 2 ¾¾¾¾¾ ® (ii) CH 3 - CH = CH - CH = CH - CH 3 + HCl ¾¾
®
2. Determine the number of elements of unsaturation in each of the following molecular formula.
(a) C4 H 8 O (b) C4 H 4 O 2 (c) C5H5NO 2 (d) C6H3NClBr
3. Determine the degree of unsaturation in the following compounds and write down the structure of the isomeric cyclic compounds
in each case. (a) C6H12 (b) C4H6.
4. Assuming that unsaturation in the following compounds is present in the form of ring and C=C bonds only, i.e., no CºC bond is
present, determine the number of C=C bonds in the following compounds :
(a) a-Pinene (C10H16) containing two rings (b) Anthracene (C14H10) containing three rings
(c) Pyrene (C16H10) containing 4 rings.

6.8 Illustrative Examples on Alkenes :

Example 1 :
Draw and name the possible geometrical isomers of the following
(i) CH 3 CH = CH - CH = CH 2 (ii) CH 3 CH = CH - CH = CHCH 2 CH 3
(iii) CH 3 CH = CH - CH = CHCH 3
Solutions :
(i) Only two geometrical isomers are possible, because each carbon atom of one of the double bonds has two
different substituents, while one of the carbon atoms of the other double bond has two hydrogen.
H3C CH = CH2 H3C H
C C C C
H H H CH = CH2
Z-1, 3-Pentadiene (cis ) E -1, 3-Pentadiene (trans)
(ii) Both double bonds meet the conditions of geometrical isomers and hence 4 diastereomers are possible.
H H H CH2CH3
H3C C C H3C C C
C C CH2CH3 C C H
H H H H
cis, cis or (Z , Z)-2, 4-Heptadiene cis, trans or (Z, E)- 2, 4-Heptadiene

H3C H H3C H
C C CH2CH3 C C H
H C C H C C
H H H CH2CH3
trans, cis or (E, Z)- 2, 4-Heptadiene trans, cis or (E, E)- 2, 4-Heptadiene
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(iii) The four possible structures are
H H H CH3
H3C C C H3C C C
C C CH3 C C H
H H H H
cis, cis-2, 4-Hexadiene cis, trans-2, 4-Hexadiene

H H H CH3
H C C H C C
C C CH3 C C H
H3C H H3C H
trans, cis or (Z, E)- 2, 4-Hexadiene trans, trans or (E, E)-2, 4-Hexadiene

Note that cis, trans- and trans, cis are identical and hence only three geometrical isomers are possible in case of
2, 4-hexadiene.

Example 2 :
Give the major product formed in each of the following reaction :
Br CH3 Br CH3
(CH3)2CO
(a) + NaOH (b) + (C2H5)3N

Solutions :
Br Br
NaOH in (C2H5)3N :
(a) acetone + (b) +

Major (E2) Minor (E2) Minor (E2) Major (E2)

Hindered base, as Et3N:, gives Hofmann product as major isomer.

Example 3 :
1-Octene when treated with NBS gives unexpected primary bromide as the major product rather than 2º bromide.
Solution :
é . . ù
NBS
CH 3 (CH 2 )4 CH 2 CH = CH 2 ¾¾¾ ® ê CH 3 (CH 2 )4 C H CH = CH 2 ¬¾
® CH 3 (CH 2 )4 CH = CH CH 2 ú
CCl 4 êë úû
2º allylic 1º allylic

¾¾
® CH 3 (CH 2 )4CH.CH = CH 2 + CH 3 (CH 2 )4 CH = CH CH 2 Br
|
Br
3 - Bromo -1- octene (17%) 1- Bromo - 2 - octene (87%)

Primary bromide is favoured because it involves reaction at the less hindred radical.

Example 4 :
What product would you expect from reaction of 4, 4-dimethylcyclohexene with NBS?
H3C a

H3C
b
Solution :
The compound has two allylic positions, marked a and b. Further, the free-radical formed from each of the allylic
positions is resonance hybrid of two structures. Thus, in all four bromo products will be formed.
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. Br
CH3 a
NBS
NB
S . +
CH3 (a) Br
I II
b
(b)
NB .
S Br
º
.
Br
III IV

However, structures III and IV are identical, so in all three products are formed.

Example 5 :
Give the configuration of the products obtained from the following reactions.
(a) 1-Butene + HCl (b) 1-Butene + HBr + peroxide
(c) 3-Methyl-3-hexene + HBr + peroxide (d) cis-3-Hpetene + Br2
(e) trans-3-Heptene + Br2 (f) trans-3-Hexene + Br2

Br 2 Br 2
(g) CH2Cl2 (h) CH2Cl2

H3C CH3 H3C CH2CH3

H2, Pt H2, Pt
(i) (j)
H3C CH3 H3C CH2CH3
Solution :
*
(a) CH 3 CH 2 C H(Cl)CH 3 . The product has one chirality center, so equal amounts of the R and S enantiomers will be
formed.
(b) CH3CH2CH2CH2Br. The product does not have a chirality center, hence there are no stereoisomers.
* *
(c) CH 3 CH 2 C H(CH 3 ) C H(Br)CH 2 CH 3 . Two chirality centers are present in the product. The reaction involves
radical intermediate, two pairs (erythro and threo) of enantiomers are formed.
* *
(d) CH 3 CH 2 C H(Br)C H(Br)CH 2 CH 2 CH 3 . Two chirality centers are created in the product. Because the reactant is
cis and addition of Br2 is anti, the threo pair of enantiomers is formed.
* *
(e) CH 3 CH 2 C H(Br)C H(Br)CH 2 CH 2 CH 3 . Because the reactant is trans and additon of Br2 is anti, the erythro pair of
enantiomers is formed.
* *
(f) CH 3 CH 2 C H(Br)C H(Br)CH 2 CH 3 . Because the reatant is trans and addition of Br 2 is anti, erythro pair of
enantiomers is expected. However, the two chirality centers are identical the erythro product will be a single
meso compound.

Br CH2CH3 + H3C Br
(g)
H3C Br Br CH3
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Br CH2CH3 + H3CH 2C Br
(h)
H3C Br Br CH3

H H
H H + H H
(i) H3C CH3 (j)
H3C CH2CH 3 CH3CH2 CH3
(No enantiomer)

Example 6 :
(a) Calculate the DH0 for the addition of HBr on ethene, the DHo (bond dissociation energy) for the various bonds
are given below.
C=C 152 kcal/mol C – Br 69 kcal/mol
C–C 91 kcal/mol H – Br 87 kcal/mol
C–H 101 kcal/mol
(b) Tell whether the reaction is
(i) exothermic or endorthermic, (ii) exergonic or endergonic
Solution :
H H
H H
(a) C=C + H – Br H–C–C–H
H H
H Br
DHo involved in bond breaking DHo involved in bond forming
p bond* = 61 kcal/mol. C–H = 101 kcal/mol.
H – Br = 87 kcal/mol. C – Br = 69 kcal/mol.
------------------- ---------------------
DH ototal = 148 kcal/mol DH ototal = 170 kcal/mol.

*DHo for carbon-carbon p bond = DHo for carbon-carbon double bond (i.e. s + p bonds) – (DH0 for carbon-carbon s bond)
= 152 kcal/mol – 91 kcal/mol = 61 kcal/mol.
DHo for the reaction = DHo for bonds being broken – DH0 for bonds being formed
= 148 kcal/mol – 170 kcal/mol. = – 22 kcal/mol.
(b) The negative value for DHo indicates that the reaction is exothermic. Since DHo has a significant negative
value (–22 kcal/mol.), it can be said that DGo is also negative, i.e. the reaction is exergonic. In case the value
of DHo were close to 0, it can't be said that the sign of DGo is the same as DHo.

Example 7 :
Three isomeric alkenes A, B and C, C5H10, are hydrogenated to give 2-methylbutane. A and B give the same 3°
alcohol on oxymercuration-demercuration, while B and C give the different 1° alcohols on hydroboration-oxidation.
Deduce the structures of A, B and C.
Solution :
C
|
(i) The three isomers must have C - C- C - C as the skeleton, indicated by the formation of 2-methylbutane by all
the three.
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(ii) Since A and B give a 3° alcohol, both must have the = C(CH 3 )2 or H2 C = C - grouping.
|
CH3

(iii) Since B and C give 1° alcohols, both must have H2C = grouping. Thus A, B, and C should be

CH3 CH3 CH3

| | |
H 3 C - C = CH - CH 3 H 2 C = C - CH 2 - CH 3 H 3 C - CH - CH = CH 2
[A] [B] [C]

Example 8 :
A hydrocarbon (A) of the molecular formula C10H10, on oxidation, gives a tricarboxylic acid (B) with the structure
given below as the main product. Deduce the structure of A.

HOOCCH 2 CHCH 2COOH

|
(B) CH2COOH

Solution :

20 + 2 - 10
(i) Degree of unsaturation in A = =6
2
(ii) Appearance of three —COOH groups in B by the oxidation of A indicates that the latter has three acetylenic
bonds which is in agreement with the 6 degree of unsaturation.
(iii) Oxidative product (B) has three carbon atoms less indicating the presence of three º CH groupings which are
lost as HCOOH or CO2 during oxidation.
(iv) Hence strucutre of A should be

Oxidation
HC º C.CH 2 . CH.CH 2 .C º CH ¾¾¾¾¾
® HOOC.CH 2 .CH.CH 2.COOH + 3CO 2
| |
CH2Cº CH CH2 .COOH
(A) (B)

Example 9 :
An organic compound A reacts with HI to form two products B and C. On reaction with alcoholic KOH, B regenerates
A, while C gives an alkene which on reductive ozonolysis gives acetone as the exclusive product. Give the structure
of A and explain the reactions.
Solution :
Formation of acetone indicates that C is a symmetrical alkene of the formula Me2C = CMe2 (2,3-dimethylbutene) thus its
precursor B should be the corresponding alkyl halide.

CH3 CH3 CH3 CH3

| | | |
- HI HI HI
CH 3 - C = C - CH 3 ¬¾¾
¾ CH 3 - C - C - CH 3 ¬¾¾ Alkene ¾¾® B
| |
I H
C A

Since the alkene A forms two isomeric products with HI, it should be unsymmetrical dimethylbutene, i.e. 2,3-dimethylbutene-
1 or 3,3-dimethylbutene-1. However, only the latter explains the formation of the products with HI.
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CH3 CH3 CH3
| H
+ + |
I–
|
CH 2 CH C CH 3 ¾ ¾¾ ® CH 3 CH C CH 3 ¾ ¾
¾® CH 3 CH C CH 3
| | | |
CH3 CH3 I CH3
A 2° carbocation B
3,3-Dimethylbutene-1

CH3 CH3 CH3 CH3

| | | |
I–
CH3 CH C CH3 ¾ ¾
¾ ® CH 3 CH C CH 3
+ |
I
3° carbocation C

Example 10 :
Deduce the structure of the compound X, C10H14 that is hydrogenerated with three eq. of H2/Pd to give 1-isopropyl-
4-methylcyclohexane, and, on reductive ozonolysis gives the following products.
H2 C = O OHC - CH 2 - C - C - CH 3 CH 3 - C - CH 2 - C - H
|| || || ||
(A) O O O O
(B) (C)
Solution :
(i) The given compound has 4° of unsaturation coming from three C=C's (indicated by uptake of 3 eq. of H2) and one
cyclohexane ring (indicated by the formation of 1-isopropyl-4-methylcyclohexane).

(ii) Formation of 1-isopropyl-4-methylcyclohexane, by hydrogenation of X, indicates the presence of

as the carbon-framework of X. So now we must introduce three double bonds in the above mentioned frame-work.
(iii) Formation of CH2 = O (A) on reductive ozonolysis indicates the presence of = CH2 grouping and that too outside
the ring.
(iv) In compounds (B) and (C), two methyl groups are present, hence these must also be present in X, hence the =CH2
group can be present only in the isopropyl group.
(v) Since both compounds (B) and (C) have one –CH2 in between the two carbonyl groups, the two double bonds
(responsible for the creation of carbonyl groups) in the ring must be separated by one –CH2. Hence X should
have following structure which explains all the ozonolysis products.

O3
OHC CH 2 C C CH 3 + O=CH2
|| ||
O O
(X) (B) (A)
+
O O
|| ||
H3 C C CH2 C H
(C)

Example 11 :
Write down the structure of the two products formed in the following reaction.
H3C CH3 Br 2, hv
C=C Two isomeric products
H3C CH3
2,3-Dimethyl-2-butene
Give proper mechanism for this reaction.
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Solution :

.
H3C CH3 . H3C CH2 H3C . CH2
Br
C=C (–HBr)
C=C C – C
H3C CH3 H3C CH3 H3C CH3

Br 2

Br
. H3C CH2Br H3C CH2
Br + C=C + C – C
H3C CH3 H3C CH3

Example 12 :
Predict the different possible products in the dehydrobromination of 1,2-dibromopropane with alc. KOH. Which
product you expect to be the major?
Solution:

alc.
1 2 3 KOH
Br C H 2 - C HBr C H 3 ¾¾¾® CH 2 = CBrCH 3 + BrCH = CHCH 3 + BrCH 2 CH = CH 2
I (Major ) II III

The C1, being 1°H is more acidic than the C2, it is more easily removed by OH– than the 2°H of –CHBr. Further, the
C1–H is less sterically hindered and moreover the C1 has 2 H's while C2 has 1 H so there are two times more chances
for the H of C1 to be removed leading to II as the major product. Allyl bromide (III) is also formed in small amount
because 1°H of CH3 is less acidic than the 1°H of CH2Br, and the vinyl bromide (I and II) is more stable by virtue of
delocalization of electrons from Br to C = C.

Example 13 :
Propose a mechanism for the following reaction.

CH2 CH3
+
H

H3C
H3C CH3
CH3

Solution :
For solving such problems, keep in mind about the relative stability of the species and structure of the required
product.

CH2 CH3 CH3 CH3

+
+
H 1,2-methyl shift for
+
getting required product H3C + (–H )
H3C
H3C CH3 H3C CH3 H CH3 CH3
3° allylic carbocation
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Example 14 :
Propose a mechanism for the following reaction

+
H
OH heat

Solution :

CH2
3 2
1 +2 +
+ +
(i) H + ring contration –H
1
OH
(ii) –H2O rearrangement for getting the
3° carbocation required six-membered ring
3° carbocation
(7-membered ring) (6-membered ring)

Example 15 :
Propose mechanism for the following reactions
C6H5
+
LiCl in CH3OH H
(a) + Br2 Three products (b) 2 C6H5
C6H5
Solution :
+ Br
Br –
Br – Br Br
(a)
–
Cl HOCH3 Br
from
Br LiCl
Br Br

Cl +
H–O
. . CH3 OCH3

C6H5 H C6H5
+ + +
H C6H5
(b) –H
C6H5 C6H 5 +
C6H5 C6H5

Example 16 :
Propose a mechanism for the following reactions :

+
H HBr Br
(a) (b)
O
OH
CH2Br
OH O
Br2
(c)
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Solution :

+
+ +
H + +
(a) OH
Cyclization –H
.O:
. OH OH OH
+
H adds to most Formation of more More stable alkene
electronegative atom stable 3° carbocation

+ –
Br Br
HBr + +
(b)
3° carbocation
2° carbocation with 6-membered ring

+
Br
.. CH2Br CH2Br
: OH .. .. –
(c) :OH O
+O – H
Br –Br Br
+ HBr

Example 17 :
An organic compound (X), C5H9Br, does not react with bromine or with dilute KMnO4. However, its product (Y) due
to dehydrobromination, decolorises bromine as well as KMnO4 colour. Compound Y on ozonolysis gives another
compound Z, C5H8O2. Assign the most probable structure(s) to X and explain the reactions.
Solution :
(i) Degree of unsaturation in X is one.
(ii) Since the compound reacts neither with bromine nor with KMnO4, the degree of unsaturation must be due to ring.
(iii) Ozonylysis product of Y has same number of carbon atoms as the compound X, so unsaturation must be in the
ring which may be five membered or 4-membered.

Br
CHO
–HBr CHO

X Y Z

CHO
–HBr OHC
or Br CH3

[X] [Y] [Z]

cis or trans cis or tra ns

[X] may also be a cyclopropane derivative.

Br
O CHO
–HBr
CH3C – CHCH3
CH3 [X]
CH3 CH3 [Y] CH3 [Z]
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Example 18 :
(a) A hydrocarbon (A) of the molecular formula C10H16 undergoes oxidative or reductive ozonolysis to form two
moles of the same compound (B). (A) takes up three eq. of H2/Pd at 120°C. Deduce all possible structures for
the compounds (A) and (B) if neither (A) nor (B) is resolvable.
(b) What would have been the structures of A and B if each of them were resolvable?
(c) What would have been the structure of (A) under following assumptions.
(i) It is nonresolvable, but gives same hydrogenation properties as the original compound A.
(ii) It gives single product on oxidative ozonolysis, and a different but single compound on reductive
ozonolysis product, neither of the ozonolysis product is resolvable.
Solution :
(a) Compound A has 3° of unsaturation. Since compound A on ozonolysis gives two moles of the same compound
B, A must be symmetrical and should have only one C=C bond. The 2° of unsaturation must be in the form of two
rings. Reaction with three eq. of H2 at elevated temperatures indicates that A has two cyclopropyl ring (recall
that among cycloalkanes, only cyclopropyl ring reacts with H2 and that too at elevated temperatures). Thus the
alkene A belongs to RR'C = CRR' type. Inability to be resolved means an absence of chiral atom in A and B. The
possible structures for A (I to IV) and B (V and VI) are

CH3 CH3 CH3 O3

C=C and C=C O=C
CH3 CH3

I II V
(A) (B)

CH3 H H H
H
O3
H CH3H and H3C H H CH3 O H CH3
H3C
CH3 H CH3 CH3 CH3

III IV VI
(A) (B)
(b) For both (A) and (B) to be resolvable, each cyclopropyl ring must be substituted and the double bond must be
exocyclic to each ring. Further, the substituents are either two trans CH3 groups or one C2H5 and one H, cis or gem-
dimethyls would give achiral molecules.
Arrange the trans methyls to avoid planes and points of symmetry to preclude the possibility of meso isomer.
Thus the possible structures for (A) and (B) under these conditions are

H CH3 CH3

H3C CH3 H H O H H

H CH3 CH3
(A') (B')
rac, trans- Dimethylcyclopropanone

Et
Et
O
H Et H

H
(A') (B')
rac - Ethylcyclopropanone
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(c) To expalin different products on oxidative and reductive ozzonolysis, the alkene should be of RCH = CHR
type (where R is a cyclopropyl group).

reductive oxidative
2RCHO ¬¾¾¾¾
¾ RCH = CHR ¾¾¾¾¾
® [2RCHO ¾¾
® 2RCOOH]
ozonolysis ozonolysis

However, note that the R's can't be methylcyclopropyl groups because then the ozonolysis products would
be a resolvable racemate of chiral enantiomers.
Hence R is either cis- or trans- cyclopropyl-CH2CH = CHCH2-cyclopropyl.

ALKYNES OR ACETYLENES

Alkynes or acetylenes (CnH2n–2) have a —C º C— moiety and are isomeric with alkadienes, which have two
double bonds. Thus the degree of unsaturation of an alkyne having one—C º C— moiety is 2. For acetylene (C2H2),

2 ´ No. of C atoms + 2 - No. of H atoms 2 ´ 2 + 2 - 2

Degree of unsaturation = = =2
2 2
In IUPAC system, acetylenes are called alkynes and their corresponding groups obtained by the removal of one
hydrogen atom are called alkynyl.
HC º CH Ethyne and HC º C– Ethynyl
CH3.C º CH Propyne and CH3C º C– Propynyl
Alkynes are isomeric with alkadienes, cycloalkenes and bicycloalkanes. Thus CH3CºCCH3, butyne-2 (C4H6) is
isomeric with

H2C = CH—CH = CH2 and

1, 3-Butadiene
Cyclobutene

The triple bond, characteristic of acetylenes (—C º C—), is formed by sp hybridisation. Thus only two of the four
p orbitals of C are sp hybridised. The two unhybridised p orbitals (py and pz) are at right angles to each other and also to the
axis of the sp hybrid orbitals. Sidewise overlap of the py and pz orbitals on each carbon forms the py and pz bonds
respectively.

1. Give IUPAC names of the following :

(i) HC º C–CH2–CH=CH2 (ii) CH3–CH=CH–C º C–C º CH (iii) CH3C º CCH2–
2. Give structures and IUPAC names for all alkynes with the formula C6H10.
3. Why is the C º C distance shorter (124 pm) than the C=C (134 pm) and C–C (154 pm)?
4. Why geometrical isomerism is not possible in CH3C º CC2H5?
5. Is optical isomerism possible in alkynes? If yes, give the structure of the lowest alkyne that can exhibit optical isomerism.
6. An alkyne of the formula C6H8 has three degree of unsaturation and shows geometrical isomerism. Give the probable structure of
the alkyne.
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6.9 Preparation of Alkynes

6.9.1 Synthesis of Alkynes by Elimination Reactions :

Alkynes can be prepared by double dehydrohalogenation of a geminal or vicinal dihalide. The two
dehydrohalogenation steps in the base-promoted reaction occur sequentially, alkenyl halides (vinyl halides) are formed
as intermediates.
X X X
| | |
base, ( - HX) base, ( - HX)
R - CH - CH - R ' ¾¾¾¾¾¾
® R – CH = C - R ' ¾¾¾¾¾¾
® RC º CR '
fast slow
The second dehydrohalogenation step (dehydrohalogenation of vinyl halides) is more difficult than the first, so
rather strongly basic conditions or high temperatures are required to eliminate second molecule of HX. When weaker
bases like alcoholic KOH and low temperatures are used, the intermediate alkenyl halide may be isolated. Thus double
dehydrohalogenation of alkyl dihalides is carried out by under extremely basic conditions, viz.,
(i) heating with fused (molten) KOH at about 200°C
(ii) heating with alcoholic KOH at about 200°C
(iii) heating with potassium tert-butoxide or sodium amide at a lower temperature.
Heating an alkyl dihalide either with fused KOH or alcoholic KOH at about 200°C yields an internal alkyne,
while heating with sodium amide gives terminal alkyne as the final product. Thus any of several isomers of dibromopentane
give mostly 2-pentyne on heating with fused KOH at 200°C. Actually in each case, the alkyne initially formed rearranges
to the most stable isomer, 2-pentyne.

Br Br Br Br ü
| | | | ï
CH 3 - CH - CH - CH 2 CH3 or CH 2 - CH - CH 2 CH 2 CH 3 or ï
2,3-Dibromopentane 1,2-Dibromopentane ï KOH
ý¾¾¾® CH3 - C º C - CH 2 CH 3
Br Br ï 200°C 2-Pentyne
| |
Br CH - CH 2 CH 2 CH 2 CH 3 or CH 3 C (Br)CH 2 CH 2 CH 3 ï
ï
1,1-Dibromopentane 2,2-Dibromopentane þ

Formation of internal alkyne (non-terminal alkyne) as the final product is due to rearrangement of the less stable
terminal alkyne (e.g. 1-pentyne) to the more stable highly substituted alkyne (as in alkenes) in presence of weak base like
KOH. However, this rearrangement (i.e. terminal to internal alkyne) is not possible in presence of very strong base (NaNH 2)
because the strong base converts the terminal alkyne to alkynide salt which, being very strong base, cannot rearrange.
NH -
2 ® CH CH CH C º C :-
CH 3 CH 2 CH 2 C º CH ¾¾¾ 3 2 2
On the other hand, strongly basic NaNH2 converts the internal alkyne to the terminal alkyne on heating to
150°C.
NaNH , 150° C H O
2
® CH3 CH 2 CH 2 C º C :- Na + ¾¾¾
CH 3 C º CCH 2 CH 3 ¾¾¾¾¾¾¾ 2
® CH 3 CH 2 CH 2 C º CH
Pentyne - 2 Pentyne -1
In short,
(i) NaNH2, 150°C R X
KOH
Terminal alkyne C=C
More stable internal alkyne
H (ii) H2OR' 200°C
Recall that the vicinal dihalides and geminal dihalides are easily prepared from alkenes and aldehydes (or
ketones) respectively.

Br Br
| |
B r2 ( i) 3 NaNH
CH 3 CH2 CH CH2 ¾ ¾¾® CH 3 CH 2 CH C H2 ¾ ¾ ¾ ¾ ¾¾
2 ® CH CH C CH
3 2
B utene 1 CCl4 (ii) H 2 O Butyne 1
NaOH, 200°C

CH 3 C CCH3
Butyne 2
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O Cl
|| |
PCl 5 ( i ) 3 NaNH
H3C CH2C CH 3 ¾ ¾ ¾ ® H 3CCH2 C CH3 ¾ ¾ ¾ ¾ ¾¾
2 ® H CCH C CH
3 2
| (ii ) H2 O
Cl
NaOH, 200°C
H3CC CCH3
vicinal-Tetrahalogen compounds and vicinal-alkenyl dihalides can be converted to alkynes by heating with Zn
or Mg.
Br Br
| |
C H OH
R - C - C - R ' + 2Zn ¾¾¾¾¾
2 5 ® R - C º C - R'
| | heat
Br Br
Br Br
| |
H3 C - C = C - CH 3 + 2Zn ¾¾
® H 3 C - C º C - CH 3

6.9.2 By Alkylation of Acetylide Ions

As we shall see later, alkynes with a terminal triple bond (R–C º C–H) are acidic and react readily with sodium
(or sodium amide) forming salts called acetylides. These acetylides are good nucleophiles and react with primary alkyl
halides (not sec or tert) to form higher alkyl alkynes (SN2 reaction).
1
® R - C º C - Na + +
R–C º CH + Na (or NaNH2) ¾¾ H 2 (or NH 3 )
2

R - C º C - + R ' - X ¾¾
® R - C º C - R ' + X-
NOTE :
(i) This method is used to prepare higher alkynes.
(ii) Alkyl halides, used for alkylation should be 1° with no bulky substituents or branches close to the reaction
center., 2° and 3° alkyl halides will also undergo elimination reaction (E2 elimination) in presence of acetylides,
strongly basic compounds.

Acetylenes having at least one terminal hydrogen atom can also be alkylated by means of Grignard reagents.
HC º CH + CH 3 MgBr ¾¾
® HC º C - MgBr + CH 4

HC º C - MgBr + CH 3 Br ¾¾
® HC º C - CH 3 + MgBr2

6.9.3 Kolbe's method

Electrolysis of a solution of sodium or potassium salt of maleic or fumaric acid gives acetylene at anode.
CHCOONa CH
|| ¾¾
®||| + 2CO 2 + 2NaOH + H 2
CHCOONa CH

6.9.4 Industrial Methods

(i) Acetylene and propyne can be prepared by the controlled, high-temperature partial oxidation of methane.
1500° C
6CH 4 + O 2 ¾¾¾¾ ® 2CH º CH + 2CO + 10H 2
(ii) Acetylene and propyne can be prepared by the hydrolysis of carbides, e.g.
CaC 2 + H 2 O ¾¾® HC º CH + Ca(OH)2
Since acetylene forms an explosive mixture with air, the latter is displaced from the flask by oil gas. Impurities
like H2S, NH3, arsine and phosphine present in acetylene are removed by passing the gas through an acidic
copper sulphate solution. The pure gas is collected over water.
Mg 2 C3 + H 2 O ¾¾
® CH 3 - C º CH + Mg(OH)2
Propyne
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6.9.5 Acetylene can be prepared by heating iodoform or chloroform with silver powder or zinc.

CHI 3 + 6Ag + I 3 CH ¾¾
® HC º CH + 6AgI

1. Explain the formation of A as the major product in the following reaction :

Br Br
| |
1 alc. KOH
CH 3 C HCH 2 Br ¾¾¾¾¾® CH 3 CH = CHBr + CH 2 = CHCH 2 Br + CH 3 C = CH 2
(A) (B) (C)

2. Give the product formed in each case :

(a) HC º C :- Na + + Br2 ¾¾
® (b) HC º C : - Na + CH 3 CH 2 CH 2 Br ¾¾
®

(c) HC º C : - Na + + CH 3 CH 2 CH 2 Cl ¾¾
® (d) CH 3 C º C : - + (CH 3 )2 CHCH 2 Br ¾¾
®

3. Give steps involved in the synthesis of the following compounds :

(a) 2-Hexyne from acetylene (b) 5-Methyl-2-hexyne from acetylene
(c) 3-Octyne from 1-bromobutane (d) Ethylcyclohexylacetylene by alkylation process
4. Formulate the reaction between calcium carbide and water to form acetylene as a Bronsted acid-base reaction.
5. Give reactions for the following conversions :
(i) Propene to propyne (ii) 2-butene to 2-butyne (iii) Ethyne to 2-hexyne

6.10 Physical Properties

Being compounds of low polarity, physical properties of alkynes are nearly same as that of alkenes and alkanes.
These are insoluble in water but quite soluble in usual organic solvents of low polarity, viz. ether, benzene and CCl4. These
are less dense than water.
Alkynes are colourless and odourless; however, the garlic like odour associated with common acetylene is due
to the presence of impurities like H2S, PH3 etc. Acetylene liquefies at –84°C under ordinary pressure. However, since liquid
acetylene is dangerously explosive, use or storage of acetylene in the form of liquid is prohibited and hence it is stored and
transported in acetone solution, soaked on porous solid like asbestose kept in steel cylinders under high pressure.

6.11 Chemical Properties

Chemical properties of alkynes are mainly due to two factors.

(i) Presence of p-electrons. Due to the presence of p bonds, alkynes (—C º C—) have loosely held p electrons; hence,
like alkenes, they undergo electrophilic additions very easily. However, additions on alkynes differ from that of
alkenes in the following two respects.
(a) A carbon-carbon triple bond is less reactive than a carbon-carbon double bond towards electrophilic
addition reactions. This is because of the fact that the sp hybridised carbon of alkynes has more s character
than that of the sp2 hybridised carbon of alkenes. Now since greater is the s character of a carbon atom, more
strongly will be the attraction for p electrons and hence lesser will be their availability for reaction.
(b) In addition to electrophilic additions, alkynes also undergo nucleophilic additions with electron rich
reagents (nucleophiles), like water, HCN, RCOOH and ROH.
(ii) Presence of acidic hydrogen atoms. Hydrogen atom attached to the triply bonded carbon atom can be easily removed
by a strong base, hence acetylenes or 1-alkynes are considered as weak acids.
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6.11.1 Addition of Hydrogen

Catalytic hydrogenation of alkynes takes place in two stages first forming an alkene and then alkane.
H /Cat. H /Cat.
R – C º C – R ' ¾¾¾¾
2 ¾® R - CH = CH - R ' ¾¾¾¾ 2 ¾® R - CH 2 - CH 2 - R '
However, hydrogenation can be stopped at the alkene stage by using calculated amount of hydrogen and
choosing suitable reaction conditions. Further, if the triple bond is not present at the terminal carbon atom, the alkene
formed may be cis or trans depending upon the nature of the reducing agent.
R R R H
H2/Catalyst Na or Li in liq. NH3 ;
C C R — C C—R C C
(cis-addition) or LiAlH4(trans addition)
H H H R
cis-( syn-) trans -(anti-)

syn-Addition of hydrogen (Synthesis of cis-alkenes)

Hydrogenation of an alkyne can be stopped at the alkene stage by using a partially deactivated (poisoned)
catalyst. The most common partially deactivated metal catalyst is Lindlar's catalyst (metallic palladium, deposited on
calcium carbonate, or barium sulphate, poisoned with lead acetate and quinoline). The catalytic hydrogenation of alkynes
is similar to the hydrogenation of alkenes. The reaction takes place on the surface of the catalyst leading to syn addition in
both cases.
A number of other catalysts for semihydrogenation of alkynes have been developed. These include Pd supported
on barium sulphate, and a nickel boride also known as P-2 catalyst. Nickel boride can be prepared by the reduction of
nickel acetate with sodium borohydride.
O
||
NaBH
(CH 3 C O)2 Ni ¾¾¾¾
4 ® Ni B
2
C2 H 5 OH

Hydrogenation of alkynes in the presence of P-2 catalyst also causes syn addition of hydrogen.

H /Ni B R R
2 2
RC CR ¾ ¾ ¾ ¾ ¾ ¾ ¾¾ ¾ ¾ ¾® C C
or H 2 , Pd /CaCO3 , quinoline H H
cis -2-Butene

anti-Addition of hydrogen (Synthesis of trans- alkenes)

Anti addition of hydrogen atoms to the triple bond occurs when alkynes are reduced with sodium (or lithium)
metal in amonia, ethylamine, or alcohol at low temperatures. This reaction called, a dissolving metal reduction, produces
an (E)- or trans- alkene.
H3 C H
Na/Li
CH3 – C C – CH3 C=C
liq. NH3 H CH3
2-Butyne trans -2-Butene
The mechanism for this reduction involves successive electron transfer from sodium (or lithium) atoms (steps 1
and 3) and proton transfer from ammonia, or amines, or alcohol (steps 2 and 4) used as a cosolvent.

. .–.
CH3 – C º C – CH3 + Na.
H – NH2
CH3 – C = C – CH3 Step 2
Step 1
A radical anion (a strong
base) species with a – charge
and an unpaired electron)

. CH3 .–. CH3 H CH3

Na . H NH
2
CH3 C C ¾¾ ¾® CH3 C C ¾¾¾¾ ® C C
step 3 step 4
H (Slow)
H H3C H
A vinylic radical A vinylic anion (base)
Since trans-vinylic anion is more stable (bulky alkyl groups are farther apart) than the cis-, the former is formed
faster leading to tans-alkene as the final product.

Note that sodium amide and sodium in liquid ammonia are different, sodium amide is a strong base, used for
removing a proton from a terminal alkyne. On the other hand, sodium in liq. NH3 is used as a source of electrons in the
reduction of an alkyne to a trans alkene.
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1. Give steps involved in each of the following conversions.

(a) trans-2-Pentene to cis-2-pentene (b) cis-2-Pentene to trans-2-pentene
CH3
|
(c) cis-Cyclodecene to trans-cyclodecene (d)
Propyne to 2-methyl-1-penten-3-yne, CH 3 C º C C = CH 2
2. Can you convert a mixutre of 60% trans-2-pentene and 40% cis-2-pentene to a pure cis-2-pentene?

6.11.2 Electrophilic Addition to alkynes takes place in two stages.

X Y X Y
| | | |
XY
—C º C — + XY ¾¾
® — C = C— ¾¾¾
® — C- C—
| |
X Y
As mentioned earlier, addition of an electrophile to alkynes takes place slowly than that on alkenes as evidenced
by the fact that in some reactions, a catalyst (generally a metal salt is needed.) The low reactivity of alkynes is belived to be
due to following two factors.
(i) The bridged intermediate carbocation formed by the initial attack of an electrophile on the triple bond is a highly
strained system, and hence less stable.
E

Å
—C º C — + E —C C—
Highly strained bridged carbocation

The formation of cyclic carbocation as an intermediate is borne out by the fact that the olefinic intermediate is
always trans.
(ii) Due to sp hybridization of acetylenic carbon atom, p-electrons are more tightly held by the carbon nuclei and
hence they are less easily available for combination with electrophiles.
(a) Addition of halogens (Br2, Cl2). Addition of halogens takes place in two stages, first forming a trans-1, 2-
dihaloalkene and then 1, 1, 2, 2-tetrahaloalkane.
R X
X2 X2
R—C C — R' C C R — CX2 —X 2 — R'
X R'
However, the reaction may be limited to the formation of halogenated alkene stage by choosing proper
conditions like use of bromine water instead of bromine alone which will form tetrabromo derivative.
Addition of Cl2 on ethyne is important as it leads to the formation of industrially important compounds.

CH CHCl CHCl2 CCl2

Cl 2 Cl | BaCl ||
||| ¾¾¾ ® || ¾¾¾
2® ¾¾¾¾
2®
CH CHCl CHCl2 ( - HCl) CHCl
Ethyne 1, 2 - Dichloroethene 1, 1, 2, 2 -Tetrachloroethane Trichloroethylene
(Westron) (Westrosol)

Westron and westrosol are used as industrial solvents for rubber, fats and varnishes.
(b) Addition of halogen acids (HCl, HBr, HI) takes place according to Markownikoff's rule.

CH CH HCl CH3
||| + HCl ¾¾
® || 2 ¾¾¾ ® |
CH CHCl CHCl2
Ethyne Vinyl chloride

The order of reactivity of halogen acids is HI > HBr > HCl > HF; HF adds only under pressure.
Addition of HCl on ethyne can be limited to vinyl chloride in presence of mercuric ions (catalyst).
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In case of unsymmetrical alkynes, addition takes place according to Markownikoff's rule.
CH 3 - C HI
CH 3 - CI HI CH 3 - CI2
||| ¾¾® || ¾¾® |
CH CH2 CH3
Propyne 2 - Iodopropene 2, 2 - Diiodopropane

Br H H Br
| | | |
HBr
CH 3 C º CCH 2 CH 3 ¾¾¾
® CH 3 - C = C - CH 2 CH 3 + CH 3 - C = C - CH 2 CH 3
2 -Pentyne 2 - Bromo - 2 - pentene 3 - Bromo - 2 - pentene
( E and Z isomers) ( E and Z isomers)

Br Br
| |
HBr
¾¾¾
® CH 3 - C - CH 2 CH2 CH 3 + CH3 CH 2 C CH 2 CH 3
| |
Br Br
In presence of peroxides, anti-Markownikoff's product is obtained.

CH3 - C CH3 - CH CH 3 - CHBr

HBr, peroxide || HBr
||| ¾¾¾¾¾¾® ¾¾¾ ® |
CH CHBr CH2Br
Propyne 1- Bromopropene 1, 2 - Dibromopropane

(c) Addition of other acids e.g. CH3COOH, HOCl, conc. H2SO4.

CH HgSO 4 CH 2 HOOCCH 3
CH 3
(i) ||| + CH 3 COOH ¾¾¾¾ ® || ¾¾¾¾¾® |
CH CHOCOCH 3 CH(OCOCH 3 )2
Acetylene Vinyl acetate Ethylidene acetate

CH CHOH CH(OH)2 –H2O CHO

HOCl
(ii) + HOCl
CH CHCl CHCl2 CHCl2
Unstable Dichloroacetaldehyde

CH CH2 H SO
CH3
(iii) ||| + H 2 SO 4 (conc.) ¾¾
® || ¾¾¾¾
2
conc.
4® |
CH CHHSO 4 CH(HSO 4 )2
Vinyl hydrogensulphate Ethylidene hydrogensulphate

Ethylidene hydrogensulphate on boiling with water produces acetaldehyde.

CH3 H2O CH3 –H2O CH3

(boil)
CH(HSO4)2 CH(OH)2 CHO
Unstable Acetaldehyde

(d) Hydration of alkynes by addition of water : Like alkenes, alkynes undergo acid-catalyzed addition of
water in the presence of mercuric ion as a catalyst. A mixture of mercuric sulphate in aqueous sulphuric
acid is commonly used as the reagent.
The reaction follows Markovnikov's rule leading to the formation of an enol which immediately rearranges
to the more stable carbonyl compound (keto-enol tautomerization). Since alkynes possess only limited
solubility in aqueous sulphuric acid, methanol or acetic acid is often added as a co-solvent.

OH O
| ||
H 2 SO4
CH 3 CH2 C CH H 2 O ¾ ¾ ¾¾ ® CH3 CH2 C H CH2 CH3 CH 2 C CH 3
Pentyne 1 HgSO4 An enol A ketone

H SO , Hg 2 +
CH 3 CH2 C º CCH 2 CH 3 ¾¾¾¾¾¾®
2 4
CH 3 CH 2 COCH 2 CH 2 CH 3

2 4 H SO , Hg 2 +
CH 3 C º CCH 2 CH 3 ¾¾¾¾¾¾® CH 3 COCH 2 CH 2 CH 3 + CH 3 CH 2 COCH 2 CH 3
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Mechanism :
2+ +
Hg Hg+ Hg
.. | .. |
H 2 O: H2 O :
CH 3 C º CH + : Hg 2 + ¾¾
® CH3 C = = CH ¾ ¾ ¾¾
® CH3 C C H ¾ ¾ ¾¾® CH 3 C CH
electrons present water attacks the | |
+ :O
in 5 d AO more substituted C H O
..H .. H

Hg+ +
| H O:
¾ ¾3¾¾ ® CH 3 C CH 2 CH 3 C CH 3
CH 3 C CH 2 æ Hg+ , ö | ||
|| ç ÷
è H2O ø OH O
O
The mechanism of the mercury (II) - catalyzed alkyne hydration is analogous to the oxymercuration reaction of
alkenes. In the former case, vinylic carbocation containing mercury loses proton to water to form a mercury-containing
enol intermediate. Now mercury is lost due to acidic conditions (H3O+), thus requiring no NaBH4 as in case of alkenes.

1. One mole of Br2 and 1 mole of butyne-1 are reacted to form corresponding dibromide, which should be the better choice for adding
one compound to another?
(i) Bromine solution added to butyne-1. (ii) Butyne-1 added to bromine solution.
2. Alkenes are more reactive than alkynes toward addition of electrophilic reagents (e.g. Br2, HBr, etc.) yet it is easy to stop the
reaction at the alkene stage when 1 molar equivalent of the reagent is used. Explain.
3. Give the product in the following reaction.
1 eq. HBr
CH 2 = CHCH 2 C º CH ¾¾¾¾¾
®

4. Alkynes are less reactive than alkene toward addition of Br2. Explain on the basis of stability of bromonium ion.
5. Although alkenes are more reactive than alkynes toward addition reaction, reverse is true regarding catalytic hydrogenation.
Explain.
6. Acetylene does not dissolve in conc. H2SO 4, while ethylene and other alkynes dissolve. Explain.
7. List the alkynes needed to synthesize the following ketones in the best possible yields.

O O O
|| ||
(a) Me2 CH C CH 3 (b) CH 3 CH 2 C CH 2 CH 2 CH 3 (c) C – CH2

(e) Hydration of alkynes by addition of borane (hydroboration - oxidation) : Borane adds to alkynes in the
same way as in alkenes to form enol which rearranges to the more stable carbonyl compound.

THF OH - , H O
3CH 3 C º CCH 3 + BH 3 ¾¾¾® CH 3 CH = CCH 3 ¾¾¾¾¾¾
2 2
®
| H 2O
BH2

3CH3 CH CCH 3 3CH 3 CH 2 C CH 3

| ||
OH O
(i) The reaction stops at the alkene stage in the internal alkynes because the bulky groups on the boron-
substituted alkene prevent further addition of borane. However, in case of terminal alkynes, hindered
dailkylborane must be used to prevent the addition of the two molecules of borane across the triple
bond. One such borane is disecondary-isoamylborane, also called as disiamylborane (siamyl stands
for secondaryisoamyl), and abbreviated as Sia2BH.

é CH3 ù
ê | ú
ê(CH 3 )2 CH - CH —ú– BH or Sia 2 BH
ê ú
ë û2
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In case unhindered dialkylborane is used, terminal alkynes add two molecules of diborane to form
aldehyde as the final product.

BR2
HBR2 H2O2
CH3CH2 º CH CH3CH2CH2CH CH3CH2CH2CHO
H2O
BR2

Thus hydroboration / oxidation sequence is complementary to the direct, mercury (II)-catalyzed

hydration reaction of a terminal alkyne because different products are obtained.
O O
|| (i) BH 3 , THF H2 O, H 2SO 4
||
R - CH 2 - C - H ¬¾¾¾¾¾ ¾ R - C º CH ¾¾¾¾¾¾ ® R - C - CH 3
(ii) H 2 O 2 HgSO 4
An aldehyde A ketone

(ii) In case of unsymmetrical alkynes, boron adds on the less substituted carbon, thus anti-Markovnikov
addition of water takes place.
Alkenylboranes are readily cleaved to alkenes on boiling with acetic acid or propanoic acid (similarity
with alkylboranes which give alkanes on similar treatment).
BH CH COOH
CH 3 C º CH ¾¾¾
3 ® [CH CH = CH] B ¾¾¾¾¾®
3 3
3 CH 3 CH = CH 2
THF

6.11.3 Nucleophilic Addition Reactions

Due to decreased reactivity of a carbon-carbon triple bond towards electrophilic additions, alkynes are found to
be susceptible to nucleophilic attack. Addition of hydrogen cyanide, methanol and carbonyl compounds in presence of
sodium ethoxide are important examples.

CH CHCN CHCN
CN H
(a)
CH CH CH2
Acrylonitrile

Acrylonitrile is extensively used for the manufacture of buna N.

CH CHOCH3 CHOCH3
OCH3 H
(b)
CH CHOCH3 CH2
Methyl vinyl ether

O
– –
CH OCH3
–
C C—CH2O
H—C—H
(c)
(—CH3OH)
CH CH CH
O

CH3OH
C—CH2OH H—C—H/CH3ONa
C—CH2OH
–
(—OCH3 ) CH
repetition
C—CH2OH

Thus the net result is the replacement of the acetylenic hydrogen atom(s) by CR 2OH group.

6.11.4 Oxidation of Alkynes with Permanganate

(i) Using aq. KMnO4 in nearly neutral conditions.

é OH OH ù O O
ê | | ú || ||
KMnO 4 -2H2 O
R - C º C - R ' ¾¾¾¾¾¾ ® êR- C - C - R ' ú ¾¾¾¾ ® R - C- C- R '
H 2 O, neutral | |
ê ú
ë OH OH û
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(ii) Using warm, basic permanganate, diketone formed above undergoes further oxidation forming salts of carboxylic
acids.
O O
|| ||
KMnO 4 , KOH
® R - C - O + R '- C - O -
R - C º C - R ' ¾¾¾¾¾¾¾ -
H 2 O, heat

Alkynes are not affected by peroxyformic acid and chronic acid.

6.11.5 Ozonolysis
Ozonolysis requires neither oxidative nor reductive work up, it is followed only by hydrolysis. Carbon dioxide
is obtained from the CH group of a terminal alkyne.
3 (i) O
CH 3 C º CH ¾¾¾¾ ® CH 3 COOH + CO 2
(ii) H 2 O

3 (i) O
CH 3 CH 2 C º CCH 3 ¾¾¾¾ ® CH 3 CH 2 COOH + CH 3 COOH
(ii) H 2 O
Since a triple bond is less reactive than a double bond, yields of oxidation products are sometimes low.

1. Give the product when 2-butyne is treated with BH3.THF.

2. Complete the following
BD .THF CH COOD
CH 3 C º CCH 3 ¾¾¾¾¾
3 ® [A] ¾¾¾¾¾®
3 [B]
3. Give the products of
(i) Mercuric-ion catalyzed addition of water, and
(ii) Hydroboration oxidation for each of the following
(a) 1-Butyne (b) 2-Butyne (c) 2-Pentyne
4. Complete the following :
(a) CH º CH + Br2 ¾¾
® (A) (b) CH º CH + 2HBr ¾¾
® (B)

H SO /HgSO
2 4 4
(c) CH 3 - C º CH + CCl 3 Br ¾¾
® (C) (d) C º CH + D 2 O ¾¾¾¾¾¾¾ ® (D)

(e) CH 2 = CHCH 2 C º CH + HBr ¾¾

® (E) (f) CH º CCH = CH 2 + HBr ¾¾
® (F)
5. Alkynes undergo nucleophilic addition, such as addition of CN–, while alkenes do not undergo such reactions. Explain.
6. Complete the following reaction :
CH ONa
(i) CH 3 CHO + HC º CD ¾¾¾¾¾
3 ®
CH ONa
(ii) = O + CH 3 C º CH ¾¾¾¾¾
3 ®

7. Give the product expected by the oxidation of cyclodecyne with

(i) dilute, neutral KMnO4, and (ii) warm basic KMnO4.
8. An alkyne undergoes oxidative cleavage to give following compounds.
COOH
HOOC + CH 3CH2COOH
COOH
Propose a structure for the alkyne.
9. Deduce the structural formula of a compound, C 10H10 that gives HOOCCH2CH(CH2COOH)2 as the organic compound on
oxidative cleavage.
10. Complete the following :
C CCH3

O3/ H2O KMnO4 BH CH COOD

(i) C + D A + B (ii) CH 3 CH 2 C º CH ¾¾¾
3 ® E ¾¾¾¾¾®
3 F
heat
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6.11.6 Acidic Nature

Hydrogen atom or atoms attached to the triply bonded carbon atoms can be easily removed by a strong base,
thus 1-alkynes are considered as weak acids.

® R - C º C - + H - Base
R – C º C : H + Base ¾¾
The acidity of acetylene or 1-alkynes can be explained on the basis of molecular orbital concept according to
which formation of C–H bonds in acetylene involves sp-hybridised carbon atom. Now since s electrons are closer to the
nucleus than p electrons, the electrons present in a bond having more s character will be correspondingly more closer to the
nucleus. The amount of s character in various types of C–H bonds is as follows.
Type of C–H bond º C–H = C–H –C–H
% of s character in C 50% 33.3% 25%
Thus owing to high s character of the C–H bond in alkynes (s = 50%), the electrons constituting this bond are
most strongly held by the carbn nucleus (i.e. the acetylenic carbon atom or the sp orbital acts as more electronegative
species than the sp2 and sp3) with the result the hydrogen present on such a carbon atom (º C–H) can be easily removed as
a proton. The acidic nature of the three types of C–H bonds follows the following order.
º C–H > = C–H > –C–H
sp sp2 sp3
Being most electronegative*, the carbon of acetylene is best able to accommodate the electron pair in the anion left
after the porton is lost. In other words, anion of acetylene is the most stable and hence most acidic, while anion of ethane
is the least stable (because sp3 carbon is the least electronegative) and hence least acidic.
CH º CH + : B – HB + HC º C : – (Most stable)

H3C–CH3 + : B– HB + H3C–CH2 :– (Least stable)

Relative acidities HOH ~- HOR > CH º CR > HNH2 > H2C = CH2 > CH3–CH3
–OH ~ –OR < –C º CR < –NH < –CH = CH < –CH –CH
Relative basicities - 2 2 2 3
Because of acidic nature, acetylenic hydrogen atom can be easily replaced by certain metals to give the metallic
derivative called acetylides or alkynides. Acetylene has two such hydrogen atoms, 1-alkynes have one such hydrogen
atom and the other alkynes nil.

H-C º C-H , CH 3 CH 2 - C º C - H , H 3 C - C º C - CH 3
Acetylene 1- Butyne 2 - Butyne
(having two acidic hydrogen) (one acidic hydrogen) (no acidic hydrogen)

Alkynides (dry) are generaelly unstable and explosive. These are easily converted into original alkynes when
heated with dilute acids.

NaC º CNa + 2HNO 3 ¾¾

® HC º CH + 2NaNO 3
Hence this reaction can be used for the purification, separation and identification of alkynes.
(i) Formation of sodium acetylides : Acetylenes and monoalkylacetylenes react with sodium in liquid ammonia or
sodamide to form acetylides.
liq. NaNH
H - C º C - H + Na ¾¾¾
® H - C º C - Na 2
¾¾¾¾ ® NaC º CNa
NH 3 Monosodium acetylide 120º Disodium acetylide

NaNH
CH 3 - C º C - H ¾¾¾¾
2
® CH3 - C º CNa
Sodium propynide

Similarly, HC º CH + CH 3 MgI ¾¾
® HC º CMgI + CH 4
Acetylenicmagnesium iodide

These alkynides are ionic in nature.

As discussed earlier the sodium alkynides react with primary alkyl halides to form higher alkynes.
S 2
CH 3 - C º CNa + ICH 3 ¾¾¾
N
® CH 3 - C º C - CH 3 + NaI

* Remember that higher the electronegativity of an atom, greater is its ability to hold bonding electrons close to it. The order of
electronegativity of the three type of carbon atoms is sp > sp 2 > sp 3.
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(ii) Addition of acetylide ions to carbonyl groups : Like other carbanions, acetylide ions are strong nucleophiles
and strong bases. Thus in addition to displacing halide ions in SN2 reactions, they can add to carbonyl groups,
to form alkoxide ions which again being strong bases react with water or a dilute acid to give corresponding
alcohol.
R R
R | + |
H3 O
RC C: C O ¾¾® RC C C O ¾ ¾ ¾¾ ® RC C C OH
R' | |
R' R'
Alcohol (1 °, 2 ° or 3 °)

where, R and R' may be H or any alkyl group

Note that these reactions are similar to those of Grignard reagents.

(iii) Formation of copper and silver acetylides : Copper and silver alkynides are obtained by passing alkynes in the
ammonical solution of cuprous chloride and silver nitrate respectively.

HC º CH + Cu 2 Cl 2 + 2NH 4 OH ¾¾
® CuC º CCu ¯ + 2NH 4 Cl + 2H 2 O
1444 424444 3
Ammonical cuprous chloride Copper acetylide ( red ppt.)

HC º CH + 2AgNO 3 + 2NH 4 OH ¾¾
® Ag C º CAg ¯ + 2NH 4NO 3 + 2H 2 O
1444424444 3
Amm. silver nitrate Silver acetylide ( white ppt.)

Silver and copper acetylides are bonded more covalently than other acetylides. These are not very soluble and
form characteristic precipitates. These are much less basic and less nucleophilic.
These reactions are used for detecting the presence of acetylenic hydrogen atom. For example, butyne-1 having
acetylenic hydrogen atom gives red and white precipitate with ammonical cuprous chloride and ammonical
silver nitrate solution, respectively, while butyne-2 does not give such precipitate.
CH 3 CH 2 C º CH CH 3 C º CCH 3
Butyne -1 Butyne - 2

It is important to note that these heavy metal acetylides are likely to explode. Hence they should be destroyed
while still wet by warming with nitric acid; the strong mineral acid regenerates the weak acid, acetylene.
HNO
3
CH 3 C º CAg ¾¾¾¾ ® CH 3 C º CH + Ag +
(iv) Reaction with Grignard reagents :

HC º CH + CH 3 MgI ¾¾
® CH 4 + HC º CMgI
RI
HC º CMgI ¾¾® HC º CR

1. Is there any inconsistency between the facts that the C–H bond in acetylene has the greatest bond energy of all C–H bonds and hence
it is the most acidic?
2. Comment on the feasibility of the following reactions :

(i) CH 3 C º CH + aq. NaOH ¾¾

® (ii) CH 3 CH 2 C º CMgI + CH 3 OH ¾¾
® (iii) CH 3 C º C - + NH 4+ ¾¾
®
3. Butyne-1 reacts with ethyl magnesium bromide to form gas A which does not decolourise Br2 water or alkaline KMnO4. Identify
gas A.
4. Complete the following :
KMnO KNH
(i) CH º CH + Br2 ¾¾
® A ¾¾¾¾
4® B (ii) CH 3 CHBrCHBrCH 2 CH 3 ¾¾¾¾
2® C

Ag(NH ) + HNO BH CH COOH dil. aq KMnO

(iii) 3 2
HC º CCH 2 CH 3 ¾¾¾¾¾¾ 3
® D ¾¾¾¾ ®E (iv) CH 3 C º CH ¾¾¾
3 ® F ¾¾¾¾¾®
3 G ¾¾¾¾¾¾
4¾
®H

Alc. KOH3 BrCCl

(v) ClCH 2 CH(CH 3 ) . CHCl . CH 3 ¾¾¾¾¾
® I ¾¾¾¾ ®J+K
KMnO 4

5. Give all steps used for the conversion of 2-bromobutane to trans-2-butene.

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6. Identify (A) to (C) in the following reactions :

A H
CO
t
/P
2
3H
H

C2H5C CCH3 C
N
a/ 4
N nO
H
3 KM
B

7. Name the product and give mechanism for the reaction of propyne with Br 2 + NaOH.

6.11.7 Rearrangement of alkynes

(i) When heated with ethanolic potassium hydroxide, the triple bond of an alkyne migrates towards the centre of
the chain, e.g.
ethanolic
CH 3 CH2 C º CH ¾¾¾¾¾
® CH 3 C º CCH 3
KOH
1- Butyne 2 - Butyne

(ii) When heated with sodamide in an inert solvent (paraffin), the triple bond of an alkyne shifts towards the end of
the chain, e.g.
NaNH
CH 3 C º CCH 3 ¾¾¾¾
2
® CH3 CH 2 º C - Na +
paraffin
2 - Butyne

6.11.8 Polymerisation
Alkynes undergo polymerisation to give linear or cyclic products depending upon the temperature and catalyst
used.

Linear polymerisation
Acetylene when passed into cuprous chloride solution containing ammonium chloride, its two molecules combine
together to form vinylacetylene; since two molecules are involved, the reaction is more correctly known as dimerisation.
Cu Cl
HC º CH + HC º CH ¾¾¾¾
2 2
® CH 2 = CH - C º CH
NH 4 Cl Vinylacetylene

The dimer product may further be converted into trimer.

Cu Cl
CH 2 = CH - C º CH + CH º CH ¾¾¾¾
2 2
® CH 2 = CH - C º C - CH = CH 2
Vinylacetylene Divinylacetylene

The dimer of acetylene, i.e., vinylacetylene is a very important compound since it reacts with HCl to form 2-
chloro-1, 3-butadiene, commonly known as chloroprene which is used in the manufacture of a synthetic rubber, neoprene.
Cl
|
CH 2 = CH - C º CH + HCl ¾¾
® CH 2 = CH - C = CH 2
Vinylacetylene Chloroprene

Alkynes, when passed through a red hot iron tube, undergo cyclic polymerisation to form aromatic hydrocarbons.

CH CH
HC HC HC CH
Red hot tube

HC HC HC CH
CH CH
Acetylene (3 molecules) Benzene
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CH3 CH3

C C
HC HC HC CH
Red hot tube

C C C C
HC CH
H3C CH3 CH3 CH3
Propyne (3 molecules) 1, 3, 5-Trimethylbenzene
(Mesitylene)

Acetylene, when treated with nickel cyanide under pressure, forms cyclo-octatetraene

Ni(CN)
4CH º CH ¾¾¾¾¾
2
®
pressure
Cyclo-octatetraene

6.11.9 Combustion
Acetylenes burn in air or oxygen to form CO2 and water with the evolution of large amount of heat.
3n - 1 2n - 2
C n H2 n - 2 + O 2 ¾¾
® nCO 2 + H 2 O + Heat
2 2
e.g. 2CH º CH + 5O 2 ¾¾
® 4CO 2 + 2H 2 O + 312 kCal
The combustion of acetylene is used industrially for welding and cutting of metals in which oxy-acetylene flame
having high temperature (3000°C) is produced.

6.11.10 Other Reactions of Acetylene

(i) Addition of arsenic trichloride : Acetaldehyde adds on arsenic chloride in presence of AlCl3, Cu2Cl2 or HgCl2 to
form 2-chlorovinyldichloroarsine, commonly known as Lewisite.
CH CHCl
||| + ClAsCl 2 ¾¾
® ||
CH CHAsCl2
2 - Chlorovinyldichloroarsine (Lewisite)

Lewisite is a powerful poisonous gas. It is four times active than the mustard gas. It causes immediate casualities
since it readily penetrates clothing and body tissues.
Its toxic nature is found to be due to its reaction with —SH groups of enzymes. However, the action of lewisite
may be checked by its antidote developed by Britain in World War II under the name of BAL (British Anti-
Lewisite). Actually, BAL combines with the lewisite to form a cyclic, non-toxic compound.

CH2SH CH2 —S
AsCH = CHCl
CHSH + Cl 2AsCH = CHCl CH—S

CH2OH CH2OH
BAL Lewisite Non-toxic cyclic compound

electric spark
(ii) 2HC º CH + N 2 ¾¾¾¾¾¾
® 2HCN

CH CH
(iii) 2 + S (iv) 2 + NH3
CH CH
S N
Thiophene
H
Pyrrole
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Applications of acetylene and its derivatives
1. Acetylene is used (a) for illuminating purposes in hawker's lamps and light houses,
(b) for artificial ripening of fruits, (c) in the form of oxyacetylene flame for welding, cutting and cleaning iron and
steel; and (d) for producing several chemicals like acetaldehyde, acetic acid, ethyl alcohol, acetone, benzene etc.
2. Westron (acetylene tetrachloride) and westrosol (trichloroethylene) are used as industrial solvents.
3. Vinyl chloride, vinyl acetate and vinyl ethers are used in the production of plastics (e.g. polyvinyl chloride
commonly known as PVC) and artificial rubber.
4. Vinyl cyanide, also known as acrylonitrile (CH2 = CHCN) is used for the production of synthetic rubber (buna
N) and synthetic fibre (orlon).
5. Chloroprene (2-chloro-1, 3-butadiene) is used in the manufacture of neoprene (a synthetic rubber).
6. Lewisite (ClCH = CHAsCl2) is a powerful poisonous gas.

6.12 Illustrative Examples on Alkynes / Dienes

Example 19 :
Arrange each of the following in order of decreasing heat of hydrogenation.
(a) 1,2-hexadiene, 1,3-hexadiene, 1,4-hexadiene, 1,5-hexadiene, 2,4-hexadiene, and 1,3,5-hexatriene.

(b)

(c) 1-Pentyne, 2-pentyne, 1,4-pentadiene, 1,2-pentadiene, trans-1,4-hexadiene, trans-1,3-pentadiene.

Solution :
Observe following points carefully in the given structures in the following order for decreasing heat of hydrogenation
or increasing order of stability :
(i) Number of double bonds
(ii) Presence of conjugation
(iii) Possibility of cis-trans isomerism
(iv) Degree of substitution of the alkene or alkyne decreasing DH

> C = CH2 > >

(a)
Maximum D H (two cumulative (two isolated double
(3 double bonds) double bonds) bonds, least substituted)
Least stable

> >
(two double bonds, (conjugated diene, (conjugated diene,
more substituted) less substituted) more substituted)
Minimum D H, most stable

(b) > > > >

Max. D H Min. D H

(c) C = CH 2 > > >

cumulated diene terminal alkyne Internal alkyne

> >
isolated diene trans isolated diene conjugated trans diene
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Example 20 :
Give steps involved in the conversion of acetylene to (a) rac-3,4-dibromohexane, (b) meso-3,4-dibromohexane.
Solution :
(i) 2NaNH H 2 , Lindlar
(a) 2
HC º CH ¾¾¾¾¾¾® CH 3 CH 2 C º CCH 2 CH 3 ¾¾¾¾¾¾ ®
(ii) 2CH 3 CH 2 Br catalyst

CH3CH 2 CH2CH3 Br2 CH3CH 2 CH2CH3

C=C H C — C Br + Enantiomer
H H
cis-
Br H

CH3CH2 H CH3CH2 Br
Br 2
(b) CH 3 CH 2 C CCH 2 CH 3 ¾ ¾ ¾ ¾ ¾ ¾
Na , liq. NH
3® C=C C–C H
H CH2CH3 H CH2CH3
trans- Br
meso-

Example 21 :
Give mechanism involved in the following conversion :
CH3 CH3
H2S O4

OH

Solution :

CH3 CH3 CH3 CH3 CH3

H
+ +
H H2O +
+ H 3O
(–H2O) +
OH + H H H

3° carbocation 3° allylic carbocation (more stable) (Major)

Highly substituted alkene

Example 22 :
Give steps involved in the preparation of each of the following compounds.
(a) Cyclodecyne from acetylene and 1,8-dibromooctane.
(b) 3-Methylpent-1-yne from 1-pentyne
Solution :
NaNH
(a) 2
HC º CH ¾¾¾¾ ® HC º C : - Na + + Br(CH 2 )8 Br ¾¾
® HC º C(CH 2 )8 Br

Br Br
–
C: CºC
NaNH2

Cyclodecyne
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Intramolecular cyclization leading to rings with more than six carbons are difficult, and intermolecular reactions
predominate. However, intramolecular cyclization may be forced by using very dilute solutions, which makes
intermolecular alkylation difficult.
(b) Here 1-pentyne must be converted to dianion by using two moles of a very strong base such as butyllithium per
mole of 1-pentyne.

CH3 CH3
.–. | + |
2BuLi - CH3 I - H O
CH3 CH 2 CH 2 C º CH ¾¾¾¾ ® CH 3 CH 2 CHC º C : ¾¾¾® CH3 CH2 CHC º C : ¾¾¾¾
3
® CH3 CH 2 CHC º CH
step 1 step 2

Step 1 : Remember that propargylic H's (H present on C atom attached to acetylenic carbon) are acidic
enough, hence it is easily removed as proton by a strong base. It is because such C is attached to sp (acetylenic)
C which is electronegative. Further the corresponding anion stabilizes due to resonance.

.. ..
C C C ¬¾® C C C
| |

Step 2 : The propargylic carbanion is more basic than the acetylenic carbanion, hence RX preferrentially
attacks the former carbanion.

Example 23 :
Predict the product(s) in the following reaction.

sun or
+ Br2 (low conc.)
lamp

Solution :
Two products are formed due to the formation of allylic free radical.

.
CH2 CH2 CH2 CH2 CH2Br
Br. Br 2
+
(–HBr) .
Br

Example 24 :
Give steps involved in the synthesis of 1-hexen-5-yne from CH3CHOHCH3.
Solution :
The two three-carbon fragments (CH2=CHCH2 – and – CH2C º CH) of CH2 = CHCH2CH2C º CH are first synthesised
separately and then they are joined by Corey-House reaction.
H SO , heat Br
(a) CH 3 CHOHCH 3 ¾¾¾¾¾¾
2 4
® CH3 CH = CH 2 ¾¾¾
2®

Br
|
(i) NaNH Cl , heat
2
CH 3 CHCH 2 Br ¾¾¾¾¾ 2
® CH 3 C º CH ¾¾¾¾¾
® ClCH 2 C º CH
(ii) H 2 O A

2 Cl , heat
(b) CH 3 CH = CH 2 ¾¾¾¾¾
® ClCH 2 CH = CH 2
B

(i) Li ClCH C º CH
(c) ClCH2 CH = CH2 ¾¾¾® (CH 2 = CHCH 2 )2 CuLi ¾¾¾¾¾¾
2 ® CH2 = CHCH 2 CH 2 C º CH
(ii) CuI 1-Hexen - 5 - yne
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Example 25 :
How will you prepare (S)-(E)-4-deuterio-2-hexene from an alkyne and an alkyl halide.
Solution :
The structure of the required product
H H
C2H5 C = C – CH 3
D H
indicates that the required alkyl halide is C 2H5C(H)(D)X and the alkyne should be CH 3C º CH. However, the
stereochemical aspect should be noted carefully. The alkyl halide and the product has same priority among groups,
but this particular reaction being SN2 proceeds with inversion so the alkyl halide used should be the R enantiomer
because the product is S enantiomer. Thus

H H H H
– S N2 Na, C2 H5 OH
CH3C C + Br C2H5 C2H5 C CCH3 C2H5 C = C – CH3
(anti - addition of
D D H atoms) D H
(R )– ( S )– (S)–(E )–4-Deutero-2-hexene

Example 26 :
Complete the following by supplying structure to the bracketed compounds.
H2S O4 Br2 fused KOH
heat
[A] [B] 200°C
OH
NaNH 2 NaNH2 (i) CH3COC2H5
[C] [D] [E] [F]
150°C, H2O +
(ii) H 3O
2HBr (i) Sia2BH
[H] [D] – [G]
(ii) H2O2, OH
Solution :
Br

[A] Br
[B] anti-addition of Br2

[C], internal alkyne formed [D], heating with NaNH2

during heating with fused gives terminal alkyne
KOH at high temp.

OH
+ –
NaC

CH3
[E] [F], Alkynides give 3° alcohols with ketones

Br
O

H Br
[G], Alkynides react with [H]
Sia2BH to form aldehydes
(anti-Markovnikof, addition)
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Example 27 :
Hydrocarbon(X), C7H12, on reaction with boron hydride followed by treatment with acetic acid yields(A). On reductive
ozonolysis (A) yields a mixture of two aldehydes (B) and (C). Of these only (B) can undergo Cannizzaro reaction. (A)
exists in two geometric isomers A-1 and A-2, of which A-2 is more stable. Give structure of (X), (A), (B), (C), (A-1) and
(A-2) with proper reasoning.
Solution :
3 (i) BH 3 (i) O
C 7 H12 (X) ¾¾¾¾¾¾¾
® (A) ¾¾¾¾¾¾¾¾® (B) + (C)
(ii) CH 3 COOH (ii) Zn/CH 3 COOH
(two (responds
geometric Cannizzaro
isomers) reaction)

Above set of reactions leads to following conclusions :

(i) Compound (X) has 2º of unsaturation; however since compound (X) gives compound (A) which in turn undergoes
ozonolysis indicating that (A) is still unsaturated and hence 2º of unsaturation in (X) must be in the form of a
carbon-carbon triple bond.
BH3 CH3COOH
–CºC– – CH = C – B – CH = CH –
3
[X] [A]

(ii) The ozonolysis product (B) undergoes Cannizzaro reaction, while (C) does not. It shows that (B) has
O
||
CH 3 - C - group while (C) has a quaternary carbon at a-position.

O R O
|| | ||
[A] ¾¾
® CH 3 - C - + R - C - C -
|
R
(B) (C)

Thus the parent alkene [A] and [X] should be

R CH3 CH3
H H
R – C – C = C – CH3 or CH3 – C – C = C – CH3 CH3 – C – C º C – CH3
R CH3 CH3
C7 Alkene (A) (C7H12), X

CH3 CH3 CH3H

| (i) BH 3 |
(i) O 3 | | H
CH 3 - C - C º C - CH 3 ¾¾¾¾¾¾¾ ® CH 3 - C - CH = CHCH 3¾¾¾¾¾¾¾¾ ® CH 3 - C - C = O + O = C - CH 3
| (ii) CH 3 COOH | (ii) Zn/CH3 COOH | [B]
CH3 CH3 CH3
[X] [A] [C]
cis - and trans-

Example 28 :
An alkyne, when treated with ozone followed by dimethyl sulphide gives methanoic acid, hexanal and 3-oxobutanoic
acid. Can you assign the structure to the alkyne on the basis of this information only?
Solution :
Yes. Remember that alkynes on ozonolysis gives carboxylic acids, while reductive ozonolysis (as in the present case)
of alkenes gives aldehydes and ketones. Further remember that formation of methanoic acid as one of the products
indicates that the alkyne is terminal, i.e. it has –C º CH type of grouping.
To get the structure of the parent compound, arrange the ozonolysis products in such a way that when they are joined
by replacing the carboxyl groups (derived from C º C linkage) or carbonyl group (derived from C = C linkage in
reductive ozonolysis) by the corresponding linkage (C º C, or C = C), the structure of the parent compound is obtained.
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Hexanal 3-Oxobutanoic Methanoic

acid acid
H CH3 OH OH
| | | |
Thus here, CH3 (CH2 ) 4 C O O C CH2 C O O C H
Carbonyl group from Carboxylic groups from
C=C C C
(ii) H2O
(i) O3 , (CH3)2S
H CH3
| |
CH3 (CH 2 ) 4 C = C CH 2 C C H

Example 29 :
An organic compound Z, when treated with ethanolic silver nitrate gives a white precipitate which is soluble in
dilute acid. The compound absorbs five equivalents of hydrogen in presence of Pt to form n-butylcyclohexane. The
compound when treated with sufficient amount of ozone, followed by dimethyl sulphide and water gives following
four well-known compounds.
O O O O O O O
|| || || || || || ||
H - C OH H - C - C- H H - C - C - OH H - C - CH 2 CH 2 - C - CHO
I II III IV
Prepare a structure for the compound Z.
Solution :
(i) Reaction with ethanolic AgNO3 to form white precipitate soluble in dil. acid, indicates the presence of –C º CH
grouping.
(ii) Intake of 5 equivalents of H2 indicates the presence of 5p bonds. Now we are to assign the position of these p
bonds in the skeleton of n-butylcyclohexane.
5H2 /Pt
Z CH2CH2CH2CH3
n-butylcyclohexane
(iii) Since the compound has C º CH group, the triple bond must be present at the end carbon atom of the side chain.
(iv) Note that the ozonolysis is reductive one, so aldehydic and ketonic functional groups developed in the products
must be coming from the double bonds; while the –COOH groups in the product must be coming from carbon-
carbon triple bond. Since only two –COOH groups are present in the products, the compound should have only
one triple bond. Further the presence of six carbonyl groups in the products indicates the presence of three
double bonds.
Now join the two carbons of the –COOH groups through a carbon-carbon triple bond. Further formation of III
indicates the position of one of the double bonds too.
O O O
O3 || || ||
CH = CH C CH H - C - C - OH + H - C - OH + Other Products
(CH3) 2 S III I
Formation of products II and IV can be explained by the following structure of Z.

H H
C C
H O
O O
II
O3 + O = C — C – OH
CH = CH – C º CH
(CH3)2S + III
O O
Z (cis or trans) +
CH C — CHO
O
C C
HO – C – H
H2 H2
IV I
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6.13 Characteristics of Alkanes, Alkenes and Alkynes

1. An alkane shows negative tests to all functional groups. These are insoluble in water, dilute acids, dilute base and
concentrated sulphuric acid.
2. Alkenes are characterised by the following tests :
(a) Rapid decolorization of bromine in carbon tetrachloride without evolution of HBr.

C C + Br2/CCl4 —C—C—
Red
Alkene Br Br
Colourless
This test is also given by alkynes.
(b) Alkenes decolourise a cold, dilute, neutral, aqueous permanganate solution (Baeyer test) and forms brown
precipitate of MnO2.

–
C C + MnO4 —C C— + MnO2

OH OH
Alkene Purple Colourless Brown

Remember that this test is also given by alkynes and aldehydes.

(c) Alkenes are soluble in cold concentrated sulphuric acid (difference from alkanes). However, remember that
other compounds like those containing oxygen and those which are readily sulphonated are also soluble in cold
conc. H2SO4.
3. Alkynes can be detected by combination of the following tests :
(a) Like alkenes, alkynes (i) decolourise bromine in CCl4 without evolution of HBr, (ii) decolourise cold, neutral,
dilute permanganate solution, (iii) are not oxidised by chromic anhydride.
(b) On ozonolysis, alkynes yield carboxylic acids, whereas alkenes yield aldehydes and ketones, e.g.
(i) O 3
CH 3 C º CCH 2 CH 3 ¾¾¾¾® CH 3 COOH + HOOCCH 2 CH 3
(ii) H 2 O

(i) O 3
CH 3 CH = CHCH 2 CH 3 ¾¾¾¾® CH 3 CHO + OHC.CH 2 CH 3
(ii) H 2 O
(c) Acidic alkynes, also known as terminal alkynes (º CH), react with certain heavy metal ions, chiefly Ag+ and Cu+,
to form insoluble alkynides. Formation of a precipitate upon addition of an alkyne to either of the following
solutions :
(i) a solution of AgNO3 in alcohol,
(ii) an ammonical solution of AgNO3,
(iii) an ammonical solution of cuprous chloride
indicate an acidic alkyne. This reaction can be used to differentiate terminal alkynes (acidic alkynes) from non-
terminal alkynes (non-acidic alkynes)
R - C º CH R -C º C-R
A terminal alkyne A non - terminal alkyne

1. Give a simple test to distinguish between

(a) 1-butene and 2-butene (b) 1,3-dibromopropane and 1,2-dibromopropane
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EXERCISE 6.1 (MCQ - ONE option correct)

1. Which of the following alkenes exhibit cis-trans isomerism? 9. cis-2-Butene has higher boiling point than the trans-analog. It is
because of
Br
(a) hydrogen bonding in the cis-isomer
(i) (ii)
(b) higher molecular mass of the cis-isomer
(c) vander Waal forces in the cis-isomer
(d) polarity in the cis-isomer.
10. Melting point of the cis-ethylene bromide is –53°C, the expected
(iii) (iv)
melting point for the trans-isomer should be
(a) –53°C (b) –68°C
(a) (ii) and (iii) (b) (iii) (c) –6°C (d) can't be predicted.
(c) (ii) and (iv) (d) All the four 11. If the photochemical chlorination of excess of deuterated toluene
2. The number of isomers possible for amylene is (C 6H5CH2D) with 0.1 mol of Cl2 forms 0.0868 mol of HCl and
(a) 3 (b) 4 0.0212 mol of DCl, the relative amounts of DCl and HCl formed
(c) 5 (d) 6 from C6H5CHD2 will be
3. In 1, 2-elimination of HX (a) 0.0414 : 0.0462 (b) 0.0212 : 0.0868
(c) 0.0462 : 0.0414 (d) 2 : 2.05.
H X
12. How many types of hydrogen are present in 6-methyl-2-heptene?
—C—C— + :B C C (a) 4 (b) 5
(c) 6 (d) 7
The electron pair of the newly formed p-bond is provided by 13. Which of the following can undergo nucleophilic addition?
(a) the lone pair of electrons present on the base B (b) (a) CH2 = CH2 (b) CH2 = CHCN
the pair of electrons forming C–X bond (c) CH2 = CH–CH = CH2 (d) None.
(c) the pair of electrons forming C–H bond 14. Addition of Br2 on butene-2 is a
(d) either of the three
(a) stereoelective reaction (b) stereospecific reaction
4. Which of the following chloride will exclusively give 2-methyl-2-
(c) both (a) as well as (b) (d) neither (a) nor (b).
butene on dehydrohalogenation by a strong base?
15. The decreasing order of hydrogen bromide on the following
(a) 2-chloro-2-methylbutane
alkenes is
(b) 2-chloro-3-methylbutane
CH2 = CH2, CH3CH2CH = CH2, CH2 = CHCl, (CH3)2C = CH2
(c) 1-chloro-2-methylbutane
I II III IV
(d) None of the three
(a) I > III > II > IV (b) IV > II > I >III
5. Isobutene can be prepared from tert-butanol by
(c) III > I > II > IV (d) II > IV > I > III
(i) heating it in the presence of acid
16. In the reaction of propene with HBr in presence of light, first
(ii) treating it with HCl followed by reaction with alcoholic
step involves the
potash
(a) addition of H atom
(iii) treating it with p-tosyl chloride followed by reaction with
(b) addition of H+ ion
potassium tert-butoxide.
(c) addition of bromine atom
(a) method (i) only (b) methods (i) and (ii) only
(d) none of the three.
(c) all above methods (d) method (ii) only
6. Isobutene is the exclusive product of dehydrohalogenation (by 17. Which of the following is involved in the following reaction?
a strong base) of
CH3 CH3
(a) isobutyl chloride (b) tert-butyl bromide (c) |
HCl
|
both (a) and (b) (d) none of the two CH 2 = CHCHCH 3 ¾¾¾
® CH 3 CH 2 C(Cl)CH 3
3 - Methyl -1- butene 2 - Chloro - 2 - methylbutane
7. Dehydration of tert-butyl alcohol and sec-butyl alcohol is carried
out by heating with 20% H2SO 4 at 90°C and 60% H2SO 4 at (a) Shifting of H+ from position 1 to 2
100°C, n-butyl alcohol can best be dehydrated by heating with (b) Shifting of H– from position 1 to 2
(a) 50% H2SO 4 at 130°C (b) 20% at 150°C (c) Shifting of CH3+ from position 1 to 2
(c) 75% H2SO 4 at 140°C (d) 60% at 95°C (d) Shifting of CH3– from position 1 to 2.
8. 2-Butene can be obtained by the electrolysis of an aqueous 18. Which of the following is true during electrophilic addition of
solution of HBr to alkenes?
(a) 1, 2-Dimethylmaleic acid (i) In aqueous solution of HBr, electrophile is H3O+
(b) 2, 2-Dimethylbutandioic acid (ii) Aqueous solution of HBr is a better electrophile than dry HBr.
(c) 3, 3-Dimethylbutandioic acid (a) (i) is true (b) (ii) is true
(d) 2, 3-Dimethylbutandioic acid (c) (i) & (ii) both are true (d) None is true.
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19. Addition of D2O in presence of D+ to 2-methyl-2-butene gives (a) A free carbonium ion is formed as an intermediate
(a) (CH3)2C(OD).CH2CH3 (b) A free carbonium ion is not formed as an intermediate
(b) (CH3)2C(OH)CD2CH3 (c) Bromine adds in syn manner in case of cis-2-butene and in
(c) (CH3)2 C(OD).CHD.CH3 an anti manner in case of trans-2-butene
(d) all the above (d) Bromine adds in anti manner on cis-2-butene and in syn
20. Reaction of alkene with cold concentrated sulphuric acid manner on trans-2-butene.
followed by heating with water is one of the important methods 29. Like bromination of butene-2, hydroxylation of butene-2 by
for the preparation of alcohols. Which of the following fact is alkaline permanganate also involves the formation of a cyclic
not in accordance with this method? intermediate, hydroxylation of trans-2-butene will give
(a) It can be used for the preparation of tert-butanol (a) meso-glycol
(b) It can be used for the preparation of isopropanol (b) racemic-glycol
(c) It can be used for the preparation of isobutanol (c) the reaction is not stereospecific
(d) All the above statements are correct (d) no product.
21. The favourable conditions for the hydration of water are (i) (BH 3 )2
(a) low water concentration and high temperature 30. Predict the product P. CH3CH = CH2 ¾¾¾¾¾¾¾
-®P
(ii) H 2 O 2 /OH
(b) low water concentration and low temperature
(a) CH3CH2CH2OH
(c) high water concentration and high temperature
(b) CH3CHOHCH3
(d) high water concentration and low temperature
(c) a and b in equal amounts
2 98% H SO
4 (d) neither of the two.
22. CH2 = CH2 ¾¾¾¾¾¾ ® CH3CH2OSO3H
31. Which of the following is identical in cis-3-hexene and trans-3-hexene?
H O, heat
2
¾¾¾¾¾
® CH3CH2OH + H2SO 4 (a) Rate of hydrogenation
The two consecutive steps in the above set involves (b) Product of hydrogenation
(a) electrophilic addition and elimination (c) Adsorption of alumina
(b) electrophilic addition and SN1 (d) None of the three is identical
(c) electrophilic addition and SN2 32. Baeyer's reagent is
(d) nucleophilic addition and elimination (a) alkaline permanganate solution
23. The rate-determining step in the following reaction is (b) acidified permanganate solution
(c) neutral permanganate
CH 2 = CH 2 + HOCl ¾¾
® CH 2 OHCH 2 Cl
(d) aqueous bromine solution
(a) addition of OH– (b) addition of OH+ 33. Markownikoff's rule provides guidance of HBr on
(c) addition of Cl + (d) addition of Cl–
CH3 CH3
24. Reaction between isobutene and isobutane in presence of acid to
form isoctane involves (a) CH2 = CH2 (b) C C
(a) methyl shift H H
(b) intramolecular hydride shift
(c) intermolecular hydride shift
(d) none of the three CH3 H CH3 H
25. Propene is treated with mercuric acetate in methanol solution, C C C C
(c) (d)
followed by reduction with sodium borohydride. The product
H CH3 CH3 H
formed is
(a) CH3CH2CH2OH (b) CH3CHOHCH3 34. Of the following compounds, which will have a zero dipole moment?
(c) CH3CH2CH2OCH3 (d) CH3CH(OCH3).CH3 (a) 1, 1-Dichloroethylene
26. Which of the following is true regarding free radical addition of (b) cis-1, 2-Dichloroethylene
HBr on propene? (c) trans-1, 2-Dichloroethylene
(a) It is faster than that of ethylene and form isopropyl (d) None of the three.
bromide 35. The molecule(s) that will have dipole moment is/are
(b) It is slower than that of ethylene and forms isopropyl (i) 2, 2-dimethylpropane (ii) trans-2-pentene
bromide (iii) cis-2-hexene (iv) 2, 2, 3, 3-tetramethylbutene
(c) It is faster than that of ethylene and forms n-propyl bromide (a) only (ii) (b) only (iii)
(d) It is slower than that of ethylene and forms n-propyl (c) (ii) and (iii) (d) (iii) and (iv)
bromide.
36. Which of the following has smallest heat of hydrogenation per
27. The probability factor for bromination of cylcohexane to mole?
cyclohexene is
(a) 1-Butene (b) trans-2-Butene
(a) 12 : 2 (b) 12 : 4
(c) cis-2-Butene (d) 1, 3-Butadiene
(c) 12 : 18 (d) 12 : 10.
37. Anit-Markownikoff's addition of HBr is not observed in
28. Addition of bromine on cis- and trans-2-butenes exclusively give
(a) propene (b) butene
racemic- and meso-2, 3-dibromobutane respectively. What does
(c) but-2-ene (d) pent-2-ene
these reactions indicate?
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Na/alcohol
The reaction of CH 3CH = CH (b) CH 2 = CH - CH = CH 2 ¾¾¾¾¾¾
®
38. OH with HBr gives
CH 3 - CH = CH - CH 3

(a) CH 3CHBrCH 2 OH Na/alcohol

(c) CH 2 = CH - CH = CH 2 ¾¾¾¾¾¾
®

CH 3 CH 2 CH 2 CH 3
(b) CH3CH 2CHBr OH (d) All are feasible.
44. CH2 = CH–CH = CH–CH3 + HI ¾¾®
CH3–CHI–CH = CH–CH3
(c) CH3CHBrCH2 Br
Above product may be regarded as
(a) 1, 2-adduct
(d) CH3CH 2CHBr Br (b) 1, 4-adduct
(c) both 1, 2-as well as 1, 4-adduct
39. If heat of hydrogenation of 1, 3-pentadiene and 1, 4-pentadiene (d) none of the two
are X and Y kCal respectively, heat of hydrogenation of 2, 3-
45. 1, 3-Butadiene is treated with hot KMnO 4/NaIO4, the product(s)
pentadiene will be
formed is(are)
(a) between X and Y
(a) 2HCHO + OHC – CHO
(b) less than X as well as Y
(b) 2HCOOH + HOOC–COOH
(c) greater than X as well as Y
(c) 2CO2 + HOOC–COOH
(d) It can't be predicted.
(d) 4CO 2
40. Which of the following statement is true regarding 1, 3-butadiene?
46. Reaction of propylene bromide with the equivalent amount of
(a) It can exist in cis and trans forms
alcoholic KOH gives mainly
(b) It can exist in transoid and cisoid conformations (c)
(a) CH3CH = CHBr (b) CH2 = CHCH2Br
Both (a) and (b) are correct
(c) CH3C(Br) = CH2 (d) all the three compounds.
(d) Neither (a) nor (b) in correct.
47. Ethyne when treated with bromine water gives
41. Observe the resonating structures of 1, 3-butadiene
(a) only 1, 2-dibromoethene
+ -
CH 2 = CH - CH = CH 2 ¬¾® CH 2 - CH - CH = CH 2 (b) only 1, 1, 2, 2-tetrabromoethane
I II (c) both (a) and (b)
+ - (d) none of the two
¬¾
® C H 2 - CH = CH - CH 2
III CH CHBr Br BrCHBr
2
48. ||| + Br2 ¾¾
® || ¾¾¾ ® |
(i) Among the three structures, structure I contributes more CH CHBr BrCHBr
than the other two structures. I II

(ii) All the three structures contribute equally. The compound I will predominate under which conditions?
(iii) Resonance energy of 1, 3-butadiene is quite high. (i) By using excess of ethyne.
(iv) Resonance energy of 1, 3-butadiene is small. (ii) By driping the bromine water into a solution of ethyne.
Which of the above statement(s) is(are) true? (iii) By bubbling ethyne into a solution of bromine in carbon
(a) (i) and (iii) (b) (ii) and (iii) tetrachloride.
(c) (i) and (iv) (d) (ii) and (iv) (a) (i) (b) (ii)
CH3 (c) (i) and (ii) (d) (i) and (iii)
| 49. Formation of acetylene from calcium acetylide can be represented
42. Isopropene, CH 2 = C - CH = CH 2 is treated with HCl, the
as
products formed will be a mixture of
Ca 2 + C º C 2 - + 2HOH ¾¾
® H - C º C - H + 2OH - + Ca 2 +
CH 3 CH 3
| | In the above reaction, which one is correct?
(i) CH 3 - C - CH = CH 2 (ii) CH 2 = C - CH = CH3 (a) The stronger acid (acetylene) is displaced from its salt by
| |
Cl Cl a weaker acid (water)
(b) The weaker acid (acetylene) is displaced from its salt by a
CH3 CH 3 stronger acid (water)
| |
(iii) CH 3 - C = CH - CH 2 Cl (iv) ClCH 2 - C = CH - CH 3 (c) The weak acid (acetylene) is displaced from its salt by
another weak acid (water)
(a) (i) and (iii) (b) (ii) and (iii)
(d) The weaker acid (acetylene) is displaced from its salt by
(c) (ii) and (iv) (d) All the four. neutral substance (water).
43. Which of the following is (are) feasible?
50. Which of the following alkyne will form 2-butanone on hydration?
Na/alcohol (a) CH3CH2C º CH (b) CH3C º CCH3
(a) CH 2 = CH 2 ¾¾¾¾¾¾
® CH 3 - CH 3
(c) Both (d) None
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51. If addition of HBr on CH 2 = CHCH 2C º CH gives 61. Catalytic hydrogenation of which of the following is most
CH3CHBrCH2C º CH, addition of HBr on CH º CCH = CH2 exothermic?
would give
(a) CH2 = CBrCH = CH2 (b) CH º CCHBrCH3
(a) (b)
(c) Both (d) CH2 = CBrCHBrCH3
H 2 /Pt D /Pt
52. CH3C º CCH3 ¾¾¾¾ ® A ¾¾¾¾
2 ®B
The compounds A and B, respectively are (c) (d)
(a) cis-butene-2 and rac-2, 3-dideuterobutane
62. The relative rate of catalytic hydrogenation of the following alkenes
(b) trans-butene-2 and rac-2, 3-dideuterobutane
is:
(c) cis-butene-2 and meso-2, 3-dideuterobutane
(d) trans-butene-2 and meso-2, 3-dideuterobutane
53. The compound X in the following reaction is CH 3 C º
2(i) H / Pt I II III IV
CCH3 ¾¾¾¾¾
®X
(ii) Br2
(a) I > II > III > IV (b) III > II > I > IV
(a) d-2, 3-Dibromobutane (c) IV > I > II > III (d) IV > I > II = III
(b) l-2, 3-Dibromobutane
CH2C º N
(c) dl-2, 3-Dibromobutane
O
(d) meso-2, 3-Dibromobutane. H2, Pd/C
63. product P is :
54. Identify Y in the following :
2H /Catalyst CH I
CH 3 C º CC 2 H 5 ¾¾¾¾¾¾
® X ¾¾¾¾
2 2® Y
Zn(Cu) CH2C º N CH2CH2NH2
(a) meso-2, 3-diiodobutane OH OH
(b) racemic-2, 3-diiodobutane (a) (b)
(c) cis-1-ethyl-2-methylcyclopropane
(d) trans-1-ethyl-2-methylcyclopropane
CH2C º N CH2CH2NH2
55. Identify the reagent from the following list which can easily
O O
distinguish between 1-butyne and 2-butyne
(c) (d)
(a) bromine, CCl4 (b) H2, Lindlar catalyst
(c) dilute H2SO 4, HgSO4 (d) ammonical Cu2Cl2 solution.
56. Which of the following hydrocarbons has the lowest dipole 64. Which of the following statement is true regarding the addition
moment? reaction of an alkene?
(a) Stereoselectivity of a reaction may vary from 1 to 50%
CH3 CH3
(b) Stereoselectivity of a reaction is always 50%
(a) C=C (b) CH3C º CCH3 (c) Stereospecificity of a reaction is always 100%
H H
(d) Stereospecificity of a reaction may vary from 1 to 75%
(c) CH3CH2C º CH (d) CH2 = CH–C º CH 65. An organic compound takes up one molar equivalent of hydrogen
57. The compound having both sp and sp2 hybridised carbon atom is and gives methylcyclohexane. The original compound can exist
(a) propene (b) propyne in ............ isomeric forms.
(c) propadiene (d) butadiene (a) 1 (b) 2
58. The number of sigma and pi bonds in 1-buten-3-yne are (c) 3 (d) 4
(a) 5s and 5p (b) 7s and 3p
66. 3-Chloro-3-methylhexane is formed by the addition of HCl on :
(c) 8s and 2p (d) 6s and 4p
59. Which of the following reaction will yield 2, 2-dibromopropane? (a) (b)

(a) HC º CH + 2HBr ¾¾
® (c) (d) Any of the three
67. How many types of C–H bonds are present in cyclohexene?
(b) CH 3 C º CH + 2HBr ¾¾
®
(a) 2 (b) 3
(c) CH 3 CH = CH 2 + HBr ¾¾
® (c) 4 (d) 5
68. Which of the C–H bond in the structure drawn below is strongest?
(d) CH 3 CH = CHBr + HBr ¾¾
®
H
60. The product(s) obtained via oxymercuration (HgSO 4 + H2SO 4) b
H c H
of 1-butyne would be
a
(a) CH3CH2COCH3
(b) CH3CH2CH2CHO
(c) CH3CH2CHO + HCHO (a) a (b) b
(d) CH3CH2COOH + HCOOH. (c) c (d) all are equal
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69. Arrange the following compounds in order of increasing oxidation fractional distillation
level. C 5 H 11 Cl ¾¾¾¾¾¾¾¾¾
® M (isomeric products)
Identify N and M
Cl O
(a) 6, 4 (b) 6, 6
(c) 4, 4 (d) 3, 3
I II III IV
79. The reagent(s) for the following conversion,
(a) I < II < IV < III (b) I < II < III < IV
Br ?
(c) I < II < III » IV (d) I < IV » III < II H H
Br
70. The reactivities of ethane, ethylene and acetylene are of the order is/are
(a) ethane < ethylene < acetylene (a) alcoholic KOH
(b) ethane < acetylene < ethylene
(b) alcoholic KOH followed by NaNH2
(c) acetylene < ethylene < ethane
(c) aqueous KOH followed by NaNH2
(d) acetylene = ethylene > ethane
(d) Zn/CH3OH
71. Ozonolysis of 2-methylbutene-2-yields
80. The number of stereoisomers obtained by bromination of trans-
(a) Only aldehyde (b) Only ketone
2-butene is
(c) Both aldehyde and ketone
(a) 1 (b) 2
(d) None
72. Which one of the following has the smallest heat of hydrogena- (c) 3 (d) 4
tion per mole? 81. 1-Methylcyclopentene can be converted into the given compound
(a) 1-butene (b) trans-2-butene
OD
(c) cis -2-butene (d) 1,3-butadiene
73. Propyne and propene can be distinguished by D
(a) conc. H2SO4 (b) Br2 in CCl4
CH3
(c) dil. KMnO4 (d) AgNO3 in ammonia
74. In the presence of peroxide, hydrogen chloride and hydrogen iodide
by the use of which of the following reagents ?
do not give anti-Markovnikov addition to alkenes because
(a) dil. D2SO 4
(a) both are highly ionic
(b) Hg(OAc)2 + D2O followed by NaBD4
(b) one is oxidizing and the other is reducing
(c) one of the steps is endothermic in both the cases (c) B2D6 followed by D2O, AcOD
(d) all the steps are exothermic in both the cases (d) B2D6 followed by D2O2, NaOD
75. The nodal plane in the p-bond of ethene is located in 82. Which of the following produces chiral molecule after treatment
(a) the molecular plane with H2 in the presence of Lindlar’s catalyst ?
(b) a plane parallel to the molecular plane
(c) a plane perpendicular to the molecular plane which bisects
(a) (b)
the carbon - carbon s -bond at right angle
(d) a plane perpendicular to the molecular plane which contains
the carbon - carbon s -bond.
76. Which of the following is used for the conversion of 2-hexyne into
trans-2-hexene? (c) (d)
(a) H2/Pd/BaSO 4 (b) H2, PtO2
(c) NaBH4 (d) Li-NH3/C 2H5OH

77. CH 3 - CH = CH 2 + NOCl ¾¾
®P OH

Identify the product P.

(a) CH 3 - CH - CH 2 (b) CH 3 - CH - CH 2 83. ? reagent which can be used is

| | | |
NO Cl Cl NO
(a) conc. H2SO4, D (b) Al2O 3, D
NO (c) ThO2, D (d) All
|
(c) C H 2 - CH 2 - CH 2 (d) CH 3 - CH 2 - C H 84. Two C4H6 isomers give the same C4H8O product with HgSO4
| | |
NO Cl Cl and dil. H2SO4. However, these isomers give different C4H6Br4
products with excess bromine. What are these isomeric
CH3 hydrocarbons ?
(a) cyclobutene and 1-butyne
H3C Cl2, hn (b) 1, 2-butadiene and 1, 3-butadiene
78. N (isomeric products)
(c) 3-butyne and cyclobutene
CH3
(d) 2-butyne and 1-butyne
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321
(a) 6:3:1 (b) 9:3:1
Å KOH
(c) 6:4 (d) 8:4
H /KMnO 4
85. ¾¾¾¾¾¾ ® Product ¾¾¾®
D
Product. 89. Which of the following compounds form single product in each
D
of the following reactions ?
I. Ozonolysis
O O
II. Catalytic hydrogenation
III. Hydrogenation followed by monochlorination
(a) HO (b)

(a) (b)
O O

O O
(c) (d)

(c) (d) HO 90. The correct stability/order of following is :

CH3
O O
I. II.
86. 3 2CH MgBr (i) 2CO H3C
HC º CH ¾¾¾¾¾¾
® (A) ¾¾¾¾¾¾®
2
Å (B)
(ii) KOH/H

H SO D
¾¾¾¾
2 4 ® (C) ¾¾® (D)
HgSO 4
III. IV.
O
P CH3
(a) CH 3 - C - COOH
(a) I > II > III > IV (b) III > IV > II > I
O (c) II > IV > III > I (d) IV > III > II > I
P
(b) CH 3 - C - CH 3 91. The correct order of rate of acid catalyzed hydration of following
compounds is :
O
P I. CH 3 - C º CH II. CH 2 = CH 2
(c) HOOC - C - CH 2 - COOH

O III. IV.

CH – C
O (a) II > I > IV > III (b) III > I > IV > II
(d) CH – C (c) I > III > IV > II (d) III > IV > II > I
O
CH3
H3C C2H5 H3C C2H5
Ph Ph Ph Ph MeO 92. C= C C– C
87. H CH3 H CH3
OH
Ph (P) (Q)
(I) (II) (III) (IV)
The transformation of P to Q can be carried out by using the
Order of rate of electrophilic addition reaction with HBr will be
reagents
(a) IV > I > III > II (b) I > II > III > IV
(a) Dil. H2SO4, CH3MgCl, H+
(c) I > III > II > IV (d) IV > I > II > III
88. The ozonolysis reaction of the given compound gives products (b) HOCl/H+, CH3MgCl(1 eq.), H+
in the ratio : (c) CH3CO3H/D, CH3MgCl, H+
(d) Cl2/HClO4, CH3MgCl(1 eq.), H+
93. cis-But-2-ene ¾¾
® trans-But-2-ene
This conversion is best carried out by using the sequence of
reagents
(a) Br2/CCl4, NaNH2, Na/NH3 (l )
(b) H2O/H+, Al2O3/D
(c) Hg(OAc)2/H2O, NaBH4, ThO2
(d) Br2/H2O, alc. KOH, Na/NH3(l)
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CH3 CH3
(1) BD3 – THF O3/ Zn/ H2O
94. (X) H3C H HH (major) 98. A B + C
– – –
(2) H2O2/ OH
OH D OH
D OH
CH2 – OH
The reactant (X) is –
COO

H3C H3C CH3

(a) (b) CHO

H3C CH3 D CH3

Reactant A is :

H3C CH3 H3C CH3

D
(c) (d)
CH3
H3C H (a) (b)

95. From the following reactions,

ˆˆ† NH 3 + HC º CLi
HC º CH + LiNH 2 ‡ˆˆ

ˆˆ† NH -2 + RH
NH 3 + R - ‡ˆˆ

predict which of the following orders regarding acid strength is (c) (d)
correct ?

(a) RH < NH3 < HC º CH (b) RH > NH3 > HC º CH

(c) RH > NH3 < HC º CH (d) RH < NH3 > HC º CH 2NBS Alc.KOH Pd/C
99. + ¾¾
® A ¾¾¾¾
® B ¾¾¾¾¾
® C ¾¾¾¾
®D
- H2
96. Ethylene combines with sulphur monochloride to form
(a) Phosgene (b) Mustard gas The final product D in the above sequence of reactions is
(c) Methyl isocyanate (MIC) (d) Lewisite (a) Benzene (b) Tetralin

97. Br (c) Decalin (d) Naphthalene

Ph - CH = CH - CH = CH 2 ¾¾¾®
2
Major product
CCl 4
(Formed by more stable H3C
carbocation) CH3 D
100. C = O + Ph3P = C X
Major product is ? H3C – H2C CH2 – CH3

(a) Product X will be :

Ph - CH - CH = CH - CH 2
| |
Br Br H3C CH3
(a) C= C
H3C – H2C CH2 – CH3

Br
| H3C CH2 – CH3
(b) Ph - CH - CH - CH = CH 2 (b) C= C
| H3C – H2C CH3
Br
(c) Both (a) and (b)

(c) Ph - CH = CH - CH - CH 2 H3C
| | (d) C = PPh3
Br Br H3C – H2C

101. How many alkene structures are possible for C5H10 ?

(d) Ph - CH - CH 2 - CH - CH 3 (a) 4 (b) 10
| |
Br Br (c) 6 (d) 5
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323
(a) X is 2, 5-dimethyl-3-hexyne; Y is cis-2, 5-dimethyl-3-hexene
O
(b) X is 2, 5-dimethyl-3-hexyne; Y is trans-2, 5-dimethyl-
O 3 /Zn/H2 O NaOH C – CH3
102. (1) ¾¾¾¾¾¾® (2) ¾¾¾¾
® 3-hexene
(c) X is 2, 5-dimethyl-1, 5-hexadiene; Y is 2, 5-dimethyl-
The reactant (1) will be : 3-hexyne
(d) X is 2, 5-dimethyl-2, 4-hexadiene; Y is cis-2, 5-dimethyl-
3-hexene
(a) (b)
106. Which of the following statements is correct ?
(a) Alkynes are more reactive than alkenes towards halogen
CH2
additions
(b) Alkynes are less reactive than alkenes towards halogen
(c) (d)
addition
(c) Both alkynes and alkenes are equally reactive towards
103. Which of the following on treatment with CH º CH produce
halogen additions
gas(es) :
I. NH2– II. CH3 (d) Primary vinylic cation is more reactive than secondary vinylic
III. OH– IV. Na in liq. NH3 cation
(a) II, III and IV (b) I, II and III
(c) I, II and IV (d) I, III and IV Br -H O
107. ¾¾¾¾¾
2 2 ® Product(s)
NaCl

O
The product(s) in the above reaction that cannot be formed is :
H3CO – C H
104. + Product Br Br
H C – OCH3
(a) (b)
O Cl Br

Here, the product will be :

Cl Br
O O (c) (d)
H H
OH OH
C – OCH3 C – OCH3
(a) (b)
C – OCH3 C – OCH3
H H Me
Me H Na in NH3 (l)
O O X
108.
H H2-Pd-BaSO4
Y
(c) Both (a) and (b) in equimolar ratio H quinoline

O The correct statements regarding X and Y is/are

H
C – OH (a) Both X and Y are optically inactive
(d) + CH3OH (b) Both X and Y are optically active
C – OH
H (c) X is optically inactive whereas Y is active
O (d) X is optically active whereas Y is inactive.
109. The synthesis of 3-octyne is achieved by adding a bromoalkane
105. A C 8H14 hydrocarbon (X) is reduced by sodium in liquid
into a mixture of sodium amide and an alkyne. The bromoalkane
ammonia to a single C8H15 product (Y). Both of these compounds
and alkyne respectively are
undergo hydrogenation (Pt catalyst) to give 2, 5-dimethylhexane.
(a) BrCH2CH2CH2CH2CH3 and CH2CH2C º CH
Ozonolysis of Y with an oxidative workup produces a single
(b) BrCH2CH2CH3 and CH3CH2CH2C º CH
C4H8O2 carboxylic acid. Reaction of Y with perbenzoic acid
(C6H5CO3H) gives a chiral C8H14O product, but reaction with (c) BrCH2CH2CH2CH2CH3 and CH3C º CH
bromine gives an achiral C8H14Br2 product. What are X and Y ? (d) BrCH2CH2CH2CH3 and CH3CH2C º CH
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EXERCISE 6.2

11. Acetylene is
DIRECTIONS for Q. 1 to Q. 24 : Multiple choice questions with (a) Red coloured gas (b) Garlic in colour
one or more than one correct option(s). (c) Soluble in acetone (d) Useful in polymer industry
12. Reaction of Br2 on ethylene in presence of NaCl gives
1. Which of the following statement is true?
(a) Catalytic hydrogenation can't convert an optically inactive (a) BrCH 2 - CH 2 Br (b) ClCH 2 - CH 2 Br
compound to optically active product (c) ClCH 2 - CH 2 Cl (d) NaCH = CHNa
(b) Catalytic hydrogenation may convert an optically inactive
compound to optically active product H / Pt O / H O/ Zn HCN
13. A(C 4 H 6 ) ¾¾¾¾
2 ® B(C 4 H 8 ) ¾¾¾¾¾¾®
3 2 C ¾¾¾® D
(c) Catalytic hydrogenation may be heterogeneous as well as
homogeneous D has chiral carbon and can be hydrolysed to lactic acid. Hence A
(d) Hydrogenation of ethylene by a mixture of H2 and D2 in is :
absence of catalyst forms three products, CH3 CH3, CH2D (a) CH3 – C º C – CH3 (b) CH2 = CH – CH = CH2
CH2D and CH2DCH3
2. Which product is formed when the following alcohol is heated
with sulphuric acid?
(c) (d) CH3
CH2OH
+
H H /Pt O /H O
heat 14. C4 H 6 ¾¾¾¾
2 ® C 4 H8 ¾¾¾¾¾
3 2 ® CH COOH
3
(A) (B)

CH3 Hence A and B are :

(a) CH3C = CCH3, CH3CH = CHCH3
(a) (b)
(b) CH2 = CHCH = CH2, CH3CH = CHCH3

(c) , CH3CH = CHCH3

(c) (d) All the three

3. Monobromination of butene-1 with NBS gies (d) none

(a) CH2BrCH2CH = CH2 (b) CH3CHBrCH = CH2 15. Hydroboration oxidation and acid hydration will yield the same
(c) CH3CH = CHCH2Br (d) CH3CH2CHBrCH2Br product in case of :
4. C4H6 may contain
(a) only single bonds (b) a double bond
(a) (b)
(c) a triple bond (d) two double bonds
5. Which of the following contains acidic hydrogen?
(a) ethene (b) ethane (c) CH2 = CH2 (d) CH3 – CH = CH – CH3
(c) ethyne (d) butyne-1 16. Following are used as anaesthetics in surgical operations :
6. Which of the following will react with sodium metal? (a) C2H4 (b) N2O
(a) ethyne (b) butyne-1 (c) CHCl3 (d) solid CO2
(c) butyne-2 (d) ethane
7. Markownikoff’s rule provides guidance of addition of HBr on t-BuOK
17. CH3 ¾ ¾ ¾ ¾ ® Product
(a) CH2 = CH2 (b) CH3.CH=CH2 Br
(c) CH3.CH=CH.CH3 (d) CH2 = CHBr
Which is/are correct statements about the product :
8. Ammonical silver nitrate reacts with
(a) Ethyne (b) Ethylene
(c) Butyne-1 (d) Butyne-2 (a) —CH3 is an endocyclic Saytzeff product
9. Chlorination can be done on
(a) CH3–CH3 (b) CH2 = CH2
(c) CH3–CH=CH2 (d) CH º CH (b) CH2 is an exocyclic Saytzeff product
10. Kolbe’s electrolytic method can be applied on
CH2.COOK
(a) CH 3 .CH 2 .COOK (b) (c) CH2 is an exocyclic Hofmann product
CH2.COOK

CH.COOK CH2.COOK
(c) (d) (d) —CH3 is an endocyclic Hofmann product
CH.COOK CH 2.COONa
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18. Baeyer test is for : D , Li/NH (l ) H /Ni Cl /hv
22. CH3 - C º CCH3 ¾¾¾¾¾¾¾
2 3 ®(X) ¾¾¾¾
2 ®(Y) ¾¾¾¾
2 ® (Z)
(a) testing alkenes (b) testing alkynes
(c) testing alkanes (d) testing aromatic compounds The correct statements are :
(a) (X) is single stereoisomer formed as Z-but-2-ene.
4HgSO /H SO
2 4 3 BH /THF
19. A ¾¾¾¾¾¾¾ ® B ¾¾¾¾¾¾
-®
H 2 O 2 /OH (b) (Y) is a mixture of two enantiomers obtained by syn-
addition of hydrogen atoms.
B is identical when A is :
(a) CH º CH (b) CH3 – C º CH (c) (Z) is a mixture of four structural isomers.
(c) CH3 – C º C – CH3 (d) CH3 – CH2 – C º CH (d) All monochloro isomers are chiral.
23. Outline the best synthesis of 4, 4-dimethyl-2-pentyne using
20. A + HCl ¾¾
® 2 - chloro - 2, 3 - dimethyl - butane. Hence A
NaNH2 in liquid NH3 and following compounds.
can be

CH3 CH3 CH 3
| |
| CH3 C º CH
(a) CH 3 - C - CH = CH 2 (b) CH 3 - C - C H - CH 3 I. II. H 3 C - C - Br
| | | |
CH3 CH3 OH CH 3

CH3 CH3 CH3 CH 3

| | | |
(c) CH 3 - C - CH = CH 2 (d) CH 3 - C = C - CH 3 III. H 3 C - C - C º CH IV. CH3I
| |
OH CH 3

(i) O
21. A ¾¾¾¾¾¾
3 ®
(Hydrocarbon) (ii) Zn/H 2O
V. CH3 - C º CBr

H (a) I + II (b) III + V

H
+ O+ (c) III +IV (d) II + V
O O O O
H 24. Consider the following molecules :
Structure of A can be :
Me H
Me I. Me H II. Me Me

H H
(a) Me
CH = C
Me Me Me
III. H IV.
H
Me H
H Me
Me
(b) Me

Me
H
H
V. Me VI.
Me Me
Me H
Me H Me
(c)
Me
and select the correct options given below :
(a) I and II are diastereomers
Me Me (b) IV and V are chiral molecules
(c) I, II and III are achiral molecules
(d) (d) At normal temperature, there are three isolable stereo-
Me
isomers of V and VI
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28. Which of the following statement is true?
INSTRUCTION for Q. 25 to 75 : Read the passages given below and (a) Reactions in Q. 2 and 3 are stereoselective
answer the questions that follow. (b) Reactions in Q. 2 and 3 are stereospecific
(c) Reactions in Q. 2 and 3 are regioselective
(d) Reaction in Q. 2 is regioselective, while in 3 it is regiospecific.
PASSAGE 1
29. Dehydrohalogenation of alkyl halides is (one or more may be
One of the common methods for the preparation of alkenes is
correct) :
dehydrohalogenation of alkyl halides.
(a) regioselective (b) regiospecific
Br (c) stereoselective (d) stereospecific
|
CH 3CHCH 2 CH 3 + Base ¾¾
® CH 3 CH = CHCH 3 30. Which of the above mentioned compounds does not show
geometrical isomerism as well as enantiomerism but either of the
+ CH 2 = CHCH2CH 3 two? (one or more may be correct).
Nature of major product (alkene) depends upon the stability of (a) B (b) D
alkene and size of the base used. Use of a small base gives mainly (c) E (d) F
highly substituted alkene (Saytzeff product), while a bulky base gives 31. 2-Methylcyclohexanol is heated with conc. sulphuric acid, the
the least substituted as the major product (Hofmann product). product formed is (one or more may be correct).
Dehydrohalogenation of alkyl halides follows E2 or E1 mechanism. CH3
E2 mechanism occurs in a single step reaction; while E1 mechanism is (a) (b)
a two step process involving carbocation formation. Nature of the CH3
major product, i.e. which alkene is formed in greater amount depends
upon the nature (especially size) of the base and stability of the alkene
formed. Where geometrical isomerism is possible, cis- or trans- isomer (c) (d)
may be formed in greater amount depending upon the nature of alkyl CH3
halide.
Another common method for the preparation of alkenes is
dehydration of alcohols with conc. H2SO4 or conc. phosphoric acid. PASSAGE 2
Mechanism of dehydration of alcohols resembles the E1 mechanism. The most usual properties of alkenes are the electrophilic addition.
The reaction generally occurs in two steps : addition of electrophile
25. An alkyl halide can undergo dehydrohalogenation by E2 as well followed by addition of nucleophile. The intermediate formed is an
as E1 mechanism. Which of the two mechanisms will give good ordinary carbocation, cyclic cation or a transition state. One of the
result for the required alkene? important addition reactions is hydration of alkenes to alcohols.
(a) E2 mechanism (b) E1 mechanism (I) Hg(OAC)2 HO H
C=C C–C
(c) Both (d) E1 ³ E2 (ii) NaBH4

Br (i) BH3 H OH
| C=C – C–C
Et 3 N (ii) H2O2, OH
26. CH 3 CH 2 C CH 3 ¾¾¾ ® CH 3 CH = C CH 3
| |
CH 3 CH 3 dil. H2SO4 OH H
(A) (B) C=C C–C

Additions on alkenes may be syn- or anti-depending upon the

+ CH 3 CH 2 C = CH 2 nature of the reagent.
|
CH 3
(C) 32. anti-Stereochemistry is observed during
(a) addition of Br2 (b) hydroboration-oxidation
The main product is
(c) addition of HOCl (d) none of the three
(a) B (b) C
33. Hydration of propene to form n-propyl alcohol through
(c) both in equal amounts (d) None
hydroboration-oxidation reaction suggests the formation of :
Cl (i) (BH )
3 2
|
OH -
CH 3 CH = CH 2 ¾¾¾¾¾¾¾ - ® CH 3 CH 2 CH 2 OH
CH 2 = CHCH 2 CHCHCH 3 ¾¾¾® (ii) H 2 O2 , OH
27.
|
CH3 (a) 1º carbocation as an intermediate
(D) (b) 2º carbocation as an intermediate
(c) carbocation is not formed as an intermediate
CH 2 = CHCH = CHCHCH + CH 2 = CHCH 2 CH = CCH 3 (d) nothing about formation of intermediate
| | 34. Reaction of alkene with Br2, HOCl, alk. KMnO4, OsO4 and per
CH 3 CH3
(E) (F) acids involves formation of cyclic cation as intermediate. Which
of the above reaction involves syn addition?
Here the major product is : (a) reaction of HOCl (b) reaction of alk. KMnO4
(a) E (b) F
(c) E=F (d) Reaction not possible (c) reaction of peracids (d) reaction of OsO4
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35. Non-Markownikoff's syn-hydration of propene is possible in – +
(a) hydroboration/oxidation 43. Br + CH3C º C: Na Major product is
(b) oxymercuration-demercuration
(c) aq. acid (a) C º CCH3 (b)
(d) reaction with HCl in presence of peroxide followed by
treatment with aq. KOH OH
(c) (d) C º CCH3
C º CCH3
PASSAGE 3
Acidic properties of terminal alkynes plays a central role in alkyne
chemistry. The acidity of hydrocarbons increases with the increasing s-
PASSAGE 4
character of theorbitals. i.e. sp3 < sp2 < sp.
Catalytic hydrogenation of a carbon-carbon double bond follows
Alkynide ions are strong nucleophiles and thus like other
nucleophiles they react with alkyl halides especially primary. Alkynide following path :
ions are also sufficiently strong bases and cause dehydrohalogenation
of 2º and 3º alkyl halides. Heavy metal alkynides are not very soluble
and form characteristic precipitates. However, like other alkynides,
H H H H C=C
these alkynides are converted back to the parent alkyne on treatment
H2 C=C
with dilute acids.
Catalyst Hydrogen adsorbed Complex of alkene
36. The charge separation is maximum in on catalyst surface to catalyst

(a) CH º C - (b) CH 2 = CH -

- C
(c) CH 3 CH 2- (d) C º C- H H C
C=C

37. CH3CH2C º CH can be converted into CH 3CH 2C º C: by H H +

reaction with Alkane product Regenerated Insertion of hydrogen

catalyst into carbon-carbon double bond
(a) sodium hydroxide (b) sodamide
Mechanism of alkene hydrogenation. The reaction takes
(c) sodium ethoxide (d) sodium ter- butoxide
place with syn stereochemistry on the surface of
º 38. Which of the following reaction is not possible? (one or more may insoluble catalyst particles.
be correct)
(a) HC º CH + CH3Li
(b) CH º C:– Na+ + CH3OH On the basis of the above mechanism, answer the following questions :
(c) HC º C:– Na+ + CH2 = CH2 44. Which of the following statement is true regarding adsorption of
(d) CH2 = CH2 + NaNH2 hydrogen over the catalyst?
39. 1-Hexene (b.p. 64ºC) and 1-hexyne (b.p. 71ºC) can't be separated (a) It is a physical process
from each other by distillation. However, the two can be separated (b) It is a chemical reaction
completely by reacting the mixture with sodamide followed by :
(c) It involves pairing of electrons between metal and hydrogen
(a) distillation
(d) The metal used should belong to transition series
(b) reaction with ammonical silver nitrate
45. The complex between alkene and hydrogen-adsorbed catalyst is
(c) both (d) none of the two
formed by
40. Which of the following is a strong nucleophile?
(a) overlapping of p-orbital of carbon with the d-orbital of the
(a) CH3CH2C º CNa (b) CH3CH2C º CAg metal
(c) Both (d) None
(b) overlapping of s-orbital of carbon with the d-orbital of the
(i) NaNH metal
2
41. CH 3 CH 2 C º CH ¾¾¾¾¾¾¾¾®
(ii) CH 3 CH(Br)CH 3 (c) overlapping of s-orbital of hydrogen with the p-orbital of
carbon
CH 3 CH = CH 2 + Product
(d) no overlapping occurs
If the above reaction occurs through E2 mechanism, the other 46. Which of the following statement is/are true?
main product should be
(a) Hydrogenation does not occur at all in absence of catalyst
(a) CH3CH2C º CCH(CH3)2
(b) The two hydrogen atoms are added stepwise
(b) CH3CH2C º CH
(c) Both hydrogen atoms are added in one step
(c) Both (d) CH3CH2CH = CH2
(d) Catalyst decreases the activation energy of the reaction
42. Sodium acetylide can cause (one or more may be correct) :
47. If a mixture of H2 and D2 is used in place of H2, the product
(a) nucleophilic substitution
formed by ethylene will be
(b) nucleophilic addition
(a) CH3CH3 (b) CH2D CH2D
(c) electrophilic substitution
(c) CH2D CH3 (d) all the three
(d) elimination.
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53. Dimerization of isobutene can be performed by
PASSAGE 5
(a) HCl (b) HF
CH3 CH3 CH3 (c) Both (d) None
+
H
PASSAGE 7
OH + H + H Three isomeric alkenes A, B and C, C5H10, are hydrogenated to
give 2-methylbutane. A and B give the same 3° alcohol on
oxymercuration-demercuration, while B and C give the different 1°
CH3 CH3 alcohols on hydroboration-oxidation.

+ 54. The alkene (A) is

CH 3
|
A B (a) (CH3) 2CHCH=CH2 (b) CH 2 = C CH 2 CH 3

48. Step 2 of reaction involves conversion of (c) (CH3 )2 C = CHCH 3 (d) (CH 3 )2 C = C = CH 3
(a) a 2° carbocation to a 3° carbocation 55. The alkene (B) is
(b) a 3° carbocation to a cyclic carbocation
CH 3
(c) a 3° carbocation to a 2° allylic carbocation. |
(a) (CH3) 2CHCH=CH2 (b) CH 2 = C CH 2 CH 3
(d) a 3° carbocation to a 3° allylic carbocation
49. The final product is a mixture of A and B in which (c) (CH 3 )2 C = CHCH 3 (d) (CH 3 )2 C = C = CH 3
(a) A is major (b) B is major 56. The alkene (C) is
(c) Both in equal amounts (d) Nothing is certain
50. The final product will behave like an CH 3
|
(a) aliphatic compound (b) aromatic compound (a) (CH3) 2CHCH=CH2 (b) CH 2 = C CH 2 CH 3
(c) both (d) none
(c) (CH 3 )2 C = CHCH 3 (d) (CH 3 )2 C = C = CH 3

PASSAGE 6
PASSAGE 8
Isobutene, when heated with sulphuric acid, phosphoric acid or
Hydrocarbon A(C7H12) was treated with HBr / peroxide to
HF undergoes dimerization forming a mixture of two alkenes each
provide B(C7H13Br) as the only product. Reaction of B with tert-
having 8 carbon atoms. Since reaction is catalysted by acids, it is an
butoxide ion / base gives C (isomeric with A) in addition to other
electrophilic addition and proceeds as below :
olefin(s). Treatment of C with ozone, followed by Zn/H2O produces
only following compound.
CH 3 CH 3
| |
H+ 3 2 2 (CH ) C = CH CHO
CH 3 - C = CH 2 ¾¾¾
® CH 3 - C - CH3 ¾¾¾¾¾¾¾ ®
(Step 1) Å (Step 2) CHO
3° carbocation

CH 3 CH 3 57. What is the correct structure for A?

| | HSO -4
CH 3 - C - CH 2 - C - CH 3 ¾¾¾¾¾¾¾¾
®
Å | ( - H 2SO 4 )(Step 3)
CH 3 (a) (b)
Dimeric 3 ° carbocation

CH 3 CH 3 CH 3 CH 3
| | | | (c) (d)
CH 2 = C - CH2 - C - CH3 CH 3 - C = CH - C - CH3
| |
CH 3 CH 3 58. What is the correct structure for B?
A B

Less sterically hindered alkene is the major product Br

(a) (b)
Br
51. Which of the two alkenes is major product
(a) A (b) B Br
Br
(c) both in equal amount (d) can’t be predicted (c) (d)
52. Both (A) and (B) can be converted into identical product by
(a) oxidation (b) reduction
(c) chlorination (d) heating to high temperature
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329
59. The correct structure for C is
H CH3
(c) H3CO C º CH (d) HO C º CH
(a) (b)
CH3 CH3

65. The compound Y can be

(a) CH 3 - CH 2 - CH - CH 2 CH 3
(c) (d) None of these |
OH

PASSAGE 9 (b) CH 3 - O - CH - CH 2 - CH 3
|
CH 3
Synthesis I :
H2
HC CH A B C HBr, ether (c) CH 3CH 2 - O - CH - CH 3
NaNH2, NH3 C3H7Br Lindlar catalyst
|
CH 3

Br
CH 3
CH3–CH2–CH 2–CH–CH3 |
(d) HO - C - CH 2 - CH 3
Synthesis II : |
CH 3
COOH
66. The compound W can be :
Br2 CH3Cl KMnO4
FeBr3 D AlCl3
E (a) CH 3 O - CH - COOH
|
CH 3
Br

60. In synthesis I, compound A is (b) HOH 2 C - CH - COOH

|
(a) ethene (b) ethane CH 3
(c) 1,3-butadiene (d) acetylide ion
61. In synthesis I, compound B is (c) CH 3 - CH 2 - CH - COOH
(a) 1-pentyne (b) 2-pentyne |
CH 3
(c) 1-pentene (d) 2-pentene
62. In synthesis I, compound C is (d) CH 3 - CH - CH - COOH
(a) trans-2-pentene (b) cis-2-pentene | |
(c) 1-pentene (d) 2-pentene OH CH 3
63. In synthesis II, compound E is
PASSAGE 11
(a) p-bromomethylbenzene
‘X’(C4H6) on catalytic hydrogenation by H2/Ni produces ‘Y’
(b) m-bromomethylbenzene
(C4H8). ‘Y’ on dichlorination by Cl2/hv forms ‘Z’ (C4H6Cl2),
(c) p-bromophenol
mixture of total six isomers (all dichloro isomers). Reductive
(d) p-bromobenzaldehyde. ozonolysis of X produces a single compound W (C4H6O2).

PASSAGE 10 67. The compound X can be

Compound X (C 5H 8O) on reaction with H 2 /Ni gives Y (a) (b)
(C5H12O). Y on monchlorination gives Z (C6H11ClO), which is a
mixture of 5 products of different structural formula (although
some of these have stereoisomers also). Oxidative ozonolysis of (c) (d)
X produces W (C4H8O3) along with one more product.
X, Y and W are chiral compounds. Lucas and 2, 4-DNP tests are 68. The compound of fractions obtained by fractional distillation of
negative for X. mixture Z is
(a) 3 (b) 4
64. The compound X can be (c) 5 (d) 6
H 69. The number of dioxime isomers formed by ‘W’ on reaction with
H
NH2OH.
(a) HOH2C C º CH (b) O = HC CH = CH2 (a) 1 (b) 2
CH3 CH3 (c) 3 (d) 4
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PASSAGE 12 73. + Rate = x

Na/ NH (l) Isobutyl bromide
(C6 H10 ) ¾¾¾¾¾¾
3 ® (Y) ¾¾¾¾¾¾¾¾
®
Inert solvent
(X)

CH3 CH3
Li/ NH3(l) Oxidation +
Rate = y
(Z) O2N O2N
CH 3 - (CH 2 )3 - COOH
+
The correct order is :
CH 3 - CH - CH 2 - COOH
| (a) x>y (b) x<y
CH 3
(c) x=y (d) can’t predict
70. The compound (X) is

(a) CH3 - (CH2 )3 - C º CH

O
(b) CH3 - (CH2 )2 - C º C - CH3
74. + P
CH 3
|
(c) CH 3 - CH - CH 2 - C º CH O

CH 3
| Product P in the above reaction will be :
(d) CH 3 - CH - C º C - CH 3

71. The compound (Z) is O

O
(a) (Z)-Hex-2-ene (b) (E)-Hex-2-ene
(c) (Z)-2-Methylpent-2-ene (d) (E)-2-Methylpent-3-ene
(a) (b)
72. The compound (Y) is

–Å O O
(a) CH3 – (CH2)3 C CNa

CH3
–Å
(b) CH3 – CH – CH2 – C CNa
O O
(c) CH 3 - (CH 2 )3 - CH = CH - CH 3
Trans
(c) (d)
CH3
O O
(d) CH3 – CH – CH = CH – CH3
Trans

75. + Product
PASSAGE 13 HOOC COOH
Diels-Alder reaction involves the 1, 4-addition of an alkene to a
conjugated diene to form an adduct of six-membered ring. The (a) Product is a mixture of two geometrical isomers in unequal
double bond compound is called the dienophile. concentration
Electron withdrawing substituents in the dienophile such as
(b) Product is exclusively cis, cyclic and unsaturated
>C = O, –CHO, –CN, –NO2, etc. promote the reaction.
dicarboxylic acid
The reaction rate is also accelerated by the presence of electron –
releasing groups in the dienes. Triply bonded compounds, allenes (c) Product is exclusively trans, cyclic and unsaturated
and benzyne may also function as dienophiles. Beside the acyclic dicarboxylic acid
hydrocarbons, dienes may be alicyclic hydrocarbon, in which the
conjugated double bonds may be wholly or partly inside the (d) Product is a mixture of two geometrical isomers but in
ring, some heterocyclic and some aromatic hydrocarbon. These equal concentration
reactions are highly stereospecific.
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331
79. Match the following column I with column II :
Instructions for Q. 76 to 80 : Following questions are Multiple Column-I Column-II
Matching type Questions : (Reaction) (Products)

OCH3
O
76. Column I Column II (i) Na in liq. NH
A. ¾¾¾¾¾¾¾¾
+
3®
(p)
(ii) H 3 O /H 2 O

Br
|
(A) CH 2 CH 2CHCH 3 (a) Stereoselective
O
- +
CH CH O Na
¾¾¾¾¾¾¾
3 2 ® ¾¾¾¾¾
®
Na in
E2 B. liq. NH 3 (q)

N+ Me3
| C. H 2C = CH - CH = CH2 (r) (4 + 2)-addition
(B) CH 3 CH 2 CHCH 3 (b) Stereospecific
CH 2 = CBr2
¾¾¾¾¾® reaction
D , aq.KOH

heat
¾¾¾
®
E2
OH
D. H+ (s) Birch reduction
(C) cis-2-Butene + Br2 (c) Hofmann product ¾¾¾
®
OH
(D) trans-2-Butene + Br2 (d) Saytzeff product
(t) CH3OH

77. Column I Column II 80. Match the following questions :

(Reaction on C = C) (Nature of reactant Column-I Column-II
/ product)
(A) OsO 4 (a) Toxic
A. (p) Optically inactive due to
(B) Acidic KMnO4 (b) Aldehydes
(C) O3 / (CH3)2S (c) Alcohols Cold dil. KMnO internal compensation
¾¾¾¾¾¾¾¾
4®

(D) O3 / H2O2 (d) Carboxylic acids

78. A series of reactions is given below :
B. (q) Optically inactive due to

[B] [C] [D] [Adduct]

(i) CH CO H
external compensation
¾¾¾¾¾¾
3
+ ®
3
(ii) H 3 O
Pick up the appropriate reagent and corresponding product pair
from the respective column X and Y :
Column I - X (Reagent) Column II - Y (Product) D
C. ¾¾¾
2®
(r) Product has two chiral centres
Ni

(A) alcoholic potash (a)

Br
D. ¾¾¾2 ®
(s) Diastereomers will be formed
H O 2

COOH
(B) Ag+/Br2, heat (b) COOH
(t) Overall syn addition
Br
(C) acidic KMnO4 (c)
Br

(D) Ethylene (d)

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332
Statement-2 : P 1 is formed by more stable carbocation
intermediate.
Instructions for Q.81 to 91 : Following questions are Assertion and
Reasoning Type Questions : Peroxide
87. CH3 - CH = CH - CH 3 + HX ¾¾¾¾¾
®
Note : Each question contains STATEMENT-1 (Assertion) and
STATEMENT-2 (Reason). Each question has 5 choices (A), (B), (C),
CH 3 - CH - CH 2 - CH 3
(D) and (E) out of which ONLY ONE is correct. |
X
(a) Statement-1 is True, Statement-2 is True; Statement-2 is a correct
explanation for Statement-1.
Statement-1 : The stereochemistry of product is same whether
(b) Statement-1 is True, Statement-2 is True; Statement-2 is NOT a HCl or HBr is used as reactant.
correct explanation for Statement-1.
Statement-2 : The reaction mechanism with HCl and HBr are
(c) Statement -1 is True, Statement-2 is False. same in above conditions.

(d) Statement -1 is False, Statement-2 is True. 88. Statement-1 : Alcoholic KOH converts CH3 – CH2 – Br into
CH2 = CH2, whereas aqueous KOH converts CH3 – CH2 – Br
(e) Statement -1 is False, Statement-2 is False.
into CH3 – CH2 – OH.

Statement-2 : Alcoholic KOH is more basic than aqueous KOH.

81. Statement 1 : Addition of HBr to 1, 3 – Butadiene gives 1,2
89. Statement-1 : 1-Chloro-2-methylbutane may rotate the plane of
product at low temperature and 1, 4 product at high temperature.
polarised light anti-clockwise.

Statement 2 : For 1, 2 product to be formed the activation

Statement-2 : Two counter-rotating circularly polarized beams
energy requirements are less.
travel with different velocities through the chiral medium.
82. Statement-1 : With respect to alkenes, the electrophilic addition
90. Statement-1 : A mixture of cis-2-butene and trans-2-butene on
reaction and elimination reaction are reversible
addition with ozone produces three stable ozonides.
Statement-2 : because, the direction of the reaction is controlled
Statement-2 : Formation of ozonide is an example of addition
by decrease in free energy of the reaction
reaction.
83. Statement 1 : CH2 = CH2 > R – CH = CH2 > R – CH = CH – R
91. Statement-1 : In presence of an organic peroxide, when HCl is
decreasing order of addition of H2
added to propene, 1-chloropropane is the major product.
Statement 2 : Addition of H2 takes place by the formation of
Statement-2 : Peroxide facilitates free radical mechanism.
transition state therefore least substituted alkene will be more
reactive.

84. Statement 1 :1-Butene on reaction with HBr in the presence of a Instructions for Q. 92 to 100 : Following questions are Integer Type
peroxide produces 1-bromo-butane. Questions :

Statement 2 : It involves the free radical mechanism.

85. Statement 1 : Trans-2-butene on reaction with Br2 gives meso- 92. How many free radicals can be produced during following
2, 3-dibromobutane. reaction (ignoring resonating structure) ?

Statement 2 : The reaction involves syn-addition of bromine.

86. Statement-1 : In the reaction NBS, hn

¾¾¾¾®
CCl 4

HBr
¾¾¾® +
35°C
Br
(P1) major Br (P2)
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333

D /Ni
Cl 2
96. ¾¾¾¾
2 ® C8 H14 D 4
93. (a) ¾¾¾ ® (A) number of monochloro derivatives
hn

Find the total number of isomers formed in the end product.

formed.
97. How many alkenes, alkynes, alkadienes can be hydrogenated to
form isopentane (include all isomers).
Br2
(b) ¾¾¾® (B) number of fractions obtained after
D brine 98. For the given reaction write the correct code :

fractional distillation of product mixture. alc.KOH/ D

CH 3 - CH 2 - CH - CH 3 ¾¾¾¾¾¾
®
|
Give the sum of the products obtained in above two reactions. Br

alc.KOH Code :
94. Br ¾¾¾¾¾
® Number of alkenes produced.

(01) If the reaction is regioselective but not stereoselective.

(02) If the reaction is stereoselective but not regioselective.

H2/ Ni Cl 2 /hn Monochlorination
95. ( )¾¾¾¾¾¾¾¾¾¾¾ ® (All isomers)
(a) (c) (03) If the reaction is both regioselective and stereoselective.
O3
( )
(b) (04) If the reaction is none of regioselective and stereoselective.
(X)
99. Total no. of alkynes that on ca talytic reduction gives
3-ethyl-4-methylheptane.
Calculate sum of number of products formed in the reaction a,
b and c. 100. The total number of cyclic isomers possible for a hydrocarbon
with the molecular formula C4H6 is 5.
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EXERCISE 6.3 (Subjective Problems)

1. How a symmetrical molecule like bromine acts as an electrophile Hg(OAc)2

during addition on alkenes? (v) CH 2 = CHCH 2CH 2CH 2OH
2. Define Saytzeff rule for orientation of elimination in terms of
+
number of hydrogen atoms on carbon atoms of the substrate –H NaBH4
(i.e. in terms of Markownikoff's rule). G H
O
3. Compare the relative rates of addition of HCl, HBr and HI to
alkenes. 10. Which alcohol of each pair would you expect to me more easily
4. Solubility of alkenes in water increases in presence of Ag+ salts. dehydrated?
Explain. OH
5. Dehydrohalogenation of isopropyl alcohol by alcoholic KOH (a) OH
requires several hours of refluxing, while it can be carried out and
immediately at room temperature by potassium t-BuO – in
dimethyl sulphoxide (DMSO). Explain. OH
6. Write the structures for the products of the following addition (b)
reactions : and

(a) (CH 3 )2 C = CHCH 3 + ICl ¾¾

® OH

(b) (CH 3 )2 C = CH 2 + HSCH 3 ¾¾

®
and
(c) CH 2 = CHCF3 + HCl ¾¾
® (c) OH
+ OH
(d) Me 3 N CH = CH 2 + HI ¾¾
® 11. Arrange the compounds of each set in order of reactivity
7. Give the structure of the alkene and reagent used for the towards dehydrohalogenation by strong base
preparation of Br
(a) (CH3)3CI, (b) CH3CHBr2,
(a) Br
(c) CH2(Br)CH(Cl)CH3, (d) CH2(Cl)CH(OH)CH2Br.
8. Predict the product(s) and give mechanism to explain the
following : Br
CH3
| and
conc. H SO
(a) CH 3 CHOH. C .CH 3 ¾¾¾¾¾¾
2 4
® Pr oduct(s)
|
Br
CH3

HF
Br
(b) CH 2 = CH 2 + (CH 3 )3 CH ¾¾¾
® Product(s)
(b) , and
(c) CH 2 = CH - C(CH 3 )3 + HCl ¾¾
® Product(s) Br
CH 3 Br
|
n - C 4 H 9OH, heat
(d) CH 3 - CH - CH - CH 2 CH 3 ¾¾¾¾¾¾¾ ¾ ® Product(s) Br
| (no base)
(c) , ,
OTs Br
14 300° C
(e) CH 3 CH = CH 2 + Br2 ¾¾¾¾
® Product(s)
9. Complete the following : and
Br Br
(i) Alkene (A) + Re agent(B) ¾¾
®
12. Is it possible to dehydrate neopentyl alcohol with an acid? If
CH3 CH3 yes, give the possible product(s).
| |
CH 3 - CH - CH 2 - C - CH 3 13. Heat of combustion of three alkenes (1-pentene, cis-2-pentene
| and trans-2-pentene) were found to be 804.3, 805.3 and 806.9
OH kCal/mole. Can you get any concrete result from these data?
14. Addition of an electrophile to 2, 4-hexadiene gives two
(ii) + HOBr C intermediates. Write their structures and tell which one is more
stable?
15. Dehydration of butanol-1 gives expected product butene-1 and
KMnO4 KMnO4 rearranged product butene-2. Can we convert 1-butanol to 2-
(iii) E D butene without involving any rearrangement?
heat (cold)
16. What will happen when a solution of c hlorine in
HBr tetrachloroethylene (Cl2C = CCl2) is kept in dark at room
(iv) F
dark temperature?
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335
17. In a polymer having regularly alternating groups, the monomer
units are always linked in a head-to-tail manner. Comment. OH
18. Which alkene of each pair is expected to be more reactive towards OH
addition of sulphuric acid? (iii) (iv)
(a) Ethylene and propylene
(b) Propylene and 2-butene CH2OH CH3 CH2OH
(c) 2-Butene and isobutene
(d) 1-Pentene and 2-methyl-1-butene (v) (vi)
(e) Ethylene and vinyl chloride
(f) Vinyl chloride and 1, 2-dichloroethylene
(g) Ethylene and acrylic acid HO CD3 HO CH2CH3
(h) Propylene and 3, 3, 3-trifluoropropene. D D
19. Reaction of 2-butene with HCl in presence of alcohol forms a (vii) (viii)
D
compound of molecular formulaC6H14O as one of the products.
How will you explain its formation? 28. Complete the following :
20. Deduce the structures of alkenes A to F which on ozonolysis
gave products mentioned against them
hot KMnO
4
A ¾¾
® CH 3 CH 2 CHO (i) ¾¾¾¾¾¾ ® All possible products
heat

O
OH
B ¾¾
® + HCHO KMnO
[A] ¾¾¾¾
4® +
(ii) heat
O O
C ¾¾
® CH 3 CO.CHO + 2CH 3 .CO.CH 3 ; C6H 5 CO3 H
(iii) ¾¾¾¾¾¾ ® [B]
CHCl3 at 25° C
D ¾¾
® CH 3 COCH 2 CH 2 CH 2 CH 2 CHO
(i) BD , THF
3
(iv) ¾¾¾¾¾¾
® [C]
E ¾¾
® CH 3 CHO + HCHO + CHO.CH 2 .CHO ; -
(ii) H 2O 2 / OH

F ¾¾
® CHO.CH 2 CH 2 CH 2 .CHO
21. Predict the stereochemistry of the product formed by the (v) + : CBrCl Two Products
addition of Br2 on (a) cis-1, 2-dideuterioethene and (b) trans-1,
2-dideuterioethene. O
22. Predict the products formed by the addition of one mode of
Ozonolysis
bromine to C6H5CH = CH–CH = CH2. Which one of them is (vi) [D] ¾¾¾¾¾®
expected to be most stable?
23. When isobutene is treated with chlorine in dark at 0°C in the O
absence of peroxide, a substitution (methallyl chloride) rather
OH
than addition is the main product. Explain.
24. Propene (CH3CH = CH2) when treated with bromine and water
gives CH3CHOHCH2Br (a secondary alcohol), on the other (i) O3 O
(vii) E 2
hand allyl bromide (CH2BrCH = CH2), on similar treatment (ii) H2O
mainly gives CH2Br.CHBr.CH2OH, a primary alcohol. Explain. 29. (a) Write down structures of the isomeric dimers obtained by
25. n-Butyl-tert-butyl ether dissolves in cold concentrated H2SO 4, the dimerisation of isobutene.
however on standing, an acid insoluble layer having a polymer (b) Write down the ozonolysis products of cis- and trans-2-
separates out. Explain. butenes.
26. Complete the following : 30. Which of the following isomeric compound will have lower
heat of combustion in each of the following pairs?
(i) cis-2-Butene and trans-2-Butene
(i) alc. KOH
Br ¾¾¾¾¾ ® Products (ii) trans-2-Hexene and 2-methyl-2-pentene
(iii) Octane and 2, 5-dimethylhexane.
31. Predict the major monochloro products in the following :
300° C
(ii) + Br2 ¾¾¾¾
® Main product

(i) (ii)
H - C - COOH
(iii) || + D2 ¾¾
® Product(s)
H - C - COOH

CH3 - C- H (iii) (iv)

dil. KMnO
4 HCOOOH
(iv) B ¬¾¾¾¾¾ ¾ || ¾¾¾¾¾® A
H - C- C2H 5 32. Give mechanism of the following reaction.
conc. H2SO4
27. Predict the product(s) of dehydration of the following alcohols :
(i) (CH3)2CH.CHOH.CH3 (ii) (CH3)2C(OH).CH(CH3)2
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33. Tetrachloroethylene adds chloride only in presence of AlCl3. 47. Predict the relative C–C bond lengths in CH3CH3, CH2 = CH–
Comment. CH = CH2 and HC º C–C º CH.
34. (a) Give IUPAC name of the following : 48. What happens when 1-butyne is (i) ozonolysed, (ii) treated
with hot KMnO4.
(i) (ii) 49. Give reaction involved in the conversion of 2-butyne to
(i) meso-2, 3-dibromobutane
(ii) racemic-3-chloro-2-butanol
(b) Give the state of hybridisation of each carbon in the
(iii) meso-2, 3-butanediol
following compounds :
(iv) racemic-2, 3-butanediol.
(i) (ii) 50. Mention the chemical methods that would distinguish between
(i) 2-pentyne and 2-pentene
(iii) (ii) 2-pentyne and 1-pentyne
35. Give the products obtained from the acid-catalysed dehydration (iii) 1, 3-pentadiene and 2-pentyne
of CH2 = CH.CH2.CH(OH).CH3. Predict which will be major (iv) 2-hexyne and isopropyl alcohol.
product, if any. 51. Identify A to H in the following :
36. Give the products obtained from the reaction of 2-methyl-1, 3-
butadiene with bromine. (i) BH 3 , THF 3 (i) BD , THF
(i) B ¬¾¾¾¾¾¾
¾ RC º CR ¾¾¾¾¾¾¾
®A
(ii) CH 3COOD (ii) CH 3COOH
37. (a) Give the various possible products formed by the addition
of one mole of Br2 to one mole of 1, 3, 5-hexatriene. CH3ONa
(ii) O= =O + CH3C º CH C
(b) Which products will be obtained under thermodynamic
controlled conditions?
2(i) 2NaNH
2 5 Na + C H OH Br
38. (a) Write down the different resonating structures of the (iii) HC º CH ¾¾¾¾¾¾ ® D ¾¾¾¾¾¾ ¾
® E ¾¾¾
2® F
(ii) 2CH 3 Br
following carbocation having + charge on different carbon
atoms. 2+
(i) NaNH2 H2SO4/Hg
Å (iv) C º CH G H
CH 2 = CH - CH = CH - CH = CH - CH 2 (ii ) CH3Br
(b) Which of the canonical structure will react with the (i) O
3 KMnO
nucleophile (Nu–) to give the thermodynamic controlled (v) J ¬¾¾¾¾
(ii) H2 O
CH 3 CH 2 C º CCOOH ¾¾¾¾ 4® I
heat
product?
39. Arrange the following alkenes in the order of decreasing 52. (a) Name the alkyne used for the synthesis of the following
reactivity towards HBr : ketone :
O
CH 3 - CH = CH - CH 3 , CH 2 = CH - CH 2 - CH3 ,
I II
C—CH2
CH 3 CH 3
| | (b) Name the smallest stable cycloalkyne. Why cyclohexyne
CH 2 = CH - CH = CH 2 , CH 2 = C - C = CH 2 is not stable?
,
III IV
53. An alkyne an oxidation gives two moles of CH3COOH and one
CH 3 - CH = CH - CH = CH 2 mole of glutaric acid, draw its probable structure.
V 54. A hydrocarbon gives red precipitate with ammonical silver
40. Give structures of the products expected from the reaction of 1, nitrate and forms following compounds on ozonolysis :
3-butadiene with (a) 1 mol of HCl, and (b) 2 mole of HCl. (a) methanoic acid,
41. Suggest a mechanism for the following reaction : (b) pentanal and 4-oxopentanoic acid
Suggest the structure of the hydrocarbon.
H3PO4 55. (a) Name the smallest alkynes that can show geometrical/
optical isomerism.
(b) Partial reduction of alkynes is always stereospecific,
42. Draw the orbital picture of 1, 2-propadiene and 1, 3-butadiene. comment on the statement.
43. Is the fact that conjugated dienes are more stable and more (c) Which type of alkynes will give same product on oxidative
reactive than isolated dienes is an incongruity? hydroboration and hydration.
44. What products are formed in the following reaction? 56. Explain the following :
(i) Although acetylene is acidic in nature, it does not react
CH 2 = CH - CH = CH - CH = CH 2 + Br ¾¾ ®
with NaOH or KOH.
Name the type of intermediate formed in the reaction. (ii) The C º C distance is shorter than the C = C and C–C
45. Arrange the following in the increasing order of distances.
dehydrobromination : (iii) Although the C–H bond in acetylene has the greatest bond
Br Br Br energy of all the C–H bonds, yet it is most acidic.
, and (iv) The CH2 = CH– is more basic than HC º C –.
(v) The C º C bond although has two p bonds, it is less reactive
46. Addition of HCl to 3, 3-dimethyl-1-butyne gives a mixture 2, than the C = C towards electrophilic addition reactions.
2-dichloro-3, 3-dimethylbutane (44%), 1, 3-dichloro-2, 57. Draw the stereochemical structure of the product in the
3-dimethylbutane (34%) and 2, 3-dichloro-2, 3 dimethylbutane (18%). following reactions :
Explain. 2 H , Lindlar catalyst
R - C º C - R ¾¾¾¾¾¾¾¾®
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58. Deduce the structural formula of a compound of molecular (b) Mycomycin, a naturally occurring antibiotic is found to
formula C6H10 which (i) adds 2 moles of hydrogen to form 2- have following structure.
methylpentane, (ii) forms a carbonyl compound in aqueous HC º C - C º C - CH = C = CH - (CH = CH)2 CH 2 COOH
H2SO4 –HgSO4 solution, and (iii) does not react with ammonical
AgNO3 solution. What will be the action of plane polarized light on the
solution of this compound. Explain your answer.
59. An unsaturated optically active compound (A) of the molecular
formula C6H12 absorbs a mole of hydrogen to form unresolvable 69. An optically active hydrocarbon A (C 6H10 ) on catalytic
compound (B). Write structures of A and B. How will you hydrogenation gives optically inactive hydrocarbon B(C 6H14).
prepare (A) from its corresponding alkyl bromide? Propose structures to A and B.
60. An aqueous solution of potassium salt of a dibasic acid liberated 70. The sex attractant pheromone of the codling moth of the
a hydrocarbon at anode. The hydrocarbon took up one molecule molecular formula C13H24O absorbs two molar equivalents of
of hydrogen to form n-butane. Assign structure to the salt of hydrogen to form 3-ethyl-7-methyl-1-decanol. On reductive
dicarboxylic acid. ozonolysis, it forms following three products
61. A hydrocarbon of the molecular formula C 10H16 absorbs three O O O
moles of hydrogen to form C10H22. On ozonolysis it yields HO
following compounds : H H
O O
(i) (ii) CH 2O Assign structure to the pheromone.
71. Four isomeric hydrocarbons A, B, C and D of the molecular
H formula C6H10 show following characteristics.
(i) All the four are soluble in cold concentrated sulphuric acid
OHC and decolorize colour of bromine in carbon tetrachloride.
(iii) O (ii) A reacts with ammonical silver nitrate to give red
O precipitate.
Assign structure to the hydrocarbon. (iii) Oxidation with hot alkaline permanganate solution gives
62. A 10.02 mg sample of a hydrocarbon (mol. wt. in the range of different products; A gives only pentanoic acid, B gives
80–85) absorbs 8.40 ml of hydrogen gas at 0°C and 760 mm only propanoic acid, C gives only adipic acid; and D gives
pressure. Ozonolysis of the hydrocarbon gave methanal and a mixture of acetic acid and oxalic acid in 2 : 1 molar ratio.
glyoxal. Assign the probable structure to the hydrocarbon. Assign structures from A to D.
63. An unsaturated hydrocarbon A, having 87.2% C, takes up 72. An optically active compound A (C7H11Br) reacts with hydrogen
hydrogen and yields another hydrocarbon B with 84.1% C. bromide, in the absence of peroxide, to form two isomeric
Compound A on ozonolysis gives acetic acid, acetone and pyruvic products B and C (C7H12Br 2). Compound B is optically active,
acid. Assign structures to A and B. while C is not. Reaction of B with one mol of potassium tert-
64. An organic compound A, having carbon and hydrogen, adds butoxide regenerated A, while similar reaction with C gives
one mole of hydrogen in the presence of platinum as catalyst to racemic mixture of A.
form n-hexane. On vigorous oxidation with KMnO 4 it gives a When A is treated with potassium tert-butoxide, a new
single carboxylic acid containing three carbon atoms. Assign compound D (C7H10) is formed which on reductive ozonolysis
structure to the compound A. gives 2 mol of formaldehyde and 1 mol of 1 ,3 -
65. One mole of a hydrocarbon (A) reacts with one mole of Br2 cyclopentanedione. Propose structures from A to D, keeping
giving a dibromo compound C 5H10Br 2. Substance (A) on stereochemistry in mind.
treatment with cold, dilute alkaline KMnO 4 solution forms a 73. Which member of the following pairs is more stable than the
compound C 5H12O 2. On ozonolysis, (A) gives equimolar other in each case?
quantities of propanone and ethanal. Deduce the structural
formula of (A).
or
66. A hydrocarbon A (molecular formula C 5 H10 ) yields 2- (a)
methylbutane on catalytic hydrogenation. A adds HBr (in (A) (B)
accordance with Markownikoff's rule) to form a compound B
which on reaction with silver hydroxide forms an alcohol C,
C5H12O. Alcohol C on oxidation gives a ketone D. Deduce the or
structures of A to D and show the reactions involved. (b)
(A) (B)
67. There are six different alkenes A, B, C, D, E and F. Each on
addition of one mole of hydrogen gives G which is the lowest
molecular weight hydrocarbon containing each one asymmetric or
carbon atom. None of the above alkenes gives acetone as a (c)
product on ozonolysis. Give the structures of A, B, C, D, E and (A) (B)
F. Identify the alkene which is likely to give a ketone containing 74. Write down the structure(s) of the intermediate(s) formed in the
more than five carbon atoms on treatment with a warm following reaction, commonly known as pina colone
concentrated solution of alkaline KMnO 4. Show various rearrangement.
configurations of G in Fischer projection.
CH3 CH 3 CH 3
68. (a) Ricinoleic acid, an unsaturated fatty acid isolated from | | |
H 2 SO4
castor oil, was assigned following structure. CH 3 - C - C - CH 3 ¾¾¾¾ ® CH 3 - C - C - CH 3
| | heat || |
COOH OH OH O CH3
OH 75. (a) Draw and name all possible isomers of formula C3H5Cl.
Write the structures of all the possible stereoisomers of (b) Cholesterol, C27H46O, has only one pi bond. What other
ricinoleic acid. information can be drawn regarding its structure?
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SOLUTIONS
EXERCISE 6.1
1 (c) 11 (d) 21 (d) 31 (b) 41 (c) 51 (a) 61 (d) 71 (c) 81 (d) 91 (d) 101 (d)
2 (d) 12 (c) 22 (c) 32 (a) 42 (a) 52 (c) 62 (c) 72 (b) 82 (a) 92 (c) 102 (b)
3 (c) 13 (b) 23 (c) 33 (d) 43 (b) 53 (c) 63 (c) 73 (d) 83 (b) 93 (a) 103 (c)
4 (d) 14 (c) 24 (c) 34 (c) 44 (c) 54 (c) 64 (c) 74 (c) 84 (d) 94 (c) 104 (c)
5 (c) 15 (b) 25 (d) 35 (c) 45 (c) 55 (d) 65 (d) 75 (a) 85 (b) 95 (a) 105 (b)
6 (c) 16 (c) 26 (c) 36 (b) 46 (a) 56 (b) 66 (d) 76 (d) 86 (a) 96 (b) 106 (b)
7 (c) 17 (b) 27 (b) 37 (c) 47 (a) 57 (c) 67 (b) 77 (b) 87 (d) 97 (b) 107 (c)
8 (d) 18 (a) 28 (b) 38 (b) 48 (c) 58 (b) 68 (a) 78 (a) 88 (c) 98 (c) 108 (c)
9 (d) 19 (c) 29 (b) 39 (c) 49 (b) 59 (b) 69 (d) 79 (b) 89 (a) 99 (d) 109 (d)
10 (c) 20 (c) 30 (a) 40 (b) 50 (c) 60 (a) 70 (b) 80 (a) 90 (d) 100 (c)

1. In (i), one doubly bonded carbon atom has two 2H’s while in (iii) one doubly bonded carbon atom has two C2H5’s.
2. Amylene (C5H10) can exist in five structural isomeric forms among which one can show cis-trans isomerism.
CH3
CH3CH2CH2CH = CH2 CH3CH2CH = CHCH3 (cis-trans) (CH3)2CH—CH = CH2 CH3CH2C = CH2 CH3CH = C(CH3)2
X
–
3. —C—C— ——® C=C + H : B + :X
H :B

4. The first two compounds will give a mixture of two alkenes, while the third will exclusively form 2-methyl-1-butene.
CH3 CH3 CH3 CH3 CH3
+
H , heat Hcl alc.
5. (i) CH3—C—CH3 ———® CH3—C = CH2 (ii) CH3—C—CH3 ——® CH3—C—CH3 ——® CH3—C = CH2
KOH
OH OH Cl
CH3 CH3 CH3
TsCl tert-BuOK
(iii) CH3—C—CH3 ——® CH3—C—CH3 ————® CH3—C = CH2 + TsOH
OH OTs

CH3 CH3 CH3

(–HCl) (–HBr)
6. CH3—CH—CH2Cl ——® CH3—C = CH2 ¬——— CH3—C—CH3
Br
Isobutyl chloride 2-Methylpropene (Isobutene) tert-Butyl bromide

7. The order of reactivity of alcohols towards dehydration is 3° > 2° > 1°. Hence for dehydration of primary alcohols more concentrated
H2SO 4 and high temperature must be used.
2 1
CH3CHCOONa CH 3CH
8. ——® + CO2 + 2NaOH + H 2
CH3CHCOONa CH 3CH
3 4
9. In trans-isomer polarity developed by one —CH3 group is cancelled by polarity of the order —CH3 group placed in opposite direction
while the cis-isomer is polar although weak causing high boiling point than the trans-isomer.
10. Melting point of the trans-isomer is higher than that of cis-isomer due to molecular symmetry in the former case.
11. First calculate the value of isotopic effect (KH/KD) per hydrogen atom from the chlorination of C6H5CH2D.
KH Moles of HCl formed/No. of available H atoms 0.0868/2
= = = 2.05
KD Moles of DCl formed/No. of available D atoms 0.0212/1
Similarly, for C6H5CHD2
KH Moles of HCl formed/No. of H atoms
=
KD Moles of DCl formed/No. of available D atoms
Moles of HCl 2 Moles of HCl 2.05
2.05 = ´ or =
Moles of DCl 1 Moles of DCl 2
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1¢
CH3
1 2 3 4 5 6 7
12. CH3—CH = CH—CH2—CH2—CH—CH3
(i) C1 is 1° allylic ; (ii) C2 and C3 are vinylic ; (iii) C4 is 2° allylic ; (iv) C5 is 2° ; (v) C6 is 3° ; (vi) C1¢ and C7 are 1°.
The order of reactivity of these H’s is 2° allylic > 1° allylic > 3° > 2° > 1° > vinylic
13. Alkenes having strong electron-withdrawing group on one of the doubly bonded carbon atom undergo polarization in such a manner that
the b-carbon becomes electron deficient and thus becomes the site for an electron rich reagent (nucleophile).
–
OC H – – C2H5OH
CH2 == CH—C º N ———®
2 5
[C2H5OCH2—CH—C º N ¬—® C2H5OCH2—CH = C = N] ———® C2H5OCH2CH2C º N
H
14. Addition of bromine to alkenes is both stereoselective as well as stereospecific. It is stereospecific as stereoisomeric alkenes react
differently, i.e. they give stereochemically different products. It is stereoselective since a given isomer gives only one diastereomer (or one
pair of enantiomers).
15. The relative reactivities of alkenes towards HX are directly related to the stabilities of the intermediate carbocations. Isobutene (IV) forms
the most stable 3° carbocation followed by butene-1 (II) which forms 2° carbocation. Ethylene (I) and vinyl chloride (III), both form 1°
carbocation, but the carbocation from vinyl chloride will be less stable because electron-withdrawing halogen intensifies the positive
charge and thus destabilizes the carbocation. Hence vinyl chloride will be less reactive than ethylene.
16. In presence of light addition of HBr takes place through free radical mechanism where addition of bromine atom (bromine radical, Br.)
is the first step.

CH3 CH3 CH3 CH3

+ + –
H 1, 2-hydride shift Cl
17. CH2 = CH—CH—CH3 ——® CH3—CH—C—CH3 ———————® CH3—CH2—C—CH + 3 ——® CH2—CH2—C—CH3
3º carbocation
H Cl
(More stable)
2º carbocation 2-Chloro-2-methylbutane

18. In aqueous solution, HBr reacts with water to form H3O+, a weaker acid. Dry HBr is a stronger acid than H 3O+, former can better transfer
H+ to an alkene. Further, H2O is a nucleophile and can react with R+ to give an alcohol.

CH3 CH3 CH3 CH3

+ +
D D2O –D
19. CH3—C = CH—CH3 ——® CH3—C—CH—CH3 ——® CH3—C—CHD—CH3 ¬ —— CH3—C—CHD—CH3
Å
+
D OD2 OD

20. Addition of H2SO 4 to alkenes takes place according to Markownikoff’s rule, so isobutanol (CH3)2CHCH2OH, can’t be prepared by this
method ; isobutene will be forming tert-butanol.
OSO3H OSO3H
CH 3 CH3
H2SO4
C = CH2 ———® C—CH3 + (CH3)2CHCH2
CH3 CH3 (Not found)

21. Hydration of alkenes to form alcohols and dehydration of alcohols to form alkenes are reversible.
+
H
RCH = CH2 + H2O RCH2CH2OH
(–H2O)

Low H2O concentration and high temperature favour alkene formation because the volatile alkene distills out of the reaction mixture and
shifts the equilibrium toward alkene. On the other hand, hydration of alkenes occurs at low temperature and with dil. acid which provides
a high concentration of H2O as reactant.
22. First step involves addition of H+ (from acid) forming ethyl hydrogen sulphate as the final product. Ethyl hydrogen sulphate, being 1°,
undergoes SN2 mechanism.
d– d+
23. Addition of hypochlorous acid (HO—Cl) to alkenes is an electrophilic addition, so Cl+ will be adding at the first (rate determining) step
to the p bond.
24. Reaction of an alkene in presence of acid forms a carbocation. Carbocation is a strong acid and hence can abstract tert-hydride ion from
isobutane to form isooctane

CH 3 CH 3
Å
(CH3)3C—CH 2C + H— C(CH 3)3 ——® (CH3)3C—CH 2— CH

CH 3 CH 3
Carbocation Isobutane Isooctane
(a strong acid)
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+
HOCH3 OCH3
Hg(OAc)2 +
CH3OH –H NaBH4
25. CH3CH = CH2 — ———® CH3—CH—–CH2 ———® CH3—CH—–CH2 ——® CH3—CH—CH2HgOAc ———®
Hg Hg
OCH3
AcO OAc AcO OAc
CH3—CH—CH3 + Hg + AcOH

This method of formation of ethers is preferred to Williamson synthesis where elimination reaction competes substitution reaction,
provided appropriate alkene is readily available.
26. Due to the formation of more stable 2° free radical , the final product will be n-propyl bromide, CH3CH2CH2Br. Due to the
presence of electron repelling methyl group, the transition state will be more stable than that of the CH 2 = CH2, hence addition of HBr on
propene will be faster.
27. In cyclohexane either of the 12H atoms can be brominated, while in cyclohexene, only 4H atoms at the allylic position can be brominated.
However, cyclohexene is brominated faster than cyclohexane because in the former an allyl radical is formed.

28. A cyclic bridged ion (bromonium ion) is formed as an intermediate. In this way configuration of the parent alkene is retained in the
intermediate. In the second step, the nucleophile attacks the side opposite the bridging group to yield the anti addition product.
Å
Br
C C

Br
29. Note that here the electrophile is MnO 4– which has more than one electrophilic oxygen atoms. Thus here both the carbon atoms are linked
separately to two oxygen atoms and thus the configuration of the intermediate will be the configuration of the product, i.e. the addition
takes place in syn-manner although a cyclic intermediate is formed.
–
O O
–
O O Mn C——C
C C + Mn O O + O O C——C
O O C——C Mn
– OH OH
O O
(±) – glycol

30. The hydroboration-oxidation process gives products corresponding to anti-Markownikoff’s addition of water. Remember that carbocations
are not intermediates in these reactions, hence rearrangement does not occur in hydroboration.
H Cl
C C
Cl H
31. cis-3-Hexene and trans-3-hexene will form same product on hydrogenation.
32. Baeyer’s reagent is dilute (nearly 1%) alkaline KMnO4 solution.
33. Only in isobutene, Me2C = CH2, the two doubly bonded carbon atoms are different in terms of number of hydrogen atoms attached.
34. trans-1, 2-Dichloroethylene is symmetrically substituted, dipole moment due to one C—Cl bond is cancelled by equal but opposite dipole
moment due to other C—Cl bond.
35. 2, 2-Dimethylpropane and 2, 2, 3, 3-tetramethylbutane are symmetrical molecules
CH3 CH3 CH3
H3C—C—CH3 H3C—C—–C—CH3
CH3 CH3 CH3
36. More the number of double bonds in an alkene, higher will be the heat of hydrogenation. Among molecules having one double bond, more
substituted, viz-2-butene will be more stable (Saytzeff rule). Further, among isomeric alkenes trans-isomer is more stable because bulky
groups are far apart from each other and thus its heat of hydrogenation will be less than the cis-isomer.
37. In but-2-ene (CH3CH = CHCH3), both of the doubly bonded carbon atoms are similar.
38. The intermediate carbocation is more stable, because positive charge is in conjugation with the benzene nucleus, due to possibility of
resonance.
39. Heat of hydrogenation is a measure of stability, more stable an alkene, less is its heat of hydrogenation and vice-versa. Stability of
alkadiene follows the order.
Conjugated diene > Isolated diene > Cumulative diene
(1, 3-pentadiene) (1, 4-pentadiene) (2, 3-pentadiene)
Thus the order of heat of hydrogenation is
Cumulative diene > Isolated diene > Conjugated diene.
40. Due to rotation about C2—C 3 single bond, two conformations of 1, 3-butadiene are possible, namely s-trans (transoid) and s-cis (cisoid),
the symbol s-refers to the fact that the isomerism is with respect to single bond.
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341

H H
C H H C
H C C H

C H C H
H C H C
H H
s-trans (More stable) s-cis (Less stable)

However, it should be noted that the energy barrier for conversion of s-trans to s-cis form is quite low (5 kCal/mole).
41. Structure (I) is non-polar and has more (11) bonds than the polar structures (II) and (III), each having 10 bonds. Thus structure (I) should
contribute more. Since the contributing structures are not equivalent, the resonance energy of 1, 3-butadiene is small.
42. H+ adds to C 1 to form a more stable allylic 3° carbocation rather than to C 2 or C 3 to form a nonallylic 1° carbocation
+ +
(CH 2—CH(CH 3)CH = CH 2 and H 2C = C(CH 3)CH 2—CH 2 , respectively) or to C4 to yield to a 2° allylic carbocation.

CH3 CH3
+
1 2 3 4 H Å
CH2 = C—CH = CH2 ——® CH2 = C—CH—CH3
Isoprene 2° allylic carbocation
+ (less stable, not formed)
H

CH3 CH3 CH3

–
Cl
CH3—C—CH = CH2 ——® CH3—C—CH = CH2 + CH3—C = CH—CH2
Å
3° allylic carbocation (more stable) Cl Cl
(also favoured by —CH3 group) (i) (iii)

43. Intermediate in the reduction of isolated double bond would give a high-energy dianions having localized charge on two adjacent carbon
atoms, a highly unstable feature
– – –
2e
RHC = CHR ——® RCH = CHR
On the other hand, reduction of one of the double bonds of butadiene would give a resonance stabilized allylic carbanion, a highly stable
intemediate.
2e
– – – – –
H2C = CH—CH = CH2 ——® H2C—CH—CH = CH2 ¬—® H2C—CH = CH—CH2
allylic carbanion
44. Addition of HI on C1 and C2
1 2 3 4 5
HI
CH2 = CH—CH = CH—CH3 ——® CH3—CHI—CH = CH—CH3 (1, 2-adduct)
1
Addition of HI on C and C 4
5 4 3 2 1
CH3—CH = CH—CH = CH2 ——® CH3—CHI—CH = CH—CH3
45. Hot KMnO4/NaIO4 are strong oxidising agents which will give CO2 and COOH–COOH.
46. Due to – I effect of Br, the terminal carbon, atom bearing Br group becomes more acidic, hence one equivalent of alcoholic KOH reacts
with its hydrogen rapidly while removal of less acidic hydrogen becomes difficult.
H Br
47. HC º CH + Br2 water ¾¾ ® C=C
Br H
trans-1, 2-Dibromoethene
Addition of second molecule of Br2 is prevented partly by the low concentration of Br2 in the form of bromine water and partly by the fact
that the – I effect of bromine groups decreases the nucleophilic reactivity of the double bond.
48. Additon of Br2 on the triple bond can be restricted by using excess of alkyne and by using bromine water rather than bromine itself.
49. Acetylene is a weaker acid than water.
O
H2SO4
50. CH3CH2C º CH + H2O ¾¾ ¾® CH3CH2CCH3 ¬¾¾ CH3C º CCH3
2+
Hg 2-Butanone
51. An isolated double bond is more reactive than an isolated triple bond. However, in case of HC º CCH = CH2, addition of HBr will
preferentally take place on triple bond as it leads to formation of conjugated diene.
52. Catalytic hydrogenation of alkynes gives cis-alkene which in turn adds deuterium atoms in presence of H 2 again in cis-manner forming
meso-2, 3-dideuterobutane.
53. Alkynes add hydrogen in cis-manner ; the cis-alkene adds bromine in anti manner forming racemic product.
CH3 C2H5 H3C C2H5
H2 / Cat CH2I2
54. CH3C º CC2H5 ¾¾ ¾® C=C ¾¾ ¾®
Zn(Cu)
H H H
H
cis-1-Ethyl-2-methylcyclopropane
cis
55. Terminal alkynes, (having º CH e.g. 1-butyne), react with ammonical Cu2Cl2 giving red precipitate.
56. CH3C º CCH3, being linear and having symmetrical structure, has lowest dipole moment.
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sp2 sp sp2 sp2 sp2 sp 2 sp2 86. (a 3 2CH MgBr
HC º CH ¾¾¾¾¾¾
® BrMg - C º C - MgBr
57. H2C = C = CH2 CH2 = CH—CH = CH2 -2CH 4
Propadiene Butadiene
(i)2CO
58. CH2 = CH—C º CH No. of s bonds = 7 ; No. of p bonds = 3 ¾¾¾¾¾¾
2 ®
Å HOOC – C C – COOH
(ii)H2O/ H (B)
HBr HBr
59. CH3C º CH ¾¾¾ ® CH3C(Br) = CH2 ¾¾¾ ® CH3CBr2CH3 H2SO4 HgSO4
O
H 2 SO 4/Hg 2 + P b a
60. CH3CH2C º CH ¾¾¾¾¾¾® CH3CH2COCH3. - CO2
HOOC- C- CH3¬¾¾¾ ¾ HOOC – C – CH2 – COOH
69. The oxidation level in compounds having same number of carbon D
atoms can be calculated as below : (C)
O
Oxidation level = (sum of number of C – O, C – N and C – X
bonds – sum of C – H bonds) b-Keto acid
In I oxidation level = 0 – 12 = –12; In II, oxidation level 87. (d) Rate of electrophilic addition µ Nucleophilicity of alkene
= 0 – 6 = –6 µ stability of carbocation, so order IV > I > II > III.
In III oxidation level = 1 – 9 = –8; 88. (c)
In IV, oxidation level = 2 – 10 = –8
Thus oxidation level is : I < IV = III < II
O O
B OD
D D O + CH2 = O
D 2 O2 ¾¾¾
3®
81. (d) B2 D 6
¾¾¾¾
® ¾¾¾¾ ®
NaOD
3 O
Syn addition 4 moles 6 moles

H
¾¾¾¾¾¾¾¾
2 ® C=C– H
82. (a) Pd-BaSO 4 O3
(Syn Addition CHO
H H 89. (a)
poisoned palladium CHO
catalyst)

OH H2/ Ni

Cl2
Single product
Al2O3
83. (b)
D
E2 (Bimolecular elimination without rearrangement) O
84. (d) C4H6 ¾¾
® C4 H8 O O3
(b)
Br Br
| | H2/ Ni O
Br2
CH 3 - C - C - CH 3 ¬¾¾¾ ¾ CH 3 - C º C - CH 3
| | excess Cl2
Br Br More than one product
dil. H2SO4,
HgSO4
O O3
P (c) CHO CHO
CH 3 - CH 2 - C - CH 3 2 moles

Br Br H2/ Ni
| |
Br2
CH 3 - CH 2 - C - CH ¬¾¾¾ ¾ CH 3 - CH 2 - C º CH
| | excess
Br Br
dil. H2SO4,
HgSO4 O
O
P H–C CHO
CH 3 - CH 2 - C - CH 3 O3
(d) +|
H–C CHO
O
H2/ Ni
O
HÅ /KMnO
85. (b) ¾¾¾¾¾¾
4®
D –
OO

O O 90. (d) Stability µ Resonance

µ Hyperconjugation
OH - D Length of conjugation is equal in all I, II, III and IV.
¾¾¾® ¾¾® But hyperconjugation is IV > III = II > I a nd
O O hyperconjugation in structure III is more and hence more
OH stable than II.
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343
101. (d) CH 3 - CH 2 - CH 2 - CH = CH 2 ,
CH 3 - CH 2 - CH = CH - CH 3 ,
H– CH2 + ..
H CH2 – CH 3 - CH 2 - C = CH 2 , CH 3 - CH =C - CH 3 ,
(II) | |
CH 3 CH 3
–
..
H2C H2C CH 2 =CH - CH - CH 3
|
– CH 3

H – CH2 .. +
H CH2
+
H CH2
102. (b)
O O
(III)
CH3 –
..
–
O3/ Zn C – CH3 OH C – CH3
91. (d) Rate of acid catalysed hydration of alkenes µ Stability of
carbocation produced C– H C– H

Å O O
Å O O
Q >
C – CH3 C – CH3
–H2O
Å Å
> CH 2 - CH 3 > CH 3 - C = CH 2 (stability) D
OH
\ correct answer is III > IV > II > I.
103. (c) ® CH º C - + NH 3
CH º C - H + NH 2 ¾¾
H3C C2H5 (2) CH 3 MgCl
92. (c) C–C ¾¾¾¾¾¾ ® CH º C - H + CH -3 ¾¾
® CH º C - + CH 4
(3) H +
H CH3
O
CH º CH + Na in liq. NH 3 ¾¾ ® CH 2 = CH 2
CH3 104. (b) Diels-Alder reaction is highly stereospecific and it is syn
H3C C2H5 addition where the configuration of dienophile is retained.
C– C 106. (b) Alkynes are less reactive due to unstable intermediate
H CH3 formed.
OH
107. (c) It is a case of anti-addition in which cyclic bromonium ion
Me is formed.
Cl
–
H Br NaNH2 Cl
93. (a) + Enantiomer
Br H
Br
Me
Br
–
Br2 + Br
Me – C C – Me ¾¾¾
® Br
Na/ NH3(l) Br
OH
–
OH

Me CH3 Br
108. (c) With Na in NH3 (l), addition is anti.
BD3– THF
Me H Me
94. (c) H2O2– OH
–
Me H
H (syn addition) H H
H Optically inactive
Me Me Me D Me H
X
Me H HD and Me H HO Me But with Pd-BaSO4 – quinoline, hydrogen addition is cis
and the product is
H OH H H Me
Me H
Br – Br Me H
97. (b) Ph – CH = CH – CH = CH2
H Optically active
H H
Br
+d Y
Ph – CH = CH – CH – CH2 Ph – CH = CH – CH – CH2 109. (d) Only (d) can form 3-Octyne
® CH 3CH 2 C º C - Na +
Br NaNH
Br CH 3CH 2 C º CH ¾¾¾¾
- NH
2
+d 3
More stable Thermodynamically
CH CH CH CH Br
more stable compound ¾¾¾¾¾¾¾
3 2 2
(S 2)
2
®
N
100. (c) It is Wittig reaction CH3CH 2 C º CCH 2 CH 2 CH 2 CH 3 + NaBr
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EXERCISE 6.2
1 (b,c) 2 (b,c) 3 (b,c) 4 (c, d) 5 (c, d)
MCQ > 1 6 (a, b) 7 (b, d) 8 (a, c) 9 (a, c) 10 (a, b, c, d)
CORRECT 11 (b, c, d) 12 (a, b) 13 (a, b) 14 (a, b) 15 (b, c, d)
OPTION 16 (a, b, c) 17 (a, c) 18 (a, b) 19 (a, c) 20 (a,b,d)
21 (a, c, d) 22 (b, d) 23 (c) 24 (a,b,c,d)
25 (a) 26 (c) 27 (a) 28 (c) 29 (a,c)
PASSAGE 1
30 (b,c) 31 (b,c)
PASSAGE 2 32 (a,c) 33 (c) 34 (b,d) 35 (a)
36 (c) 37 (b) 38 (c,d) 39 (a) 40 (a)
PASSAGE 3
41 (b) 42 (a,b,d) 43 (b)
PASSAGE 4 44 (b,c,d) 45 (a) 46 (b,d) 47 (d)
PASSAGE 5 48 (d) 49 (b) 50 (a)
PASSAGE 6 51 (a) 52 (b) 53 (b)
PASSAGE 7 54 (c) 55 (b) 56 (a)
PASSAGE 8 57 (a) 58 (d) 59 (c)
PASSAGE 9 60 (d) 61 (a) 62 (c) 63 (a)
PASSAGE 10 64 (c) 65 (b) 66 (a)
PASSAGE 11 67 (d) 68 (c) 69 (c)
PASSAGE 12 70 (b) 71 (b) 72 (a)
PASSAGE 13 73 (a) 74 (c) 75 (b)
76 (A) – d; (B) – c; (C) – a,b; (D) – a,b
77 (A)-a, c ; (B)-b, d ; (C)-a, b ; (D)-a, d
MATCH THE
78 (A)-d ; (B)-c ; (C)-b ; (D)-a
FOLLOWING
79 (A)-a, d, e ; (B)-d ; (C)-a, c ; (D)-a, b
80 (A)-b, c, e; (B)-a, c; (C)-b, c, e; (D)-c, d
81 (a) 82 (a) 83 (a) 84 (a) 85 (c)
A/R 86 (d) 87 (c) 88 (a) 89 (a) 90 (b)
91 (d)
92 4 93 1 94 5 95 6 96 3
INTEGER
97 6 98 3 99 3 100 5

CH3
Me D H
Y= + M1
H D

21. (a, c, d) ; CH3

Me Total = 2
CH = C
Me Z = CH3 – CHD – CHD – CH2 + CH3 – CHD – CH – CH3
(a)
Cl Cl
Me (I) (II)
Me Me
+ CH3 – CHD – CD – CH3
Me
Cl
Me ; Me (III)
(d) CH3 CH3
(c) –
23. (c) NaNH
H3C – C – C CH ¾¾¾¾®
2
H3C – C – C C
CH3 D
22. (b, d) X= CH3 CH3
C= C
D CH3 CH3
(I) CH I
¾¾¾®
3 H3C – C – C C – CH3
CH3
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345
24. (a, b, c, d) (I) and (II) represent cis and trans-1, 4-dimethyl- 70. (b) 71. (b) 72. (a)
cyclohexane and both posses a plane of symmetry. 73. (a) The rate is accelerated when diene is attached with electron
(III) represents cis-1, 3-dimethylcyclohexane and it also releasing and dienophile with electron withdrawing but here
possesses a plane of symmetry. in second case it is reserved. So, x > y.
(IV) represents trans-1, 3-dimethylcyclohexane and do not
possess a plane of symmetry. O O
(V) represents trans-1, 2-dimethylcyclohexane and has no
plane of symmetry.
(VI) represents cis-1, 2-dimethylcyclohexane. 74. (c)

H H O O
ˆˆ† 75. (b) Diels-Alder’s reaction is stereospecific because it takes
H ‡ˆˆ H
Me Me
place through concerted process.
Me Me VI (b)
VI (a) HOOC HOOC HOOC
Each structure [VI (a) and VI (b)] is chiral molecule, but or
they are interconvertible by a ring flip. Therefore although, HOOC HOOC HOOC
the two structures represent enantiomers, they cannot be cis cis
separated because they are interconvertible readily. So these 79. A - (p, s, t); B - (s); C - (p, r); D - (p, q)
simply represent different conformations of the same
compound. So, VI (a) and VI (b) are not configurational OCH3 OCH3 O
stereoisomers, they are conformational stereoisomers. This
means that at normal temperature, there are only three (A) Na in liq. NH H O+
¾¾¾¾¾¾¾
3® ¾¾¾¾
3 ®
isolable stereoisomers of 1, 2-dimethylcyclohexane. H 2O

+ CH3OH
H H (B) Birch reduction
CH3O H 2 /Ni
C º CH¾¾¾¾
64. (c) ® CH3O CH2 – CH3 CH2
Br Br Br
CH3 CH3 (C) + D Br aq. KOH
¾¾® ¾¾¾¾¾
®
(X) (Y) CH2

Ozonolysis

H OH OH OH O
+
H Å
CH3O COOH + HCOOH (D)
Å
OH
CH3 +
H
(W)
Å
Cl Å
OH OH O
H 2 /Ni Cl 2 / hv
¾¾¾¾® Cl
67. (d) ¾¾¾¾® + 80. A - (q, r, t); B - (p, r); C - (q, r, t); D - (r, s)
(A) trans-alkene (symmetrical + syn-hydroxylation) ®
(1) Racemic mix. of 1, 2-diol, having two chiral carbon.
(B) trans-alkene (symmetrical)¾¾¾¾¾¾¾¾ ® meso-
Cl Cl anti hydroxylation
O compound
+ (C) trans-alkene (symmetrical) ¾¾¾¾¾¾
® Racemic mixture
syn addition

Cl Cl (D) Bromohydrin formation having two chiral centres and so

CHO CHO (2), (3) isomers d + l + meso mixture of products are diastereomers.
W 84. This reaction is followed by anti Markonikoff rule
Sol. 70-72 H H H H H H H H
| | | | | | | |
Peroxide
NaNH / Liq.NH
CH3 - (CH2)3 - C º C- CH3 ¾¾¾¾¾¾¾¾
2 3® CH - (CH ) - C º CNa H - C - C - C = C + HBr ¾¾ ¾¾® H - C - C - C - C – Br
3 23
(X) (Y)
| | | | | | |
CH3 H H H H H H H
Li/ NH3(l) CH3 – CH – CH2 – Br 1 Butene 1 Bromo butane

H CH3 CH3(CH2)3 – C C – CH2 – CH– CH3 In this reaction anti Markonikoff’s addition is explained on
C= C CH3
the basis of the fact that is in the presence of peroxide the
C3H7 H addition takes place via a free radical mechanism.
(Z) O
85. The statement 1 that trans-2 butene reacts with Br2 to produce
CH3(CH2)3 – COOH +HOOC – CH2 – CH– CH3 meso-2, 3-dibromobutane is correct but it does not involve
CH3 syn-addition of Br2.
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86. (d) 94. 5

HBr
¾¾¾® + Major
35°C
Br product [Five]
P1 P2 2 2 1
Br
–
Br 95. 6
Å ¬¾®
H /hn Cl / hn
Å C ¾¾¾¾
2 ® C ¾¾¾¾
2 ®
More stable (a) (c)
carbocation (1) Cl
Peroxide CH2 – CH2Cl *
87. (c) CH 3 - CH = CH - CH 3 + HBr ¾¾¾¾¾¾¾¾¾¾ ® CH – CH3
free radical mechanism
O3
CH 3 - CH - CH 2 - CH 3 C + C
| CHO
Br ( ±) (1) d + l (2)
OHC C CHO + CH2O
Peroxide
CH 3 - CH = CH - CH 3 + HCl ¾¾¾¾¾¾¾®
Ionic mechanism CHO 4 moles
CH 3 - CH - CH 2 - CH 3 a = 1; b = 2; c = 3 Sum =1 2 3 = 6
| 96. 3
Cl (± )
CH3 CH3
88. (a) Alcoholic KOH causes E2 with CH3 – CH2 – Br whereas
aqueous KOH cause SN2. H D H D
89. (a) There is no necessary co-relation between the (R) and (S) H D H D
designation and the direction of rotation of plane polarised
light. Hence R-1-chloro-2-methylbutane may rotate the CH2 CH2
plane clockwise or anticlockwise. Mirror image
90. (b) H H Me H CH2 CH2
O O
Me Me Me H D D H
H
O O O O H D D H
(I) (II) and its enantiomer
CH3 CH3
91. (d) Peroxide effect is observed only with HBr not with HCl and
HI. 97. 6
.3 C C C
.1 | | |
C = C - C - C, C - C = C - C, C - C- C = C
92. 4
. C C C
4. 2 | | |
C - C - C º C, C = C - C = C, C-C =C =C
Cl Cl 98. 03
99. 3
93. 1 (a) =1 =4 CH 3 - CH 2 - CH 2 - CH - CH - CH 2 - CH 3
| |
Cl CH 3 CH 2 - CH 3
Cl 3-Ethyl-4-methylheptane

=2 =4 CH º C - CH 2 - CH - CH - CH 2 - CH 3
| |
CH 3 CH 2CH 3
Cl = 1 =2
Cl CH 3 - CH 2 - CH 2 - CH - CH - CH 2CH 3
| |
Br CH 3 C º CH
(b) ¾¾¾¾®
2
D aq.NaCl
CH 3 - C º C - CH - CH - CH 2 CH 3
| |
OH Cl Br CH 3 CH 2CH 3
+ + 100. 5.
D D D
The number of cyclic isomers for a hydrocarbon with molecular
Br Br Br formula C4H6 is 5.
Diastereomeric Diastereomeric Diastereomeric The structures are
pair pair pair CH3 CH2
Boiling points of diastereomers are different.
Now (A) = 14 (B) = 6 and
Then, (A + B) = 14 + 6 = 20 CH3
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EXERCISE 6.3
1. As the bromine molecule comes near p electron cloud of alkene, the unshared pair of electrons on the bromine atom near the double bond
is repelled because of electron-electron repulsion making this end of bromine molecule partially positive and the other end partially negative.
2. Removal of hydrogen takes place from the carbon carrying the fewer hydrogens. (i.e. poor becomes poorer).
3. The relative reactivity depends on the ability of HX to donate an H+ (i.e. acidity) to form R+ in the rate-controlling first step. The acidity
and reactivity order is HI > HBr > HCl.
4. Ag+ coordinates with the alkene by p–dp bonding to give an ion similar to a bromonium ion, but more soluble.
5. t-BuO– in dimethylsulphoxide is not solvated via hydrogen bonding and hence it is a much stronger base than the highly solvated OH –
in alcohol.
Ag+

C C

6. (a) (CH3)2C = CHCH3 + ICl ——® (CH3)2C(Cl)CH(I)CH3

d+ d-
Since Cl is more electronegative than I ; in I - Cl , I will add to the carbon that has more hydrogens.
(b) (CH3)2C = CH2 + HSCH3 ——® (CH3)2C(SCH3)CH3
d+ d–
Here H is less electronegative than S H—SCH 3 , thus it will add on the carbon atom having more hydrogen atoms.
(c) CH2 = CHCF3 + HCl ——® CH2Cl . CH2 . CF3
Note that the addition is anti-Markownikoff. This is due to the presence of strong electron-attracting, CF3 group which destabilizes
+
positive charge present on adjacent carbon in CH3 C HCF3, hence +CH2CH2CF3 (a 1° carbocation) is the intermediate rather than
+
CH3 C HCF3 (a 2° carbocation).
+ +
(d) Me 3 N CH = CH2 + HI ¾¾® Me3 N CH2CH2I
Here anti-Markovnikov’s addition is due to the presence of positive charge on N which destabilizes the carbocation having positive
+ + + +
charge on an adjacent carbon. [Thus a more stable carbocation, Me3 N CH2 C H2 will be formed than Me3 N C HCH3.]
7. (a) Here the reagent added seems to be HI, thus alkene should be (CH3)2C = CH2
(CH3)2C = CH2 + HI ——® (CH3)3CI
(b) Here the reagent added seems to be HBr and thus alkene is CH2 = CHBr
CH2 = CHBr + HBr ——® CH3CHBr2
(c) Here the reagent added may be BrCl and thus the alkene will be CH2 = CHCH3
d+ d–
CH 2 = CHCH 3 + Br Cl ——® CH 2BrCHClCH 3
Alternatively, the reagent added may be HBr and thus the alkene will be CH2 = CClCH3.
peroxide Mark.
anti-Mark. CH2 = CClCH 3 + HBr ———® CH 3C(Cl)(Br)CH 3
CH2BrCHClCH3 ¬————
addition
Alternatively, the reagent added may be HCl and thus the alkene will be CH2BrCH = CH2
CH2BrCH = CH2 + HCl ——® CH2Br . CHCl . CH3
d+ +
However, this possibility is discarded because in this case, the intermediate carbocation will be Br CH 2 CHCH3 which is less stable

d+ +
than Br CH 2 CH 2 CH 2 and thus here the reaction will lead to the formation of BrCH2CH2Cl rather than CH2Br.CHCl .CH3.
(d) Here the reagent may be HOCl and thus the alkene is BrCH2CH = CH2. Alternatively, the reagent may be HOBr and thus the alkene
will be CH2 = CHCH2Cl.
BrCH2CH = CH2 + HOCl ——® CH2Br . CHOH . CH2Cl
CH2 = CHCH2Cl + HOBr ——® CH2Br . CHOH . CH2Cl

CH3 CH3 CH3

+ + CH3 shift Å
H
..

8. (a) CH3CHOH—C—CH3 ——–® CH3CH—C—CH3 ——–—® CH3—CH—C—CH3

(– H2O)
CH3 CH3 CH3
2° carbocation 3° carbocation (more stable)

CH3 CH3
+
–H
——–® CH3—C = C—CH3 + CH3—CH—C = CH2
CH3 CH3
2, 3-Dimethylbutene-2 2, 3-Dimethylbutene-1
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HF Å (CH ) CH +
3 3
(b) H2C = CH2 ——® H 3C—CH2 ————® CH3CH3 + (CH3)3C

H CH3
+ + + : CH3 shift
: H shift ———–®
CH2 = CH2 + C(CH3)3 ——® CH2—CH—C(CH3)3 ———® CH3—CH—C—CH3
1° carbocation
CH3
2° carbocation

CH3 CH3
(CH3) 3CH + +
CH3—CH—C—CH3 ———–® CH3—CH—CH—CH3 + (CH3)3C

Ch3 CH3
3° carbocation

CH3 CH3 CH3

+ Å : CH3 shift Å –
H Cl
(c) CH2 = CH—C—CH3 ——® CH3CH—C—CH3 ¬——— ® CH3CH—C—CH3 ——®

CH3 CH3 CH3

2° carbocation 3°carbocation

Cl Cl
CH3—CH—C(CH3)3 + (CH3)2CH—C(CH3)2
3-Chloro-2, 2-dimethylbutane 2-Chloro-2, 3-dimethylbutane

CH3 OTs CH3 CH3

– Ots Å
rearranges
(d) CH3—CH—CH—CH2CH3 ——® CH3—CH—CH—CH2CH3 ————® CH3—C—CH2—CH2CH3
: H shift
Å
2° carbocation 3° carbocation
Å Å
–H –H

CH3 CH3 CH3

| | |
CH3—CH—CH = CHCH3 CH3—C = CHCH2CH3 CH2 = C—CH2—CH2CH3
4-Methyl-2-pentene, I 2-Methyl-1-pentene, III
2-Methyl-2-pentene, II
(Disubstituted alkene) (Trisubstituted alkene) (Disubstituted alkene)

The relative amount formed is in the order II > I > III

(e) 14 . 14 . . Br214 14 14
CH3CH = CH2 + Br ——® [ CH 2CH = CH2 ¬ —® CH2 = CHCH2] ——® Br CH2CH = CH2 + CH2 = CHCH 2Br
9. (i) The3° alcohol is formed by acid-catalysed hydration (by dil. aq. H2SO 4) of alkene A.
CH3 CH3 CH3 CH3 CH3 CH3

CH3—CH—CH = C—CH3 or CH3—CH—CH2—C = CH2 + dil. Aq H2SO4 ——® CH3—CH—CH2—C—CH3

(A) (B) OH
(ii) Addition of HOBr takes place by Markownikoff rule, i.e. the positive Br adds to the carbon having more hydrogen. Further,
addition is anti, hence Br will be trans to OH but cis to CH3.

Br H3C

H OH
(racemic) (C)

Br
Hot Cold
(iii) COOH KMnO4 KMnO4 (iv)
(E)
OH OH (D) (F)

– +
Hg(OAc )2 –H NaBH4
¾¾ ¾ ®
(v) OH H2C— O O
| +
OH Hg2+ Hg
(G) (H)
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349
10. The order of dehydration of alcohols is 3° > 2° > 1°.

OH OH
(a) (b) (c)
OH
11. Reactivity of alkyl halide towards dehydrohalogenation depends upon the stability of the alkene formed (more substituted is an alkene,
more will be its stability).
Br Br

(a) Br
Br
Br

(b) Br
Br

Br
(c) Br Br, Br
(No reaction)
12. Although neopentyl alcohol has no a—H atom, yet it easily undergoes dehydration because 1° carbocation formed rearranges to the more
stable 3° carbocation which has a—H atom(s), hence undergoes dehydration.
CH3 CH3
+ Å : CH3 shift Å +
H H
CH3—C—CH2OH ——® CH3—C—CH2 ——— —® CH3—C—CH2CH3 ——® CH2 = C—CH2CH3 + CH3—C = CH.CH3

CH3 CH3 CH3 CH3 CH3

1° carbocation 3° carbocation (Minor) Major (more substituted)
13. Yes, heat of combustion of an alkene provides a direct measure of the stability of an alkene. More stable an alkene is, less will be its energy
content and thus heat of combustion. Now we know that more highly branched alkene is more stable (Saytzeff rule), further among cis,
trans-isomers, latter is more stable because of less crowding and less vander Waals strain. Thus the value of heat of combustion
corresponds with the three alkenes as below :
CH3 H CH3 C2H5
C=C C=C
H C2H5 H H CH2 = CHCH2CH2CH3
trans-2-Pentene cis-2-Pentene Pentene-1
(804.3 kcal) (805.3 kcal) (806.9 kcal)

E
+ + +
14. CH3CH = CH—CH = CHCH 3 ——® CH3CH—CH—CH = CHCH3 + CH3 —CH—CH—CH = CHCH 3

E E
(More stable allylic type)

OH
+ +
H H2O H
15. Yes. CH3CH2CH2CH2OH ——® CH3CH2CH = CH2 — ————® CH3CH2CHCH3 ——® CH3CH = CHCH3
(dil. H2SO4)
Butanol-1 2-Butene
16. No reaction will take place : (a) dichloroethylene in deactivated towards electrophilic addition due to presence of four chlorine atoms, (b)
free radicals are not formed in dark and thus free radical addition reaction does not occur.
17. Head-to-tail arrangement of the monomer units is due to the fact that 2° radicals are formed faster in every step rather than a 1° radical.
For example,
. . .
Rad—CH2—CH—CH—CH2 ¬ —– Rad—CH2—CH + CH2 = CH —–® Rad—CH2—CH—CH2—CH
G G G G G G
1° Radical (less stable) 2° Radical Monomer 2° Radical more stable
(leading tail-to-tail arrangement) (leading to head-to-tail arrangement)
18. Addition of H2SO 4 on alkenes is an electrophilic addition reaction. Reactivity of alkenes towards addition of acids is governed by the
following facts.
(i) Alkene capable of forming 3° carbocation will be more reactive than that which forms 2° carbocation which in turn will be more
reactive than that which forms 1°carbocation.
(ii) An electron-withdrawing group intensifies the positive charge on the carbocation and will thus destabilise it. Hence its presence will
slow down the formation of carbocation and will thus decrease the reactivity of alkenes towards electrophilic additions. On the
other hand, presence of electron-pushing group will facilitate electrophilic additions. Therefore,
(a) CH3CH = CH2 > CH2 = CH2 (b) CH3CH = CHCH3 > CH3CH = CH2
Propylene Ethylene 2-Butene Propylene
(2° carbocation) (1° carbocation) (two + I groups) (one + I group)
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CH3 CH3
(c) C = CH2 > CH3CH = CHCH3 (d) CH2 = CCH2CH3 > CH2 = CHCH2CH2CH3
CH3 2-Methyl-1-butene 1-Pentene
Isobutene 2-Butene (3° carbocation) (2° carbocation)
(3° carbocation) (2° carbocation)
(e) CH2 = CH2 > CH2 = CHCl (f) CH2 = CHCl > CHCl = CHCl
Ethylene Vinyl chloride Vinyl chloride 1, 2-Dichloroethylene
(– I group) (one –I group) (two – I groups)

(g) CH2 = CH2 > CH2 = CHCOOH (h) CH3CH = CH2 > F3CCH = CH 2
Ethylene Acrylic acid Propylene 3, 3, 3-Trifluoropropene
(– I group) (+ I group) (– I group)

Cl
+ + –
H Cl
19. CH3CH = CHCH3 ——® CH3CHCH2CH3 ——® CH3CHCH2CH3
–—®

C2H5OH
+
–H
CH3CHCH2CH3 ——® CH3CHCH2CH3
+
HOC2H5 OC2H5
(C6H14O)

CH2 O

ozonolysis
20. CH3CH2CH = CHCH2CH3 —— —–—® 2CH3CH2CHO ; + CH2O
(A) (B)

CH3 CH3
(CH3)2C = C—CH = C(CH3)2 ——® 2(CH3)2CO + CH3COCHO ; º CH3COCH2CH2CH2CH2CHO
(C) O
(D)
CHO
CHO
CH3CH = CH CH 2 CH = CH2 ——® CH3CHO + OHCCH2CHO + CH2O ;
(E) CHO
(F)

Br D H Br Br H
21. (a) C—C H + C—C (b) C—C—D
D D D D
H Br Br H H Br
meso
racemic mixture

22. C6H5CH = CH—CH = CH2 + Br2 ——® C6H5CH—CH—CH = CH2 + C6H5CH—CH = CH—CH2 + C6H5CH = CH—CH—CH2

Br Br Br Br Br Br
(A)
(B) (C) (Most stable)
23. Reaction of chlorine in dark, at low temperature and in absence of peroxides should be ionic. This reaction involves electrophilic addition
followed by E1 elimination.

CH3 CH3 CH3

+
–H
CH3—C = CH2 + Cl2 ——® CH3—C—CH2Cl ——® CH2 = C—CH2Cl
Å
3° carbocation Methallyl chloride
(Open carbocation is
shown only for simplicity)

Note that here the second step is elimination rather than addition. It is due to high stability of 3° carbocation which is less reactive towards
Cl–, and more prone to lose one of six hydrogens to form the branched alkene.
24. Let us take the case of propene
Å Å
Br OH2
3 2 1 – : OH2
Br
CH3CH = CH2 ——® CH3® –CH—CH2 ——® CH3CH—CH2Br
Note the possibility of the dispersal of positive charge on C2 due to presence of electron-pushing —CH3 group on the adjacent carbon
atom.
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Now let us take the case of allyl bromide
Å
Br Br
3 2 1 Å
..
Br H2O +
BrCH2—CH = CH2 ——® Br—CH2–¬ CH—CH2 ——® Br—CH2—CH—CH2OH2
Note that here positive charge on C 2 will be intensified due to the presence of electron-withdrawing —CH2Br group on the
adjacent carbon atom and hence the corresponding intermediate will be less stable. Thus positive charge is more likely to be developed
on C1 and the product formed will be BrCH2CHBr . CH2OH.
25. n-Butyl-tert-butyl ether dissolves in cold conc. H2SO 4 due to the formation of oxonium salt. However, on standing it decomposes to form
isobutene which undergoes polymerisation in presence of acid forming polyisobutene.
H
+ + +
H –H
n–C4H9—O—CMe3 ——® n–C4H9—O—CMe3 ——® n–C4H9OH + (CH3)3C ——® (CH3)2C = CH2
+

CH3 CH3 CH3

+
H
(CH3)2C = CH2 ——® CH3—C—CH2—C—CH2—C—
Isobutene
CH3 CH3 CH3

Polyisobutene

26. (i) Alc. KOH

¾¾ ¾ ¾ ® + +
Br (–HBr)

Major (Minor) (Minor)

(More substituted)

(ii) Reaction of Br2 with cyclohexene at 300°C proceeds through free radical bromination. However, cyclohexene has three types of
hydrogen atoms (allylic, alkyl a vinylic type), whose order of reactivity is allylic > alkyl > vinylic. Thus allylic bromination will be
the main reaction.
Allylic H’s
Alkyl H’s Br
Vinylic H
Br , 300°C
¾ ¾2¾ ¾ ¾ ®

COOH
H—C—COOH Syn- H—C—D
(iii) + D2 ———–®
addition
H—C—COOH H—C—D
Maleic acid
(cis-isomer) COOH
meso

(iv) Hydroxylation by alk. KMnO4 and HCO3H takes place in syn and anti manner respectively. Thus
CH3 CH3 CH3
CH3—C—H
H OH HO H alk HCO3H H OH
+ ———®
anti-
———®
HO H H OH KMnO4 H—C—C2H5 H OH
(syn-addition) addition
trans-isomer
C2H5 C2H5 C2H5
(B) racemic mixture (A) meso

– H2O
27. (i) (CH3)2CH . CHOH . CH3 ——–® (CH3)2C = CHCH3 + (CH3)2CHCH = CH2
(Major) (Minor)

OH CH3
– H2O
(ii) (CH3)2C—CH(CH3)2 ——–® (CH3)2C = C(CH3)2 + CH2 = C—CH(CH3)2
(Major) (Minor)

OH OH
–H2O –H2O
(iii) ¾ ¾¾ ® + ; (iv) ¾¾ ¾ ® +

(Major) (Major)
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CH2OH

(v) ¾¾ ® + +
I II III
Formation of II and III
+
CH2OH CH2
H +
+ – +
( i) H : H shift –H
¾¾ ¾¾® ¾¾ ¾¾® ¾¾ ®
(ii) –H2O

¾¾®
II
alkyl shift

Å –H
+

¾¾ ®

III

Å
CH3 CH3 CH2 CH2CH3 CH2CH3 CH—CH3
CH2OH
Å
+ +
(i) H methyl –H
(vi) ¾¾ ¾¾® ¾¾¾¾® ¾¾ ® +
(ii ) –H2O shift
1° carbocation 3° carbocation Both alkenes are trisubstituted

CD2

OH CD3 CD3 (Minor)

+
Å
+ –D
(i) H CD3
(vii) ¾¾ ¾¾®
(ii ) –H2O
–H +

(Major)

Remember that the C—H cleavage is nearly seven times faster than the C—D cleavage, hence product corresponding to elimination
of H+ will predominate than that which involves elimination of D+.

HO CH2CH3 CH2CH3 CHCH3

D D D Å D D D
+
(viii) (i) H –H
+
¾¾ ¾® ¾¾ ¾®
D (ii ) –H2O D D
(Major)
¾®

CHCH3 CH2CH3 CH2CH3

D D D D D

+ +
D D

28. Hot KMnO4 oxidises = CH2 to CO2

O

KMnO4
(i) ¾¾ ¾® + CO2 + CH3COOH
Heat
COOH
OH
KMnO4
(ii) ¾¾ ¾ ® +
[A]
Heat O O
(iii) The more substituted double bond is more nucleophilic and hence it will react faster with peroxy acids than the less substituted
double bond.
O

C6H5CO3H
¾ ¾ ¾ ¾ ¾¾ ¾®
CHCl3 at 25°C
(B)
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353

–
(i) BD3, THF (ii) H O /OH
(iv) 2 2
¾ ¾ ¾¾ ¾¾ ¾ ¾¾ ¾ ¾¾ ¾® (v) + : CClBr ¾ ¾® +
(anti -Mark. hydration) D
OH C C
(C)
Br Cl Cl Br
(vi) Join the two carbon atoms of the group.

¾¾ ®

O [D]

(vii) Ozonolysis is done in absence of zinc dust, hence the aldehyde formed will be oxidised to acids.
H OH

(i) O3 oxi
¾¾ ¾® 2 O ¾¾ ® O
(ii ) H2O

(E)
1, 2-Dicyclopentyl ethylene

CH3 CH3 CH3 CH3 CH3

29. (a) dimeri-
2CH3—C = CH2 ——–®
sation CH3—C—CH2—C = CH2 + CH3—C—CH = C—CH3
Isobutene
CH3 CH3

Ozonolysis
(b) or ¾¾ ¾¾¾ ® 2
O
cis-2-Butane trans-2-Butene Ethanal
30. We know that lesser is the heat of combustion of a compound, more will be its stability. Thus the more stable isomer in the various pairs
will have less heat of combustion.
(i) trans-2-Butene (ii) trans-2-hexene (iii) 2, 5-Dimethylhexane.
Cl Cl

mono- (Abstraction of allylic H)

31. (i) ————–® (Abstraction of 3° H) (ii) ——®
chlorimation

Cl

(iii) ——® (Abstraction of 3° H)

Cl
(iv) ——® (Abstraction of 3° H)

+ +
–
+
H H Å –H
32. Å Å ———® ——®

– Å
33. Presence of four chlorine atoms decreases considerably the electron density of the two olefinic carbon atoms ; hence weak electrophile
(Cl2) can add only when it can produce Cl+ ion easily which happens in presence of AlCl3.
Cl Cl
C=C
Cl Cl
AlCl3 + Cl2 ——® AlCl4– + Cl+
–
+ + AlCl
Cl2C = CCl2 + Cl ——® Cl2 C—CCl3 ——–4® Cl3C—CCl3
34. (a) (i) 1, 2-Propadiene (ii) 5-Ethyl-1, 4, 6-octatriene
2 4 6
(b) (i) 1 3 5 C1 to C4 = sp 2 ; C 5 and C6 = sp
2 4
(ii) 1 3 5 C1 and C5 = sp 3 ; C2 and C4 = sp 2, C3 = sp

(iii) C1, C3, C4 and C5 = sp 2 , C2, C7 and C8 = sp ; C6 = sp 3.

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+
H
35. CH2 = CH—CH2—CHOH—CH3 ———® CH2 = CH—CH = CH—CH3 + CH2 = CH—CH2—CH = CH2
(—H2O)
1, 3-Pentadiene (major) 1, 4-Pentadiene (minor)
Although 1, 3-pentadiene is less substituted, it will be major product because it is a conjugated diene (possibility of resonance).
1, 4-Pentadiene is although more substituted, it is an isolated diene, hence resonance is not possible.
CH3
CH3 BrCH2—C—CH = CH2
Å
allylic 3° carbocation (more stable)
36. CH2 = C—CH = CH2
Å
CH2 = C—CH—CH2Cl
CH3
allylic 2° carbocation (less stable)

CH3 CH3 CH3

–
Br
BrCH2—C CH CH2 ——® BrCH2—C—CH = CH2 + BrCH2—C = CH—CH2Br
Å Br
37. (a) In the first step, Br+ adds at C1 to form a 2° allylic type of carbocation, whose positive charge can delocalize on C 2, C4 and C6
forming three corresponding products (I, II and III) during attack of Br – at the second stage. However, a fourth product (IV) is also
possible due to addition of Br2 on C3 and C4.

1 2 3 4 5 6 Å +
Br
CH2 = CH—CH = CH—CH = CH2 ——® [BrCH2—CH—CH = CH—CH = CH2
+ +
¬ —® BrCH2—CH = CH—CH—CH = CH2 ¬—® BrCH2—CH = CH—CH = CH—CH2]
–
Br
——® CH2—CH—CH = CH—CH = CH2 + CH2—CH = CH—CH—CH = CH2
Br Br Br Br
I II
+ CH2—CH = CH—CH = CH—CH2 ; CH2 = CH—CH—CH—CH = CH2
Br Br Br Br
III IV

(b) Thermodynamic-controlled conditions favour the most stable product. Among the four products, I and III are conjugated dienes
and hence more stable than the isolated dienes II and III. Further, III is more stable than I because its doubly bonded carbon atoms
are more substituted.
+ +
38. (a) CH2 = CH—CH = CH—CH = CH—CH2 ¬ —® CH2 = CH—CH = CH—CH—CH = CH2
I II
+
¬ —® CH2—CH = CH—CH = CH—CH = CH2
III
(b) Thermodynamically-controlled product is the more stable product, which will be formed by the attack of Nu– on III or I (same).
Å –
Nu
CH2—CH = CH—CH = CH—CH = CH2 ——® CH2—CH = CH—CH = CH—CH = CH2
III
Nu Conjugated triene
Products from canonical structure II will be a triene with 2 conjugated double bonds.
39. Reactivity of alkenes towards HBr is determined on the basis of relative stability of the intermediate carbocation. The more stable a
carbocation, more easily it is formed and hence more will be the reactivity of the alkene from which it is derived.
Conjugated dienes form the more stable allyl carbonium ions and hence they are more reactive than alkenes. Further, presence of alkyl
group(s) on the unsaturated carbons increases reactivity because of the formation of the more stable (3° > 2° > 1°) carbocation and/or
because of charge dispersal by + I alkyl groups.
Structures of the intermediate carbocations formed by different alkenes are drawn below.
+ + + +
CH3—CH—CH2CH3 or CH3—CH2—CH—CH3 ; CH3—CH—CH2CH3 or CH2—CH2—CH2CH3
2° carbocation 2° carbocation 2° carbocation 1° carbocation
From I From II

CH3 CH3 CH3

+ + + +
CH3—CH—CH = CH2 or CH2—CH2—CH = CH2 ; CH3—C—–C = CH2 or CH2—CH—C = CH2
allylic 2° carbocation 1° carbocation allylic 3° carbocation 1° carbocation
with —CH3 group
From III From IV
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355
+ +
CH3—CH2—CH—CH = CH2 or CH3—CH—CH2—CH = CH2
allylic 2° carbocation with 2° carbocation
—C2H5 group (more + I effect)
From V
We know that order of stability of the carbocations is allylic 3° > allylic 2° with —C 2H5 group > allylic 2° with —CH3 group > 2°
carbocation > 1° carbocation. Thus the reactivity of alkenes is
IV > V > III > I > II
Hcl
40. (a) CH2 = CH—CH = CH2 ——® CH3 . CHCl . CH = CH2 + CH3 . CH = CH . CH2Cl
1, 2-Adduct 1, 4-Adduct

H
+ Å Cl
–
(b) (i) CH3CHClCH = CH2 ——® CH3CHClCHCH3 ——® CH3CHClCHClCH3
2° carbocation
+ + –
H Cl
(ii) CH3CH = CHCH2Cl ——® CH3—CHCH2CH2Cl ——® CH3CHClCH2CH2Cl
——®

+ 2° carbocation I
H
+
CH3CH2CHCH2Cl
2° carbocation II (unstable)
In (ii) case, carbocation I is more likely to be formed because the positive charge is farther from the electron-withdrawing —Cl ;
while in carbocation II the positive charge is present near to carbon having —Cl leading to intensification of the positive charge which
leads to unstability of the carbocation.
1
2 4 6 8 + 6 8 8
+
1 3 5 7 H 1 2 4 7 2 7
41. ——® 5 Cyclization 3 6 Å –H
+
3 ——— —————® ——®
2 6
3° cation involving C and C 4 5
3° cation
This reaction is analogous to acid-catalysed dimerization of alkenes. Since both of the double bonds (of two alkene molecules in
dimerization) are present in the same molecule, reaction leads to cyclization.
42. In the molecule of 1, 2-propadiene (allene), the central carbon atom is sp hybridised while the H
terminal carbon atoms aresp 2 hybridized. The central carbon atom forms a s-bond with each of the H
2
terminal sp hybridized carbon atom. The remaining two p-orbitals of the central carbon atom form
two p-bonds by sideways overlapping with the p-orbitals of the terminal carbons. C C C
Since the two p orbtials of the central carbon are directed at right angles to each other, the two MO’s
(or the two p bonds) will be at right angles to each other. The two hydrogens on C 1 are in a plane at H H
right angles to the plane of the two hydrogens on C 3.
Because there is no free rotation about the two p bonds, the two hydrogens on each of the two terminal carbon atoms have a fixed spatial
relationship.

Thus when the two substituents on each of the two terminal carbon atoms of allene are C C
different as in 2, 3-pentadiene (CH3CH = C = CHCH3), the molecule lacks symmetry and
will be chiral. C C

Molecular orbital picture of 1, 3-butadiene. Each carbon in butadiene is sp 2 hybridized and forms three sigma bonds. The terminal
carbons forming two sp 2-s bonds with hydrogen and sp 2-sp 2 bond with carbon ; while the middle carbon atoms form two sp 2-sp 2 bonds
with adjacent carbons and one sp 2-s bond with hydrogen. Thus each carbon atom of butadiene has one unhybridized p orbital, each
containing one electron. Thus the four p-orbitals of butadiene are adjacent and parallel and overlap to form an extended p system
involving all the four carbon atoms. This results in greater stability and decreased energy.
43. No. Reactivity depends on the relative values of energy of activation. Although the ground state enthalpy for the conjugated diene is
lower than that of the isolated dienes, the transition-state enthalpy for conjugated system is lower by a greater amount.
Eact for conjugated < Eact for isolated and rateconjugated > rateisolated

Br
+ Å
44. CH2 = CH—CH = CH—CH = CH2 ——® CH2—CH—CH = CH—CH = CH2
1, 3-Hexadiene Br Doubly allylic cation
Å Å
¬ —® CH2—CH = CH—CH—CH = CH2 ¬ —® CH2—CH = CH—CH = CH—CH2

Br Br
–
Br
º CH2—CH CH CH CH CH2 ——® CH2—CH—CH = CH—CH = CH2
Br – Br Br
Resonance hybrid of doubly allylic cation 5, 6-Dibromo-1, 3-hexadiene
(conjugated diene)
+ CH2—CH = CH—CH—CH = CH2 + CH2—CH = CH—CH = CH—CH2
Br Br Br Br
3, 6-Dibromo-1, 4-hexadiene 1, 6-Dibromo-2, 4-hexadiene
(Not formed, Isolated diene) (conjugated diene)
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45. Increasing order of stability of the dehydrobrominated products will be

> >
Conjugated triene Conjugated diene Simple alkene
\ Order of the dehydrobromination of the parent compounds will be
Br Br Br
> >

Cl Cl
H
+
Cl Å –
HCl
46. (CH3)3C—C º CH ——® (CH3)3C—C = CH2 ——® (CH3)3C—C = CH2 ——® (CH3)3C—C—CH3
3, 3-Dimethyl-1-butyne Vinylic cation
Cl
2, 2-Dichloro-3,
—–®

methyl shift 3-dimethylbutane

CH3 CH3 CH3 CH3 CH3 CH3

–
Cl HCl
CH3—C C CH2 ——® CH 3—C == C—CH2Cl ——® CH3—C—–C—CH2Cl
Å Cl
Allylic cation 1, 3-Dichloro-2, 3-dimethylbutane
(The addition of HCl is controlled
——®

–
Cl by the – I effect of chlorine, already
present in the molecule)
CH3 CH3 CH3 CH3
HCl
CH3—C—–C = CH2 ——® CH3—C—–C—CH3
Cl Cl Cl
2, 3-Dichloro-2,
3-dimethylbutane

47. Bond length becomes shorter with the increase in s character of the carbon involved in bond formation, thus relative C—C bond lengths
should decrease in the order
H 3C—CH 3 > H2C = CH—CH = CH2 > HC º C—C º CH
sp
3
sp 3 sp
2
sp
2
sp
2 2
sp sp sp sp sp

48. (i)

(ii)
49. (i) 2-Butyne to meso-2, 3-dibromobutane. The principle reactions involved are

Since addition of Br2 to alkenes is anti, for obtaining meso-2, 3-dibromobutane we must take trans-alkene which in turn can be
obtained by the reduction of alkyne with sodium in liquid ammonia.

(ii) 2-Butyne to racemic-3-chloro-2-butanol. Since halohydrin formation is anti, for obtaining racemic product we must take cis-alkene
which in turn is obtained by the partial reduction of alkyne with hydrogen in presence of Lindlar catalyst. Thus the necessary
reactions will be
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(iii) 2-Butyne to meso-2, 3-butanediol. It can be achieved in two ways.

(a)

(b)

(iv) 2-Butyne to racemic-2, 3-butanediol. It can also be achieved in two ways.

(a)

(b)

50. (i) 2-Pentyne takes up two moles of H2, while 2-pentene takes only one mole to form fully saturated compound.
(ii) Only 1-pentyne (a terminal alkyne) gives precipitate with ammonical silver nitrate, while 2-pentyne (a non-terminal alkyne) does
not do so.
(iii) 1, 3-Pentadiene and 2-pentyne can be distinguished by their ozonolysis followed by identification of products :

(iv) 2-Hexyne gives positive test with Br2—CCl4 solution and Baeyer’s test ; isopropyl alcohol is oxidised by chromic anhydride CrO 3,
in aqueous sulphuric acid within two seconds (clear orange solution turns blue-green and finally becomes opaque).

51. (i) Remember that addition of BH3 to alkynes takes place in syn manner to form cis-isomer (cis-trivinylborane) which on hydrolysis
with CH3COOH gives cis-alkenes. Further, one hydrogen (or deuterium) is added at each step so in both cases product will be
same, i.e.

A =B =

(ii)
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CH3
CH3 H H Br
( i) 2NaNH2 Na/C2H5OH Br2
(iii) HC º CH ————® CH3C º CCH3 —————–® C=C ————–®
anti-addition H Br
(ii ) 2CH3Br (anti -reduction)
(D)
H CH3
trans-(E) CH3
meso-(F)

(iv)

(v) I and J are mixtures of CH3CH2COOH and (COOH)2.

52. (a)

(b) The linear structural unit with sp hybridised carbon atoms can’t be bridged with only two carbon atoms, i.e. —C—C º C—C—
group can’t form cyclic compound having a bridge of two carbon atoms and hence following structure is not feasible.

The lowest stable cycloalkyne is cyclooctyne.

53. Formation of 2 moles of CH3COOH indicates the presence of two º CCH3 groupings, while formation of glutaric acid indicates the
presence of º C—(CH2)3—C º grouping. Thus the alkyne is

54. (i) Formation of methanoic acid (HCOOH) suggests the presence of º CH grouping.
(ii) Formation of an aldehyde (pentanal, CH3(CH2)3CHO) indicates the presence of an olefinic linkage having CH3(CH2)3CH =
grouping.
(iii) Formation of 4-oxopentanoic acid indicates the presence of a grouping having C = C as well as C º C ; the grouping should be =
C(CH3)CH2CH2C º .
Thus the hydrocarbon should have the following structure

55. (a) Smallest alkyne that can show geometrical isomerism should have H, CH3, H and HC º C— groups on the two doubly bonded
carbon atoms, arranged in the manner given below.
H
H H
C=C HC º C—C—CH3
HC º C CH3 C2H5
The smallest alkyne than can show optical isomerism should have H, CH 3, C2H5 and C º CH groupings around the central carbon
atom.
(b) Non-terminal alkynes (RC º CR) give stereospecific products on reduction, alkynes having acetylenic hydrogen on reduction gives
only one product.

(c) Symmetrical alkynes give same ketone either on oxidative hydroboration or on hydration.

56. (i) Acetylene is a very weak acid (pKa = 25) and hence only on extremely strong base like amide ion (NH2–) can successfully
remove a proton. Alternatively,

As the products are stronger base and stronger acid, the reaction is not feasible.
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(ii) The carbon nuclei in C º C are shielded by 6 electrons (from 3 bonds) rather than by 4 or 2 electrons as in C = C and C—C,
respectively. With more shielding electrons present, the carbon atoms of –C º C— can get closer, thereby affording more orbital
overlap and stronger bonds. Alternatively, this can be explained on the basis of hybrid orbitals.
(iii) Bond energy is a measure of homolytic cleavage,
Acidity is do to heterolytic cleavage,
(iv) HC º C – is the conjugate base of the acid HC º CH, while H2C = CH– is the conjugate base of the acid CH2 = CH2. Since HC º CH
is stronger acid (due to sp hybridised carbon) than H2C = CH2 (due to sp 2 hybridised carbon), a stronger acid always has weak base
and vice-versa.
(v) The low reactivity of alkynes towards electrophilic addition reactions is
believed to be due to following two factors.
(a) The bridged intermediate cation formed by the initial attack of
electrophile on the triple bond is less stable because it is a highly strained
system.
Due to formation of cyclic intermediate carbocation, the olefinic
intermediate products would invariably be trans.
(b) In acetylenic carbon atoms, the p electrons are more tightly held by the carbon nuclei and hence they are less easily available
for reaction with electrophiles.
57. Catalytic hydrogenation of alkynes takes place in cis manner.

58. Molecular formula C6H10 corresponds to alkynes (CnH2n–2). C º C is confirmed by the fact that it takes 2 moles of hydrogen to form fully
saturated compound. Its non reactivity towards ammonical silver nitrate indicates that the alkyne is non-terminal, i.e. no acetylenic
hydrogen is present. Formation of 2-methylpentane on hydrogenation suggests the following carbon-framework.

59. Since the compound A with molecular formula C6H12 is optically active, its four substituents should be different. Further, compound A
on hydrogenation absorbs a molecule of hydrogen to form optically inactive compound B, one of the substituents of A should be
unsaturated analogue of the other fully saturated, viz. —CH = CH2 and —CH2—CH3. Thus the four substituents in A should be H, CH3,
—CH2CH3 and —CH = CH2. Hence structure A and B will be as below :

Preparation of A from its corresponding bromide.

[B]
60. Since the hydrocarbon takes up a molecule of hydrogen to form n-butane, it should be butene-1 or butene-2. However, only butene-2,
being symmetric, can be obtained by the electrolysis of the potassium salt of a dicarboxylic acid.

61. The hydrocarbon, C10H16 contains 10 carbon atoms, but the total number of carbon atoms in the three products is only nine, the missing
carbon atom must be found in a second molecule of HCHO. Hence number of molecules of ozonolysis products must be four which agrees
with the presence of three double bonds (cleavage at three places gives four products). Hence hydrocarbon must have following structure.
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8.40 ml 10.02 mg
62. m moles of H2 absorbed = m moles of compound »
22.4 ml/m mole 80 mg/m mole
m moles of H 2 absorbed 8.40/22.4
Degree of unsaturation = m moles of the compound = =3
10.02/80
Thus the hydrocarbon contains either three double bonds or one double bond and one triple bond. It is interesting to note that the
ozonolysis products (HCHO and OHCCHO) contains only three carbon atoms which can’t account the molecular weight (80—85) of the
compound, it indicates that the original compound should have six carbon atoms (6 × 12 = 72) which in turn indicates that two moles
of each ozonolysis product are obtained per mole of hydrocarbon. Thus the hydrocarbon should have following structure (recall that
formation of HCHO indicates the presence of terminal = CH2 grouping).
H2C = CH—CH = CH—CH = CH2
1, 3, 5-Hexatriene
63. Determination of empirical formula of A and B.
For A For B
Element C H C H
Percentage 87.2 12.8 84.1 15.9
87.2 12.8 84.1 15.9
Mole % = 7.27 = 12.8 =7 = 15.9
12 1 12 1
7.27 12.8 7 15.9
Ratio =1 = 1.76 =1 = 2.27
7.27 7.27 7 7
Simple ratio 1×4=4 1.76 × 4 = 7 1×4=4 2.27 × 4 = 9
Empirical formula C4H7 C4H9

Note that the ozonolysis products have 2 + 3 + 3 = 8 carbon atoms, so the molecular formula of A should be (C 4H7)2 = C8H14 and hence
for B, it should be C8H18. The difference in the molecular formulae of A and B indicates the presence of two C = C double bonds in A. We
know that the precursor of the carboxylic acids is aldehydes, so the three initial ozonolysis products of A should be
CH3CHO, CH3COCH3 and CH3COCHO
(precursor of CH3COOH) (precursor of pyruvic acid)
Hence, compound A which can explain the formation of the above compounds on ozonolysis should be

64. Since the compound A (hydrocarbon) absorbs only one mole of hydrogen to form n-hexane it must be n-hexene. The position of double
bond in n-hexene is established by its oxidation to a single C3 carboxylic acid which is possible only when the double bond is present in
the middle of the chain to give two moles of the same C3 carboxylic acid. Thus n-hexene must be hexene-3.

65. Since the hydrocarbon (A) adds one mole of bromine to form dibromo compound C5H10Br2, it has one double bond which is further confirmed
by its reaction with dilute alkaline KMnO4 (Baeyer’s reagent) to form C5H12O2 (hydroxylation, introduction of two —OH groups).
Since the hydrocarbon C5H10 (A) on ozonolysis gives equal amounts of propanone (CH3COCH3) and ethanal (CH3CHO), it must have
following structure.

66. For this type of problem, students are advised to summarise the whole problem in the form of reaction

Let us draw some conclusions from the above set of reactions.

(i) The molecular formula C5H10 (CnH2n) for A indicates that it is an alkene having one double bond.
(ii) Since the alcohol C on oxidiation gives a ketone D, C must be a secondary alcohol and henceB must be a secondary bromide.
(iii) The structure of 2-methylbutane, the hydrogenated product of A, indicates that the
secondary bromide must have following structure.
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361
(iv) Thus the corresponding olefin A must have structure A which on Markownikoff addition of HBr gives the bromide B, the other
possible alkene A’ will not give B when HBr is added on it according to Markownikoff rule.

Thus the reactions involved can be represented as below :

67. Possible structure for (G), the lowest molecular weight hydrocarbon containing only 1 chiral carbon atom will be that in which the central
(chiral) carbon atom has one H, one CH3, one C2H5 and one C3H7 group, i.e.,

Note that none of the alkenes gives acetone on ozonolysis. So the possibility of isopropyl group in (G) in place of n-propyl is discarded.
The possible six different alkenes capable of giving (G) on addition of one mole of hydrogen may thus be written by inserting one double
in the structure of (G) at different positions.

Alkene capable of giving a ketone containing more than five carbon atoms on treatment with a warm conc. alkaline KMnO 4 solution is
(C).

The possible Fisher projection of (G) are

68. (a) Four stereoisomers are possible

OH OH
CH3 (CH2)5 – C – CH2 CH3 (CH2)5 – C – CH2
(CH2)7COOH H
H C=C + Enantiomer ; C=C
H H H H (CH2)7COOH + Enantiomer
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(b) It will rotate the plane polarized light because the molecule although does not have any chiral center, it is chiral.

H H H (CH = CH)2CH2 COOH

C=C=C C=C=C
(CH = CH)2CH2COOH H
HC º C – C º C HC º C – C º C

Enantiomers

CH3 CH3

H2 / Pt
69. HC º C H CH3CH2 H

CH2CH3 CH2CH3
or its enantiomer optically inactive
[A] [B]

2H
70. Pheromone, ¾¾¾
2®
HO
C13H24O Pt

O O
HO HO + O +
O
H H
Pheromone

71.
[A] [B] [C] [D]

H3 C H3C Br H3C CH3

HBr
72. +
CH2
Br Br CH3 Br Br
Optically active meso (optically inactive)
(+) - or (–) - [A]
[B] [C]

Me3COK Me3COK

Br H3C H3C CH3

+ +
H2C CH2 CH2 H2C
CH3 Br Br Br

Both are same, [A] Different (±) – A

H3C
Me3COK
+ 2CH2O
CH2 H2C CH2 O O
Br
(+) - or (–) - [A] [D]
73. (a) - (A) endo; (b)- (A) - trans; (c) - (B) - Tetrasubstituted.
CH3 CH3 CH3 CH3
+
74. CH3 – C+ – C – CH3 CH3 – C – C – CH3 CH3 – C – C – CH3
OH CH3 :OH CH3 +OH
:

more stable protonated

carbonyl group

75. (a) CH3CH = CHCl CH3C(Cl) = CH2 CH2Cl CH = CH2 Cl

cis- / trans-
(b) It has 5º of saturation, one p bond is present, so four rings must be present.
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7.1 Introduction 7.10 Theory of Orientation and Carbocation Stability

7.2 Methods of Preparation of Benzene 7.11 Methods of Preparation of Alkylbenzenes
7.3 Reactions of Benzene 7.12 Reactions of Alkylbenzenes
7.4 Structure of Benzene 7.13 Alkenylbenzenes
7.5 Concept of Aromatic Character (Aromaticity) 7.14 Tests of Arenes
7.7 Role of Inductive and Hyperconjugative Effects in 7.15 Predicting Orientation in Disubstituted Benzenes
Aromatic Substitution of the Substituted Benzenes 7.16 Nucleophilic and Free-Radical Substitutions
7.8 Orientation of Some Special Groups Illustrative Examples (Aromatic Hydrocarbons)
7.9 Theory of Reactivity and Orientation Based on EXERCISES
Carbocation (s-complex) Stability SOLUTIONS

7.1 Introduction

Aromatic compounds are benzene and compounds that resemble benzene in chemical behaviour, which
will be discussed at length later on.
Benzene was first isolated by Faraday in 1825 from the gas obtained by pyrolysis of whale oil. The major source
of benzene and its derivatives is coal-tar followed by petroleum. Coal-tar is the distillation product obtained by dry
distillation of coal at 1000—1300°C in absence of air, after removing the gaseous product (coal gas, a mixture of CH4 and
H2) and leaving behind the residual portion, known as coke. Chemically, coal-tar is a mixture of aromatic hydrocarbons,
their oxygenated derivatives and some heterocyclic compounds.
Coal-tar on fractional distillation gives various fractions, viz. light or crude naphtha, middle oil or carbolic acid,
heavy oil or creosote oil, green oil or anthracene oil and pitch as residue. Benzene, toluene and xylenes are obtained from
the light oil fraction.
Coal-tar cannot meet the demand of large quantities of aromatic hydrocarbons needed for industrial purposes,
hence many of aromatic hydrocarbons are synthesised from alkanes (obtained from petroleum) by catalytic reforming
which involves, cyclization, aromatization (dehydrogenation) and sometimes isomerization. For example,

CH3
CH3
CH2
Catayst – 3H2
CH2 ¾ ¾ ¾¾ ¾ ¾ ¾¾ ¾ ® ¾¾ ®
CH2 (500°C, 10-12 atm)
CH2 Cyclohexane Benzene
n-Hexane
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The aryl group. In general the univalent group obtained by removing a hydrogen atom from the nucleus of the
aromatic compound is known as aryl group (Ar—). The univalent group obtained by the removal of one hydrogen atom
from benzene nucleus is named as phenyl (C6H5—, Ph—, or f) group. Removal of two hydrogen atoms from the benzene
nucleus gives rise to bivalent phenylene group. Some of the common aryl groups are
CH3

Phenyl o-Toluyl o-Phenylene p-Phenylene

7.2 Methods of Preparation of Benzene

1. From acetylene (Berthelot).
red hot tube
3CH º CH ¾¾ ¾ ¾¾ ®

2. From sodium benzoate and phenol (Laboratory methods).

COONa OH

CaO Zn dust
+ NaOH ¾¾ ® ¬¾ ¾ ¾¾
(heat)

Sod. benzoate Benzene Phenol

3. From benzenediazonium chloride.
N2Cl

SnCl2/NaOH
(a) + 2[H] ¾¾ ¾¾¾ ¾® + N2 + HCl

N2Cl

+
Cu
(b) + H3PO2 + H2O ¾¾ ® + H3PO3 + N2 + HCl
Hypophosphorous acid
4. From chlorobenzene (Reduction).
Cl

Ni—Al
+ 2[H] ¾¾ ¾ ¾¾ ¾® + HCl
alloy, NaOH

5. From sulphonic acids (Desulphonation)

SO3H

130–150°C
+ H2O (steam) ¾¾ ¾ ¾¾ ® + H2SO4

SO3H D D

+ + D D
H , heat D2O (excess), H , heat
+ D2O
D D
D
Benzene-d6
Benzene-d 6 (C6D 6) is a common solvent used in NMR studies.
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7.3 Reactions of Benzene

Benzene is a quite stable compound. Although it has three double bonds, it is resistant to oxidation and usual
reagents which add to the carbon-carbon multiple bonds under ordinary conditions. However, it gives certain addition
reactions under vigorous conditions. On the other side, benzene undergoes electrophilic substitution reactions readily,
actually these are considered to be the characteristic reactions of benzene nucleus.

7.3.1 Addition Reactions

(i) Addition of hydrogen (Reduction of benzene).

Ni, 200°C
+ 3H2 ¾ ¾ ¾¾ ¾ ®

Cyclohexane

Benzene can also be reduced to cyclohexa-1,4-diene on treatment with Na in liquid ammonia and a proton
source usually ethanol (Birch reduction). Reaction is possible only in conjugated compounds and involves
following steps.

H H H H H H H
+e C2H5OH +e C2H5OH
¾¾ ¾ ¾® ¾¾ ¾ ¾¾ ¾® ¾¾ ¾ ¾® ¾¾ ¾¾®
(from Na) (proton donor) (from Na)
. .
H H H H H

If Birch reduction is carried out with Na in liquid NH3 in presence of primary alkylamine, (solvent) at
60—130°C, 1, 4-cyclohexadiene is further reduced to cyclohexene. It is because here ammonia acts as proton
donor to form strongly basic NH2– ion which rearranges 1, 4-cyclohexadiene (non-conjugated) to conjugated
1, 3-cyclohexadiene liable to be reduced by Birch reduction.

H H H H H H H H
H H
NH2 NH3
¾¾¾® ¬¾¾¾® ¾¾¾® H
H
H
H

H H H
+e NH3 +e NH3
¾® H
H
¾¾ ® ¾¾ ® ¾¾ ®
. .
H H H
(ii) Addition of chlorine or bromine (not iodine).

Cl
Cl Cl
Sun-light
+ 3X2 ¾¾ ¾¾¾ ®
(X=Cl or Br)
Benzene Cl Cl
Cl
Benzene hexachloride

Note that this is an example of halogen addition and not halogenation. Halogen addition is a free radical
reaction and occurs in presence of sunlight and without evolution of HX, while halogenation is an electrophilic
substitution that takes place in presence of Lewis acid (halogen carrier) and with evolution of HX.
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Benzene hexachloride (BHC) can exist in nine stereoisomeric forms ; five of them have actually been isolated.
They are called a, b, g, d and e forms. This mixture of stereoisomeric hexachlorides is valuable insecticide
commonly known as BHC or 666. The insecticidal properties are due to the g-isomer called gammexene or
lindane.
Zn/H2O CHO
(iii) Ozonolysis. Benzene adds three molecules of ozone to form a
+ 3O3 ¾ ¾ ¾¾ ® 3 ½
triozonide which on decomposition with water gives three molecules
CHO
of glyoxal, OHC—CHO.
Glyoxal

7.3.2 Coupling Reaction

Benzene when passed through a red hot iron tube at 700—800°C forms diphenyl.

red hot iron tube

2 ¾¾ ¾¾¾ ¾¾¾ ®
700—800°C

Biphenyl

7.3.3 Oxidation
O
Although benzene ring is resistant to oxidation under ordinary
conditions, drastic conditions may rupture the ring. For example, benzene is O2, V2 O5
oxidised to maleic anhydride when its vapours mixed with air are passed over ¾¾ ¾¾® O
500°C
heated V2O5 catalyst.

On strong heating with chromic acid or potassium permanganate, it O

is oxidised to form carbon dioxide and water as the final products. Maleic anhydride

7.3.4 Combustion
Like other aromatic compounds arenes are inflammable and burn with a sooty flame to form CO2 and water.
2C6H6 + 15O2 ¾¾® 12CO2 + 6H2O

7.3.5 Substitution in Benzene Nucleus (Aromatic Substitution)

The replacement of an atom, generally hydrogen, or a group attached to carbon of benzene ring by another group
is known as aromatic substitution. Like substitution at aliphatic system, aromatic compounds may also undergo three
types of substitutions.
(i) Electrophilic substitution, SE. These reactions involve attack by an electrophile or electron-seeking reagent.
(ii) Nucleophilic substitution, SN. These involve attack by a nucleophile or electron-donating reagent.
(iii) Free-radical substitution. These involve attack by a free radical.
However, unlike aliphatic system1, electrophilic substitution reactions are most common in aromatic compounds
and all the common and well known substitution reactions like nitration, halogenation, sulphonation and Friedel-Craft
reactions (alkylation and acylation) are examples of electrophilic substitution.

Why aromatic compounds undergo electrophilic substitution reactions? Due to the presence of p-electron clouds above
and below the plane of benzene ring (or any other aromatic ring), the ring serves as a source of electrons and is easily
attacked by electrophiles (electron loving reagents). Further substitution reactions in benzene rather than addition are due
to the fact that in the former reactions resonance-stabilised benzene ring system is retained while the addition reactions
lead to the destruction of benzene system. For example, addition of one molecule of hydrogen on benzene would destroy
benzene ring and forms cyclohexadiene which is less stable than benzene. Hence electrophilic substitution reactions are the
characteristic reactions of aromatic compounds.
(a) Electrophilic aromatic substitution
The electrophilic aromatic substitution reactions proceed by a common mechanism. Therefore, we will first deal
the mechanism, in general, and then apply it to specific substitution reactions like nitration, halogenation, etc.
General mechanism. Electrophilic aromatic substitution reactions are believed to proceed by bimolecular (S E2)
mechanism which involves three steps.

1. In aliphatic system, nucleophilic substitution reactions are the most common followed by free radical substitution.
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(i) Generation of an electrophile (electrophilic reagent). First of all the attacking electrophile, say X +, is generated
from the reagent, say XY.
X : Y ¾¾® X+ + : Y–
Electrophile
(ii) Formation of the intermediate carbocation. On the approach of the electrophile X +, benzene undergoes
electromeric effect (as shown by the curved arrow) with the result one carbon atom of the benzene ring gets
positively charged and the other gets negatively charged. The electrophile then attacks on the negative
centre resulting in the formation of an intermediate known as aronium cation, carbocation, s-complex1 or
the pentadienyl cation2, I.

H X H X H X H X
+ + +
X
¾¾ ® ¬¾® ¬ ¾® º +

+
I II III IV
Electromeric effect Resonating structures of the Resonance hybrid4 of
in benzene benzenonium ion3 the benzenonium ion
Where X+ = NO2+ (nitronium ion) in nitration
= Cl+ (chloronium ion) in chlorination
= SO3 (sulphur trioxide) in sulphonation
= CH3+ (methyl cation) in alkylation
+
= C OCH3 (acetyl cation) in acetylation
The carbocation I is stabilised by resonating structures I, II and III ; and the resonance hybrid can be
represented by the structure IV. Thus note the positive charge on the intermediate carbocation is not confined
to one carbon but is dispersed over the entire molecule especially on the o- and p-positions with respect to
the carbon carrying the attacking reagent. Since formation of intermediate carbocation is a slow step, it
constitutes the rate determining step of the complete reaction.
(iii) Formation of the product. The reaction is completed by abstraction Cl
of a proton from the carbon atom bearing electrophile by an H Cl
anionic species (: Y–) present in the reaction mixture to form a –
Y
substituted product. + ¾¾® + HY
Fast
We will apply this general mechanism on nitration,
Substituted benzene
halogenation, sulphonation and Friedel-Craft’s alkylation and IV
acylation at a later stage.
(b) Evidence in support of electrophilic character of substitution
Electrophilic nature of aromatic substitution reactions is proved by the following facts.
1. Such substitutions can be accomplished by reagents containing pre-formed electrophilic species. For example,
benzene can be easily nitrated by salts like nitronium nitrate (NO2+NO3–) and nitronium perchlorate (NO2+
ClO4–) clearly indicating that NO2+ (an electrophile) is the real nitrating agent.
2. In certain Friedel-Craft’s alkylation reactions, rearranged alkyl groups are found to be present in the
substituted product. For example, Friedel-Craft’s reaction of benzene with n-propyl chloride gives
isopropylbenzene rather than n-propylbenzene. This can be explained on the basis of formation of n-propyl
cation (an electrophile) which rearranges to the more stable isopropyl cation (another electrophile) which
then attacks on benzene forming isopropylbenzene.
+ rearrangement +
CH 3CH 2CH 2 Br ¾¾® CH 3 CH2 CH 2 ¾¾¾¾¾¾¾
® CH 3 C HCH 3
n-Propyl bromide n - Propyl cation Isopropyl cation
(primary carbocation) (sec . carbocation)

3. The observed reactivity and orientation (discussed later on) in aromatic compounds are in accord with the
electrophilic character of these reactions.
1. Since a discrete s-bond has been formed.
2. Since the intermediate has no longer a benzene structure but an unstable cation with four p electrons delocalized over five carbon nuclei
(the sixth carbon atom is a saturated carbon and forms sp 3 hybrid bond), it is known as pentadienyl cation.
3. Note that benzenonium ion is not flat because the carbon bonded to Cl and H is tetrahedral.
4. For the sake of simplicity we will write only one of the resonating structures of the resonance hybrid in our further discussion, and not
the hybrid itself.
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(c) Evidence in favour of two step mechanism
Theoretically, an electrophilic aromatic substitution reaction can proceed via one step or two step mechanism.
However, before discussing the evidence in favour of actual two step mechanism, let us summarise both the
mechanisms.

Å Å
One step mechanism. C6H5—H + XÅ ¾ ¾ ® X– – – C6H5 – – –H ¾ ¾ ® C6H5 —X + H

slow + H
Two step mechanism. (i) C6H5 —H + X Å ¾¾ ¾ ® C 6H5
X
+ H fast
(ii) C 6 H5 Q ¾ ¾ ¾® C H — X + H : Y
+ :Y 6 5
X
However, all electrophilic aromatic substitution reactions proceed via two steps which has been proved by
isotope tracer technique. Benzene (or other aromatic compound) labelled with deuterium (the heavier isotope of
hydrogen having a mass of 2 amu) was nitrated (or halogenated, sulphonated, etc.) and its rate of nitration was
determined. It was observed that the rate of nitration of deuterated benzene and ordinary benzene (i.e. the rate of
replacement of deuterium or protium by —NO2 group) was same
K
C6 H 5 ¾ D + HONO2 ¾¾® C6H5 — NO2 + HOD
Deuterated benzene

K'
C6 H5 ¾ H + HONO2 ¾¾® C6H5 — NO2 + H2O ; K = K¢
Ordinary benzene
Hence we can safely conclude that there is no isotopic effect1 in aromatic substitution.
Now since a carbon-deuterium bond is broken more slowly than a carbon-hydrogen (protium) bond, had the
mechanism of the above reaction been one step (involving breaking of carbon-hydrogen bond), the rate of
replacement of deuterium and hydrogen must have been different. The same rate of nitration can easily be
explained on the basis of two-step mechanism. In the two-step mechanism, since the rate determining step (first
step) does not involve the cleavage of C—H or C—D bond, it does not effect the rate of replacement of H or D.
Cleavage of C—H bond actually takes place in the second step (fast step) of the reaction which, being fast, does
not affect the rate of reaction. Thus absence of isotopic effect established the two-step mechanism for electrophilic
aromatic substitution reaction in which formation of carbocation (first step) is the rate determining step.
(d) Electrophilic aromatic substitution reactions versus electrophilic addition reactions of alkenes
There are certain similarities between the electrophilic aromatic substitution reactions of benzene and electrophilic
addition reactions of olefins. But before we summarise the various points of similarities, let us rewrite the
mechanism of both the reactions.

H X
X

+d d– —Y
– + Y–
+ X—Y ¾¾¾® ¾¾¾® + HY
Slow Fast
Benzene
Substituted benzene

d– –
+d —Y + Y–
H2C=CH2 + X—Y ¾¾¾® H2C—CH2 ¾¾® H2C—CH2
Slow Fast
Olefin
X Y X
Addition product

Now let us summarize the similarities between the two reactions.

(i) Both types of reactions are polar, two-step processes and involve the attack of electrophilic reagent on the
sp2 hybridised carbon.
(ii) In both cases the rate determining step is the attack of an electrophile at carbon (first step) to form carbocation.

1. A difference in reaction rate due to a difference in the isotope present in a reaction system is called as isotope effect.
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So we see that the two reactions are quite similar upto the formation of carbocation but after this the two
reactions differ very much as one regenerates the original structure with a substituent, i.e. a substituted product is formed,
while the other (addition on olefins) gives an addition product and thus the original structure (presence of double bond)
is destroyed. The difference is due to the fact that in substitution reactions the regenerated benzene nucleus, obtained by
the loss of proton from the carbocation, stabilizes itself by resonance while there is no such comparable large resonance
stabilisation in case of addition reactions on alkenes which thus tend to add the nucleophile.
Now let us discuss important examples of electrophilic substitution reactions of benzene.
1. Nitration
Nitration is brought about by treating the aromatic compound with nitrating mixture (a mixture of concentrated
nitric acid and conc. sulphuric acid). Remember that the —NO2 group is electron-withdrawing group, so its
presence deactivates benzene ring for further nitration. Hence nitration of benzene (not having —NO2) is easier
than nitrobenzene (having —NO2 group).
NO2 NO2

HNO3/H2 SO4
¾ ¾ ¾¾ ¾ ¾®
55°C
NO2
Benzene Nitrobenzene m-Dinitrobenzene
Mechanism.
The three steps of the reaction are given below.
(i) Generation of electrophile. In nitration, nitronium ion, NO2+ is the active nitrating agent (electrophile). It is produced
by the reaction of nitric acid and sulphuric acid.
HO—NO2 + H2SO4 H2O+ — NO2 + HSO4–
+
H2O —NO2 H2O + NO2+
H2O + H2SO4 H3O+ + HSO4–

On adding, HONO2 + 2H2SO4 NO2+ + H3O+ + 2HSO4–

Thus note that here sulphuric acid acts as an acid and protonates nitric acid (which thus acts as a base) to form
protonated nitric acid. The latter decomposes into nitronium ion (electrophile) and water. Water, so formed, is
absorbed by another molecule of sulphuric acid.
N2O5 in CCl4 in presence of P2O5 is used as nitrating agent when anhydrous conditions are used.
N2O5 NO2+ + NO3–
(ii) Formation of carbocation.

H NO2 H NO2 H NO2 H NO2

+ +
NO2 +
¾¾ ¾ ® ¬® ¬® º +

(iii) Formation of the final product.

NO2
H NO2
–
+ + HSO4 ¾® + H2SO4

2. Halogenation
Aromatic halogenation (e.g. chlorination and bromination) is generally brought about by treating the aromatic compound
with halogen in cold, dark and in the presence of a strong Lewis acid (halogen carrier) like Fe, I2, ferric halide or
aluminium halide. The usual practice is to add to the reaction mixture (aromatic compound + halogen), some
iron fillings which are converted by the halogen into the corresponding ferric halide.

AlCl
C6 H6 + Cl 2 ¾¾¾¾
3
® C6 H 5 Cl + HCl
Benzene Chlorobenzene
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Mechanism.
The common three steps of the reaction are as below.
(i) Formation of electrophile. The metallic halide (Lewis acid) polarises the halogen molecule to yield the electrophile,
X+ (halonium ion). For example,
FeCl3 + Cl2 ¾¾® FeCl4– + Cl+
(ii) Formation of carbocation.

H Cl H Cl H Cl H Cl
+ +
Cl +
¾¾ ® ¬® ¬® º +

(iii) Formation of final product.

H Cl Cl

–
+ + FeCl4 ¾ ¾® + FeCl3 + HCl

s-Complex Chlorobenzene

Halogenation can also be effected by other reagents like hypochlorous or hypobromous acid in presence of
strong acids like HCl which protonates the hypohalous acids thus making them powerful electrophiles.
HOCl + H+ H2O+—Cl H2O + Cl+
Since the reaction between benzene and fluorine is very vigorous, direct fluorination of arenes is not possible.
Now since hydroiodic acid (HI) is a strong reducing agent it will reduce iodobenzene (formed by the iodination
of benzene) to benzene back, iodination should be carried out in presence of an oxidising agent like iodic acid,
nitric acid or mercuric oxide.
C6H6 + I2 ¾¾® C6H5I + HI
5HI + HIO3 ¾¾® 3I2 + 3H2O
or 5C6H6 + 5I2 + HIO3 ¾¾® 5C6H5I + 3I2 + 3H2O
3. Sulphonation
Sulphonation is brought about by the action of sulphuric acid containing an excess of SO3 (oleum).

SO3H

+ H2SO4 ¾ ® + H2O

Benzene Benzenesulphonic acid

Mechanism
The reaction mechanism involves the following steps.
(i) Formation of electrophile. Here the electrophile is free sulphur trioxide which is present as such in oleum (conc.
H2SO4 + SO3) or may be produced by the dissociation of sulphuric acid.
..
O
..
..

.. ..
S O
..
..

..
..
O
..
..

..

HO — SO 2 OH + H 2 SO 4 SO3 + H3O+ + HSO4–

Sulphuric acid (2 moles)

The electrophilic character of SO3 is due to the presence of electron deficient sulphur atom as is obvious from the
structure of its molecule (Note that sulphur has 6 electrons).
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(ii) Formation of carbocation.

– – – –
H SO3 H SO3 H SO3 H SO3
+ +
SO3 º
¨ ¨ +

(iii) Transfer of proton to form the resonance-stabilised sulphonic acid anion.

–
H
– SO3
SO3
–
+ + HSO4 + H2SO4

s-Complex Benzenesulphonic acid anion

Note that all steps of sulphonation reaction are reversible.

(iv) Reaction between sulphonic acid anion and hydronium ion to form the final product.
–
SO3 SO3H

+
+ H3O + H2O

The equilibrium of this reaction lies to left.

With some aromatic compounds and at certain acidities, the electrophile may be HSO3+ or molecule that can
readily transfer SO3 or HSO3+ to the aromatic ring.
4. Friedel-Craft’s alkylation
This reaction involves the action of an alkyl halide on aromatic compound in the presence of anhydrous aluminium
chloride* (catalyst).
Mechanism
The reaction mechanism involves the following steps.
(i) Generation of electrophile. Here the electrophile is alkyl carbocation.
R—Cl + AlCl3 R+-------Cl–—AlCl3
(ii) Formation of carbocation.

H R H R H R H R
+ – + +
R----- Cl AlCl 3
¾¾ ¾¾¾ ¾¾¾ ® ¬® ¬® º +
–
(– AlCl 4 )
+

Note that complex formation with AlX3 is observed in case of only primary alkyl halides ; in case of secondary
and tertiary alkyl halides Lewis acid acts as electron deficient species and alkyl carbocation is produced directly.
(iii) Transfer of proton from the carbocation to form the final product.
R
H R
–
+ + AlCl4 ¾ ¾ ® + AlCl3 + HCl

It is important to note that in higher alkyl halides, the alkyl carbocation, formed at the initial stage may undergo
rearrangement to form the more stable (2° or 3°) rearranged carbocation and thus the unexpected alkylbenzene
is formed as the product. For example, benzene when treated with n-propyl chloride gives isopropylbenzene
rather than n-propylbenzene.

* Since the function of AlCl 3 is to generate the carbocation by abstracting the halogen from the alkyl halide, other Lewis acids like BF3 ,
FeCl3, HF etc. can be used in place of AlCl3.
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CH(CH3)2

AlCl3
+ n-CH3CH2CH2Cl ¾¾ ¾¾ ®

Benzene Isopropylbenzene

It is due to the rearrangement of the n-propyl cation (1°) to the more stable iso-propyl cation (2°).
Å Å
CH3—CH—CH2 ¾¾® CH3—CH—CH3

H
n-Propyl cation (1°, less stable) Isopropyl cation (2°, more stable)
Now it is the more stable isopropyl cation that attacks the benzene molecule to form isopropylbenzene.

H CH(CH3)2 CH(CH3)2

Å + –
CH3CHCH3 AlCl 4
¾¾ ¾ ¾¾ ® ¾¾ ¾® + AlCl3 + HCl

Isopropylbenzene (Cumene)

Similarly,

CH 3 CH 3
| |
AlCl
C6H6 + CH3 CHCH 2 Cl ¾¾¾3¾ ® C6H5— C ¾ CH 3
|
CH 3

Isobutyl chloride tert-Butylbenzene

Modifications of Friedel-Craft's alkylation

Like alkyl halides, alcohols and alkenes can also provide carbocations in presence of acids like BF 3, mineral
acids etc. hence alcohols and alkenes can also be used as alkylating agent for aromatic rings.

CH 3 CH 3
| |
BF3
C6H6 + CH3 CCH 2 OH ¾¾¾ ® C6H5 ¾ C ¾ CH2 CH3
| |
CH 3 CH 3

Neopentyl alcohol tert-Pentylbenzene

H SO
C6H6 + (CH 3 )3 COH ¾¾¾¾
2 4®
C 6 H 5 ¾ C(CH 3 )3
tert -Butanol tert - Butylbenzene
H 2SO 4
® C 6 H 5 ¾ C(CH 3 )3
C6H6 + (CH 3 )2 C = CH 2 ¾¾¾¾
Isobutene tert - Butylbenzene

Limitations of the Friedel-Craft's alkylation :

(i) Friedel-Craft reactions (both alkylation as well as acylation) either fail or give poor yields when any of the
following powerful electron-withdrawing groups are present on the aromatic ring because these groups make
the ring less reactive.
+
–NO 2 , - N Me 3 , - COOH, - COR, - CF3 , - SO 3 H

Further the yields are also poor when the ring bears –NH2, –NHR, or –NR2 groups. This is partly due to the fact
that the strongly basic nitrogen fixes up the Lewis acid required for ionisation of alkyl halide and partly because
of the presence of positive charge on nitrogen due to which the group becomes electron-withdrawing and hence
deactivates the benzene nucleus towards electrophilic substitution.
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373
+
H2N H2N – AlCl3

..
+ AlCl 3

(ii) Alkyl carbocations are susceptible to carbocation rearrangements.

(iii) Aryl and vinyl halides cannot be used as the halide component because they do not form carbocation readily.
5. Friedel-Craft’s acylation
This is quite similar to alkylation.
COCH3

anhy.
+ ClCOCH3 ¾¾ ¾ ® + HCl
AlCl3
Benzene Acetyl chloride Acetophenone

Mechanism
Here the electrophile is acylium ion (acyl cation).
+
RCOCl + AlCl3 ¾¾® R C O + AlCl4–
Formation of carbocation and then the final product.
H COR COR

+ + –
RCO AlCl4
¾¾® ¾ ¾ ¾® + AlCl3 + HCl

It is important to note that monosubstituted alkylbenzenes (e.g. C6H5CH2CH3) are generally prepared through
acylation process rather than the direct alkylation. One of the reasons is that in direct alkylation as soon as one
alkyl group is introduced, the benzene nucleus becomes more active than benzene itself, because of electron-
releasing character of the alkyl group, and hence further substitution takes place leading to the formation of
polyalkylated product. On the other hand, in acylation as one acyl (e.g., CH3CO—) group is introduced, the ring
is deactivated and hence the introduction of the second acyl group becomes difficult. The monoacylated benzene
is then easily reduced to monoalkylated benzene by Clemmensen reduction (Zn + Hg/HCl) or Wolf-Kishner
reduction (NH2.NH2 + OH–).
AlCl 3 Zn-Hg/HCl
C6H6 + CH3COCl ¾¾¾® C6H5COCH3 ¾¾¾¾¾¾¾® C6H5CH2CH3
or NH2 –NH 2 + OH –
Benzene Acetyl chloride Acetophenone Ethylbenzene
AlCl 3
[c.f. C6H6 + CH3CH2Cl ¾¾¾® C6H5CH2CH3 ¾¾® C6H4(CH2CH3)2].
O
||
However, reduction of - C - CH 3 to –CH2–CH3 must be done carefully.

Since Clemmensen reduction involves acidic conditions, it must be used when the compound does not have any
acid sensitive group; similarly, Wolf-Kishner reduction (using basic conditions) must not be used with ketones
having base-sensitive functional groups.

O
C–CH 3 CH2CH3

–
H2NNH2, OH
heat
(W. K. reduction)

it will react
OH with HCl OH
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CH2CH3 C – CH3 CH2CH3

–
Zn (Hg) H2 NNH2 , OH
HCl heat + (CH3)3N
+ (Clemmensen + (W. K. redu.)
CH2CH2N (CH3)3 reduction) CH2CH2N (CH3)3 CH=CH 2
– –
Cl Cl
Later on, Friedel-Craft reaction was extended for preparing other compounds by replacing alkyl and acyl halides
by other reagents. For example,
AlCl 3
(a) C6 H6 + Cl.CO.Cl ¾¾¾® C6 H 5 COCl + HCl
Benzene Carbonyl chloride Benzoyl chloride
AlCl 3
(b) C6H6 + ClCONH 2 ¾¾¾® C6H 5 CONH2 + HCl
Chloroformamide Benzamide
6. Gattermann Koch aldehyde synthesis.
CHO

AlCl 3
+ CO + HCl ¾ ¾ ¾® + HCl

Benzene Benzaldehyde
7. Chloromethylation (Blace reaction).
CH2Cl

ZnCl2
+ HCHO + HCl ¾¾ ¾ ® + H2O

Benzene Benzyl chloride

1. Sometimes nitration of aromatic compounds is done simply by heating with conc. HNO 3 alone instead of a mixture of conc. HNO3
and conc. H2SO 4. Name the electrophile and its formation in the reaction from nitric acid alone.
2. Sometimes, HSO3+ is found to act as an electrophile in sulphonation, write an equation for its formation from H 2SO 4.
3. Suggest a likely electrophile formed in each of the following electrophilic substitution reaction
H 3PO 4 H+
(a) C6H6 + RCH = CH2 ¾¾¾® C 6H5—CH(R)CH3 (b) ArH + HONO ¾¾® Ar—NO + H2O
CF3 COOH
(c) ArH + Ar¢N2+ Cl– ¾¾® Ar—N = N—Ar¢ (d) ArH + Tl(OCOCF3)3 ¾¾¾¾¾® ArTl (OCOCF3)2
4. Suggest mechanism of deuteration of C6H6 with DCl.
5. Reaction of benzene with mercuric acetate, Hg(OCOCH3)2 in presence of H+ (from HClO4) gives acetoxymercurobenzene. The
reaction has a significant isotope effect, suggest the mechanism for mercuration of benzene.
6. How will you prepare n-propylbenzene from benzene by Friedel—Craft alkylation in quantitative yield ?
7. Identify A to E in the following :

CH 3
D 2 SO 4/D 2 O ½ AlCl 3
(i) ¾¾¾¾¾® A (ii) + CH3— C ¾ CH 2 Br ¾¾¾® B
heat
½
CH 3

AlCl 3 AlCl 3
(iii) + CH2Cl2 ¾¾¾® C (iv) + (CH3)2 CHCH2OH ¾¾¾® D

AlCl 3
(v) + CH3CH2CH = CH2 ¾¾¾® E
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7.4 Structure of Benzene

1. Kekule’s structure of benzene. From analytical data, the empirical formula of benzene is found to be CH and its
molecular weight 78. Hence its molecular formula is C6H6. Since it has lesser number of hydrogen atoms than the
saturated compound having 6 carbon atoms, it seems to be unsaturated. In practice, one molecule of benzene is
found to add 3 moles of chlorine (in presence of sunlight), 3 moles of hydrogen at 200°C and 3 moles of ozone
indicating that benzene has three double bonds. However, benzene undergoes all the above addition reactions
under abnormal conditions, moreover it does not discharge Baeyer’s reagent colour ; does not react with halogen
acids, these facts indicate that benzene is somewhat less reactive than the unsaturated aliphatic compounds
towards addition reactions. Furthermore, benzene gives special substitution reactions like nitration, chlorination,
sulphonation, acylation etc. very easily (these reactions are not shown by unsaturated compounds.) These
observations lead to the conclusion that although benzene contains three double bonds, these double bonds are
different from that present in aliphatic compounds. Benzene, when heated with hydrogen in presence of nickel
as catalyst, forms cyclohexane, a six-membered cyclic compound.

Ni—H2
C6H6 + 3H2 ¾ ¾ ¾¾® or C6H12
200°C
Cyclohexane

Hence benzene must be cyclohexane having three double bonds. Kekule in 1865 proposed given
structure for benzene which he saw in dream.
Benzene

2. Objections to Kekule’s formula. However, the Kekule’s structure could not explain the following characteristic
properties of benzene.
(i) Isomer number. According to Kekule structure, two ortho disubstituted products are possible, viz. 1, 2—(having
a single bond between carbon–1 and carbon–2) and 1, 6– (having a double bond between carbon – 1 and
carbon – 6).

X X
1 X X 1
6 2 6 2
5 3 5 3
4 4

(Substituents on carbons linked via single bond) (Substituents on carbons linked via double bond)

But in practice only one ortho disubstituted product is known.

However, Kekule overcame this objection by suggesting that the double
1 1
bonds in benzene are not static but in a state of rapid oscillation between
the two forms I and II with the result each C—C pair has a single bond 6 2 6 2
half of the time and a double bond the other half. 5 3 5 3
4 4
Hence there is no difference between any two pairs of adjacent positions I II
viz. 1, 2- and 1, 6-positions with the result there will be only one ortho
disubstituted benzene.
The Kekule’s dynamic formula for benzene was supported from the work of Levine and Cole (1932) who subjected
o-xylene (1, 2-dimethylbenzene) to ozonolysis and obtained a mixture of glyoxal, monomethylglyoxal and
dimethylglyoxal in the ratio of 3 : 2 : 1.

CHO CH 3 CO CH 3 CO
(i) O 3
o–Xylene ¾¾¾¾¾® 3 | + 2 ½ + |
(ii) H 2 O/Zn CHO CHO CH 3 CO
Glyoxal Monomethylglyoxal Dimethylglyoxal

The formation of the above three products in this ratio is possible only if o-oxylene exists as a mixture of structure
III and IV in dynamic equilibrium.
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CH3 O O CH3 CH3CO

CH3
CH3 O O
3O3 H2O CH3CO
¾¾ ¾® O ¾ ¾ ¾® Dimethylglyoxal
Zn +
O O
III CHO
O O 2
CHO
o-Xylene o-Xylene triozonide Glyoxal

CH3 O O CH3CO
CH3
CH3 O O
2 CHO
3O3 H2O
¾¾ ¾® O ¾ ¾ ¾® Monomethylglyoxal
CH3 Zn
O +
IV O CHO
O O
CHO
o-Xylene o-Xylene triozonide Glyoxal

(ii) Unusual stability of benzene. Although benzene contains three double bonds, it is quite stable and does not normally
undergo addition reactions. In place of addition reactions, benzene readily undergoes substitution reactions.
(iii) Heat of hydrogenation1 of benzene. On the basis of the fact that the heat of hydrogenation for a C = C of an alkene is
about 28—30 (average 28.6) kcal per mole, heat of hydrogenation for cyclohexatriene (benzene) having three C = C
linkages should be about (3 × 28.6) 85.8 kcal/mole, however its actual value is only 49.8 kcal/mole.

Cyclohexene Cyclohexa-1, 3-diene Cyclohexatriene (Benzene)

D H(Obs. and cal.) = 28.6 kcal. D H(cal.) = 28.6 × 2 = 57.2 kcal. D H(cal.) = 28.6 × 3 = 85.8 kcal.
D H(obs.) = 55.4 kcal. D H(obs.) = 49.8 kcal.

This indicates that benzene evolves (85.8 — 49.8) 36 kcal less energy than predicted which means that benzene
contains 36 kcal less energy than the cyclohaxatriene (Kekule structure for benzene). In other words, benzene
molecule is more stable than cyclohexatriene by 36 kcal.
(iv) Carbon-carbon bond length in benzene. Kekule’s structure for benzene should also have two types of carbon-carbon
bonds, viz. C—C (bond length 1.54 Å) and C = C (bond length 1.34 Å). However, X-ray diffraction studies have
shown that all the six carbon-carbon bonds in benzene are equal with a bond length of 1.39 Å which is intermediate
between C—C single bond length and C—C double bond length.
(v) Heat of combustion of benzene. The calculated heat of combustion2 for cyclohexatriene (Kekule’s structure of benzene)
is 824.1 kcal, while the actual value for benzene is only 789.1 kcal. This suggests that the actual benzene
molecule is more stable than the cyclohexatriene type by (824.1 – 789.1) 35 kcal.
3. Present day position regarding structure of benzene. The peculiar behaviour (i.e. limitations of Kekule’s structure)
of benzene is explained on the basis of valence bond theory and the molecular orbital theory.

(A) Valence bond theory (Resonance theory). According to the valence bond
or resonance theory, benzene can’t be represented by any one structural
formula but as a hybrid of structures I and II.
I II

1. It is the quantity of heat evolved when one mole of an unsaturated compound is fully hydrogenated. It is abbreviated as DH.
2. There is a characteristic contribution from each type of bond, e.g. for C—H bond the value is 54 kcal, for C—C it is 49.3 kcal and for C
= C it is 117.4 kcal. Thus the calculated value of the heat of combustion for cyclohexatriene (having 6C—H, 3C—C and 3C = C bonds)
will be 6 × 54 + 3 × 49.3 + 3 × 117.4 = 824.1 kcal.
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In other words the true structure of benzene is represented neither by I nor by II, it lies somewhere in between the
two. This imaginary intermediate stage is known as resonance hybrid. It has 36 kcal/mole of energy less than
either of the contributing structures ; this represents the resonance energy of the mole-cule. As the contributing
structures (I and II) are exactly equivalent and have same stability, they make equal contribution to the overall
resonance hybrid. Further since the contributing structures are identical, stabilisation of benzene due to resonance
is expected to be large. The resonance hybrid structure of benzene explains all the properties of benzene.
(i) Isomer number. Since all the carbon-carbon bonds in benzene are equivalent, there can be no distinction
between any two ortho disubstituted products. Hence in all, only three disubstituted products (one o-, one
m- and one p-) are possible.
(ii) Bond lengths. According to resonance hybrid structure, benzene contains no true carbon-carbon double and
single bonds. In other words, all the carbon-carbon bonds in benzene are equivalent and are intermediate
between single and double bonds which agrees with the observed carbon-carbon bond length (1.39 Å) in
benzene.
(iii) Unusual stability. The unusual stability and peculiar behaviour of benzene is due to high resonance energy
(36 kcal/mole) of benzene. In general, a resonance hybrid is always more stable than any of the contributing
structures.
Substitution reactions in benzene rather than addition are due to the fact that in the former reactions resonance-
stabilised benzene ring system is retained while the addition reactions lead to the destruction of benzene system.
For example, addition of one molecule of hydrogen on benzene would destroy benzene ring and forms
cyclohexadiene which is less stable than benzene.
(B) Molecular orbital theory. The molecular orbital theory provides the fullest description of the benzene ring. It is
based on spectroscopic and X-ray analysis according to which benzene is a flat regular hexagon molecule with
all the six carbon atoms lying in the same plane and each C—C—H angle of 120°, the C—C bond length as 1.39Å
and C—H bond length as 1.09Å. Therefore, each carbon atom of benzene must be in a state of sp2 hybridisation
(trigonal hybridisation) i.e. it possesses three sp2 hybrid orbitals inclined at an angle of 120° and a fourth pz
orbital disposed perpendicularly to the plane of sp2 orbitals. Two of the three sp2 hybrid orbitals of each carbon
atom overlap with the two sp2 hybrid orbitals of the two adjacent carbon atoms forming two C—C s bonds, and
the third sp2 hybrid orbital of each carbon atom overlaps with the s orbital of hydrogen atom to form a C—H s
bond. Thus after overlapping of the sp2 orbitals, each carbon atom has two C—C s bonds, one C—H s bond, and
one unused pz orbital disposed at right angle to the plane of ring.

H H
1 s 2

s
H 6 3 H

5 4

H H

Each sp 2 hybridised carbon of benzene forming two C–C s and one C–H s bond
and containing a p-orbital with one electron.

Now as in the formation of ethylene and other olefins, sideways overlapping of the remaining six pz orbitals may
generate three p-bonds in benzene. But in benzene molecule, the pz orbital on each carbon atom can overlap in
two manners. In one way, the pz orbitals of C1 and C2, C3 and C4, and C5 and C6 can overlap to form three p-bonds
between the respective atoms [Fig. (i)]. In other way, the pz orbitals of C2 and C3, C4 and C5, and C6 and C1 can
overlap to form three p-bonds between the respective atoms [Fig. (ii)].

1 2
1 2

(i) 6 3 6 3

5 4
5 4
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1 2
1 2

6 3 6 3
(ii)
5 4
5 4

Overlapping of pz orbitals in two possible ways.

Note that the above formulae (i) and (ii) correspond to the two Kekule structures. However, the pz orbital of any
one carbon can overlap with either of the two adjacent pz orbitals since they are at an equal distance. Further
since the system is cyclic and planar, all the six pz orbitals overlap equally and continuously to form a p
molecular orbital [Fig. (i)] comprising of two continuous ring-like electron clouds, one lying above and the other
below the plane of carbon atoms [Fig. (ii)].

H H
1 2
s
C C
6 3 s
H C C H

C C
5 4
H H
(i) (ii)

Orbital picture of benzene showing the ring-like electron clouds.

Thus we see that the six electrons of the p orbitals cover all the six carbon atoms, and are said to be delocalised.
This delocalisation of p electrons results in stronger bonds and more stable molecule. Note that the above structure (ii)
corresponds to the resonance hybrid of the Kekule structures. The delocalisation of p electrons of the benzene
molecule explains its unusual stability. The delocalisation (resonance) energy of benzene is 36 kcal.
Evidence in favour of orbital structure. The molecular orbital structure (ii) of benzene explains all the known
characteristics of benzene.
H
(i) Flat ring structure. Since each carbon atom of benzene ring is in sp2
1.09 Å
hybridised state, each C—C—H bond angle is of 120° and hence 2 C
1.39 Å
2
(sp -sp )
C
the resulting molecule will be flat. It is this flatness that permits
the overlap of the p orbitals in both directions, resulting H C C H
delocalization of electrons and thus stability of the molecule. 120°
120° C C 2
s(sp -s)
120°

Bond angles and bond lengths in benzene.

(ii) Bond length. In benzene molecule, each C—C bond length = 1.39 Å, each C—H bond length = 1.09 Å.
(iii) Isomer number. According to molecular orbital theory, since all the six carbon atoms of benzene are completely
equivalent, hydrogen atom attached to these will also be equivalent. Hence benzene should form only one
monosubstituted and three disubstituted products.
(iv) Unusual stability. This is due to delocalisation of electrons. Due to delocalisation of electrons, the term
resonance energy is sometimes replaced by delocalisation energy.
(v) Electrophilic substitution. Since benzene ring is surrounded by the loosely held p-electrons cloud above and
below the plane of atoms, it is readily attacked by electron-seeking reagents (electrophiles). Remember that
despite of delocalisation, p electrons are more loosely held than the s electrons and are thus readily available
to an electrophile. Further, since substitution reactions lead to resonance stabilised substituted benzene
derivatives, electrophilic substitutions are the main reactions of benzene.
4. Representation of benzene. For convenience, benzene ring is generally represented as a regular hexagon containing
a dotted line circle [Fig. (i)] or a solid line circle [Fig. (ii)]; actually the circle denotes the cloud p electrons.
It is understood that a carbon is present at each corner of the hexagon, and
each carbon carries a hydrogen atom, unless another atom or group is
indicated specifically.
(i) (ii)
Representation of benzene ring.
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7.5 Concept of Aromatic Character (Aromaticity)

Benzene and other organic compounds which resemble benzene in certain characteristic properties are called
aromatic compounds. These characteristic properties constitute what is commonly known as aromatic character or
aromaticity. Such important properties are summarised here.
(i) Unusual stability. Aromatic compounds are highly stable as shown by their low heats of hydrogenation and
low heats of combustion. For example, heat of hydrogenation of benzene is only 49.8 kcl/mole as compared to
that of the hypothetical cyclohexatriene (85.8 kcal/mole). Similarly, heat of combustion of benzene (789.1 kcal)
is low as compared with that for cyclohexatriene (about 824.1 kcal).
(ii) Substitution rather that addition reactions. Aromatic compounds although possess double bonds, they do not
undergo addition reactions. On the other hand, they undergo electrophilic substitution reactions like nitration,
halogenation, sulphonation and Friedel Craft’s reactions.
(iii) Resistant to oxidation. Aromatic compounds are resistant to oxidation by aq. KMnO4, HNO3 and other mild
oxidising agents.
(iv) Cyclic flat molecules. Aromatic compounds generally contain five-, six- or seven-membered rings and are found
to have flat (or nearly flat) structures.

7.5.1 Theoretical Criteria for Aromaticity

On the basis of molecular orbital treatment of various aromatic compounds, it has been observed that an aromatic
compound must fulfill the following theoretical requirements.
(a) It must have an uninterrupted cyclic cloud of p electrons above and below the plane of the molecule (often called
a p cloud). Let us look what has this means?
(i) For the p cloud to be cylic, the molecule must be cyclic.
(ii) For the p cloud to be uninterrupted, every atom in the ring must have a p orbital.
(iii) For the p cloud to be formed, each p orbital must be able to overlap with the p orbitals on either side of it.
Therefore, the molecule must be planar.
(b) The p cloud must contain an odd number of pairs of p electrons. (4n + 2) p electrons, where n is an integer i.e. its
value may be 0, 1, 2, 3, 4 ... This rule is known as 4n + 2p rule or Huckel rule. Thus according to Huckel rule, the
number of p electrons in an aromatic compound may be 2 (n = 0), 6* (n = 1), 10 (n = 2), 14 (n = 3), 18 (n = 4), etc. ;
in benzene it is 6 (n = 1). Huckel’s rule is strongly supported by several examples.
Let us observe the beauty of validity of the above two points in deciding aromaticity of benzene, cycloheptatriene
and cyclooctatetraene.
1. Benzene. It is a cyclic and planar compound having three alternate double bonds. Thus each carbon of the ring
has a p orbital (electron) and hence a continuous (cyclic) cloud of 6 p electrons is present. Thus according to
Huckel rule :
4n + 2 = 6 ; \ 4n = 4 or n = 1
Now since here n = 1 which is an integer, the compound (benzene) obeys Huckel rule and hence must be
aromatic.
2. Cycloheptatriene. It is a cyclic and planar. It has three double bonds and six p electrons. But not that here one of
the carbon is saturated (sp3 hybridised) and hence does not possess a p orbital with the result a continuous
(cyclic) bond of p electrons is not possible. Therefore, this compound although obeys Huckel rule (because here
n comes out to be 1 as in benzene), it is not aromatic because of absence of cyclic cloud of p electrons.
3
sp Hybridised carbon

Benzene Cycloheptatriene Cyclooctatetraene

Aromatic, n = 1 Non-aromatic, n = 1 Non-aromatic, n = 1.5

Absence of cyclic cloud of p electrons

* The Huckel number 6 is the most common in aromatic system and hence the term aromatic is commonly used for the 6 p electrons.
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3. Cyclooctatetraene. It is a cyclic compound having four alternate double bonds. Thus here the number of p
electrons is 8 which does not fit in Huckel rule (because n comes out to be 1.5 which is not an integer).
4n + 2 = 8 ; \ 4n = 6 or n = 1.5
Hence cyclooctatetraene is non-aromatic. Moreover, it is found to be tub-shaped (not planar).
4. Non-benzenoid compounds. On the basis of the above considerations, it is apparent that an aromatic compound
need not necessarily contain a benzene ring, and actually several compounds not having benzene ring are
found to be aromatic in nature. Thus in other words, we can say that an aromatic compound may be benzenoid
(having benzene ring) or non-benzenoid1 (without benzene ring). In fact all that is required for aromaticity is
the presence of a flat ring (whether benzenoid or not) with (4n + 2) p electrons in the form of continuous
electron clouds above and below the plane of the ring. The following cyclic systems fulfil the above two
conditions of aromaticity and thus are found to be aromatic in nature.

..
N
.. .
O N
Benzene Naphthalene H ×× ××
(6p electrons) (10p electrons)
Pyrrole Furan Pyridine

(Each contains 6p electrons)

NOTE
Dot (or a pair of dots) represents the electron(s) present in a p orbital lying parallel to each other and hence are capable of
overlapping and ultimately producing electron clouds. On the other hand, a pair of ‘×’ represents unused electrons in an
sp2 orbital lying perpendicular to the ring and hence do not take part in the formation of electron clouds.

5. Cyclic ions. In addition to the above neutral molecules, there are number of cyclic ions which are aromatic according
to Huckel’s rule. For example, cyclopropenyl cation, cyclopentadienyl anion and cycloheptatrienyl cation.

Å
Å Å
Cyclopropenyl Cyclopentadienyl Cycloheptatrienyl Cyclopentadienyl Cyclopentadienyl
cation anion, I cation cation, II radical, III
(2p electrons) (6p electrons) (6p electrons) (4p electrons) (5p electrons)

dfdfd
(Aromatic) Non-aromatic
Further, the Huckel rule is supported by the fact that unlike cyclopentadienyl anion I (having 6p electrons), the
corresponding cation II (having 4p electrons), and the free radical III (having 5p electrons) do not exhibit aromaticity.
It may be noted that the Huckel number 6 is the most common in aromatic system and hence the term aromatic
sextet is commonly used for these 6p electrons. Lastly, it must be noted that benzene is a perfect aromatic compound as
it has 6p electrons over a flat hexagonal ring. Since the regular hexagonal angle (i.e. 120°) is exactly the same as that of sp2
hybridised orbitals, there is no angle strain at all in the molecule. However, in case of other flat rings of smaller or bigger
size than benzene, there is always some angle strain which adversely affects the aromatic stability.
Earlier it was thought that other cyclic hydrocarbons with conjugated systems of alternating single and double
bonds would show similar stability. These cyclic hydrocarbons with alternating single and double bonds are called
annulenes. For example, benzene is the six-membered annulene, so it can be named [6] annulene, cyclobutadiene as [4]
annulene, cyclooctatetraene [8] annulene, and so on. However, cyclobutadiene and cyclooctatetraene are not aromatic, but
these are antiaromatic, as explained below.

7.5.2 Aromaticity
Planar cyclic conjugated species, less stable than the corresponding acyclic unsaturated species, are called
antiaromatic. Molecular orbital calculations have shown that such compounds have 4np electrons. In fact, such cyclic
compounds which have 4n p electrons are called anti-aromatic compounds, and this characteristic is called anti-aromaticity.
Thus antiaromatic compounds fulfill the first criterion for aromaticity but it does not fulfill the second criterion, (4n + 2)p
electrons.

1. Certain compounds (e.g. pyrrole, furan, etc.), although do not contain benzene ring, behave like benzene and hence grouped under
aromatic compounds ; such compounds are called non-benzenoid aromatic compounds.
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It is important to note that 1, 3-cyclobutadiene, is less stable than the acyclic 1, 3-butadiene which is confirmed
by the higher p electron energy of cyclobutadiene than that of 1,3-butadiene. Cyclobutadiene is such an unstable molecule
that even at 195 K, it undergoes Diel’s-Alder cycloaddition to form a dimer. The reactivity is probably due to anti-aromaticity.

195 K
+ ¾ ¾ ¾®

Thus cyclic conjugation, although necessary for aromaticity, is not the only criterion for aromaticity. Actually all
p electrons should be present in bonding orbitals in pairs. Cyclobutadiene and cyclooctatetraene are not aromatic because
in each case the two p electrons are present not in bonding orbitals but one in each, non-bonding orbitals.

nonbonding line

benzene cyclobutadiene cyclooctatetraene

Distribution of p electrons in benzene, cyclobutadiene and cyclooctatetraene
Cyclobutadiene is rectangular (not square) in shape while cyclooctatetraene is nonplanar (tub-shaped) molecule.
None of the two compounds show resonance.
In terms of Huckel rule, antiaromatic compounds have cyclic, non-planar structures with 4n p electrons. They
are destabilised by resonance. Some more examples of antiaromatic species are

. .Q Å . .Q

Cyclopropenyl anion Cyclopentadienyl cation Cycloheptatrienyl anion Cyclooctatetraene

(4p electrons) (4p electrons) (8p electrons) (8p electrons)

Relative stability order : Aromatic > Non-aromatic > Anti-aromatic

1. Using the Huckel rule, indicate whether the following species are aromatic or antiaromatic

(i) (ii) (iii) (iv) (v)

..
S..

(vi) (vii) (viii) (xi) (x)

N
..

C6H5 C6H5

(xi) (xii)
+ +
C6H5 C6H5

2. Cyclopentadiene and cycloheptatriene are not aromatic in nature, but azulene (having these two rings fused through two adjacent
carbon atoms) is aromatic in nature. Explain.
3. A red coloured compound is formed by the reaction of 2 moles of AgBF4 with 1 mole of 1, 2, 3, 4-tetraphenyl-3, 4-dibromocyclobut-
1-ene. Comment on the solubility, coloured nature and aromatic character of the compound.
4. Can you correlate the basic character of pyridine and pyrrole on the basis of delocalisation of p electrons of the cyclic cloud ?
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7.6 Substitution in the Monosubstitutedbenzenes

As discussed earlier, all the six hydrogen atoms of benzene nucleus are identical ; hence when one group (say X)
is introduced into the benzene nucleus only one product is obtained. On the other hand, when a second substituent (say
Y) is introduced in a monosubstituted derivative, three isomeric disubstituted products are possible.

X X X X
Y
–H –H
¾¾ ® ¾¾® ; ;
+X +Y
Y
Y
ortho- meta- para-
Disubstituted derivatives

However, experiments have shown that all the three products are never formed in quantitative yield and actually
the main product is either a mixture of ortho- and para-isomers (m-isomer being negligible in amount) or only the meta-
isomer (o- and p-isomers being negligible in amount). Further experiments have shown that it is the nature of the group
already present (X in the above case) on the benzene nucleus that directs the new incoming group (Y in the above case)
either to ortho and para positions (both) or only to meta position. This effect of the group already present on the nucleus is known
as directing influence of the group or orientation effect. On the basis of this effect all the known groups in organic
chemistry have been classified into two types.

7.6.1 o-, p-Directing Groups

These groups direct the incoming group predominantly to the o- and p-positions (the m-product, being negligible). Some
of the important groups of this type are
O
—
—
.. .. .. .. .. .. .. .. .. –
–NH 2, – NHR, – NR2, OH, – .OR, – .SH, – OCOR, –X
. . , – R, – C – O
..

..
.. . . .. ..
(– COO – is – COOH group in presence of alkali)
Note that all the o-, p-directing groups except alkyl and —COO– have unshared pair of electrons on the atom
attached to the benzene nucleus (key atom). Such groups, except halogens1, are electron releasing groups due to + E and +
M effects and hence increase the electron density on the benzene nucleus in the o- and p-positions (activation of the ring) and
thus they direct the new entrant to the o- and p-positions.
.. .. ..
OH OH OH
..

..

..

Electromeric effect (+ E) in o-, p-directing groups

.. +
.. ..
+ +
.. +
..
OH OH OH OH OH
..

d– d–
..

..

¬¾¾® ¬¾ ¾® ¬¾¾® º
. .–
d–
Mesomeric effect (+ M) in o-, p-directing groups
Further since such groups increase electrons density in the nucleus, they facilitate further, electrophilic substitution
and hence known as activating groups.

1. Halogens are strongly electron-attracting due to their high electronegativity.

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Chlorine (halogen) is although o-, p-directing due to + E and + M effects, it deactivates the ring due to strong – I effect.
But since + T* > – I, substitution will be taking place in o- and p- positions, but with difficulty (it is difficult to carry out the
substitution in chlorobenzene than in benzene).
Thus benzene having any of the activating groups undergoes electrophilic substitution very easily as compared
to benzene itself. Thus toluene (C6H5CH3), phenol (C6H6OH), aniline (C6H5NH2), etc. undergoes bromination very readily
than benzene.

7.6.2 m-Directing Groups

These groups direct the incoming group predominantly to the m-position (the o- and p-isomers, being negligible
in amount). Some of the important m-directing groups are
O H R OH OH
­ | | | | + +
— N = O , —C º N, — C = O , — C = O , — C = O , — S = O ,— N R 3 , — N H 3 , — CCl3
||
O
(—N+H3 is —NH2 group, e.g. aniline, in presence of acid)
Note that all the m-directing groups, except — CCl3 , either possess a positive charge or the key atom of the
substituent has an electronegative atom linked by a multiple bond. The benzene nucleus containing these groups will
undergo all the three** effects (—E, —M and —I) in such a manner that the displacement of the electrons takes place away
from the nucleus and towards the group, i.e. they withdraw electrons from the o- and p-positions, and thus direct the new
entering electrophile to the m-position which is having relatively high electrons density (since m-positions are not affected
by the existing group). Moreover, since m-positions are almost unaffected and the o- and p-positions have less electron
density, these groups are said to deactivate the benzene nucleus, i.e. they hinder the further substitution and hence known as
deactivating groups.
NO2
O ¬ N=O O ¬ N=O O ¬ N=O

Electromeric effect (– E) in nitrobenzene Inductive effect (– I) in nitrobenzene

.. .. ..
O ¬ N—O O ¬ N—O O ¬ N—O O ¬ N—O
..

..

..

.. .. ..
+ + d+ d+
¬¾® ¬¾® ¬¾® º

+ d+
Mesomeric effect (– M) in nitrobenzene

Thus benzene ring having any of the deactivating group undergoes electrophilic substitution with a great
difficulty as compared to benzene itself. Thus nitrobenzene (C6H5NO2), benzoic acid (C6H5COOH) etc. are very difficult
to nitrate while benzene can be nitrated easily.

Summary of effect of groups on electrophilic aromatic substitution

(i) Activating : o, p-directors
.. –
(a) Strongly activating : —NH2,—NHR, —NR2, —OH, — O
..

..
(b) Moderately activating : —NHCOCH3, —OCOR, —OR
(c) Weakly activating : —C6H5, —R, –CH = CH2
(ii) Deactivating : m-directors —NO2, —NMe3+, —CCl3, —CN, —COOH, —COOR, —SO3H, —CHO, — COR
(iii) Deactivating : o, p-directors : —F, — Cl, —Br, —I

* The sum of E and M effects is known as tautomeric effect (T) or conjugative effect.
+ +
** The —CCl3 , — N H 3 and — N R 3 groups undergo only —I effect.
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7.7 Role of Inductive and Hyperconjugative Effects in Aromatic Substitution of the

Substitutedbenzenes

7.7.1 Effect of Alkyl Group

Since the alkyl group does not have any lone pair of electrons, it will neither undergo electromeric effect nor
mesomeric effect (except Kekule’s structures for benzene). However, the alkyl group, e.g., methyl undergoes strong + I effect
which increases electron density in the op-positions and hence directs the entering group in these positions.
The importance of inductive effect in directing further substitution in toluene can be illuminated by the following
observation : as the hydrogen atoms of the methyl group are replaced by halogens, which exert —I effect, % of m-product
increases at the expense of the o, p-products.

CH3 CH2Cl CHCl2 CCl3

% of meta : 4 14 34 64
Activating influence : Activating Weakly deactivating Moderately deactivating Strongly deactivating

The orienting influence of the alkyl group should, therefore, be entirely due to inductive effect (but it is not so, see
later) which is in the following order :
CH3 < CH2CH3 < CH(CH3)2 < C(CH3)3
It means that the activating effect (orienting effect) of an alkyl group should also be in the same order, but in a
number of cases the order is found to be reverse. It is explained on the basis of hyperconjugation effect which is greatest in
the methyl group and lowest in tert-butyl group.

H H H H
+ + +
H—C—H H C—H H C—H H C—H

– –
¬¾® ¬¾ ® ¬¾® ¬ ¾ ® etc.
–

Hyperconjugation in toluene
Thus the o, p-directing influence of methyl group is due to inductive as well as hyperconjugation effect. Formation
of a lesser amount of ortho-product in case of tert-butyl group may partly be explained on the basis of steric hindrance.

+
7.7.2 Effect of Anilinium Ion ( NH3 )
It is very important to note that aniline is o, p-directing in aqueous solution but in presence of strong acids it
mainly gives the m-substitution product. The formation of the latter product is explained by the fact that in presence of
strong acids it forms anilinium ion which exerts a strong —I effect, due to the presence of positive charge, and thus mainly
yield the m-substituted product.
+
NH3
NH2
..

+
H
¾ ¾ ¾¾ ¾ ®

Aniline (o, p-directing due + T effect) Anilinium ion (m-directing due to – I effect)
However, the formation of a small amount of o- and p-substituted anilines in presence of strong acid is due to the
small residual concentration of free aniline, a very weak base. Due to the activated nucleus, the free aniline undergoes o-
and p-substitution very fast.
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+
7.7.3 Effect of NR3 Group
Due to the presence of positive charge, the group will exert a strong —I effect and withdraws electrons from the
o- and p-positions and thus leaves the m-positions, the point of relatively high electrons density where the substitution
will take place. That the positive charge on the nitrogen atom (or —I effect) is responsible for the m-substitution can be
proved by the fact that as the distance of the positive center from the benzene nucleus is increased by the introduction of
CH2 the percentage of m-product decreases, e.g.

+ + + +
NMe3 CH2NMe3 CH2CH2NMe3 CH2CH2CH2NMe3

% of meta 100 88 19 5

7.7.4 Effect of —CCl3 Group

The m-directing influence of the —CCl3 group is again mainly due to —I effect which can be represented as
below in case of benzorichloride.

Cl Cl

Cl ¾ ¬ C ® ¾ Cl Cl ¾ ¬ C ® ¾ Cl
¾¬

and ¾¬

Inductive effect (– I) in benzotrichloride

The m-directing influence of the —CCl3 group may also be explained by hyperconjugation.

Cl Cl Cl Cl
– – –
Cl—C—Cl Cl—C Cl Cl—C Cl Cl—C Cl

+ +
¬¾® ¬¾® ¬¾®

7.8 Orientation of Some Special Groups

7.8.1 Effect of Phenoxide

(Phenol in presence of alkali). In presence of strong alkali, phenol forms sodium phenate which easily ionises into
phenoxide ion. The phenoxide ion is o-, p-directing due to all the three effects viz. + M, + E and + I effects.

..
O O O O
..
..

..
..

..
..

..
..
..

..

¨ ¨ ¨
..

Mesomeric effect (+ M effect) in phenoxide ion

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.. ..
O O ..

..
..

..
..
O

..
..
Electromeric effect (+ E) Inductive effect (+ I) in phenoxide ion due
in phenoxide ion to the presence of negative charge

Since in the phenoxide ion, all the three effects reinforce each other, substitution is very easy.

7.8.2 Effect of Carboxylate Ion O O

–

(Carboxylic acid in the presence of alkali). Like the phenoxide ion, ions of acids in presence of C
base undergo o-, p-substitution (whereas the acids undergo m-substitution). It is again explained on
the basis of inductive effect; the presence of negative charge on the oxygen atom pushes the electrons d– d–
into the o- and p-positions of the nucleus which become the point of attack for the electrophilic attack.
d–

7.8.3 Effects Produced by the Protection of Hydroxy and Amino Groups

It is very important to note that the o-, p-substitution of the following three derivatives of phenol follows the order
given below.

: O: : O—CH3 : O—COCH3
:

Phenoxide ion Anisole Acetyl phenyl ether (Phenyl acetate)

–
O O O
+ +
:

: O—C—CH3 : O==C—CH3
:

O—C—CH3

–:
etc.

Acetyl pheyl ether showing the resonance of acetyl group.

The maximum ease for o, p-substitution of phenoxide ion is due to the fact that the negatively charged oxygen
with its three unshared electron pairs can supply electrons very effectively due to + I, + E and + M effects. On the other
hand, the methoxy and acetoxy groups have only two unshared electron pairs instead of three, so they are less susceptible
to electrophilic attack than the phenoxide ion. Moreover, in the acetoxy group the electron availability to the benzene
nucleus is further diminished by resonance in acetoxy group. Thus, although the acetoxy group is an activating o, p-
directing group, its activating effect is less than the methoxy group and much lesser than that of the phenoxide ion.
Similarly, deactivation effect of the amino group is produced by its acetylation.

–
O O
+ + +
:

NHCOCH3 NHCOCH3 NH—C— CH3 NH==C—CH3

–:
:

–
Resonance in acetanilide Resonance due to —COCH 3 group
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Summary of Directive Influence of Groups
Group Electronic effects and their net result Rate controlling effect Oreinting effect
..
—O – + E, + M, + I
.. (Phenoxide ion)
.. Strongly activating o, p
(Electron release)
.. ..
— N R2, — N HR, + E, + M, – I Strongly activating o, p
(Electron release)
.. .. ..
— N H2, — O
.. H, — O .. R
.. ..
— N HCOR, — O .. COR + E, + M, – I Moderately activating o, p
(Electron release)

—C6H5 + M, – I Weakly activating o, p

(Electron release)

—R + I, hyperconjugation Weakly activating o, p

—CH = CH2 +M (Electron release) o, p

.. .. ..
— Cl
.. , — Br
.. , ..I + E, + M, – I Weakly deactivating o, p
..

..
..

(Electron release)

—NO2, —CN, —SO3H, – E, – M, – I Strongly deactivating m

(Electron withdrawl)
—COOH, —COOR,
—CHO, —COR

+ + –I
— N H3 , — N R3 (Electron withdrawl) Strongly deactivating m
—CCl3 —I, hyperconjugation Strongly deactivating m
(Electron withdrawl)

7.9 Theory of Reactivity Based on Carbocation (s-Complex) Stability

We know that in every electrophilic aromatic substitution reaction, first step (slow and thus rate determining) is
the attack of an electrophile on benzene ring to form a carbocation.
H X
slow +
Å
+ X ¾¾ ¾ ®

Benzene Electrophile Carbocation

Further we know that the carbocation is a resonance hybrid (represented as IV) of structures I, II and III, i.e. its
positive charge is not localised on one carbon atom but dispersed over the entire ring, of course it is strongest at positions
ortho and para to the carbon atom being attacked.

H X H X H X H X
slow + +
+
+X ¾¾® ¬® ¬® º +

+
I II III IV

Now since dispersal of the positive charge stabilizes the carbocation, more the chances for the dispersal of
positive charge more is the stability of the carbocation and hence greater is the reactivity of the compound toward electrophilic
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substitution. Thus any substituent (e.g. electron-releasing groups) which stabilises the intermediate carbocation by dispersing the
positive charge will increase the overall rate of reaction, while a substituent (e.g. electron-atitracing groups) which destabilises the
intermediate carbocation by intensifying (concentrating) the positive charge will decrease the rate of reaction.
Let us compare the rates of substitution in benzene, toluene and nitrobenzene. The intermediate carbocations of
the three compounds with the electrophile X+ have the following structures.
H X H X H X

+ + +

CH3 NO2
I II III
Carbocation has no substituent Carbocation stabilised by dispersal Carbocation destabilised by
hence less stable than II of positive charge by electron- intensification of positive charge
but more than the III releasing —CH3 group by electron-withdrawing —NO 2 group

Note that in II, the —CH3 group, being electron-releasing, releases electrons and thus tends to neutralise positive
charge of the ring and itself becomes somewhat positive. This dispersal of positive charge of the ring stabilises the
carbocation and hence facilitates its formation which ultimately results an increased rate of reaction. Now since such
factor (substituent) is not present in benzene, its carbocation I is relatively less stable than II. Hence toluene undergoes
electrophilic substitution at a faster rate than benzene. This is also true when benzene has —NH2, —OH, —OCH3, —
NHCOCH3,or —C6H5 group in place of —CH3 group. However, remember that electron release by —NH2, —OH and their
derivatives (—NHCOCH3, —OCH3, —OCOCH3) is not due to the inductive effect but due to resonance.
On the other hand, in carbocation III the —NO2 group (an electron-withdrawing group) intensifies positive charge
on the ring and thus destabilises the carbocation III and hence its formation becomes difficult which ultimately results a
slower reaction. Now since such substituent is not present in benzene, its carbocation I is relatively more stable than the III.
Hence nitrobenzene undergoes electrophilic substitution at a slower rate than benzene. This is also true when benzene has
—N+Me3, —CN, —SO3H, —COOH, —CHO, —COR or — X group in place of —NO2 group.
Summary

We can say that an electron-releasing group stabilises the carbocation by dispersing its positive charge and thus activates the ring
while an electron-withdrawing group destabilises the carbocation by intensifying its positive charge and thus deactivates the ring.
Further, an activating group activates although all positions of the benzene ring, its activating effect is much more on ortho and para
positions than on meta position with the result substitution occurs mainly on the ortho and para position. Similarly, a deactivating
group deactivates although all positions in the ring, its deactivating effect is much more on ortho and para positions than on meta
position with the result further reaction occurs mainly on the meta position. In short, the activating or deactivating effect of a group is
strongest at the ortho and para-positions.

7.10 Theory of Orientation and Carbocation Stability

The ortho-, para- or meta- directing nature of the groups can also be explained on the relative stabilities of the
intermediate carbocations. For convenience, the effects of different substituents are considered under four sub-heads.

7.10.1 Ortho-, para- Directing Groups with + I Effect

The simplest example of such group is a methyl group. So let us draw and compare the intermediate carbocations
formed by electrophilic attack at the ortho, para and meta positions of toluene. Each of these carbocations is a resonance
hybrid of three structures as shown below.
CH3 CH3 CH3

H H H Ortho
+
X ¨ X ¨ X substitution
+ +

Ia Ib Ic
Especially stable (because
positive charge is present
on C carrying + I group
and hence easily neutralised)
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CH3 CH3 CH3

+ Para
¨ ¨ substitution
+ +

H X H X H X
IIa IIb IIc
Especially stable (Positive charge easily neutralised)

CH3 CH3 CH3

Meta
+ +
H ¨ H ¨ H substitution
+
X X X
IIIa IIIb IIIc
It is to be noted that in the contributing structures Ia of the ortho substitution and IIb of the para substitution, the
positive charge is located on the carbon atom carrying the methyl (an electron-releasing) group. These structures have
special significance because the electron-releasing methyl group although releases electrons to all positions of the ring, it
does so most strongly to the carbon atom nearest to it with the result the positive charge on such a carbon is highly
dispersed and hence the concerned structures (Ia and IIb) are particularly stable. On account of contribution from structures
Ia and IIb, the hybrid carbocations formed during attack at ortho and para positions are more stable than the hybrid
carbocation (having no structure like Ia and IIb) formed during the attack at meta position. As a result, o, p-substitution is
faster than meta substitution in toluene. The situation is practically the same in case of all other alkyl groups.

7.10.2 Ortho–, para– Directing Groups having Weaker –I and Stronger + M Effects
From our previous study we know that all o, p-directing groups, except alkyl groups1, exert – I and + M effects and
further that in all such groups, except halogens2, + M effect is much stronger and hence more important than the —I effect
with the result all o, p-directing groups, except halogens, activate the benzene ring for further substitution. Since activating
effect is stronger in o, p-positions than in the m-position, further substitution occurs in o, p-positions. Now let us explain
the o, p-directing effect of such groups (e.g. —NH2 group) on the basis of stabilities of the intermediate carbocations.
The carbocations formed by electrophilic attack at the o-, p- and m-positions of aniline are resonance hybrids of
the corresponding structures shown below.
+
NH2 NH2 NH2 NH2
..

..

..

+ H H H H Ortho
X ¨ X ¨ X ¨ X substitution
+ +

IVa IVb IVc IVd

Extra resonance form
especially stable
(Every atom has an octet)
+
NH2 NH2 NH2 NH2
..

..

..

+
Para
¨ ¨ ¨ substitution
+ +

H X H X H X H X
Va Vb Vc Vd
Extra resonance form
especially stable (Every
atom has complete octet)

1. Alkyl groups undergo + I effect and no mesomeric effect.

2. In halogens, two opposite effects (– I and + M) are operating. Here, although further substitution takes place in o, p-positions due to
+ M effect, the ring is weakly deactivated due to —I effect, i.e. further substitution is not easy.
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NH2 NH2 NH2

..

..

..
+ +
Meta
H ¨ H ¨ H substitution

+ X X X
VIa VIb VIc

Note that the carbocations of ortho and para substitutions are hybrids of four contributing structures, while that
of meta substitution is a hybrid of only three structures. Further, it must also be noted that the contributing structures IVd
(of the ortho substitution) and Vd (of the para substitution) are particularly stable since in these, every atom has a complete
octet of electrons except hydrogen which has a duplet. Consequently the hybrid carbocations formed during ortho and para
substitutions are much more stable than the hybrid carbocation formed during meta substitution, which has no structure
comparable to IVd and Vd, or during the attack on benzene itself. Hence substitution in aniline occurs faster than in
benzene and mainly in the ortho- and para-positions.
.. .. .. ..
A similar explanation is applicable to other groups like — N HR, — N R2, — O H, O R, etc.

7.10.3 o, p-Directing Groups having Stronger —I and Weaker + M Effects (Effect of halogens)
The effect of halogens is partly similar to that of the type of —NH2 group discussed just above (both exert + M
effect) with the significant difference that the halogens exert strong – I effect while the —NH2 type of groups exert weak
—I effect. The strong —I effect of halogens bears an important implication on the stability of the carbocations formed by the
attack of an electrophile on the ortho and para positions.
The various contributing structures of the carbocations formed by the attack of an electrophile (X+) on the o-, p-
and m-positions of a halogenobenzene (e.g. chlorobenzene) are drawn below.
.. .. .. ..
Cl Cl Cl + Cl
..
..

..
..

..
..

..
H H H H Ortho
+
X ¨ X ¨ X ¨ X substitution
+ +
VIIa VIIb VIIc VIId
Especially unstable Comparatively stable
(positive charge is (Every atom has
present on C carrying complete octet)
strong – I group)
.. .. .. ..
Cl Cl Cl + Cl
..
..

..
..

..
..

..

+
Para
¨ ¨ ¨ substitution
+ +

H X H X H X H X
VIIIa VIIIb VIIIc VIIId
Especially unstable Extra resonance form
(positive charge intensified comparatively stable
on C carrying —Cl group) (Every atom has octet of electrons)
.. .. ..
Cl Cl Cl
..
..

..
..

..
..

+ + Meta
H ¨ H ¨ H substitution
+ X X X
IXa IXb IXc
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Evidently, structures VIId (in ortho substitution) and VIIId (in para substitution) are comparatively stable since
in these structures every atom (except hydrogen) has a complete octet of electrons, while structures VIIa (in ortho
substitution) and VIIIb (in para substitution) are particularly unstable since in these structures the positive charge is
intensified to the maximum extent because electron-withdrawing substituent (—Cl) is present nearest to the carbon
bearing positive charge. However, the stabilisation by structures VIId and VIIId is more than the destablisation by structures
VIIa and VIIIb. The net result is that the carbocations formed by ortho and para substitutions are more stable than that of
meta. Hence the substitution will predominantly take place in o, p-positions.
The inductive effect (—I) of —Cl deactivates the ring particularly at ortho and para positions. However, the —I
effect is opposed by electron releasing mesomeric effect (+ M effect) which is effective only for attack at ortho and para
positions. The net result is that the ortho and para positions are deactivated to a lesser extent than the meta position.
Consequently, further substitution can take place primarily at ortho and para positions (due to + M effect) although the
rate of reaction is slower (due to —I effect) than in case of benzene.
Thus we see that in halogenobenzenes, reactivity is controlled by the stronger inductive effect while orientation
is controlled by the resonance effect.

7.10.4 Effect of m-Directing Groups

+ +
From our previous study we know that all m-directing groups are deactivating and, except — N H3 and — N R3 ,
exhibit —I and —M effects, while the two exceptional groups show only —I effect. Let us explain the deactivation and meta
orientation effect on the basis of carbocation stability. The carbocations formed by attack at the ortho, para and meta
positions of nitrobenzene are hybrids of the contributing structures given below in each case.

NO2 NO2 NO2

H H H Ortho
+
X ¨ X ¨ X substitution
+ +

Xa Xb Xc
Especially unstable
(Positive charge on C,
carrying –I group, intensified)

NO2 NO2 NO2

+
Para
¨ ¨ substitution
+ +

H X H X H X

XIa XIb XIc

Especially unstable
(Positive charge on C,
carrying – I group, intensified)

NO2 NO2 NO2

+ + Meta
H ¨ H ¨ H substitution
+ X X X

XIIa XIIb XIIc

Evidently, structures Xa (in ortho substitution) and XIb (in para substitution) are particularly unstable because
in these structures positive charge is located on the carbon atom carrying the electron-attracting (—NO2) substituent
and hence is not dispersed but intensified. Thus these structures (Xa and XIb) are particularly unstable and contribute
little to stabilise the carbocations. Thus virtually the ortho and para substituted carbocations are resonance hybrids of
only two structures while the meta substituted carbocation is a resonance hybrid of three structures and hence more stable
than the carbocations obtained from ortho and para attacks. Therefore, substituion mainly takes place at meta position.
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1. Arrange the following groups in order of activating a benzene ring toward electrophilic substitution.
(i) —NH2, —CONH2 and —NHCOCH3 (ii) —OH, —OCOCH3 and —COCH3
2. Arrange the following carbocations in decreasing stability (increasing potential energy)
CH3 CH3
H H
+ E + E + H

I II III E
3. Identify the products A to C.
CCl3 OH SO3H

NO2+ BF4– D2SO4/D2O D2SO4/D2O

(i) ¾¾ ¾¾® A, (ii) ¾¾ ¾¾® B, (iii) ¾¾ ¾¾® C
heat heat

4. Arrange the following compounds of each set in order of reactivity towards electrophilic substitution
(i) C6H5CH3 C6H5CH2COOCH3 C6H5C(COOCH3) 3
I II III
(ii) C6H5N+Me3 C6H5CH2N+Me3 C6H5CH2CH2N+Me3
I II III
O
.. .. . . ||
Q
(iii) —O H — O — . . C —CH3
O —
..

.. ..
I II III
5. Give the resonance hybrid structure for the three possible benzenonium ions formed during electrophilic substitution of
monosubstituted benzene with the electrophile E+.
6. Arrange the following compounds in order of decreasing reactivity to ring monobromination :
(i) C6H5NH2, C6H5NH3+Cl–, C6H5NHCOCH3, C6H5Cl, C6H5COCH3
(ii) C6H5CH3, C6H5COOH, C6H6, C6H6Br, C6H5NO 2
(iii) p-xylene, m-xylene, toluene, p-toluic acid, terphthalic acid.

HOMOLOGUES OF BENZENE (ARENES)

Benzene and its alkyl derivatives have CnH2n–6 as general formula, where n is the number of carbon atoms.
In case hydrogen atom of benzene is replaced by alkenyl or alkynyl groups, compounds are known as
alkenylbenzenes or alkynylbenzenes respectively.

C6H 5 C º CH ¬¾¾ C6H6 ¾¾® C6H 5 CH = CH 2

Phenylacetylene Phenylethylene (Styrene)
(Vinylbenzene)

Alkyl-, alkenyl- and alkynylbenzenes are collectively known as arenes. Thus arenes may be defined as those
hydrocarbons which contain a benzene nucleus in their structures.

7.11 Methods of Preparation of Alkylbenzenes

1. By Friedel-Craft reaction (alkylation and acylation). For details, consult reactions of benzene.

2. By Wurtz-Fittig reaction
Na
(a) C6H5Cl + 2Na + ClCH3 ¾ ¾ ¾ ® C6H5CH3 + 2NaCl
ether
Na, ether
(b) 2C6H5Cl + 2Na ¾ ¾¾ ¾ ¾ ® C 6 H 5 C 6 H 5 + 2NaCl
Fittig reaction
Biphenyl
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Such reactions may proceed via free radical or ionic mechanism. However, ionic mechanism involving formation
of organometallic compounds is found to be more reasonable.
3. From phenols
OH CH3

Zn
CH3 ¾¾ ¾® + ZnO
dust

o-, m-, p-Cresols Toluene

4. From aromatic sulphonic acids
CH3 CH3

HOH
SO3H ¾¾ ¾® + H2SO4
heat

o-, m-, p-Toluene– sulphonic acids

5. By the reduction of arenediazonium salts with hypophosphorous acid

CH 3
C6H4 + H3PO2 + H2O ¾® C6H5CH3 + N2 + HCl + H3PO3
N 2 Cl
o-, m-, p-Toluenediazonium chlorides
6. From Grignard reagents
C6H5MgBr + BrCH3 ¾¾® C6H5CH3 + MgBr2

1. Predict the product when excess of benzene is treated in presence of AlCl3 with (a) 1, 2-dichloroethane, (b) chloroform and (c)
tetrachloromethane.
2. Of the three isomeric xylenes, which has maximum melting point and lowest solubility in water.
3. How will you carry out the following conversions ?
(i) Benzene to p-nitrochlorobenzene (ii) Benzene to m-nitrochlorobenzene
(iii) Toluene to p-nitrobenzoic acid and m-nitrobenzoic acid.

7.12 Reactions of Alkylbenzenes

1. Substitution in the ring (electrophilic aromatic substitution). Since the alkyl groups are activating,
alkylbenzenes undergo electrophilic substitutions more readily than benzene.
Further, substitution will occur mainly in the o- and p-positions because the corresponding intermediate
benzenonium is more stable than that of m-. Important examples are given below.
(i) Nitration

CH3 CH3 CH3 CH3

NO2 O2N NO2
conc. HNO3 fuming HNO3
¾¾ ¾ ¾¾ ® + ¾¾ ¾ ¾¾ ¾ ®
conc. H2SO4

NO2 NO2
2, 4, 6-Trinitrotoluene
(TNT)
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(ii) Sulphonation

CH3 CH3 CH3

SO3H
conc. H2SO4
¾ ¾ ¾¾¾ ® +
SO3

SO3H

o- and p-Tulenesulphonic acids

(iii) Halogenation

CH3 CH3 CH3

X
X2, FeX3
¾¾ ¾ ¾¾ ® +
X=Cl, Br

X
(iv) Friedel Craft alkylation

CH3 CH3 CH3

CH3
CH3X, AlCl3
(a) ¾¾ ¾¾¾ ® +
0°C

CH3
o-Xylene p-Xylene

At 0°C, rate controlled products (o- and p-xylenes) are formed.

CH3 CH3

CH3X, AlCl3
(b) ¾¾ ¾ ¾¾ ®
80°C
CH3
m-Xylene

At 80°C, equilibrium controlled product (m-xylene) is formed.

(v) Friedel Craft acylation

CH3 CH3 CH3

COCH3
CH3 COCl
¾ ¾ ¾¾ ® +
AlCl 3

Toluene
COCH3

2. Substitution in the side chain (Free-radical halogenation). Alkylbenzenes when treated with Cl2 or Br2
at high temperature, in the presence of sunlight and absence of halogen carrier undergo halogenation in the side
chain. Thus

CH3 CH2Cl CHCl2 CCl3

Cl2 heat Cl2 Cl2

¾¾ ¾¾® ¾¾ ¾¾® ¾ ¾ ¾¾ ®
light heat, light heat, light
Toluene Benzyl chloride Benzyl chloride Benzo trichloride
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Mechanism
This is similar to that of halogenation of alkanes (free radical mechanism). The essential steps are summarised
below.
heat
(i) Formation of free radical : Cl—Cl ¾¾¾® Cl.
or light
.
(ii) Chain initiating step : C6H5CH3 + Cl. ¾¾® C6 H 5 C H 2 + HCl
Benzyl free radical
(More stable than toluene)
.
(iii) Chain propagating step C 6 H 5 C H 2 + Cl 2 ¾¾® CH6 CH 2 Cl + Cl .
Benzyl chloride
Steps (ii) and (iii) are repeated to form more and more benzyl chloride. Simultaneously benzyl radical can form
a new radical which can lead to formation of benzal chloride.
.
C6H5CH2Cl + Cl. ¾¾® C6H5 C HCl + HCl
.
C6H5 C HCl + Cl2 ¾¾® C 6 H 5 CHCl 2 + Cl., and so on.
Benzal chloride
.
Similarly, C6H5CHCl2 + Cl. ¾¾® C6H5 C Cl2 + HCl
.
C6H5 C Cl2 + Cl2 ¾¾® C6H 5 CCl 3 + Cl ., and so on.
Benzotrichloride
Side chain halogenation* of alkylbenzenes having a side chain more complex than methyl. For example,
CH2CH3 CHBrCH3 CH2CH2Br

Br2
¾¾ ¾ ¾¾ ®
heat, light

1-Bromo-1-phenylethane 2-Bromo-1-phenyl ethane

(sole product) (not formed)

In general, it has been observed that the hydrogen atom(s) attached to carbon directly linked to the benzene ring
is(are) preferentially replaced. Such hydrogens are know as benzylic hydrogens.
Benzylic hydrogens

CH2CH2CH3

Benzylic carbon

The greater reactivity of benzylic hydrogens (i.e. predominance of a-substituted product) is due to greater stability
g
of benzylic free radical 1 than the other. For example, the benzylic radical (C6H5 CHCH3) I obtained from
ethylbenzene is a hyrbid of the following contributing structures.
. .
CHCH3 CHCH3 CHCH3 CHCH3 CHCH3
. .
¨ ¨ ¨ ¨
.
I
& H ) II, obtained from ethylbenzene is a resonance hybrid of
On the other hand, the second radical (C6H5CH2 C 2
only two Kekule structures shown below.
. .
CH2CH2 CH2CH2

¨

II
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The greater relative stability of benzylic radical and therefore, its greater ease of formation are responsible for the
relatively greater ease of substitution of benzylic hydrogens.
It may be interesting to note that the energy content of benzyl radical (85 kcal) is almost similar to that of allyl
radical (88 kcal) ; hence the stability of the two radicals is nearly similar. The relative order of stability of the
various radicals is as given below.
_ allyl > tertiary > secondary > primary > methyl > vinyl
Benzyl ~
It is important to note that as in alkanes, orientation of side chain chlorination of ethylbenzene shows that
although chlorine atoms (chlorine free radicals) also preferentially attack benzylic hydrogen, here the preference
is less than that in bromination.

CH2CH3 CHClCH3 CH2CH2Cl

Cl2
¾¾ ¾ ¾¾ ® +
heat, light

1-Chloro-1-phenylethane 2-Chloro-1-phenylethane
(91%) (9%)

This is due to the fact that the more reactive chlorine is less selective (selectivity reactivity principle). Under
conditions where 3°, 2° and 1° hydrogens show relative reactivities of 5.0 : 3.8 : 1.0, the relative rate per benzylic
hydrogen atom of toluene is found to be only 1.3.
3. Hydrogenation.

R R

Ni, Pt, or Pd
+ 3H2 ¾¾ ¾ ¾¾ ¾ ®

Alkylcyclohexane

4. Birch reduction.
Alkali metal and liquid ammonia is a powerful reducing system. H H
In presence of alcohol, this combination of reagent reduces arenes Na, NH3
to 1,4-cyclohexadienes (nonconjugated dienes). This metal-ammonia- CH3 OH
alcohol reductions of aromatic rings are known as Birch
H H
reductions.
Benzene 1,4-Cyclohexadiene

Mechanism of Birch reduction is analogous to the mechanism for the metal-ammonia reduction of alkynes to alkenes.
The reaction involves the formation of anionic intermediates, thus electron-withdrawing substituents stabilize
the carbanions. Therefore, reduction takes place on carbon atoms bearing electron-withdrawing substituents
and not on carbon atoms bearing electron releasing substituents like alkyl and alkoxy groups. Thus alkyl
substituted arenes give 1,4-cyclohexadienes in which the alkyl group is a substituent on the double bond.

CH3 CH3 H CH3

H
Na, NH3
H and not
CH3CH2 OH H
H H H

COOH –
H COO
Na, NH3
CH3CH2 OH
H H
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5. Oxidation.
Although benzene and alkanes are quite unreactive toward the CH2R COOH
usual oxidizing agents (KMnO4, K2Cr2O7 etc.), alkylbenzenes can
be oxidised to benzoic acid. It is important to note that the alkyl
hot KMnO 4 ,
side chain, irrespective of its size or nature, is completely oxidised ¾¾ ¾¾ ¾ ¾¾ ¾ ¾¾ ®
to carboxylic group. K2Cr2O7, or dil. HNO3
An exception to this is a tert-alkyl substituent. Thus
CH3 COOH
CH3 +
COOH
K2Cr2O7, H

C(CH3)3 C(CH3)3
4-tert-Butyl-1,2-dimethylbenzene

Actually, any alkyl group having benzylic hydrogen is susceptible to oxidation; since tert-butyl group has no
benzylic hydrogen atom, it will not be oxidised.
However, remember that oxidation of a side chain is more difficult than that of an alkene, and requires prolonged
treatment with hot KMnO4.
6. Partial oxidation.
CH2CH2CH3 CH2CH2CHO
Milder oxidising agents like chromyl chloride (CrO2Cl2) or
chromium oxide in presence of acetic anyhydride oxidise CrO2Cl2
the end methyl group of the side chain to aldehydic group ¾ ¾ ¾¾ ¾ ®
(Etard reaction).

7.13 Alkenylbenzenes

7.13.1 Preparation
1. By dehydrogenation of the side chain.

CH2CH3 CH=CH2

AlCl3 Cr2O3
+ CH2=CH2 ¾¾ ¾ ¾® ¾ ¾ ¾¾¾ ®
or H3PO4 Al2O3, 600°C

Styrene (Vinylbenzene)

2. By dehydration of hydroxyalkylbenzenes.
CHOHCH3 CH2CH2OH CH=CH2

heat
or ¾¾ ¾ ®
ZnCl2

3. By dehydrohalogenation of haloalkylbenzenes.
CHClCH3 CH2CH2Cl CH=CH2

alc. KOH
or ¾¾ ¾¾®
heat

4. By decarboxylation of carboxylic acids having an unsaturated side chain.

CH=CH COOH CH=CH2

heat
¾¾ ¾¾®
(– CO2)
Cinnamic acid
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7.13.2 Chemical Reactions

Alkenylbenzenes undergo electrophilic substitution (in benzene ring) and electrophilic addition (in unsaturated
side chain and also in benzene ring) reactions.
Some important reactions are given below.
1. Hydrogenation
CH=CH2 CH2CH3 CH2CH3

H2—Ni H2—Ni
¾¾ ¾ ¾¾ ® ¾¾ ¾ ¾¾ ¾ ¾®
20°C, 3 atm. 125°C, 110 atm.

2. Oxidation
COOH CH=CH2 CHOH.CH2OH

cold KMnO4 H2O2, HCO3H

¬¾ ¾ ¾¾ ¾ ¾¾ ¾¾ ¾¾¾ ¾®
(strong reagent) (mild reagent)

3. Addition of halogen acids

CH2CH2Br CH=CH2 CHBrCH3

hn
¬¾¾ ¾¾¾ ¾¾¾ ¾ ¾ + HBr ¾¾ ¾¾ ¾ ¾¾ ®
(free radical addition) (ionic addition)

In above two reactions, opposite products is explained on the basis of the fact that in ionic reaction the electrophile
H+, while in free radical addition reaction the bromine atom (Br.), adds to the double bond in the first step of the
addition producing benzylic cation and benzylic radical respectively.
. +
CHCH2Br CH=CH2 . CHCH3

. +
Br H
¬ ¾¾ ¾ ¾¾ ¾ ¾ ¾ ¾ ¾¾ ¾ ®
from HBr, hn from HBr
Benzylic radical Benzylic cation
(More stable) (More stable)

4. Addition of halogens. In dark and in presence of a suitable catalyst, halogens react with the double bond
(electrophilic addition) as well as benzene ring (electrophilic substitution) of alkenylbenzenes. This is because
of the fact that the first step (attack of X+ ion on the p electron cloud) in both reactions is common. However,
experimental results show that addition of halogens to the side chain is first completed before the electrophilic
substitution takes place. This is due to the fact the side chain double bond is more susceptible to electrophilic
attack than the resonance stabilised benzene ring.
CH=CH2 CHClCH2Cl CHClCH2Cl

Cl2 Cl2
¾ ¾ ¾® ¾¾ ¾®
FeCl3 FeCl3
Cl

1. (a) Although styrene C6H5CH = CH2 has extended conjugation, yet it reacts faster than the simple alkenes. Explain.
(b) Tetraphenylethylene does not react with bromine in carbon tetrachloride. Comment.
2. How will you prepare p-chlorostyrene in quantitative yield from styrene ?
3. How will you prove that 1-phenylpropene (C 6H5 CH = CHCH 3) is more stable than the isomeric 3-phenylpropene
(C 6H5CH2CH = CH2)?
4. Give all steps in the conversion of
(a) ethylbenzene into phenylacetylene (b) trans-1-phenylpropene to cis-phenylpropene.
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7.14 Tests of Arenes

Following reactions of aromatic hydrocarbons with saturated side chains are used as their chemical tests to
distinguish from other hydrocarbons.
1. They are easily sulphonated by (and thus dissolve in) cold fuming sulphuric acid (difference from alkanes).
However, they do not dissolve immediately in cold conc. H2SO4 (difference from alcohols).
2. They give orange to red colours upon treatment with chloroform and aluminium chloride. These colours are due
to the formation of triarylmethyl cations, Ar3C+ which are formed by a Friedel-Craft reaction followed by a
transfer of hydride ion.
CHCl3 ArH ArH
ArH ¾¾¾® ArCHCl2 ¾¾¾® Ar2CHCl ¾¾¾® Ar3CH
AlCl 3 AlCl 3 AlCl 3

AlCl 3 + Ar CH
Ar2CHCl ¾¾¾® Ar2 C HAlCl4– ¾¾¾®
3
Ar2CH2 + Ar3C+ AlCl4–
Triarylmethyl cation
(orange to red colour)
This test is given by all benzenoid compounds which can undergo Friedel-crafts reaction. The colour produced
depends upon the nature of the aromatic system.
Benzene system gives orange to red colour Naphthalene system gives blue colour
Phenanthrene system gives purple colour Anthracene system gives green colour.

7.15 Predicting Orientation in Disubstitutedbenzenes

1. If the two groups reinforce each other, there is no competition between two positions and hence only one product
is formed, e.g.
CH3 CH3

3 3

CH3
NO2
2. If there is a competition between two op-directing groups, the one with stronger tendency to release electrons
will control the orientation. The various activating groups can be arranged in the following order of decreasing
activation of the ring
O–, NR2, NH2, OH > OR > OCOR > NHCOCH3 > C6H5 > CH3 > X
Thus, further substitution will take place at the site marked 3.
CH3 (weaker) CH3 (weak)
OH (stronger)

3 3 3

OCH3 (moderate)
3. If the competition is between op-directing and m-directing groups, the op-director controls the orientation. However,
if the m-director is situated meta to an op-director, the third group enters o to the m-directing group,
NO2 CH3 CH3
(Major) 3 3 (Minor) NO2

3
Cl NO2
3
Br
Although no suitable explanation is available for this observation, it may be presumed that the meta-directing
group possibly gives intramolecular assistance.
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7.16 Nucleophilic and Free-Radical Substitutions

Nucleophilic aromatic substitutions of H are rare. The intermediate benzenanion in aromatic nucleophilic
substitution is analogous to the intermediate benzenonium ion in aromatic electrophilic substitution.
Nu
H Nu H Nu
– O2 or K3 [Fe(CN) 6]
–
+ Nu ¾¾® º ¾¾ ¾¾¾ ¾¾¾ ® + H2O
..
(slow step)

Benzenanion

Oxidants such as O2 and K3 Fe(CN)6 facilitate the second step, which may be rate-controlling, by oxidising the
ejected hydride ion (a powerful base and a very poor leaving group), to H2O.
Free radical substitutions also proceed by an intermediate, similar to benzenonium ion and benzenanion,
having free-radical character distributed to the op-positions. Note the following two special features of the aromatic
radical substitutions.
(i) Substituents have much less effect than in electrophilic or nucleophilic substitutions, i.e. the new group may
enter at o, p or m-position.
(ii) Both electron-withdrawing as well as electron donating groups increase reactivity at o- and p-positions,
except in case of steric hindrance.

1. Predict the product in the following reaction :

NO2

–
+ CN ¾¾® Product
..

NO2
2. Predict the products in the following reaction :
heat
C6H5N = NOCOCH3 + C6H6 ¾¾¾® P

Example 1 :
Taking biphenyl as an example, draw resonance forms of a sigma complex to show that a phenyl group is o,p-
directing.
Solution :
Let us draw resonance forms of the s complex of ortho attack.
+

+ +
E E + E E E E
H H H H H H
+ +
I II III IV V VI

Similar structures are possible for the s complex of para attack; however, meta attack does not permit delocalisation
of the positive charge on the phenyl substituent, i.e. resonance structures corresponding to IV to VI are not possible
because here none of the resonating structure has a positive charge on the carbon atom adjacent to the phenyl group
(cf structure III).
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+ +
E E E
H H +
H
I II III

Thus the s complex corresponding to ortho and para attack are much more stable than that from m attack.

Example 2 :
Write down the structure of the product formed when benzene is treated with propylene oxide in presence of
aluminium chloride. Propose a mechanism for the reaction.
Solution :
We know that epoxides are quite reactive compounds and undergo ring opening under acidic conditions. This leads
to formation of an electrophile which reacts with benzene to form substituted product.
.. –
O – Al Cl 3

..
.. + –
O : O – Al Cl3 +
..

+ AlCl3 CH3 – CH – CH2

CH3 CH3 electrophile

CH3
– H
OAl Cl3 +
–
+
CHCH2OAl Cl 3
B

..
+ CH3CHCH2
(e.g. H2O)

CH3 CH3
–
CHCH2OAl Cl3 + CHCH2 OH
BH
+ AlCl3 + : B

Example 3 :
Which of the following compound is much more acidic than the others. Pick it up and explain.

Solution :
More the stability of the corresponding carbanion, more will be the acidic character of the present hydrocarbon. Thus
the corresponding carbanion formed by the four compounds will be

. .– . .– . .– . .–
CH2 CH2 CH2 CH2

I II III IV
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Although all the four structures are resonance stabilized, structure II is especially stable as its one of the resonating
structures (IIa) has an aromatic sextet. Thus among the four structures, structure II is most likely to be formed, thus
its conjugate acid is the most acidic.

.–.
CH2
–
..
–

II IIa Aromatic

Example 4 :
Purine has four nitrogen atoms, which one of them is expected to be basic? Explain.

6 ..7
1 5 N
N
..
8
2 ..
4
3N
.. N9
H
Purine

Solution :
Purine has two types of nitrogens. Lone pair of electrons on N on N1, N3 and N7 is in an sp2 orbital which is planar
with the ring. These electrons are available for bonding, and thus these three nitrogens are basic. The other type of
nitrogen is N9 whose nonbonding electron pair has in a p orbital which is perpendicular to the ring system, hence
involved in delocalisation, i.e. it forms a part of the aromatic p system. With this pair of electrons, the p system is
aromatic and has 10 electrons, a Huckel number. So this electron pair is not available for bonding and N9 is not basic.

Example 5 :
Explain why each compound is aromatic, antiaromatic, or nonaromatic.

O O H
+ .. .. B ..
H3C HN NH
NH
(a) :N :S: (b) .. (c) (d) .. (e)
.. HB .. BH
O
.. O N O N
.. H
1,3-Thiazole Pyrylium ion g -Pyrone
H
Thymine Borazole

Solution :
(a) Aromatic : 4p electrons form two double bonds plus one pair of electrons (lying in p
N S
..
..
..

orbital) from sulphur. The other pair of electrons on S and the pair of electrons of N lie in
sp2 orbitals.
1,3-Thiazole
Both N and S are sp2 hybridised; only one lp of electrons is in p orbital, hence form part of aromatic system.
(b) Aromatic : 4p electrons form two double bonds plus a pair of electrons from O making total of 6p electron system.
(c) Resonance form of g-pyrone has 6p electron aromatic system; hence aromatic.
. .–
O O
..
..

..
..

..
O
.. O
. .+
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(d) Resonance of thymine shows the presence of a cyclic p system with 6p electrons, hence aromatic.
. .–
O O

..
..
H3 C .. H3C +
NH NH
.. + . .–
N O N O

..
..
H H
(e) In borazole, each B as well as N is sp2 hybridised. Further each N has a pair of electrons in its p orbital which
gives rise to a cyclic system of six p electrons. Hence it is aromatic.
H H
.. B .. + B +
HN NH HN NH
HB .. BH HB + BH
N N
H H
Borazole

Example 6 :
Explain the following :
(a) Cyclopropenone (I) and even cycloheptatrienone (II) is more stable than cyclopentadienone (III).

O O O

Cyclopropenone, I Cycloheptatrienone, II Cyclopentadienone, III

(b) The following hydrocarbons have unusually large dipole moments.

(i) (ii)

Solution :
(a) This is due to stability of the structure obtained due to polarization of the ketonic group.

O O
O

.. – .. –
.. – O O
..
..

..
..

O
..
..

+ +
+

2p electrons, aromatic, 6 p electrons, aromatic, 4p electrons, antiaromatic,

hence stable hence stable hence unstable

(b) (i) Exceptionally large dipole moment is due to the presence of a highly stable charged resonating structure in
which one ring has positive charge and the other ring has negative charge. Further, both of the charged
rings are highly stable due to presence of aromatic system in each.

+–
+ –
:
6p electrons in each ring,
hence both are aromatic and quite stable
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(ii) In azulene too, major contributors to the hybrid have separated charges.

Other + –
resonance
– forms Resonance hybrid

Example 7 :
Classify each member of the group as aromatic, nonaromatic, or antiaromatic. For the aromatic and antiaromatic
species, give the number of p electrons in the ring.
H H
H H –
+
(a) (b) +
H H H H O N N
. .– N
H H H H2
N
(c) (d)
+
N N N
– + H H
. .– +
+ +
(e) (f) N NH HN NH N N H2
O O O
CH3
+ –
B
(g)

Solution :
(i) Observe sp3 character of any cyclic atom, if it is present, the compound will be nonaromatic, for aromatic species
all cyclic atoms should have a p orbital.
(ii) Count the number of p electrons or p electrons, if it corresponds to (4n + 2) number, i.e. 2, 6, 10, 14, etc. it is
aromatic, if it corresponds to (4n) number, i.e. 4, 8, 12, 16, etc. the species is antiaromatic.
3
sp C
H H
H H + :–
(a) `
H H H H H H
nonaromatic aromatic, 2p electrons antiaromatic, 4p electrons

(b) ..
.. .. +
sp 2 .O. N sp 2 N
. .– N
H N H2
hybridised aromatic,
aromatic, 6 p electrons aromatic, 6 p 6 p electrons (2 electrons nonaromatic
(2 electrons are present in electrons are present in sp 2 orbital) (N is sp3 hybridised)
sp 2 orbital, 2 in p-orbital)

(c)
. .– +
sp 3
nonaromatic 6 p electrons, aromatic 4p electrons, antiaromatic
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..
N
(d) +
.N. N N
H H
aromatic, 6p electrons, each nonaromatic aromatic
N is sp2, lone pair of electrons 6p electrons
2
belong to sp N, hence does not
form a part of sextet

. .– +

(e) .. ..
O
.. O O
2
nonaromatic (i) if O is sp , 8p electrons, aromatic
hence antiaromatic 6p electrons,
(ii) if O is sp2 , nonaromatic O is sp2

lp belongs to sp2 lp belongs to

hence basic p orbital
.. + .. +
(f) :N NH HN NH :N N H2
sp3
aromatic, 6 p electrons aromatic, 6p electrons nonaromatic

CH3
sp 3 carbon
+ .–.
B
(g)

nonaromatic aromatic antiaromatic aromatic, 6p electrons

2
6p electrons 8p electrons (although B is sp , it has
no free electron)

Example 8 :
Arrange the following hydrocarbons in order of decreasing stability with proper explanation.

Benzene Naphthalene Anthracene

Solution :
The stability order can be explained on the basis of resonance energy.

Total RE per mol. 36 kcal 60 kcal 84 kcal

RE per aromatic ring 36 kcal 30 kcal 28 kcal
So the stability order is, Benzene > Naphthalene > Anthracene
The difference in resonance energy is due to difference in the number of p electrons per molecule which is 6 in
benzene, 10 in naphthalene (i.e. 2 short of isolated benzene rings) and 14 in anthracene, i.e. 4 short of the three
isolated benzene rings.
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Example 9 :
Although anthracene and phenanthrene are aromatic, they undergo addition reactions easily with Br 2 in CCl4 and
that too at different positions in the two isomers.
Solution :
Anthracene and phenanthrene have less resonance energy per aromatic ring of benzene, hence these are not as strongly
stabilized as benzene. Hence they can undergo addition reactions, anthracene undergoes 1,4-addition (at the 9- and
10- positions), while phenanthrene undergoes 1,2-addition (at the 9- and 10- positions) to give products with fully
aromatic rings.

3
4 2
1 9 8 H Br 5
2 7 6 1
Br2 Br2
; CCl4 Br
3 6 CCl4 7 10
4 10 5 8 9
H
H Br H Br
Anthracene cis- and tra ns- Phenanthrene cis- and tra ns-

1,4- and 1,2- additions in the two cases is due to the formation of following more stable carbocations.

H Br H Br
+
;
+
+ H Br
3° carbocation
2° carbocation with
with two aromatic rings

Example 10 :
Give steps involved in the following conversions.
(i) Benzene to phenylacetylene
(ii) Toluene to 1-bromo-2-trichloromethylbenzene and 1-bromo-3-trichloromethylbenzene (separately)
(iii) Methoxybenzene to 2-cyclohexenone (iv) Aniline to o-nitroaniline
(v) Benzene to 2-phenylcyclopentanol (vi) Phenol to 2,4-dichlorophenol
Solution :
First write down the structure of the two concerned compounds and then work backward, retrosynthetic analysis.
Conversions involving aniline and phenol are here given only for making clear the concept of their directive influence.

C º CH
(i)

CH COCl Zn, Hg NBS

C6 H6 ¾¾¾¾¾
3
® C6 H 5 COCH 3 ¾¾¾¾® C 6H5 CH2 CH3 ¾¾¾® C6 H 5 CHBrCH 3
AlCl3 H2 O light

KOH 2 4 Br , CCl
¾¾¾® C6 H 5 CH = CH 2 ¾¾¾¾¾ ® C H CHBrCH Br ¾¾¾¾¾
(i) NaNH 2
® C 6 H 5 - C º CH
heat 6 5 2 +
(ii) H 3 O

NBS (i) NaNH , heat

2
or C6 H 5 CH 2 CH 3 ¾¾¾® C6 H 5 CBr2 CH 3 ¾¾¾¾¾¾¾
+
® C 6 H 5 C º CH
light (ii) H 3 O
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407

CH3 CCl3 CCl3

Br
(ii) and separately
Br

CCl 3 CH3 CCl3

(i) Cl2, hv or heat (i) Br2, Fe Br
(ii) Br 2, Fe (ii) Cl2, hv or heat
Br

OCH3 OCH3 OH O
+
Na. liq. NH3 H3O
(iii)
C2H5OH

NH2 NHCOCH3 NHCOCH3 NHCOCH3 NH2

NO2 NO2
(CH3CO)2O HNO3 (i) H2O, H2SO4
(iv) conc.
–
(Deactivation H2SO4 (ii) OH
of –NH2)
SO3H SO3H
(100%) (desulphonation and hydrolysis of –NHCOCH3)
(Blocking of para position)

AlCl3 Cl2
(v) + Cl hv

Cl

CH3COONa (i) BH3 . THF

CH3COOH – H
(ii) H2 O2 , OH
(syn-addition)
OH

OH OH OH OH
Cl Cl Cl Cl
H2SO4 Cl2 dil. H2 SO4
(vi) 100ºC Fe heat

SO3H SO3H
(blocking of para position)

Example 11 :
Give structures for the bracketed compound in the following series of reactions.

3 5 AlCl 2 PCl 2NaNH

C 6 H 6 + CH 3 CH 2 COCl ¾¾¾¾ ® [A] ¾¾¾ ® [B] ¾¾¾¾¾ ® [C]
heat

Br 2 2 Na H , Ni B (P - 2) Br
[G] ¬¾¾
2
¾ [F] ¬¾¾¾
¾ [C] ¾¾¾¾¾¾¾
® [D] ¾¾¾
2
® [E]
CCl 4 liq.NH 3 CCl 4 (Two isomers)
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Solution :

COCH2CH3 CCl2CH2CH3 C º CCH3

[A] [B] [C]

H H C6H5 H CH3 C6H5

C=C H Br C=C H Br
CH3 H
Br H H Br
CH3 CH3
+ +
cis Enantiomer trans Enantiomer
[D] [E] [F] [G]

Example 12 :
An organic compound, A of the molecular formula C 7H7Cl, when treated with silver borofluoride gives white
precipitate of AgCl alongwith other organic crystalline material B. The compound A takes up three equivalent of H2
in presence of catalyst, while B does not respond such reaction. The compound B is soluble in nitromethane and this
solution when treated with KCl regenerates compound A. Assign structures to A and B and explain the reactions.
Solution :

2 3H 4 AgBF
C 7 H13 Cl ¬¾¾ ¾ C 7 H 7 Cl ¾¾¾¾ ® AgCl ¯ + B
Ni [A] (Crystalline)

2 H 3 2 (i) CH NO
No reaction ¬¾¾ ¾ [B] ¾¾¾¾¾¾ ® C7 H 7 Cl
(ii) KCl [A]

Given facts suggest that [A] has reactive Cl (Cl attached to sp3
carbon) and it is nonaromatic compound having three
double bonds (indicated by hydrogenation), while B is an aromatic comound. All the given facts suggest following
structures to A and B.

Cl
sp3 +
AgBF4 –
BF4 + AgCl ¯

Tropylium chloride Tropylium cation, B

[A] 6 p electrons
(nonaromatic) (aromatic)
(i) Soluble in polar solvents
like CH3NO2
+ –
(ii) K Cl
[A]
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EXERCISE 7.1 (MCQ - ONE option correct)

1. Which one of the following is true ? 10. During monoalkylation of benzene with CH3Cl in presence of
(a) Coal consists of only free carbon atoms. anhydrous AlCl3, an excess of C6H6 must be used because this
(b) Coal is a mixture of free carbon, hydrogen and carbon will
compounds. (a) increase the chance for collision between CH3+ and C6H6
(c) Coal is a mixture of free carbon and several organic (b) decrease collision between CH3+ and C6H5CH3
compounds. (c) Both (a) and (b)
(d) Coal is a mixture of organic compounds with no free
(d) decrease the chance for collision between CH3+ and C6H6.
carbon.
2. Which one of the following is a direct source of aromatic AlCl
11. C6H6 + C6H5Cl ¾¾¾¾ 3®
P
compounds ?
In the above reaction, P is
(a) Coal (b) Petroleum
(c) Both (d) None. Cl
3. Reduction of benzene with sodium in liquid ammonia in presence
of ethanol gives C6H5
(a) (b)

(a) (b)
Cl

(c) (d)
(c) (d) No reaction.
4. Observe the following two reactions of benzene
C6H5
K1
(i) C6H6 + conc. H2SO 4 ¾¾® C 6H5SO 3H + H2O
12. In the following reaction,
K
2
(ii) C6H5D + conc. H2SO 4 ¾¾¾ ® C 6H5SO 3H + HOD
The relation between rate constants of the two reactions will be O
(a) K1 > K2 (b) K2 > K1
Conc. HNO
3
(c) K1 = K2 (d) Not definite. N ¾¾¾¾¾¾ ®X
5. During nitration of benzene with nitrating mixture, HNO 3 acts Conc. H 2SO 4
H
as
(a) an acid (b) a base
the structure of the major product 'X' is
(c) catalyst (d) reducing agent.
6. Which of the following fact is not observed during nitration of
O
benzene ?
(a) Formation of benzenonium ion (a) NO2
(b) Restoration of benzenoid nucleus N
(c) An acid-base equilibrium H
(d) All above facts are observed.
7. The C—H homolytic bond dissociation energy for benzene is
found to be 110 kcal, what should be the C—H homolytic bond O2 N O
dissociation energy of cyclohexane ?
(a) > 110 kcal (b) < 110 kcal (b)
(c) 110 kcal (d) Nothing certain. N
8. Borazole (B3N3H6), like benzene, has 6p electrons which come H
from
(a) 3 from one B and 3 from one N
(b) 2 from each B O
(c) 2 from each N
(d) In one structure 2 from each B and in other 2 from N. (c)
N
9. Give the possible structure of X in the following reaction :
H
D O NO2
C6H6 + D2SO 4 ¾¾¾
2 ®
X
SO3D SO3D
O
D
(a) (b)
(d) N
O2 N
H
D
SO3H 13. What happens when one mole of 1, 3, 5, 7-cyclooctatetraene is
D D treated with two moles of potassium ?
D (a) The corresponding dianion is formed with the liberation
(c) (d) of hydrogen gas
D D
(b) The corresponding dianion is formed with no liberation of
D hydrogen gas
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(c) The corresponding dication is formed with the liberation 19. Naphthalene is regarded as a resonance hybrid of the following
of hydrogen gas three structures.
(d) No reaction takes place.
14. Which of the following statement is true ? 1 8
9
2 7
(a) 7-Bromo cycloheptatriene (tropylium bromide) completely ¨ ¨
dissociates in water to form Br – ion and thus gives 3 6
precipitate with AgNO3 solution 4 10
5
(b) Cyclooctatetraene is non-aromatic, white its corresponding
dianion is aromatic What is true about their bond lengths of the two adjacent carbon
(c) Both are true atoms ?
(d) Neither is true. (a) C1—C 2 > C2—C 3 (b) C1—C 2 < C2 — C3
15. The order of stability of the following three compounds is (c) C1 — C2 = C2 — C3 (d) All bond lengths are equal.
+
20. Which of the following is comparatively stable ?
CH2=CH—CH2
+
Å
Cl Cl
Cl +
I II III
(a) III > I > II (b) III > II > I
(c) I > III > II (d) I > II > III.
H E H E
16. Which of the following is not an example of Friedal Craft
I II
reaction?
CH(CH3)2 (a) I (b) II
(c) Both are equally stable (d) None is stable.
AlCl3 21. n-Propylbenzene can be obtained in quantitative yield by
(a) + CH3CH2CH2Cl ¾¾ ¾® following method :
(i) By treating benzene with n-propyl chloride in presence of
AlCl3
CH(CH3)2
(ii) By treating excess of benzene with n-propyl chloride in
presence of AlCl3
(b) AlCl3
+ CH3CH=CH2 ¾¾ ¾® (iii) By treating benzene with allyl chloride in presence of AlCl3
followed by reduction
(iv) By treating benzene with propinoyl chloride in presence of
CH2CH2CH2COOH AlCl3 followed by Clemmensen reduction.
HF
¾¾ ® (a) By (ii), (iii) and (iv) (b) By (i), (iii) and (iv) (c)
(c) 0°C
By (iii) and (iv) (d) By (ii) only.
22. Ethylbenzene can be prepared from benzene by Friedal-Craft
O
reaction in the following manner
(d) None of these.
(i) By treating with ethyl chloride in presence of AlCl3
17. Which of the following is more stable ?
(ii) By treating excess of benzene with ethyl chloride in
+ presence of AlCl3
: NH2 NH2
+ (iii) By treating benzene with vinyl chloride in presence of AlCl3
H H
followed by reduction
(a) X (b) X (iv) By acetylation of benzene followed by Clemmensen
reduction.
NH2 (a) By all methods (b) By (ii), (iii) and (iv) (c)
By (ii) and (iv) (d) By (iii) and (iv).
H
23. The ortho to para ratio of the product formed by nitration of
(c) X (d) All are equally stable.
toluene was found to be 1.5. The o- to p-ratio of the product
+
formed by nitration of tert-butylbenzene should be
18. Which of the following structure is least stable ? (a) 1.5 (b) > 1.5
+ (c) < 1.5 (d) either of the three.
:

Cl Cl :
24. Chlorination of tert-butylbenzene gives substantial amount of
+ H H o-substituted product, while its bromination gives nearly
(a) X (b) X negligible amount of the product. This is due to which factor.
(a) The benzenonium ion formed in the first case is more stable
than in the second case
Cl
(b) It is difficult to produce Br+ ion than Cl+ ion
H (c) Difference in size of the electrophile
(c) X (d) All are equally stable.
(d) Chlorine is more reactive than bromine.
+
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25. Acetanilide on nitration at room temperature gives o- and p- 32. Which of the following is more reactive towards electrophilic
nitroacetanilides in significant amounts. What is true about the addition reactions ?
same reaction at 0°C.
CH= CH2
(a) Proportion of the o-product will be more than that of the
p-product
(b) Proportion of p-isomer will be somewhat more than that CH2 = CH2
of the o-isomer
I II
(c) p-Isomer will almost be the exclusive product
(d) Proportion of both isomeric products will be equal. (a) I > II
(b) II > I
26. Which of the following is not characteristic of a carbocation ?
(c) Both are equal reactive
(i) It can rearrange to a more stable carbocation (d) Depends upon the nature of reagent.
(ii) It can eliminate a hydride ion to form an alkene 33. Observe the following reactions and predict the nature of A
(iii) It can add to an alkene to form a new carbocation and B
(iv) It can abstract a hydride ion from an alkane.
HBr HBr
(a) (ii) (b) (iii) B ¬ ¾¾ ¾ ¾¾ ¾® A
hn
(c) (iv) (d) (ii) and (iv).
27. Which method is preferred for the preparation of n-propyl Br
chloride from benzene ?

AlCl3 (a) A and B both are

(a) + CH3CH2CH2Cl ¾¾ ¾®

Cl (b) A and B both are

(b) + CH3CH2CH2Cl
Na/ether
¾ ¾¾ ® Br
Br
(c) Both are undesirable
(d) Both give similar result.
(c) A is and B is (d)
28. Melting point of toluene (C6H5 CH3) is very low (–95°C) as Br
compared to benzene (5°C). This is because
(a) benzene molecules have strong van der Waal’s forces than Br
that of toluene
(b) methyl group in toluene does not allow toluene molecules
A is and B is
to associate due to electropositive nature
Br
(c) of unsymmetrical structure of toluene
34. Which of the following statement is true ? Among three iosmeric
(d) of none of the above.
xylenes :
29. Which of the following reagents can not give tert-pentylbenzene (a) o-Xylene is sulphonated most easily
as the major product ? (b) p-Xylene is sulphonated most easily
3
BF (c) m-Xylene is sulphonated most easily
(a) Benzene + 3-Methyl-2-butanol ¾¾¾ ® (d) All the three xylenes are sulphonated at same rate.
3
BF 35. Which of the following statement is true ?
(b) Benzene +Neopentyl alcohol ¾¾¾ ® (a) Allyl cation is more stable than the cyclopropenyl cation
BF due to resonance
(c) Benzene + 3-Methyl-1-butanol ¾¾¾
3®
(b) Cyclopropenyl cation is more stable than the allyl cation
(d) None of the above. due to resonance
30. What happens when aniline is treated with methyl chloride in (c) Cyclopropenyl cation is more stable than the allyl cation
presence of AlCl3 ? due to aromatic character of the former
(a) It undergoes Friedel Craft reaction to form a mixture of p- (d) Both are equally stable because both shows resonance.
36. How many isomeric diaminobenzoic acids can be converted into
methyl and o-methylaniline
m-phenylenediamine on decarboxylation ?
(b) It does not undergo Friedel Craft reaction because AlCl3 (a) 1 (b) 2
reacts with aniline instead of reacting with alkyl halide (c) 3 (d) 4.
(c) Aniline gets positive c harge and deactivated for 37. Which of the monocylic polyenes is/are expected to be aromatic?
electrophilic substitution C9 H10 (I), C 9 H9 + (II), C 9 H9– (III)
(d) Both (b) and (c). (a) II (b) III
31. When carbon tetrachloride is treated with excess of benzene in (c) II and III (d) None.
presence of AlCl3, the product formed is 38. The stability order of the three carbocations follows the order
(a) only (C6H5)3CCl + +
CH 3 C HCl (I), C H 2 CH 2 Cl (II), CH 3 CH 2+ (III)
(b) only (C6H5)4C I II III
(c) a mixture of (a) and (b) (a) I > II > III (b) III > I > II
(d) None of the two. (c) III > II > I (d) II > I > III.
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EXERCISES
39. Which effect controls the reactivity and orientation of electrophilic 47. What will be the final product when ethylbenzene is treated with
addition on vinyl chloride ? the reagent listed, below :
(I) NBS, peroxide, heat (II) alcoholic KOH, D
HCl
CH2 = CHCl ¾¾¾ ® CH3CHCl2 (III) B2H 6 (IV) H2O2, HO
(a) Inductive Ph - CH - CH 2 - OH
(b) Resonance (a) Ph - CH2 - CH 2 - OH (b) |
(c) Reactivity is controlled by the stronger inductive effect, Br
and orientation by weaker but more selective resonance OH Ph - CH - CH 2 Br
effect | |
(c) (d)
Ph - CH - CH 3 OH
(d) Reactivity is controlled by resonance effect, while orientation
is controlled by inductive effect. CH3
40. In nitration which of the following reaction is involved in the
formation of NO2+ ? Å
E
(a) HONO2 ¾¾® OH– + NO2+ 48.
(b) H2O+NO 2 ¾¾® H2O + NO2+
(c) Both (a) and (b) CD3
(d) None of the two.
41. A 50 : 50 mixture of C6H6 and C6D6 are allowed to react with a (a) EÅ attacks preferably at o-position to CH3
(b) EÅ attacks preferably at o-position to CD3
limited amount of an electrophile Y. The product will consist of
(c) EÅ can attack equally at any of the four positions
(a) equal amounts of C6H5 Y and C6D5Y (d) Not predictable here
(b) C6H5Y > C6H5D 49. Ease of oxidation in following will be
(c) C6H5Y < C6H5D
(d) No reaction will take place.
42. 1, 3, 5-Trideuteriobenzene is allowed to react with the electrophile
X to form monosubstituted product. Predict the relation between
D : H ratio of the reactant and product. NO2 CH3
(a) [D : H]Product = [D : H]Reactant (I) (II) (III)
(b) [D : H]Product > [D : H]Reactant (a) I > II > III (b) III > II > I
(c) [D : H]Product < [D : H]Reactant (c) I > III > II (d) II > III > I
(d) All the above three possibilities exist. 50. Arrange the following in the order of reactivity towards an
43. An aromatic molecule will electrophilic attack
(i) have 4n p-electrons (ii) have (4n + 2) p electrons Cl OMe Me
NO2
(iii) be planar (iv) be cyclic.
Which of the above statement(s) is/are correct ?
(a) All the four (b) (i), (iii) and (iv)
(c) (ii), (iii) and (iv) (d) (ii) and (iv).
44. When nitrobenzene is treated with Br2 in presence of FeBr3, the (I) (II) (III) (IV) (V)
major product formed is m-bromo-nitrobenzene. Statement (a) V > IV > III > II > I (b) III > V > IV > II > I
which is related to obtain the m-isomer is (c) III > IV > V > II > I (d) V > IV > III > I > II
(a) the electron density on meta carbon is increased than that
on ortho and para positions
(b) the intermediate carbonium ion formed after initial attack
of Br+ at the meta position is least destabilised 18 HClO4
(c) loss of aromaticity when Br+ attacks at the ortho and para 51. O X+Y
positions and not at meta position
(d) easier loss of H+ to regain aromaticity from the meta
position than from ortho and para positions.
45. Toluene reacts with chlorine in the presence of light to give
The products X and Y are :
(a) benzyl chloride (b) benzal chloride
(c) p-chlorotoluene (d) o-chlorotoluene. OH
Å –
(a) ClO4 ,
46. The reaction of H3CCH = CH— —OH with HBr gives

18
OH
(a) CH3CHBrCH2— —OH
Å
(b) , –
ClO4
(b) CH3CH2CHBr— —OH
OH
Å
(c) , ClO4
–
(c) CH3CHBrCH2— —Br

Å
Å
(d) CH3CH2CHBr— —Br. (d) , –
(ClO4 )2
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413
52. Identify the correct order of reactivity in electrophilic substitution
reactions of the following compounds O O O O

CH3 Cl NO2
(III)

(a) III < II < I (b) II < III < I

(A) (B) (C) (D) (c) I < III < II (d) I < II < III
(a) A>B>C>D (b) D>C>B>A Na/liq.NH 3 (i)O 3 /H 2 O
57. A ¾¾¾¾¾¾ ® B ¾¾¾¾¾¾ ® 2CO 2 + 2CH 3COOH
(c) B>A>C>D (d) B > C > A > D R -OH D
53. Arrange the compounds in decreasing order of reactivity towards Compound ‘A’ is
bromine :
O O
OMe OMe OMe OMe || ||
Me (a) Benzene (b) CH 3 - C - C º C - C - CH 3

OH Me
I II III IV (c) Toluene (d)
(a) III > II > IV > I (b) II > IV > I > III
(c) III > IV > II > I (d) IV > II > I > III
54. Which species are aromatic :
I
Cu
58. ¾¾®
¾ Product is
180 °C
(I) (II) I
Å

(III) (IV)
(a) (b)
(a) I, II & III (b) I, III & IV
(c) I & III (d) II & III
55. In the following reaction,

O
conc. HNO 3
N X
conc. H2SO4 (c) (d) Reaction not possible
H
the structure of the major product ‘X’ is

O
NO2
(a) N
H 59. [ A ] + CH 2 = CH 2 ¾
¾®

O2N Compound [A] is

O
CH = CHCHO
(b) N
(a)
H

O CH = CH 2

(c) N
H (b)
NO2

O CH = CH 2
(d) O2N N
H (c)

56. Increasing order of rate of reaction with HNO3/H2SO4 is

O O O CH = CH 2
O O
O O O
(d)
(I) (II)
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60. The final product in the following series of reactions should be 66. During nitration of benzene using a mixture of conc. HNO 3 and
conc. H2SO4, function of conc. H2SO4 is to increase the rate of
reaction by increasing the concentration of NO +2 according to
following reaction.
CH3 CH3
HNO 3 + H 2SO 4 ® NO 2+ + HSO 4- + H 2 O
(a) H3CO CH2 – CH – CH – CH2 OCH3 Here nitric acid acts as
(a) a stronger acid (b) a weaker acid
CH3 CH3 (c) a base (d) none of the three
67. Which of the two reactions proceed faster ?
(b) HO CH2 – CH – CH – CH2 OCH3
(i)

(c) HO CH – CH OH

C2H5 C2H5
(ii)

(d) H3CO CH – CH OCH3

C2H5 C2H5 (a) (i) (b) (ii)

(c) (i) = (ii) (d) Not definite
61. C 6 H 6 + D 2SO 4 ¾
¾® Product is CH2
(a) C 6 H 5SO 3 H (b) C 6 H 5SO 3 D
NBS
(c) C6 D6 (d) No reaction 68. ¾¾¾ ® P is
hv
62. Which of the following is least stable ?

O O O CH2 CH2Br
Br
(a) (b)

I II III CH2Br
(a) I (b) II Br
(c) III (d) All are equally stable (c) (d) All the three
63. Arrange the following compounds in decreasing order of reactivity
towards electrophilic substitution?
69. Which of the position in the following compound is liable to be
attacked by an electrophile ?
N N (3) (4)
H
I II III
O2N
(a) I > II > III (b) I > II = III
(c) III > II > I (d) III > I > II
64. Which of the compound undergoes electrophilic substitution most
easily ? (2)
CH3 OCOCH3 (1)

(a) 1 (b) 2
(a) (b) (c) 3 (d) 4
70. Which of the reaction is not possible ?
N(C2H5)2 CHO CH = CH2

AlCl3
(c) (d) (a) + CH2 = CHCl

65. Which one is the slow step in the chlorination of benzene? C6H5
AlCl3
(a) Cl 2 + FeCl 3 ® FeCl -4 + Cl + (b) + C6H5Cl
+ Cl
+ NH2 NH2
(b) + Cl H
AlCl3
+ (c) + CH3Cl
Cl Cl
–
(c) H FeCl4 + FeCl3 + HCl
CH3
(d) None of the three
(d) All the three
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EXERCISE 7.2
10. Toluene, when treated with Br2/Fe, gives p-bromotoluene as the
DIRECTIONS for Q. 1 to Q. 21 : Multiple choice questions with major product because CH3 group
one or more than one correct option(s). (a) is para directing
(b) is meta directing
1. The product obtained in the reaction
(c) activates the ring by hyperconjugation
Cl , hn
2 (d) deactivates the ring
C6 H 5 CH 2 - CH 3 ¾¾¾¾® is
273K
11. In the alkylation of benzene, stable s complex
(a) C6 H 5 CHCl - CH 3 (b) C6 H 5 CH 2 CH 2 Cl
Å
H H
(c) C6 H 5 CCl 2 - CH 3 (d) C6 H 5 CHClCH 2 Cl CH3
(a) (b) CH 3
2. Which of the following are true? Å
(a) Benzene tends to undergo substitution rather than addition
reactions H H
(b) All hydrogen atoms of benzene are equivalent
(c) CH3 (d) CH3
(c) The carbon-carbon bonds of benzene are alternatively short +
Å
and long around the ring
(d) There can be two o-disubstituted derivatives 12. Moth repellent is /are :
3. Which of the following characteristics does an aromatic
compound exhibit? (a) Cl— —Cl (b) perchlorethane
(a) it should have (4n + 2) p-electrons
(b) it should be planar and conjugated
(c) it should have 4n p-electrons COOH
(d) it should possess high resonance energy
4. Which of the following are obtained by the fractionation of coal (c) (d)
tar?
(a) light oil (b) middle oil
13. Toluene when treated with Br2 / Fe gives p-bromotoluene as the
(c) heavy oil (d) vegetable oil major product because the –CH3 group.
5. Which of the following statements are true for benzene?
(a) is para-directing
(a) it is a flat, regular, hexagonal molecule
(b) is meta-directing
(b) each C–C–C angle is 109°28'
(c) activates the ring by hyperconjugation
(c) the C–C bond length is 1.39Å
(d) deactivates the ring
(d) All carbon atoms are sp3 -hybridized
6. Which of the following meet the requirements of the Huckel 14. An aromatic molecule will
rule? (a) have 4n p electrons (b) have (4n + 2)p electrons
(a) Naphthalene (c) be planar (d) be cyclic
(b) Anthracene 15. Benzene is obtained from benzene diazonium chloride by
(c) 1,3,5,6-Cyclo-octateraene (a) reduction with alkaline stannous chloride
(d) 1,3-Cyclobutadiene
(b) reduction with acidic stannous chloride
7. Benzene can be obtained by
(c) action of hypophosphorus acid
CaO
(a) C6 H 5 COOH + NaOH ¾¾¾
® (d) action of ethyl alcohol
D
16. Which of the following are meta-directing?
D
(b) C6 H 5 OH + Zn ¾¾
® (a) SO 2Cl (b) COCH3
(c) CN (d) NHR
(c) C6 H 5 N = NCl + H 2 O ¾¾
® 17. The type of substitution reactions of benzene hydrocarbons are
(d) All of these (a) elimination (b) electrophilic
8. Benzene can undergo (c) nucleophilic (d) free radical
(a) substitution (b) addition
18. Benzene molecule has
(c) elimination (d) oxidation
(a) 9 sigma and 3 pi-bonds
9. Which of the following acid can be used as catalyst in Friedel-
Craft reaction? (b) 30 electrons
(a) AlCl 3 (b) BF3 (c) 12 sigma and 3 pi-bonds
(c) HCl (d) HNO3 (d) 21 electrons
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19. Which of the following hydrocarbons contains 12 secondary and 22. The intermediates formed in both of the above products differ in
2 tertiary hydrogen atoms ? their stability remarkably; which of the following statement is
true?
(a) (b) (a) Leaving Kekule’s structure, the intermediate formed in I
has 3 resonating structures while that formed in II has 2
resonating structures
(c) (d) (b) the intermediate formed in I is a resonance hybrid of 3
structures, while that formed in II has no possibility of
20. Which of the following are antiaromatic ? resonance
+ (c) the intermediate formed in I is a resonance hybrid of two
(a) (b) structures, while that formed in II has three such structures.
+ (d) None of the statement is correct.
23. Which of the above two reactions is regiospecific and which one is
(c) (d) regioselective?
N Chlorination Bromination
21. Which of the following are examples of Birch reduction ? (a) regiospecific regioselective

CH3 CH3 (b) regioselective regiospecific

(c) regiospecific regiospecific
(a) Na (d) regioselective regioselective
liq. NH3
24. From the above set of reactions, it can be concluded that
(a) bromine is more reactive and less selective than chlorine
NO2 NO2
(b) bromine is less reactive and more selective than chlorine
(c) chlorine is more reactive and more selective than bromine
(b) Na
liq. NH3 (d) bromine is more reactive and more selective than chlorine

PASSAGE 2
Na
(c) liq. NH3 We can say that electron-realeasing group stablises the carbocation by
dispersing its positive charge and thus activates the ring, while an
Na electron-withdrawing group destabilises the carbocation by intensifying
(d) CH3C º CCH3 ¾¾¾¾® CH 3CH = CHCH 3
liq. NH3 its positiive charge and thus deactivates the ring. Further, an activating
group activates although all positions of the benzene ring, its activating
effect is much more on ortho and para positions than on meta position
INSTRUCTION for Q. 22 to 36 : Read the passages given below and with the result substitution occurs mainly on the ortho and para
answer the questions that follow. positions. Similarly, a deactivating group deactivates although all
positions in the ring, its deactivating effect is much more on ortho and
para positions than on meta position with the result further reaction
PASSAGE 1 occurs mainly on the meta position. In short, the activating or
deactivating effect of a group is strongest at the ortho and para-
CH2CH3 CHBrCH3 CH2CH2Br
positions.
Br2
I. heat, light
25. Toluene when treated with a nitrating mixture forms o-nitrotoluene
1-Bromo-1-phenylethane 2-Bromo-1-phenylethane as one of the products. Which of the inntermediate best explains
(sole product) (not formed)
this ortho substitution?
{It is important to note that as in alkanes, orientation of side
chain chlorination of ethylbenzene shows that although chlorine CH3 CH3
+ H H
atoms (chlorine free radicals) also preferentially attack benzylic
hydrogen, here the preference is less than that in bromination.} (a) NO2 (b) NO2
+
CH2CH3 CHClCH3 CH2CH2Cl

Cl2 CH3
II. heat, light H
(c) NO2 (d) All equally
1-Chloro-1- 2-Chloro-1-
+
phenylethane (91%) phenylethane (9%)
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417
26. On bromination, aniline undergoes substitution in ortho and para 30. The stability order of the three compounds is
positions. Substitution in para position involves a resonance-
stabilized intermediate, which resonating structure contributes
most to the concerned hybrid
..– + .
NH2 NH2 I II III
+

(a) (b) (a) I>II>III (b) I>III>II

+
(c) I>II=III (d) I=III>II
H Br H Br

+ PASSAGE 4
NH2 NH2
In the electrophilic substitution of benzene ring, the second substituent
is directed by the group already present. Electron releasing groups (+I
(c) + (d) and +M) are ortho-para-directing and activating, whereas the electron
withdrawing groups (–I and –M) are meta-directing and deactivating.
H Br H Br
Halogens are placed under the category of +T (Tautomeric) groups
27. The correct order for the monobromination of the following because they have –Inductive and +Mesomeric effect. These groups
compounds is are deactivating but ortho-para-directing.
+ In the introduction of third group to the benzene ring, the product of
C6 H 5 NH 2 C6 H 5 N H 3 Cl - C6 H 5 NHCOCH 3
I II III minimum steric hindrance is formed.

C6 H 5 Cl C6 H 5 COCH 3 CH3
IV V
(a) I > II > III > IV > V (b) II > I > III > IV > V CH3
31. Ortho-xylene on mononitration gives :
(c) I > III > IV > V > II (d) I > III > II > V > IV

PASSAGE 3 (a) two products (b) three products

On the basis of the molecular orbital treatment of various aromatic (c) one product (d) four products
compounds, it has been observed that an aromatic compound must 32. Which of the following is not an ortho, para-directing group?
fulfill the following theoretical requirements.
(a) –F (b) –NC
(a) It must have an uninterrupted cyclic cloud of p electrons above
(c) –OCOCH3 (d) –CCl3
and below the plane of the molecule (often called as p cloud). Let
us look what does this mean ? 33. Which of the following substituted benzene derivatives would
(i) For the p cloud to be cyclic, the molecule must be cyclic. furnish three isomers when one more substituent is introduced?
(ii) For the p cloud to be uninterrupted, every atom in the ring
Cl Cl
must have a p orbital
(iii) For the p cloud to be formed, each p orbital must be able to
overlap with the p orbitals on either side of it. Therefore, the
molecule must be planar. Cl
(b) The p cloud must contain an odd number of pair of electrons,
I II
(4n +2)p electrons, where n is an integer.
Cl

28. is Cl
+
Cl
(a) aromatic Cl
(b) non-aromatic due to (a) (ii)
(c) non-aromatic due to (a)(iii) III IV
(d) non-aromatic due to (b) (a) Only I (b) I and II
29. Which of the following structure is not aromatic ? (c) I, II and III (d) IV only
.. –
PASSAGE 5
.. –
Benzene undergoes Friedel-Craft alkylation as well as acylation. With
. + long n-alkyl chains, rearranged products are obtained, thus for preparing
I II III IV
benzene derivatives with n-alkyl chains, Friedel-Craft acylation or some
(a) I and II (b) II and IV other suitable method is used.
(c) IV (d) All the four
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34. Using anhydrous AlCl3 as catalyst, which of the following 39. Column I Column II
reactions produces ethylbenzene?

CH3 CH = CH2 + C6H6 + H

(a) Cl
(A) (a) Especially unstable
X
(b) CH2 = CH2 + C6 H6
H
(B) Cl + (b) Especially stable
(c) CH3CH2 OH + C6 H6 X

(d) CH3CH3 + C6H6 O2N

(C) I NO2 (c) Deactivating but o, p-directing

AlCl3
35. + P; Here P is O2N
Cl
+
(D) H3C (d) Steric inhibition

H
X
(a) (b) 40. Column I Column II
(A) Directing influence (a) Inductive effect
of –CCl3
(B) Electrophilic (b) Mesomeric effect
substitution in
phenoxide ion
(C) Electrophilic (c) Hyperconjugation
(c) (d)
substitution in
C6H5NH2 in presence
of HCl
36. Wurtz Fittig reaction between bromobenzene and n-propyl
(D) Directing influence (d) Electromeric effect
bromide in presence of metallic sodium in dry ether mainly gives of C6H5–
(a) n-hexane (b) biphenyl 41. Column I Column II
(c) n-propylbenzene (d) isopropylbenzene Cl

(A) (a) Group attached to benzene

Instructions for Q. 37 to 43 : Following questions are Multiple
O ring is a +M group here.
Matching type Questions :
NH–C–Me
37. Column I Column II
(Group present (Electronic effect (B) (b) Group attached to benzene
ring is a –M group here.
on benzene) responsible for
directive influence)
(A) —CH = CH2 (a) +M (C) N (c) Electrophile would attack on
(B) —COOCH3 (b) –I ortho or para position
(C) —OCOCH3 (c) –M (d) Rate of electrophilic
substitution is less than that
(D) —O – (d) –E
of benzene.
38. Column I Column II 42. Column I Column II
Reactants No. of chlorinated
(A) (a) Aromatic with 6p electrons products
Cl , light
+ (A) Benzene ¾¾¾¾®
2 (a) Three compounds

(B) Toluene Cl , light

(b) Four compounds
(B) (b) Aromatic with 2p electrons
¾¾¾¾®
2

(C) Methane Cl2 , light (c) Single monochloro

– ¾¾¾¾®
derivative

(D) Benzene Cl2 , AlCl3

(C) .. (c) Nonaromatic ® (d) Six isomeric
¾¾¾¾¾
N
. .– compounds
43. Column I Column II
(A) –COOCH3 (a) Activating
(B) –N = O (b) o, p-Directing
(D) (d) Antiaromatic
(C) –NH2 (c) Deactivating
(D) –Cl (d) m-Directing
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53. Statement-1 : Aniline becomes more reactive towards
Instructions for Q. 44 to 53 : Following questions are Assertion and electrophilic aromatic substitution in presence of strongly acidic
Reasoning Type Questions : solution.
Note : Each question contains STATEMENT-1 (Assertion) and Statement-2 : The amino group is completely protonated in
STATEMENT-2 (Reason). Each question has 5 choices (a), (b), (c), strongly acidic medium. Thus the lone pair of electrons on the
(d) and (e) out of which ONLY ONE is correct. nitrogen is no longer available for resonance.
(a) Statement-1 is True, Statement-2 is True; Statement-2 is a correct
explanation for Statement-1.
(b) Statement-1 is True, Statement-2 is True; Statement-2 is NOT a Instructions for Q. 54 to 58 : Following questions are Integer Type
correct explanation for Statement-1. Questions :
(c) Statement -1 is True, Statement-2 is False.
(d) Statement -1 is False, Statement-2 is True. 54. Write total number of hydrogen atoms on all the carbon atoms
(e) Statement -1 is False, Statement-2 is False. which are connected directly by a single bond to benzylic carbon
(carbon connected to benzene ring) in the product
AlCl3
44. Statement - 1 : Alkyl benzene is not prepared by Friedel-Craft (a) +
Cl
alkylation of benzene.
Statement - 2 : Alkyl halides are less reactive than acyl halides.
ZnCl2
45. Statement - 1 : Rates of nitration of benzene and (b) +
hexadeuterobenzene are different. Cl
Statement - 2 : C–H bond is stronger than C–D bond.
O O
46. Statement - 1 : Cyclopentadienyl anion is much more stable
than allyl anion. AlCl3
(c) + Me3C – C – O – C – CMe3
Statement - 2 : Cyclopentadienyl anion is aromatic in character.
47. Statement 1 : Benzene undergo nucleophilic substitution
Me O
reactions easily and electrophilic substitutions with difficulty.
AlCl3
Statement 2 : Due to the presence of 6p electrons, benzene + Me – C – C – Cl
(d)
behaves as rich source of electrons
48. Statement - 1 : Bromobenzene upon reaction with Br2/Fe gives H
1,4-dibromobenzene as the major product.
Statement - 2 : In bromobenzene, the inductive effect of the CH4
55.
bromo group is more dominant than the mesomeric effect in
directing the incoming electrophile. Arrange the steps involved in the above conversion and give answer
49. Statement 1 : Rates of nitration of benzene and in four digits, viz. if the steps are 2, 3, 4 and 5, the answer would
hexadeuterobenzene are different. be 2345.
Statement 2 : C–H bond is stronger than C–D bond. 1. Br2/hv 2. aq. KOH
50. Statement-1 : Nitration of benzene and hexadeuterobenzene 3. conc. NaOH/D 4. O3/Zn/H2O
occur exactly at the same rate. 5. Red P/HI (excess) 6. H2/Pd (excess)
Statement-2 : The cleavage of C–H bond is not the rate- 7. NaOH / CaO / D 8. HÅ/ KMnO4 / D
determining step of the reaction. 56. Give sum of the number of carbon atoms, where hydrogen is
51. Statement-1 : Alkylbenzene is not prepared by Friedel-Craft’s added during following reaction
alkylation of benzene.
COOH
Statement-2 : Alkyl halides are less reactive than acyl halides.
Na in
52. Statement-1 : Furan has an aromatic sextet.
..O liq. NH3

.. 57. Give sum of locants in iso-octane.

Statement-2 : The two lone pairs of electrons on oxygen and a p 58. How many p electrons are present in
electron pair form an aromatic sextet. ..

EXERCISE 7.3 (Subjective Problems)

1. Arrange the various hydrogen atoms of the chain in the following 3. Arrange the alcohols in each case in order of ease of dehydration.
compounds in order of their decreasing ease of abstraction by
bromine atoms. (i) C6 H 5 CHCH 2 CH 2 CH 3 CH 2 OH. CHCH 2 CH 3
| |
OH C6H5
(i) H3C— —CH2— —CH2CH2CH3 I II

(ii) 1, 2, 4-Trimethylbenzene. C6 H 5
|
2. Label the different hydrogen atoms in order of decreasing CH 3 - C.CH 2 CH 3 C6 H 5 CH 2 CHCH 2 CH 3
reactivity (1 for the most reactive, 2 for the next etc.) of | |
abstraction by bromine atoms in 1-phenyl-2-hexene. Also write OH OH
III IV
down the possible monobromo product (s) formed on abstraction
of the most reactive, second most reactive and the least reactive
hydrogen atoms.
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UV Alc
OH ® (A) ¾¾¾¾® (B)
| (a) C6H5CH2CH2CH3 + Br2 ¾¾¾
KOH
CH 3 CH. CH.CH 3
| Cold dil hot KMnO 4
C6 H 5 ¾¾¾¾® (C) ¾¾¾¾¾¾
® (D) + (E)
V KMnO 4

(ii) C6H5CH2CH2OH, C6H5CHOHCH3, (C6H5)2C(OH)CH3 ether H 2 C = CHCH 2 Br

(iii) a-Phenylethyl alcohol, a-(p-bromophenyl) ethyl alcohol, (b) C6H5Br + Mg ¾¾¾® (F) ¾¾¾¾¾¾¾® (G)
a-(p-tolyl) ethyl alcohol. KOH Br2
4. Arrange the following compounds in order of reactivity towards ¾¾¾® (H) ¾¾¾¾® (I)
heat 300°C
addition of HCl :
Styrene, p-chlorostyrene, p-methylstyrene. H 2/Pt HBr
(c) p-CH3 . C6H4 . C º C. C6H5 ¾¾¾¾
® (J) ¾¾¾
® (K)
5. When a mixture of toluene and BrCCl3 was irradiated with UV
light, benzyl bromide and CHCl 3 are formed as the main C6H5 H
products along with HBr and C2Cl6. Explain with mechanism. C=C
(d) + Br2 (Fe) ¾¾® (L)
6. How can you distinguish between 1-phenylpropene, 2- H CH3
phenylpropene and 3-phenylpropene ? HBr
7. Write down the main product in each case ¾¾¾¾® (M).
peroxide
UV
(i) C6H5CH2CH(CH3)2 + Br2 ¾¾¾
® 11. Give structures and names of the principal products of trans-1-
AlCl 3 phenyl-1-propene with
(ii) C6H6 + (CH3)2CHCH2Cl ¾¾¾¾
® (i) H2, Ni, 200°C, 100 atm (ii) Excess Br2, Fe
CH3 (iii) cold dil. KMnO4 (iv) hot KMnO4
| (v) performic acid (vi) CHBr3, ter-BuOK.
BF3 12. Three isomeric dibromobenz enes a re converted into
(iii) + (CH3)3CCH2OH ¾¾¾
® dibromonitrobenzenes, predict the total number of the possible
isomeric dibromonitrobenzenes.
13. How many isomers are theoretically possible for the ring
CH3 mononitration of o-, m- and p-bromochlorobenzenes.
14. (i) Indicate the ring which is liable to be attacked in nitration,
AlCl 3
and give structures of the principal products
(iv) + (CH3)3CCl ¾¾¾¾¾®
100°C
CH3 (a) O2N— —

H 2 SO 4
(v) C6H6 + (CH3)2CHCH2OH ¾¾¾¾
® —CH2—
(i) Br2 , heat, light (b)
(vi) C6H5CH2CH3 ¾¾¾¾¾¾¾® O2N
(ii) NaCN

8. Give all possible products in the following reactions and mention O

(c) —C
the major product, if any
OC 6H 5
H 2 SO 4
(a) C6H5CH2CHOHCH(CH3)2 ¾¾¾¾ ® (ii) Write the structures of possible major monosubstituted
(b) C6H5CH = CHCH3 + HBr ¾¾® products formed when Br+ attacks the following molecules.
peroxide Justify your answer
(c) C6H5CH = CHCH3 + HBr ¾¾¾¾¾ ®
(d) C6H5CH = CHCH=CH2 + Br2 (equal amounts) ¾® (a) —COO—
(e) Me 3N+CH = CH2 + HI ¾¾®
AlBr3
(f) CH2 = CHCF3 + HBr ¾¾¾® . (b) — — OCH3
9. Predict the product in each of the following reaction :
OH (c) — —
|
OCH3
KOH
(i) ¾¾¾®
heat (d) HO3S— —NHCOCH3
|
CH2CH = CH2 15. Arrange the following compounds in order of acidity.
Toluene, n-pentane, diphenylmethane and triphenylmethane.
Ni 16. Arrange the following alcohols of each set in order of reactivity
(ii) C6H5CH = CH – CH = CH2 + H2 ¾¾¾® towards aqueous HBr :
30° C
(i) 1-Phenyl-1-propanol, 1-phenyl-2-propanol, 3-phenyl-1-
Pd propanol
(iii) C6H5C º CCH2C6H5 + H2 ¾¾®
(ii) Benzyl alcohol, p-hydroxybenzyl alcohol, p-cyanobenzyl
alcohol.
(iv) CH3O— —CH=CH— + HBr ¾® 17. Predict the order of reactivity for the following chlorides for (a)
S 1 and (b) S 2
10. Complete the following reactions, while writing structures of N N
the compounds (A) to (M) C6H5CH2Cl, C6H5CH(Cl)CH3, C6H5C(Cl)(CH3)2 .
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EXERCISE
421
18. Which of the annulenes upto 20 carbon atoms are expected to (vi) Ethylbenzene to E-1-phenylpropene
show aromaticity theoretically. Further, predict in which of these (vii) Ethylbenzene to p-nitrostyrene
structures aromaticity is permitted by geometry of the molecule? (viii) Tolune to p-bromobenzylbromide
19. Explain the following observations : (ix) Toluene to p-bromobenzoic acid
(a) When trityl chloride is treated with AlCl3 or trityl alcohol (x) Tolune to m-bromobenzoic acid
is treated with conc. H2SO 4, a yellow colour is obtained (xi) Toluene to p-nitrodiphenylmethane.
which is converted to white solid on dilution with water. 24. Give necessary steps involved in the following conversions.
(b) When triphenylmethane is added to a solution of NaNH 2 (i) Toluene to 1, 2, 3-trimethylbenzene
in liq. NH 3 , a deep-red solution is obtained which (ii) Benzene to 3, 4-dibromonitrobenzene
disappears on dilution with water. (iii) Toluene to p-benzylnitrobenzene
(c) When trityl chloride reacts with zinc in benzene, a red (iv) Benzene to 1, 1-diphenylethane
colour is obtained which decolorises on reaction with (v) Benzene to o-dibromobenzene
oxygen. (vi) Toluene to 2-bromo-4-nitrobenzoic acid
(d) Reaction of carbon tetrachloride with excess of benzene in (vii) m-Xylene to 5-nitroisophthalic acid.
presence of AlCl3 gives (C6H5)3CCl and not (C6H5)4C. 25. Explain the following :
20. Explain the following : (i) Nitrobenzene, but not benzene, is used as solvent for the
(i) The C—H homolytic bond dissociation energy for benzene alkylation of bromobenzene.
is considerably larger than for cyclohexane. (ii) In monoalkylation of benzene with an alkyl halide in
(ii) The relative acidic character of the following three presence of AlCl3, an excess of benzene is used.
hydrocarbons is (iii) Diphenyl can’t be prepared by the following reaction
Acetylene > Benzene > n-Pentane. AlCl 3
(iii) Cyclooctatetraene rapidly decolorizes cold aq. KMnO 4, C6H6 + C6H5Cl ¾¾¾¾ ® C 6H5C6H5 + HCl
white benzene does not do so. (iv) Sulphonation of toluene at 0°C gives 53% o- and 53% p- ;
(iv) Benzene reacts with neopentyl bromide in presence of AlCl 3 while at 100°C it gives 13% o- and 79% p–.
to form tert-pentylbenzene. (v) p-Chloronitrobenzene has less dipole moment (2.4D) than
(v) Bromination of benzene in presence of thallium acetate p-nitrotoluene (4.4D).
gives only the p-isomer. (vi) Nitra tion of toluene (C 6 H 5 CH 3 ) gives 50% o-
(vi) m-Xylene is more reactive towards ring nitration than the nitroderivative, while (C6H5)3CMe3 gives only 16%.
p-xylene. (vii) Of all the aryl halides, C6H5F gives the least amount of
(vii) Bromination of tert-butylbenzene with bromine in presence ortho product on nitration.
of AlBr3 gives isobutene as one of the products. (viii) The percentage of m-substitution of toluene varies with
(viii) Polysubstitution is a complicating factor in Friedel-Crafts the reagent.
alkylation but not in aromatic nitration, sulphonation or Reagent Br 2 in HNO3 in CH3CH2Br in GaBr3
CH3COOH CH3COOH
halogenation.
% of m 0.5 3.5 21
(ix) One mole of triphenylmethanol lowers the freezing point
(ix) The —OCH3 group strongly activates the o, p-positions
of 1000 g of 100% H2SO 4 twice as much as one mole of
but weakly deactivates the m-position ; while —CH3
methanol.
activates all positions, but mainly o, p-.
(x) Phenyl group is known to exert negative inductive effect.
(x) The rate of nitration by conc. HNO 3 falls sharply on
But each phenyl ring in biphenyl (C6H5—C 6H5) is more
addition of salts of nitric acid and increases on addition
reactive than benzene towards electrophilic substitution.
of conc. H2SO 4.
(xi) Alkylation of phenol and aniline with alkyl halide in
26. At low temperature, 1, 3, 5-trimethylbenzene reacts with HF
presence of AlCl3 give poor yields.
and BF3 to form a bright-yellow coloured solid having three
(xii) Toluene reacts with bromine in presence of light to give
reactants in the ratio of 1 : 1 : 1. The compound is poorly
benzyl bromide while in presence of FeBr 3 it gives
soluble in organic solvents and when molten conducts an electric
p-bromotoluene.
current. On heating, the compound evolves BF3 and regenerates
(xiii) Normally, benzene gives electrophilic substitution rather
mesitylene. Deduce the structure of the compound.
than electrophilic addition although it has double bond.
27. A benzenoid hydrocarbon of the molecular formula C9H12 forms
four isomeric mononitro derivatives. Can you write down the
(xiv) tert-Butylbenzene does not give benzoic acid on treatment
structure of the hydrocarbon ?
with acidic KMnO4.
28. A monosubstituted alkylbenzene of the formula C10H14 resists
21. Account for the high reactivity of pyrrole toward electrophilic
vigorous oxidation to an aryl carboxylic acid. Name the
substitution than benzene and also the orientation of
compound and write down its various monosubstituted
substitution.
isomers.
22. Predict the response of allylbenzene to the following reagents : 29. An arene of the molecular formula C 10 H 14 on vigorous
(a) cold conc. H2SO 4 oxidation gives an acidic compound, C8H6O4 which forms only
(b) Br 2 in CCl4 one monobrome derivative. Deduce the structure of the arene
(c) cold dilute neutral permanganate and draw the structures of its five isomeric monochloro
(d) CHCl3 and AlCl3 derivatives.
(e) CrO3 and H2SO 4. 30. An aromatic hydrocarbon A of the molecular formula C16H16
23. Give necessary steps to accomplish the following conversions. decolourises bromine in CCl4 and adds an equimolar amount
(i) Benzene to styrene of hydrogen. Oxida tion of A with hot KMnO 4 gives a
(ii) Benzene to p-chlorostyrene dicarboxylic acid B of the formula C8H6O4. Compound B on
(iii) Benzene to allylbenzene (3-phenylpropene) chlorination gives only one monochloro derivative. Deduce the
(iv) Benzene to n-propylbenzene. structure of the compound A. Also name the two possible
(v) Benzene to 2-phenylpropene isomers of this compound.
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EXERCISE 7.1
1 (c) 6 (d) 11 (d) 16 (d) 21 (c) 26 (c) 31 (a) 36 (c) 41 (b) 46 (b) 51 (b) 56 (d) 61 (c) 66 (c)
2 (a) 7 (b) 12 (b) 17 (b) 22 (c) 27 (b) 32 (a) 37 (b) 42 (b) 47 (a) 52 (c) 57 (b) 62 (b) 67 (c)
3 (b) 8 (c) 13 (b) 18 (a) 23 (c) 28 (c) 33 (c) 38 (b) 43 (c) 48 (a) 53 (c) 58 (c) 63 (f) 68 (b)
4 (c) 9 (d) 14 (c) 19 (b) 24 (c) 29 (d) 34 (c) 39 (c) 44 (b) 49 (d) 54 (b) 59 (b) 64 (c) 69 (d)
5 (b) 10 (c) 15 (c) 20 (b) 25 (c) 30 (d) 35 (c) 40 (b) 45 (a) 50 (b) 55 (b) 60 (c) 65 (b) 70 (d)
1. Coal is a complex mixture of several organic compounds with varying amounts of free carbon.
2. Aromatic hydrocarbons are directly obtained from coal ; as far as petroleum is concerned this is a direct source of aliphatic compounds
which can of course be converted to aromatic compounds.
3. Reduction of conjugated compounds with sodium in liquid ammonia in presence of ethanol (a proton donor) is an example of Birch
reduction in which two hydrogen atoms are added in 1 : 4 positions. Remember that, an isolated double bond is not usually affected by
the Birch reduction except in the case of end methylene (= CH 2) or in strained alkenes such as cyclopropene and cyclobutene.
4. Electrophilic substitution reactions involve two steps, cleavage of the C—H or C—D step (i.e. proton elimination) takes place in the
second (fast) step, which being fast does not affect the rate of reaction. The first (slow) step is the formation of carbocation in which C—
H or C—D bond is not affected. Thus absence of isotopic effect establishes the two-steps mechanism for electrophilic aromatic substitu-
tion in which formation of carbocation (first step) is rate determining step.
5. HNO3 accepts a proton from H2SO 4.
6. All facts are observed.

HONO2 + 2H 2 SO 4 NO2+ + 2HSO 4 – + H3O+

Base Acid Acid Base
Note acid-base equilibrium is established
–
Å H HSO4
C6H6 + NO2+ ¾¾® C6H5 ¾¾ ¾®C6 H 5 NO 2 + H 2 SO 4
NO2 Nitrobenzene
Benzenonium ion (Benzene nucleus is restored)
7. The C—H bonds in benzene are sp 2-s, while that in cyclohexane are sp 3-s. Since sp3-s bond is longer than the sp 2-s bond, the former will be
weaker and hence the value will be < 110 kcal.
H
–
8. Boron has only 3 electrons in the outermost shell, one forms B—H s bond, other forms B—N single B
+ +
s bond and the third forms second s bond of the double bond. While each N has 5 electrons in the H—N N—H
valency shell, one forms N—H s bond, second forms N—B single s bond, third forms N—B s bond – –
H—B + B—H
of the p bond and the remaining two form one p bond. N

9. D2SO 4 transfers D+, an electrophile, to form hexadeuterobenzene. H

10. Since CH3 group is an activating group, the mono methylated product (C6H5CH3) is more reactive than benzene itself leading to
formation of C6H4(CH3)2 and C6H3(CH3)3. To prevent polymethylation an excess of C6H6 is used to increase the chance for collision
between C6H6 and CH3+ and to minimise collison between CH3+ and C6H5CH3.
11. This is an example of Friedal Craft reaction, but here benzenonium ion is unstable, so it will not be formed, hence there will be no reaction.
+
–
C6H5Cl + AlCl3 ¾ ® + AlCl4

(No resonance, hence not formed)

12. The ring to which –NH group is attached is activated due to the lone pairs on N; while the ring to which –C = O is attached is deactivated.
Hence, the electrophile would go to the para-position of the activated ring.
– –
+
13. + 2K ¾ ¾ ® + 2K

1, 3, 5, 7-Cyclooctatetraene Cyclooctatetraenyl dianion

(No. of p electrons = 10
aromatic, here n = 2)

Cyclooctatetraenyl dianion is stable due to resonance.

14. Tropylium bromide dissociates easily to form tropylium cation, which once formed gets stabilised due to resonance.
Br
+ – –
AgNO3
¾¾ ¾¾¾ ® º +
(—AgBr)
Tropylium Tropylium Cyclooctatetraene Cyclooctatetraenyl dianion
bromide cation No. of p electrons = 8 No. of p electrons = 10
corresponds to 4n corresponds to 4n + 2
(Non-aromatic) (Aromatic)
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15. 3-Chlorocyclopropene is the least stable because of absence of resonance, while cyclopropenyl cation is the most stable not just due to
resonance but due to its aromaticity (it contains p-electrons which fits the Huckel rule 4n + 2 rule for n = 0). Allyl cation is stable only due
to resonance.
16. (a) and (b) are examples of Friedal Craft alkylation, while (c) is an example of intramolecular Friedal Craft reaction.
17. Resonating structure (b) is more stable because here every atom has an octet of electrons.
+
NH2
H
X

18. Structure (a) is unstable because here positive charge is present on C carrying —I group which will further intensify (localise) the charge
making the species unstable.
1 1 1
2 2 2
¨ ¨
19. 3 3 3

I II III
Examination of structures shows that C1—C 2 bond is double in two structures (II and III) and single in only one (I). On the other hand,
the C2—C 3 bond is single in two structures (II and III) and double in only one (I). Thus the C 1—C 2 bond is expected to have more double
bond character (and hence shorter) and the C2—C 3 bond to have more single bond character (hence longer).

+
20. Cl Cl
+

H E H E
I II
Especially unstable Comparatively stable
(positive charge is present on (because every atom
C bearing —Cl, a powerful has octet)
electronegative group)

21. (i) and (ii) methods will form isopropylbenzene because n-propyl carbocation, being less stable, rearranges to the more stable (2°)
isopropyl carbocation. Moreover, method (i) will lead to polyalkylation. Methods (iii) and (iv) can be used for preparing n-propylbenzene.
CH2–CH=CH2 CH2CH2CH3

( i) AlCl3 H2/Pt
+ ClCH2CH=CH2 ¾¾ ¾¾¾ ® ¾¾ ¾¾®

n-Propylbenzene

COCH2CH3 CH2CH2CH3

AlCl3 Zn/Hg
+ CH3CH2COCl ¾¾ ¾® ¾¾ ¾¾®
HCl

22. (i) and (ii) Direct ethylation using equal amount of both reagents will lead to polyalkylation. Hence method (i) is not used. However,
polyethylation can be prevented by using excess of benzene which will increase the chance for collision between CH 3CH2+ and benzene
and decrease the chance for collision between CH 3CH2+ and C6H5CH2CH3. Hence method (ii) can be used.
AlCl3
(iii) + CH2=CHCl ¾¾ ¾® Not possible

+
Because the carbocation, CH2 = C H formed as an intermediate is unstable.
COCH3 CH2CH3

AlCl3 Zn/Hg
(iv) + CH3COCl ¾¾ ¾® ¾¾ ¾¾®
HCl

Here polyalkylation is avoided because —COCH3 group introduced in benzene is deactivating and hence further —COCH3 group
will not be introduced easily. CH3 C(CH3)3
23. The bulky size of the tert-butyl group will hinder the approach of the electrophile in the ortho
positions with the result the proportion of the product will be less than that in toluene.
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24. In case of bromination, both the electrophile as well as the group already present are bulky with the result, the steric interaction will be too much
to form o-product. However, in case of chlorination Cl+ ion being smaller than Br+ ion will produce comparatively lesser steric interaction.
25. At 0°C the energy of the benzenonium ions having —NO 2 group at p-position is less than that which is having —NO2 group at the o-position,
hence the former will be more stable than the latter. Remember that the amount of the o-isomer increases with rise in reaction temperature.
26. A carbocation can lose a proton (not hydride ion) to form alkene.
27. Wurtz-Fittig method is preferred since in this case, no rearranged product is formed. As far as other products, viz. n-hexane and biphenyl
is concerned, these can be easily removed from n-propylbenzene by distillation since their boiling points differ very much from each other.
28. Benzene, being a symmetrical molecule, melts at about 100°C higher than toluene.
29. Formation of tert-pentylbenzene involves the attack of tert-pentyl cation on benzene, so any combination which can form tert-pentyl cation
will form tert-pentylbenzene.
CH 3 CH3 CH 3
| H+ + |
(a) CH3—CHOH— C ¾ CH 3 ¾¾¾® CH3—CH—C—CH3 ¾ ¾ ® CH3—CH2— C ¾ CH 3
(–H 2 O) Å
| H
H
3-Methyl-2-butanol 2°cation 3° cation (tert-pentyl cation)

CH 3 CH3 CH 3
| + |
(b) CH3— C ¾ CH 2 OH ¾¾® CH3—C—CH2 ¾ ¾ ® CH3— C ¾ CH 2 CH 3
| Å
CH3
CH 3
Neopentyl alcohol 1° cation 3° cation (tert-pentyl cation)

CH 3 CH 3
CH3 CH3
| + +
|
(c) CH 3 ¾ C ¾ CH 2 CH 2 OH ¾¾® CH3—C—CHCH2 ¾ ¾® CH3—C—CHCH3 ¾¾® CH3— C ¾ CH 2 CH 3
| Å
H H H
H
3-Methyl-1-butanol 1° cation 2° cation 3° cation
Thus all of the three combinations will form tert-pentylbenzene.
30. The lone pair of electrons on N makes aniline (a lewis base) to react with AlCl3, (a Lewis acid); hence AlCl3 is not available to CH3Cl for
forming CH3+.

Q
.. AlCl 3
C6H5 N H2 + AlCl3 ¾¾® C 6H5 . .
N H2
Å
+
Further, the positive charge on nitrogen makes the substituent strongly deactivating, comparable to — N R3.
31. Fourth chlorine atom of the CCl4 cannot be replaced by phenyl group because the carbocation required for the introduction of the fourth
phenyl group is too stable to react with benzene.
AlCl +
3 ® (C H ) C AlCl –
(C 6H5)3CCl ¾¾¾¾ 6 5 3 4
Highly stable
The triphenylmethyl cation is highly stable and moreover further introduction of the C 6H5— group is improbable due to steric hindrance.
32. C6H5CH = CH2 (alkenylbenzenes, in general) undergoes electrophilic addition reactions at a much faster rate than CH 2 = CH2 (simple
alkenes). This is due to the fact that the transition state leading to a carbocation (or a free radical, in free radical additions) in the first step
of the reaction is resonance stabilised to a greater extent than the substrate itself.
33. Formation of product A involves ionic mechanism while that of B involves radical mechanism. So the intermediate (carbocation or free
radical) formed in two cases will be

Br
+
+ –
HBr CH2 Br
or ¾¾ ¾¾¾ ®

Less stable Highly stable A

(no delocalisation of charge) due to benzylic nature

Br

CH2 CH2 H—Br

or ¾¾ ¾¾®
hn, HBr Br Br
Less stable Highly stable B
(no delocalisation of due to benzylic nature
lone electron)
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34. m-Xylene is most reactive and sulphonates at C—4 because the two CH3 groups reinforce each other.
35. Cyclopropenyl cation is more stable than the allyl cation because the structure fits the Huckel 4n + 2 rule for n = 0.
36. Proceed backwards for solving this type of questions. Remember that o-, m- and p-phenylenediamine on monosubstitution can theoreti-
cally give 2, 3 and 1 isomer respectively.
37. Among cyclonoane (C9H10), its cation (C9H9+) and anion (C9H9–), only the anion fits in Huckel rule (10p electrons) for n = 2.

+ –
+ –
C9H9 C9H9
8p electrons 10p electrons (Fits Huckel rule, n = 2)
Aromatic

38. Carbocations I and II have chlorine which due to inductive effect tends to intensify the positive charge and thus destabilize the
carbocations. Out of I and II carbocations, I is stable through its resonance effect.

+ é + .. + ù +
CH3 C H 2 > ê CH 3 ¾ CH— C l : « CH 3 ¾ CH = Cl : ú > C H2CH2Cl
êë .. .. úû
III I II

H+ + +
39. CH2 = CHCl ¾¾¾
® CH3 C HCl or C H2CH2Cl
I II
More stable due to resonance
Note that presence of chlorine (a strong electron-withdrawing group), decreases electron density on the two doubly bonded carbon atoms
and hence vinyl chloride is less reactive than ethylene towards electrophilic additions. Orientation, i.e. whether CH3CHCl2 or CH2ClCH2Cl
is formed, depends upon stability of the carbocation. Since carbocation I is more stable (due to resonance) than the carbocation II,
product corresponding to the carbocation I will be formed. Note that the same statement is applicable to aromatic electrophilic
substitution on chlorobenzene.
+
40. Protonated nitric acid (H2 O NO 2) forms NO2+ through loss of the good leaving group H2O. Unprotonated nitric acid (HONO 2) would
have to lose the more strongly basic OH– ion ; a weak leaving group.
41. Due to isotopic effect, fewer C—D bonds will be broken than the C—H bonds, hence the amount of C 6D5Y will be less than that of C6H5Y.

D Y H Y
D D
+ +
D D
D
42. Again due to isotopic effect, fewer C—D bonds will be broken than the C—H bonds, hence the amount of C 6H2D3 X will exceed than that
of C6H3D2X, hence the [D : H]product ratio will be higher than that of reactant.

D D X
H H X
+
H X H H
¾¾ ® +
D D D D D D
H H H
C6H3D3 C6H2D3X C6H3D2X
(More)

43. According to Huckel rule, aromatic compounds contain 4n + 2p electrons, further the aromatic species should be cyclic and planar.
44. Electron withdrawing groups decrease, electron density in the o- and p-positions without effecting
m-positions, thus in such cases. meta positions will although has relatively higher electron density NO2 NO2
than the ortho and para positions it is not increased due to —NO 2 group. The intermediate carbocation + H +
formed by the attack of an electrophile on nitrobenzene will have relatively unstable resonating Br
structure in case of ortho and para position.
Note that the above two structures are relatively unstable as + ive charge is present on C bearing H Br
electronegative group, while no such structure exists in case of meta substituion.
45. Chlorination of toluene in presence of light is a free radical reaction, hence it will take place in the side chain.
46. Two intermediates are possible by the attack of electrophile (H+) ; of which II is more stable because positive charge is in conjugation with
the benzene ring.
+ +
CH3CHCH2— —OH CH3CH2CH— —OH
I II (More stable)
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NBS O O O
47.(a) CH2–CH3 CH–CH3 O O
OW WO D WO
56. (d)
Br
alc. KOH B2H6 D (I) D D (II) D
Ph–CH=CH2 Ph–CH–CH2 B
D

H O O O O
3
D D
H2O 2 / NaOH
Ph–CH2–CH2–OH
D (III) D
CH3 (+Hyperconjugation) W - withdrawing group
D - donating group
48. (a)
III II I

CD3 (+H) 4D 3D 2D
O O
+H of CH3 is more as compared to CD3. So attack of E Å || ||
will take place at ortho position of CH3. 57. (b) CH 3 - C - C º C - C - CH 3 ¾¾
® 2CH 3 COOH + 2CO 2
49. (d) Ease of oxidation µ electron density.
58. (c) This is an example of Ullmann reaction.
50. (b)
59. (b) This is an example of Diels – Alder reaction, here ethylene
NO2(–M) Cl(–I) OMe(+M) Me(+H) acts as dienophile.

(I) (II) (III) (IV) (V) + ¾

¾®

18 +
OH 60. (c) H
H3CO CH = CHCH3
HClO4 Å
18 , –
51. (b) O ClO4
+ Br
–
H3CO CHCH2CH3

Benzylic carbocation

52. (c) More stronger the activating group, more will be electrophilic (i) Na (Wurtz-Fittig reaction)
substitution reaction. H3CO CHC2H5
(ii) HBr (Demethylation)
–NO2 groups is electron attractive group, so it deactivates
the benzene ring largely –Cl atom also deactivates the Br
benzene ring but this deactivation is lower to –NO2 group;
while –CH3 group activates.
HO CH – CH OH
OMe
C2H5 C2H5
53. (c) –OH is most reactive among them.
OH 61. (c) Here D + from D 2SO 4 acts as an electrophile.
62. (b) Draw the resonating structure due to C = O group only
OMe and observe the stability

O- O- O-
–OMe and –Me both exert same effect on
Me
particular site.
OMe
Me 2p electrons 4p electrons 6p electrons
, in this case –CH3 exerts only +1 effect. (aromatic) (antiaromatic) (least stable) (aromatic)
63. (d) Pyridine contains a doubly bonded N, so here N attracts
electrons from the ring making the ring electron deficient.
54. (b)
+
O Deativates ring B
+ .. .. .. +
55. (b) A C N
.. N
..– N
.. – N
.. –
NH B

Activates ring A
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On the other hand, in pyrrole N supplies electron to the ring
+
rather than attracting electrons from the ring. H
–: + slow
+ NO2 NO2
.. + + :–
N N N
H H H
D D
O D D +
.. D D
CH3 O – C – CH3 + slow
NO2
+ NO2
D D D D
64.(c) D D
Activating due to
Had the rate determining step (slow step) involved the cleavage
Electron pair on of C – H or C – D bond, nitration of benzene would have been
+I and hyperconjugation O delocalised to
(weak effects) C = O hence moderate faster than that of hexadeuterated benzene.
activating group .
CH2 CH2
N(C2H5)2 H–C=O
.
68. (b)

(less stable) (more stable)

Electron pair on Deactivating group
N causes +M effect 69.(d)
(a powerful effect) 70.(d) Vinyl and aryl halides can’t be used as the halide component
(Most activating) because they do not form carbocations readily ; –NH2, –NHR
(d) None of the three and –NR2 groups react with Lewis acids used in Friedel-
65.(b) Attack of electrophile on benzene ring (step 2) is the slow Craft reaction to form electron-withdrawing groups, which
step. deactivate the benzene nucleus for electrophilic substitution.
.. . .+ .. + –
– NH2 NH2 AlCl3
66.(c) H – .O. – NO2 + HOSO3H H – O – NO2 + HSO4
H
Nitric acid Sulphuric acid Protonated + AlCl3
(as a base) (as an acid) nitric acid

+ + – H 2SO 4 . .+ + +
NO2 + H 3O + HSO 4 H – O – NO 2 H2O + NO2 –NH 2AlCl3– is electron-withdrawing

H On the same reason, presence of electron-withdrawing group

67.(c) Electrophilic substitution in benzene is a two step reaction in +
which slow step (first step) is common in both reactions and like –NO2, - N H3 , –CF3, – COOH, –COR, –SO3H etc. make
it does not involve the breaking of C – H or C – D bond. the benzene ring less prone to Friedel-Craft reaction.

EXERCISE 7.2
1 (a, c) 2 (a, b) 3 (a, b, d) 4 (a, b, c) 5 (a, c)
6 (a, b) 7 (a, b) 8 (a, b, d) 9 (a, b) 10 (a, c)
>1 CORRECT
11 (a, b, c, d) 12 (a, b, c, d) 13 (a, c) 14 (b, c, d) 15 (a, c, d)
OPTION
16 (a, b, c) 17 (b, c, d) 18 (b, c) 19 (a, b, d) 20 (a, c)
21 (a, c)
PASSAGE 1 22 (b) 23 (b) 24 (b)
PASSAGE 2 25 (a) 26 (d) 27 (c)
PASSAGE 3 28 (a) 29 (d) 30 (b)
PASSAGE 4 31 (a) 32 (d) 33 (b)
PASSAGE 5 34 (c) 35 (a) 36 (c)
37 (A)-a ; (B)-b, c, d ; (C)-a, b; (D) - a
MATCH THE 38 (A) – b; (B) – d; (C) – a; (D) – c
FOLLOWING 39 (A) – b,c; (B) – a,c; (C) – d; (D) – b
40 (A) - a, c; (B) - a, b, d; (C) - a; (D) - a, b
41 (A) - a, d; (B) - a, c; (C) - b, d
42 (A) - d; (B) - a, c; (C) - b, c; (D) - c
43 (A) - c, d; (B) - b, c; (C) - a, b; (D) - b, c
44 (b) 45 (e) 46 (a) 47 (d) 48 (c)
A/R
49 (e) 50 (a) 51 (c) 52 (c) 53 (d)
INTEGER 54 1 55 4375 or 4357 56 5 57 8 58 2
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41. A-(a, d); B-(a, c); C-(b, d)
42. (A)-d; (B)-a, c; (C)-b, c; (D)-c O

43. (A)-c,d; (B)-b,c; (C)-a,b; (D)-b,c

(c) (d)
51. (c) Alkyl halides give polyalkylation products.
53. (d) Assertion is false, explanation is although true but it is not 9H 1H
correct explanation of assertion.
55. 4375 or 4357
54. 1

O3 , Zn
CHO conc. CH 2 OH NaOH
¾¾¾¾ ®| ¾¾¾¾ ®| ¾¾¾¾ ® CH3OH
H2O NaOH CaO, D
CHO COO-
(a) (b)
5H 2H P/I
¾¾¾
2 ® CH
4

EXERCISE 7.3

1. (i)

Hydrogen atom attached on C1 is most reactive as it is 2° dibenzylic ; followed by C 2 because of 2° benzylic, then C3 (1° benzylic),
C4 (2°) and C5 (1°).

(ii) ;

Removal of hydrogen from C-1 gives a benzylic free radical stabilized by hyperconjugation (drawn above).
Such structures are not possible for m-methyl groups, i.e. for hydrogen atoms attached on C-2 and C-4. Thus the ease of removal
of hydrogen atom will be 1 —CH3 > 4 —CH3, 2 —CH3.
Alternatively. The C1-methyl group is o, p to other two methyl groups, C4-methyl is m, p to other two methyl groups but less
sterically hindered than the C2-methyl group which is also m, p to other methyl groups but more sterically hindered. Thus ease of
abstraction of hydrogen will thus be
C1-methyl > C4-methyl > C2-methyl
1 5 5 2 3 4
2. C6H5— CH2 ¾ C H = CH ¾ CH2 ¾ C H2 ¾ CH3
1-Phenyl-2-hexene
The order of reactivity is
C1 (allylic, benzylic) > C2 (allylic) > C3 (2°) > C4 (1°) > C5 (vinylic)
Monobromo products obtained on abstracting three different types of hydrogen atoms will be as follows. Note that abstraction of
allylic hydrogen will form two products, as in the first two cases ; via a delocalized allylic radical.
1. C6H5 CH CH = CHCH2CH2CH3 and C6H5CH = CH CH CH2CH2CH3
| |
Br Br

2. C6H5CH2CH = CH CH CH2CH3 and C6H5CH2 CH CH = CHCH2CH3

| |
Br Br

3. C6H5CH2 C = CHCH2CH2CH3 and C6H5CH2CH = CCH 2 CH2CH3

| |
Br Br
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3. Remember that the alcohol that forms the most stable carbocation will be dehydrated faster.

C6 H 5 OH OH
| | |
(i) CH3— C ¾ CH 2CH 3 > HO CH . CH 2CH 2CH 3 > CH 3CH . CH . CH 3 , C6H5CH2 CH . CH 2CH 3 > HOCH2 CHCH 2CH3
| | | |
OH C6H5 C6 H 5 C6H5
III I V IV II

(ii) (C 6H5)2C(OH)CH3 > C6H5 CHOHCH3 > C6H5CH2CH2OH

(iii) p-CH3C6H4CHOHCH3 > C6H5CHOHCH3 > p-Br-C6H4CHOHCH3
4. Reactivity is determined chiefly by the stability of the carbocation being formed. This is affected by the nature of the substituent on the
ring, electron-releasing substituent increases stability of the carbocation, while electron withdrawing substituent decreases stability.
The correct order of reactivity is shown aside:

light
5. (i) BrCCl3 ¾ ¾¾ ¾® Br. + . CCl3 (ii) C6H5CH3 + . CCl3 ¾¾® C 6H5CH2 . + CHCl3
(iii) C6H5CH2 . + BrCCl3 ¾¾® C6H5CH2Br + . CCl3
Above reactions (ii) and (iii) are repeated again and again.
(iv) C6H5CH3 + Br . ¾¾® C 6H5CH2 . + HBr
Benzyl radical formed here also further undergoes reactions (iii), (ii), (iii), (ii) etc. and thus forming C6H5CH2Br and CHCl3 as the main
products.
(v) Chain terminating reaction leads to C2Cl6.
. CCl3 + . CCl3 ¾¾® Cl3C—CCl3 or C2Cl6
6. 1-Phenylpropene, 2-phenylpropene and 3-phenylpropene can be distinguished on the basis of ozonolysis.
C6H5
|
C6H5CH = CHCH3 CH3 C = CH 2 C6H5CH2CH = CH2
1-Phenylpropene 2-Phenylpropene 3-Phenylpropene

C6H5CHO + OHCCH3 ; CH3.CO.C6H5 + CH2O ; C6H5CH2CHO + CH2O

UV
7. (i) C6H5CH2CH(CH3)2 + Br2 ¾ ¾¾® C 6H5CHBrCH(CH3)2 + C6H5CH2CBr(CH3)2
(Major) I (Minor) II
Note that formation of I (major product) involves the more stable benzyl free radical while that of II (minor product) involves the
lesser stable 3° free radical.
AlCl 3
(ii) C6H6 + (CH3)2CHCH2Cl ¾ ¾¾¾® C6 H 5C(CH 3 )3
tert - Butylbenzene
Formation of the above (unexpected) product can be explained on the basis of the fact that 1° carbocation rearranges to the more
stable 3° carbocation.

CH3 CH3 CH 3
| AlCl3 | + Migration |
CH3 CHCH 2Cl ¾ ¾¾¾® CH3 CH CH 2 ¾¾¾¾® CH3— C — CH 3
– of H : +
1° carbocation 3° carbocation

(iii)
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Again formation of the above product can be explained on the basis of rearrangement of the lesser stable 1° carbocation to the more
stable 3° carbocation.

BF3 + Migration +
(CH3)3CCH2OH ¾ ¾¾® (CH 3 )3 CC H2 ¾¾¾¾® (CH 3 )2 CCH 2CH3
Q
1° carbocation of : CH 3

3-cabocation

(iv)

Note that at high temperature, thermodynamic controlled product will be formed which should have less steric strain. Kinetic
controlled product i.e. isomer having a bulky tert-butyl group ortho to —CH3 group will be formed at low temperatures.
H SO
(v) C6H6 + (CH3)2CHCH2OH ¾ ¾¾¾ 2 4
® C6H5C(CH3)3 . Here the 1° carbocation undergoes rearrangement to form the more stable 3°
carbocation which attacks benzene forming tert-butylbenzene.
H+ + +
(CH3)2CHCH2OH ¾ ¾¾® (CH3)2CH C H2 ¾¾® (CH3)3 C
1° (less stable) 3° (more stable)

Br2 , heat NaCN

(vi) C6H5CH2CH3 ¾¾¾¾® C 6H5 CHCH3 ¾ ¾¾¾® C 6H5 CHCH3
light | |
Br CN
H2SO4
8. (a) C6H5CH2CHOHCH(CH3)2 ¾ ¾¾¾® C 6H5CH = CHCH(CH3)2 + C6H5CH2 CH = C(CH3)2
(Major) I (Minor) II
Note that the product I is although a disubstituted alkene, it is more stable due to conjugation with benzene ring than the
trisubstituted alkene, II which, being non-conjugated is formed in minor amount.

+ H+ from + –
Br – C H CH C HCH
(b) C 6H5CH2CHBrCH3 ¬¾¾ 3 ¾¾® C6 H 5CHBrCH 2CH 3
H+ from HBr C H CH = CHCH ¾¾¾¾¾® C H C HCH CH ¾ Br
¾6 5 2 3 ¬¾¾¾¾¾ ¾6 5 3 HBr
6 5 2
(Major) (More stable, benzylic)

(Minor) Less stable, 2°

H
. . Br. from HBr
Br · from . H.
(c) C6H5CHBrCH2CH3 ¬¾¾ C6H5CHBr CHCH3 ¬¾¾¾¾¾ ¾C6H5CH=CHCH3¾¾¾¾® C6H 5 C HCHBrCH3 ¾¾¾® C6 H 5CH 2CHBrCH3
HBr (More stable, benzylic) (Major)

(Minor) Less stable, 2°

(d) C6H5CH = CHCH = CH2 + Br2 ¾¾® C6H5CHBrCHBr CH = CH2 + C6H5CH = CHCHBr CH2Br + C6H5CHBrCH = CHCH2Br
Eqimolar amounts (Major, due to conjugated system)

+
(e) Me 3 N CH = CH2 + HI ¾¾® Me3NCH2CH2I
+
The substituent — N Me 3 is a strong electron withdrawing group and thus favours the formation of a carbocation with the charge
on the more remote carbon atom.

(f)

AlBr3 is used to provide the stronger acid HAlBr4 that is needed for attack on the highly deactivated alkene.
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9. (i)

Alkenes when heated with KOH undergo isomerisation to the more stable, conjugated ones.
Ni
(ii) C6H5CH = CH¾CH = CH2 + H2 ¾¾¾® C6 H 5CH = CH ¾ CH 2 ¾ CH 3
30°C (conjugated alkene)

C6H5 CH2C6H5
H2—Pd
(iii) C6H5C º CCH2C6H5 ¾¾ ¾¾® C=C
H H
Catalytic hydrogenation gives cis (Z) – product.

(iv)

Br2 alc.
10. (a) C6H5CH2CH2CH3 ¾¾¾¾® C 6H5CHBrCH2CH3 ¾¾¾¾®
hv KOH

(A)

Cold dil. hot

C6H5CH = CHCH3 ¾¾¾¾® C 6H5CHOHCHOHCH3 ¾¾¾¾® C 6H5COOH + HOOCCH3
KMnO 4 KMnO 4

(B) (C) (D) and (E)

ether BrH 2C.CH = CH2

¾® C 6H5MgBr ¾ ¾¾¾¾¾¾¾
(b) C6H5Br + Mg ¾ ¾¾ ¾®
(F)

KOH Br2
C6H5CH2CH = CH2 ¾¾¾¾¾® C 6H5CH = CHCH3 ¾¾¾¾¾® C 6H5CH = CHCH2Br
heat 300°C

(G) (H) (I)

Pt HBr
(c) p-CH3.C 6H4.C º C.C6H5 + H2 ¾ ¾
¾® ¾ ¾¾® p-CH3.C 6H4. CH CH2C6H5
|
Br
(K )

+ +
In K, H+ adds to give more stable R+ which is p-CH3.C 6H4 C HCH2C6H5 rather than p-CH3.C 6H4.CH2 C HC 6H5 because of
electron release of p-CH3.
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HBr
(d) ¾¾¾¾® p-Br.C6H4—CH2 CH .CH3
peroxide |
Br
(M)

.
In M, Br. adds to give more stable R., p-BrC6H4CHCHBrCH3 which is benzylic.
H 2 , Ni
11. (i) trans- C6 H5CH = CHCH 3 ¾¾¾¾¾® C6 H11CH2CH2CH3
200°, 100 atm n-Propylcyclohexane
trans-1-Phenyl- 1- propene
Remember that hydrogenation conditions are drastic and hence benzene ring will also be reduced to cylcohexane ring.
Fe
(ii) trans-C 6H5CH = CHCH3 + Br2 (excess) ¾ ¾ ¾® p-Br.C6H4.CHBr.CHBrCH3
Note that Br2 in presence Fe acts as an electrophile, hence electrophilic addition on C = C as well as electrophilic substitution in
benzene nucleus take place.

CH3 CH3
H—C—CH3 cold dil. H OH OH H
¾¾ ¾¾® +
(iii) C6H5—C—H KMnO4 HO H H HO
(syn-hydroxylation) C6H5 C6H5
trans-1-Phenyl-1-propene racemic-mixture

hot
(iv) trans-C 6H5CH = CHCH3 ¾¾¾¾® C 6H5COOH + HOOC.CH3
KMnO 4

(v)

tert-BuOK
(vi) CHBr3 ¾ ¾¾¾¾® : CBr2 + HBr

12. Three isomeric dibromobenzenes are ortho-, meta- and para. ortho-Isomer on mono-substitution gives two isomers, meta-gives three
isomers and para gives one isomer.
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Thus, in total six isomeric dibromonitrobenzenes are possible.

13. o-Bromochlorobenzene has four different types of hydrogen atoms, thus on nitration it may form four isomeric nitrobromochlorobenzenes;
m-isomer also has four types of hydrogen atoms ; while para-isomer has only two types of hydrogen atoms hence it will form two
isomeric nitrobromochlorobenzenes.

14. In all cases, apply the following points :

1. Substitution is faster in the ring having an activated group or substitution is faster in the ring which is not deactivated.
2. Orientation will be governed by the group present on the ring that is to be substituted.
(i) (A)Substitution is faster in the ring that is not deactivated by —NO 2. Further, Ar—group is a weakly activating group, so
substitution will be taking place in o, p position to the other ring.

(a) (b)

(c)

(B) Similar explanation as in (A), Further group —CH2Ar is o,p-directing.

(C) Substitution is faster in the ring that is activated by phenolic oxygen (similar to —OR). The other ring is actually deactivated by
—COOAr.
(ii) (a) This compound is a derivative of phenol, so substitution will be taking place in o- and p-positions to the —OCOC6H5 group
forming two products.

(b) —OCH3 group is activating so substitution will be taking place in the o-position to the —OCH3 group. Further, if we consider p-
C6H4.OCH3 as a group substitution will be taking place in the o- and p-position to the unsubstituted ring. Thus, in all three
monobromo products are possible.
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(c) The middle benzene ring is having phenyl rings in the p-positions ; so only one product is possible.

(c) (d)

(d) Here both the groups reinforce each other at one positions which is o- to —NHCOCH3 and m- to —SO3H ; thus here
also one product is possible.
15. Acidity of these hydrocarbons can be explained in terms of resonance stabilization of the anion, with dispersal of negative charge which
corresponds to the following order.
Ph3C– > Ph2CH– > PhCH2– > n-C5H11–
Thus acidic character of the corresponding hydrocarbons follows the order.
Ph3CH > Ph2CH2 > PhCH3 > n-C 5H12
16. For these alcohols, reactivity is largely determined by the stability of the carbocation being formed. This is affected by electron release
or electron withdrawl by substituents on the alcohol bearing carbon atom or on the aromatic ring.
+ + +
(i) C6H5— C H—CH2CH3 > C6H5CH2 C HCH3 > C6H5CH2CH2 C H2
Benzylic carbocation 2° Carbocation 1° Carbocation

+ + +
(ii) HO— —CH2 > —CH2 > NC— —CH2

HO is electron releasing CN is electron withdrawing

17. Reactivity by SN1 is controlled by the stability of the carbocation formed, and reactivity by S N2 is controlled mainly by hindrance.
Reactivity by SN1 C6H5CCl(CH3)2 > C6H5CHClCH3 > C6H5CH2Cl
Reactivity by SN2 C6H5CH2Cl > C6H5CHClCH3 > C6H5CCl(CH3)2
18. To be aromatic, annulenes [monocyclic compounds of the general formula -[-CH = CH-]-n] should follow the Huckel 4n + 2 rule for
the p electrons (6 for n = 1, 10 for n = 2, 14 for n = 3, 18 for n = 4). Thus annulenes (with the number of p electrons indicated within the
brackets in each name) that are expected to be aromatic are [6]-annulene (benzene), [10]-annulene, [14]-annulene and [18]-annulene.
Actually for [10]-and [14]-annulenes, the geometry is unfavourable, crowding of hydrogens inside the ring causes strain and thus
prevents planarity and hence interferes with p overlap, thus ultimately diminishes aromaticity.

19. (a) The yellow colour is attributed to the stable Ph3C+, whose positive charge is delocalised to the op-positions of the three benzene
rings.
Ph3CCl + AlCl3 ¾¾® Ph 3C + + AlCl4–
(Yellow colour)

or Ph3COH + H2SO 4 ¾¾® Ph 3C + + H2O + HSO4–

(Yellow colour)
Appearance of white solid on dilution is due to the formation of Ph3COH.

Ph 3C + + 2H2 O ¾¾® Ph 3COH B+ H 3O+

Lewis acid Lewis base (White solid)

..
(b) The strong base : N H2– removes proton from Ph3CH to form the stable, deep red-purple carbocation Ph3C :– whose negative charge
is delocalized to the op-positions of the three benzene rings.
Ph3CH + :NH2– ¾¾® Ph3C:– + HNH2
Acid1 Base2 Base1 Acid2
(deep red)
The deep red colour disappears on adding water, a feeble acid, due to protonation to form Ph3CH.
Ph3C:– + H2O ¾¾® Ph3CH + OH–
Base1 Acid2 Acid1 Base2
(colourless)
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(c) Zinc removes Cl. from Ph3CCl to form the red coloured radical Ph3C.
2Ph3CCl + Zn ¾¾® 2Ph 3C. + ZnCl2
(red colour)

The red colour disappears on passing oxygen due to formation of peroxide.

.. .. .. ..
2Ph3C. + . O — O . ¾¾® Ph3C— O — O —CPh3
.. .. .. ..

Peroxide (colourless)
(d) Carbon tetrachloride reacts with excess of benzene forming first C6H5CH2Cl, then (C6H5)2CHCl and finally (C6H5)3CCl.
AlCl 3
3C6H6 + CCl4 ¾ ¾¾¾® (C6H5)3CCl + 3HCl
+
However, as soon as (C6H5)3CCl is formed, it reacts with AlCl3 to form (C6H5)3 C AlCl4–, whose carbonium ion in too stable to
+
react with benzene. Moreover, (C6H5)3 C is too sterically hindered to react further.
20. (i) In benzene, C—H bond isof sp 2-s character which is shorter and hence stronger than the sp 3-s C—H bond in cyclohexane.
(ii) Hydrogen atoms in acetylene are attached on sp hybridised carbon atoms, in benzene on sp 2 hybridised carbon atoms while in n-
pentane on sp 3 hybridised carbon atoms. Now we know that greater the s character of a carbon atom more will be the displacement
of electrons towards nucleus thus weaker will be the C—H bond. Hence the strength of the C—H bond follows the following order
sp C—H > sp2 C—H > sp3 C—H
Most acidic Least acidic
\ HC º CH > C6H6 > n-C 5H12
Alternatively, consider the corresponding three anions, viz. HC º C –, C6H5– and C5H11– . In acetylide anion, the unshared electron
pair occupies an sp orbital which has maximum s character, while the sp 3 orbital of the pentyl anion C5H11– has minimum s
character and sp 2 orbital of the phenyl anion has intermediate s character. So electrons in the sp orbital are held most tightly, while
those in the sp 3 orbital are held least tightly. Therefore, the basicity order of the three anions follows :

C5H11– > C6H5 – > HC º C –

Pentyl anion Phenyl anion Acetylide anion

Hence the corresponding acids will have the following acidic order.
HC º CH > C6H6 > C5H12
Acetylene Benzene Pentane

(iii) The number of p bonds in cyclo-octatetraene is eight which is not a Huckel number and hence the compound is not aromatic and
thus behaves as an alkene. On the other hand, in benzene the number of p bonds is 6 which is a Huckel number and thus benzene
hehaves as an aromatic compound.
(iv) Neopentyl cation, being 1° cation, rearranges to the more stable tert-pentyl cation (3°) which then reacts with benzene forming tert-
pentylbenzene.
rearranges +
(CH 3 )3 CCH 2 Br (CH 3 )3 CCH 2+ ¾¾¾¾® (CH 3 )2 CCH 2CH 3 C6 H 5C(CH 2CH 3 )(CH 3 ) 2
Neopentyl bromide Neopentyl cation tert-Pentyl cation (3° ) tert-Pentylbenzene

(v) An acid-base complex I is formed which transfers bromine without its electrons directly to the ring.

(CH3COO)3Tl + Br2 (CH3COO)3 Tl Q — BrÅ —Br

I
Due to bulky size of the complex, it attacks a substituted aromatic ring most readily at the least hindered position, i.e. para to the
substituent already present.
(vi) In m-xylene the two —CH3 groups activate (doubly) the same position, while in p-xylene the two —CH3 groups activate different
positions.

(vii) C6H5C(CH3)3 + Br2(AlBr3) ¾¾® C 6H5Br + HBr + (CH3)2C = CH2

This is an example of bromodealkylation.

Br 2 + AlBr3 Br3 AlQ — BrÅ —Br

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+
(CH3)3 C + AlBr4– ¾¾® (CH3)2C = CH2 + HBr + AlBr3
(viii) The newly introduced alkyl group activates the aromatic ring towards further substitution forming polyalkylated product as
unwanted products. In other reactions, the newly introduced group, being deactivating, deactivates the ring towards further
substitution.
(ix) Ionization of Ph3COH in H2SO 4 produces twice as many ions per mole as does CH3OH, hence twice the lowering of the freezing
point.
(a) Ph3COH + H2SO 4 ¾¾® Ph3COH2+ + HSO4–
Ph3COH2+ ¾¾® Ph3C+ + H2O
(Stable)
H2O + H2SO 4 ¾¾® H3O+ + HSO4–

On adding, Ph3COH + 2H2SO 4 ¾¾® Ph 3C+ + H 3O+ + 2HSO 4 –

1444442444443
Four ions

(b) CH3OH + H2SO 4 ¾¾® CH 3OH 2+ + HSO 4 –

1444 424444 3
Two ions

Since CH3+ in quite unstable, hence CH3OH2+ does not dissociate to form CH3+ and H2O.
(x) In biphenyl, one of the phenyl groups acts as donor and the other as electrons acceptor. This makes the phenyl ring more reactive
than benzene towards electrophilic substitution.
(xi) In presence of Lewis acid (e.g. AlCl3), —NH2 or —OH group becomes electron withdrawing.
(xii) In presence of light, toluene undergoes free radical substitution in the side chain, while in presence of FeBr 3 it undergoes electrophilic
substitution in the benzene nucleus.
(xiii) Benzene ring remains intact in substitution while addition reaction destroys benzenoid structure.
(xiv) tert-Butylbenzene does not have benzylic hydrogen atom, necessary for oxidation. Hence it can’t be oxidised by KMnO 4 to
C6H5COOH.

21. Pyrrole can undergo electrophilic substitution at position 2 or 3. However, the carbocation formed by attack at position 2 is a hybrid
of three structures (I, II and III), while the corresponding carbocation formed by attack at position 3 is a hybrid of two structures (IV
and V). Hence the carbocation formed by attack at position 2 is more stable, leading to 2-substituted pyrroles.

H X H X
Å
Å Å
H H H X, attack at X, attack at
¬® ¬® ¬¾¾¾¾¾ ¾¾¾¾¾® ¬® Å
Å Å Å
X position 2 position 3
:

N X N X N N N N
H H H H H H
III II I IV V

More stable ion

Pyrrole is highly reactive, compared with benzene, because of contribution from the relatively stable structure I, in which every atom has
an octet of electrons.
22. (a) Allylbenzene, C6H5CH2CH = CH2 dissolves or polymerises in cold conc. H2SO 4.
(b) C6H5CH2CH = CH2 + Br2 (in CCl4) ¾¾® C 6H5CH2CHBrCH2Br
Red Colourless
–
(c) C6H5CH2CH = CH2 + MnO4 ¾¾® C 6H5CH2 CH ¾ CH 2 + MnO2
Purple | |
OH OH
Colourless Brown ppt.
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(d) Orange-red colour is developed due to formation of Ar3C+ cation.
CHCl 3 , AlCl 3 ArH, AlCl 3 ArH, AlCl 3
ArH ¾¾¾¾¾¾¾¾¾® ArCHCl2 ¾¾¾¾¾¾¾¾¾® Ar2CHCl ¾ ¾¾¾¾
¾® Ar3CH
Friedel-Craft reaction Friedel-Craft reaction

AlCl 3 Ar3CH +
Ar 2CHCl ¾ ¾¾¾® Ar2CH+AlCl4– ¾¾¾¾¾¾¾¾¾® Ar2CH2 + Ar3 C AlCl4–
Transfer of hydride ion

Orange-red colour
(e) Allylbenzene does not react with chromic anhydride (CrO 3) in aq. sulphuric acid, i.e. orange colour of HCrO4– does not disappear.
+
23. (i) Benzene to styrene. Styrene can’t be prepared by Friedel-Craft reaction because CH2 = C H is unstable.
HF Br2 KOH
C6 H 6 + CH = CH ¾ ¾¾® C H CH CH ¾¾¾® C H .CHBr.CH ¾ ¾¾® C6 H 5CH = CH 2
2 2 6 5 2 3 heat 6 5 3 (alc.)
Benzene Styrene
(ii) Benzene to p-chlorostyrene. Remember that chlorine group should be introduced earlier than the introduction of the double bond,
otherwise addition of halogen as well as substitution will take place because the first step in both these reactions is common, i.e.
the attack of positively charged halonium ion on the p electron cloud. Moreover, it has been observed that addition of halogen to
the side chain double bond is completed first before the electrophilic substitution.

Conversion of benzene to p-chlorostyrene.

(iii) Benzene to allylbenzene.

(iv) Benzene to n-propylbenzene.

Direct propylation with n-CH3CH2CH2Cl will give isopropylbenzene due to more stability of the 2° carbocation (CH3)2CH+, hence
n-propylbenzene should be prepared in the following way.
AlCl 3 H 2 / Pt
C6H6 + ClCH2CH = CH2 ¾ ¾¾¾® C 6H5CH2CH = CH2 ¾ ¾¾¾® C 6H5CH2CH2CH3
(v) Benzene to 2-phenylpropene.
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(vi) Ethylbenzene to E-1-penylpropene.

(vii) Ethylbenzene to p-nitrostyrene.

(viii) Toluene to p-bromobenzyl bromide.

Remember that nuclear substitution is done earlier so as to get better yield. Otherwise —CH2Br will decrease the yield of p-bromo
isomer.
(ix) Toluene to p-bromobenzoic acid.

(x) Toluene to m-bromobenzoic acid.

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(xi) Toluene to p-nitrodiphenylmethane.

24. (i) Toluene to 1, 2, 3-trimethylbenzene. Methylation of toluene will give p-xylene, therefore it is necessary to block the para position
with a group that can later be easily removed. Such group is —CMe3.

(ii) Benzene to 3, 4-dibromonitrobenzene.

Remember that nitration should not be done earlier than bromination because such sequence will give 2, 5-dibromonitrobenzene
according to the rule ‘‘in case op-director and m-director are not reinforcing, the op-director controls the orientation and the
incoming group goes mainly ortho to the m-director’’.

(iii) Toluene to p-benzylnitrobenzene

Remember that chlorination should not be done prior to nitration because deactivated nitrobenzene can’t be alkylated with
C6H5CH2Cl.

Furthermore, nitration of benzyl chloride will give lower yield of the o- and p-isomers.
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(iv) Benzene to 1, 1-diphenylethane
C 2 H5 Cl Br2 alc
C6H6 ¾¾¾¾¾¾® C 6H5CH2CH3 ¾¾¾¾¾¾® C 6H5CHBrCH3 ¾¾¾¾¾¾®
AlCl 3 light KOH

C 6 H 6 , HF
C6H5CH = CH2 ¾ ¾¾¾¾
¾® (C6H5)2CHCH3
Note that last step is an example of Friedel-Craft reaction.

HF + C6 H 6
C6H5CH = CH2 ¾ ¾¾® C6H5 C HCH3 ¾ ¾¾
¾® (C6H5)2CHCH3
2° carbocation
(v) Benzene to o-dibromobenzene

Direct bromination of bromobenzene is not advisable as it would mainly give p-dibromobenzene.

(vi) Toluene to 2-bromo-4-nitrobenzoic acid

Remember that —CH3 should not be oxidised prior to bromination because in such case bromination of a ring deactivated by —
COOH and —NO2 groups would be very difficult and bromination will occur in the meta position to both of the groups —COOH
and —NO2.
(vii) m-Xylene to 5-nitroisophthalic acid.

Here since both of the deactivating groups reinforce each other, appreciable amount of the m-isomer can be obtained of course,
under drastic conditions.
25. (i) Benzene is more reactive than bromobenzene and hence would preferentially undergo alkylation. On the other hand, —NO 2
strongly deactivates the nitrobenzene nucleus with the result the latter does not undergo Friedel-Craft alkylation or acylation.
(ii) To avoid polyalkylation.
(iii) Since C6H5+ has a high enthalpy, it is not formed. C6H5Cl + AlCl3 ¾¾® C 6H5+ + AlCl4–
(Not formed)
(iv) Sulphonation is one of the few reversible electrophilic substitutions and therefore gives the kinetic controlled product at 0°C and
the thermodynamic controlled product at 100°C.

(v)
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(vi) Formation of lesser amount of ortho product in C 6H5C(CH3)3 is due to steric hindrance ; the bulky —C(CH3)3 group inhibits
formation of the ortho isomer and thus increases the yield of the para isomer.
(vii) In aryl halides, inductive effect operates which is strongest at the closer ortho position. Now since F has the greatest inductive effect
among halogens, its ortho positions are deactivated more than that of other aryl halides hence ortho isomer will be minimum.
(viii) This is explained on the basis of selectivity-reactivity principle, i.e. the most reactive electrophile is the least selective and gives the
maximum amount of meta isomer. The order of reactivity is :
CH3CH2+ > NO2+ > Br+
(ix) —OCH3 group is electron-releasing and activating by extended p bonding only when it is attached to the positively charged
(o, p-) positions of the benzenonium ion. It is also electron-withdrawing by induction and this factor prevails in the m-position,
which is deactivated. On the other hand, —CH3 group is electron releasing by inductive and hyperconjugative effects, and since
hyperconjugation is effective only in the o-p-positions, these positions are more activated than the m-position.
(x) Nitronium ion, NO2+, the real nitrating agent is produced according to the following scheme.
+
2HNO3 NO3– + H— O —NO2 NO2+ + NO3– + H2O
| Nitronium ion
H

When a salt of nitric acid is added, it shifts the equilibrium to the left causing the formation of undissociated acid molecules. Hence
the concentration of the nitronium ion decreases in the reaction mixture with the result rate of nitration also decreases. On the other
hand, addition of conc. sulphuric acid helps in producing the nitronium ions and hence increases the rate of nitration.

HONO 2 + 2H2SO 4 NO2 + + 2HSO4– + H3O+

Nitric acid Nitronium ion

26. BF4–

27. Four isomers are produced by arenes having two different alkyl groups in ortho or para positions. Thus C9H12 can be either of the
following structures.

28. An alkyl group, on benzene nucleus, undergoes oxidation if it has at least one benzylic hydrogen atom. Thus to resist oxidation, the
benzylic carbon atom should not have any hydrogen atom, i.e. it should be tertiary. Hence the compound in question is tert-butylbenzene
whose other isomers are sketched below.

29. (i) The acidic compound C8H6O4 must be a dicarboxylic acid, C6H4(COOH)2 and since this gives only one monobromo derivative,
the two —COOH groups should be present in para position to each other. Hence the arene should be a p-dialkylbenzene.
(ii) Since the arene forms five isomeric monochloro derivative, it should be p-isopropylbenzene only which can give rise to five isomeric
monochloro derivatives.
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Arene, C10H 14

Five isomeric monochloro derivatives.

30. (i) Molecular formula (C16H16) of the compound A indicates 9 degree of unsaturation (saturated hydrocarbon will be C16H34).
(ii) Since compound A takes up one H2 molecule, it indicates that it has one C = C linkage, thus the other 8 degree of unsaturation
must be present in the form of 2 benzene rings (one benzene ring has 4 degree of unsaturation).
(iii) Oxidation of A with hot KMnO 4 gives a dicarboxlic acid B of the formula C 8H6O4 or C6H4(COOH)2 indicating that each benzene
ring must be disubstituted.
(iv) Since the dicarboxylic acid B forms only one monobromo derivative, the two —COOH groups must be para to each other.
Thus compound A should have following structure which explains all reactions.

Cl
hot Cl2
H3C— —CH=CH— —CH3 ¾ ¾ ¾ ¾ ® 2HOOC— —COOH ¾ ¾ ® HOOC— —COOH
KMnO4 Fe
(A)
(B)

Two isomers of (A) are cis- and trans.

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8.1 Preparation of Alkyl Halides 8.4 Halogen Derivatives of Unsaturated Hydrocarbons

8.2 Physical Properties 8.5 Polyhalogen Compounds

8.3 Chemical Properties EXERCISES

ILLUSTRATIVE EXAMPLES SOLUTIONS

Compounds obtained by the replacement of one or more hydrogen atom(s) from hydrocarbons are known as
halogen derivatives. The halogen derivatives of alkanes, alkenes, alkynes and arenes are known a alkyl halides
(haloalkanes), alkenyl halides (haloalkenes), alkynyl halides (haloalkynes) and aryl halides (halobenzenes), respectively.
Halogen derivatives may be classified in several ways depending upon the type of the halogen atom, number of
halogen atom(s) and position of the halogen atom. The last type of classification deserves special attention, e.g., alkyl
halides may be classified into primary (1°), secondary (2°) and tertiary (3°) according to the nature of the carbon atom bearing
halogen.
Alkyl halides may show chain, position and optical isomerism, while alkenyl halides may show geometrical
isomerism; aryl halides show position isomerism.

1. Write structural formulas and IUPAC names of all isomers of

(a) C5H11Cl. Classify the isomers as 1°, 2° and 3° chlorides.
(b) C4H8Cl2. Classify the isomers as vic-dihalides and gem-dihalides.
2. Give the simplest examples (compound having minimum possible carbon) of monohalogen compounds which can show
(a) Geometrical isomerism (b) Optical isomerism.
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8.1 Preparation of Alkyl Halides

8.1.1 From Alcohols

Alcohols are considered the best starting materials for preparing alkyl halides. The most common method is to
treat the alcohol with HX. The order of reactivity of the hydrogen halides parallels their acidity : HI > HBr > HCl >> HF.

R — OH ¾ HX, PX or SOCl
¾ ¾ ¾3 ¾ ¾ ¾¾2 ® R — X (where , X = I, Br, Cl)
Among the various classes of alcohols, the order of reactivity with hydrogen halides is
tertiary > secondary > primary > CH3OH
Tertiary alcohols are so reactive that these are converted to alkyl chlorides in high yield within minutes on
reaction with HCl at room temperature, while secondary and primary alcohols give very low yield under these conditions.
Therefore, the more reactive HBr is used and that too at elevated temperatures to get quantitative yield of secondary and
primary bromides.
25 ° C
(CH 3 ) 2 C — OH + HCl ¾¾¾
¾® (CH 3 ) 3 C — Cl + H 2 O
tert - Butyl alcohol tert - Butyl chloride

80–100°C
—OH + HBr ———–® —Br + H2O

Cyclohexanol Bromocyclohexane

120 ° C
CH3(CH2)5CH2OH + HBr ¾ ¾ ¾¾® CH3(CH2)5CH2Br + H2O
NaBr, H SO
CH3CH2CH2CH2OH ¾¾¾¾¾
2
¾
4
® CH3CH2CH2CH2Br
heat

Tertiary alcohols react with HX by SN1 pathway, while primary alcohols react via SN2, secondary may follow
either or both of the paths (discussed in detail in Ch. 4).
Primary and secondary alcohols can best be converted to the corresponding chlorides, bromides and iodides by
the use of thionyl chloride, phosphorus bromide and phosphorus + iodine (PI3) respectively.
pyridine
CH3CH2CH2OH + SOCl2 ¾¾¾¾ ¾® CH3CH2CH2Cl + SO2 ­ + HCl ­

+ PBr3 ——® 3 + H3PO3

Phosphorous acid
3
OH Br
Cyclopentanol Cyclopentyl bromide

P +I
CH 3 CH 2 OH ¾ ¾ ¾2 ® CH 3 CH 2 I

1. Mixture of conc. HCl and anhydrous ZnCl2 is called Lucas reagent.

2. SOBr2 is less stable and SOI2 does not exist.
3. PBr5 and PI5 are highly unstable compounds, hence can’t be used for preparing bromides and iodides.

1. Give steps involved in the conversion of an alcohol into alkyl halide in presence of conc. HCl and anhydrous ZnCl 2.
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8.1.2 Halogenation of Certain Hydrocabons

Alkyl halides are almost never prepared by direct halogenation of alkanes because the reaction generally gives
a mixture of several compounds. Details have already been discussed in Ch. 5.
Cl 2
¾ ¾ ¾ ¾¾® CH3Cl ¾ Cl
CH4 ¾ heat ¾¾2 ® CH2Cl2 ¾ Cl
¾¾2 ® CHCl3 ¾ Cl
¾¾2 ® CCl4
or light

Cl 2
¾ ¾ ¾ ¾¾® CH3CH2CH2Cl + CH3CHClCH3 ¾ Cl
CH3CH2CH3 ¾ heat ¾¾2 ® ...... .
or light

However, certain compounds can form monohalogen product in good yield, e.g. CH4, CH3CH3, (CH3)4C, C6H5CH3,
CH3CH = CH2, etc.because in all of them hydrogen atom to be replaced by halogen are equivalent (remember that allylic
hydrogen atoms are much more reactive than the inert vinylic hydrogens).

Br 2, reflux
—CH3 ————® —CH2Br
light

Toluene Benzyl bromide

Cl CH2Cl
2
——®
But-2-ene 1-Chlorobut-2-ene

Bromination at allylic and benzylic positions may best be carried out by another brominating reagent, N-
bromosuccinimide (for details, consult Ch. 6).

—CH2CH3 + NBS ——® —CHBrCH3

Ethylbenzene 1-Bromo-1-phenylethane

Halogenation of alkanes takes place through free-radical mechanism.

8.1.3 Addition of Hydrogen Halides to Alkenes

Alkenes add hydrogen halides to form alkyl halides. In case of unsymmetrical alkenes, hydrogen halides add
according to Markownikov’s rule (For details, refer Ch. 6).
CH3—CH = CH2 + HX ¾¾® CH3CHX—CH3
Addition of hydrogen halides to alkenes is an example of electrophilic addition involving carbocations as
intermediates.
However, addition of H—Br (not HCl, HI and HF) on alkenes in presence of peroxides takes place in anti-
Markownikov’s way, the peroxide effect. (For details, refer Ch. 6).

CH3—CH = CH2 + HBr ¾ peroxide

¾¾¾ ¾® CH3CH2CH2X
Here the addition takes place via free-radical mechanism.

8.1.4 Addition of Halogens to Alkenes and Alkynes

[For details consult Ch. 6).

X X
C=C + X2 ——® C—C
X X
Cº C + 2X2 ——® C—C
X X
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8.1.5 Halide Exchange Method

Alkyl fluorides and alkyl iodides are best prepared by this method. In the preparation of alkyl fluorides, an alkyl
chloride, bromide, or iodide is heated with potassium fluoride in a high-boiling alcohol solvent such as ethylene glycol.
ethylene glycol
RCH2Br + KF ¾ ¾ ¾ ¾ ¾ ¾¾® RCH2F + KBr
120 °

Alkyl fluorides have the lowest boiling points of all the alkyl halides and are removed from the reaction mixture
by distillation and thus favouring the reaction to right side (Le Chatelier principle). However, the alkyl fluoride will
predominate at equilibrium even when it is not removed by distillation because the reaction favours formation of the
stronger C—F bond in place of weaker C—I, C—Br, or C—Cl bond.
Alkyl iodides may be prepared from alkyl chlorides and bromides by treatment with sodium iodide in acetone as
the solvent.

acetone
CH 3 CHBrCH 3 + NaI ¾¾¾¾
® CH3 CHICH3 + NaBr ¯
2 - Bromopropane 2 - Iodopropane

Since NaCl and NaBr are insoluble in acetone, while NaI is soluble, former are removed from the reaction
mixture by filtration causing the reaction to shift towards alkyl iodides (Le Chatelier principle).

8.1.6 Hunsdiecker Method

CH3COOAg + Br2 ¾¾® CH3Br + CO2 + AgBr
Mechanism

O O
|| ||
R - C - OAg + X 2 ¾¾
® R - C - O - X + AgX

O O
|| ||
R - C- O - X ¾ ¾
® R - C- O + X

O
||
R - C- O ¾¾
® R + CO 2

O O
|| ||
® R–X + R - C - O
R+ R - C- O - X ¾¾
(i) Reaction is used to reduce the length of carbon chain by one carbon atom.
(ii) The yield of alkyl bromide follows the order : 1° > 2° > 3°.
(iii) Yield in case of chloride is very low, while iodine under such conditions give esters (Birnbarun reaction).
2RCOOAg + I2 ——® RCOOR + CO2 + 2AgI

1. Give two methods for the preparation of 3-bromo-3-phenylpropane from 3-phenylpropene.

2. How will you prepare following compounds from an alkene only in one step (give chemical reactions).
(i) trans-1, 2-Dibromocyclopentane (ii) 1-Iodo-2-bromo-2-methylpentane
(iii) 2-2-Dibromobutane (iv) 1, 3-dibromopropane
(v) 3-Methyl-1-bromobutane (vi) 1, 1-Dichloro-cis-2, 3-dimethylcyclopropane
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3. (a) Predict which compound adds HBr faster.

CH = CH2 CH = CH2

(i) or (ii) or (iii) or

CH3

(b) Give structure of the product obtained by the addition of HBr on the following alkenes.

(i) (ii) (iii)

CH3

(iv) (v) Br (vi)

C2H5

Hint. Carbocation stability is the factor.

4. Identify (A) to (E) in the following reactions.

OH

(i) + HCl ——® A (ii) + NBS ——® B (Major) + C (Minor)

OCOCH3

(iii) + NBS ——® D + E

5. Explain the following :

(i) Free radical halogenation can be applied for the preparation of Me 3CBr in quantitative yield, while not for Me3 CCl.
(ii) Free radical monobromination of ethylbenzene gives only one product while hexene-3 gives two isomers.

8.2 Physical Properties

1. Alkyl halides are although polar in nature, these are insoluble in water but soluble in organic solvents. Their insolubility
in water is due to their inability to form hydrogen bonds with water molecules or to break the hydrogen bonds already
existing in water molecules.

2. Their densities decrease in the following order :

iodide > bromide > chloride > fluoride.
Alkyl bromides and iodides are generally heavier than water, whereas chlorides and fluorides are lighter. Methyl iodide
is the densest alkyl halide as in this compound contribution of iodine density is maximum relative to the contribution of
hydrocarbon part.
3. Boiling points of alkyl halides follow the following order :
Iodide > Bromide > Chloride > Fluoride.
Among isomeric halides, the boiling point decreases as 1° > 2° > 3°
Boiling points of chlorinated derivatives of an alkane increase with number of Cl atoms because of an increase in the
induced dipole-induced dipole attractive forces.
4. Stability order of alkyl halides is RF > RCl > RBr > RI
Alkyl iodides, on standing become violet or brown because of their decomposition in presence of light to give iodine.

2R – I ¾ Light
¾¾ ¾® R — R + I2
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1. Arrange the four CH3—X (X = – I, – Br, –F, –Cl) in decreasing order of their
(a) C—X bond lengths (b) dipole moments
(c) polarizability (d) C—X bond strength
2. Arrange the following
(a) in decreasing order of boiling points
(i) CH3F, CH3Br, CH3Cl, CH3I and CH4 (ii) CH4, CH3Cl, CH2Cl2, CHCl3 and CCl4
(b) in decreasing order of densities
(i) H2O, CH4 and CH3X’s (ii) H2O, CH3Cl, CH2Cl2, CHCl3 and CCl4.

8.3 Chemical Properties

Alkyl halides mainly undergo three types of reactions : (a) nucleophilic substitution, (b) elimination, and (c) reduction.

8.3.1 Nucleophilic Substitution

Because of high electronegativity of the halogen atom, the carbon halogen (C – X) bond is highly polarised*
colvalent bond.

+d –d +d –d
–C : X or –C : X
Thus the carbon atom of the C – X bond becomes a good site for attack by electron rich species (nucleophiles or
nucleophilic reagents). In fact nucleophilic substitution (replacement of the halide ion by a nucleophile) reactions are the
most common reactions of alkyl halides. Mechanism of nucleophilic substitutions have already been discussed at length
in Ch. 4, so readers are referred to consult Ch.4. In short, remember that 1° alkyl halides mainly undergo S N2 reaction, 3°
halides undergo SN1 while 2° halides may undergo SN2 and or SN1 reaction. Important nucleophilic substitution reactions
are summarised in the following table.
Nucleophilic Substitution Reactions of RX
R—X + : Z (nucleophile) ¾¾® R : Z + : X–
Source of : Z Product, R—Z Name of product
Na+OH– R—OH Alcohols
H2O (water) R—OH Alcohols
Na+ –OR¢ R—OR¢ Ethers (Williamson synthesis)
I– R—I Alkyl iodides
R¢COO– R—OOCR¢ Esters
K +CN– R—CN Nitriles
AgCN (covalent) R—CN + R—NC Nitriles and Isonitriles
K+NO2– R—O—N = O Alkyl nitrites
O
AgNO2 R—O—N = O + R — N Nitrites and Nitroalkanes
O

* Polarity in C—halogen bonds produces dipole moment. The dipole moment of alkyl halides is in the order of 2 – 2.2D. Vinyl chloride and
chlorobenzene showing resonance have lower dipole moments.
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K+ SH– R—SH Thiols (Mercaptans)
K+ SR– R—SR¢ Thioethers (Sulphides)
+ -
N3– R—N = N = N Azides
NH3 R—NH2 Primary amines
R¢NH2 R—NHR¢ Secondary amines
R2¢NH R—NR¢2 Tertiary amines
R3N R 4NX Quaternary ammonium salts
P(C6H5)3 [R—P(C6H5)3]+X – Phosphonium salts
Na+ C º CR– R—C º C—R¢ Alkynes
Ar—H Ar—R [Friedel-Craft reaction] Alkylbenzenes
Na+CH(COOC 2H5)2
– R—CH(COOC2H5)2 Malonic esters
Na+[CH 3 COCHCOOC2 H5]
– CH3COCH(R)COOC2H5 Acetoacetic esters

d- d+ d- d+
R '— M , e.g. CH 3 — Li R—R Alkanes (Coupling)

H – : (from LiAlH4) R—H Alkanes (Reduction)

1. Give the structure of the immediate product obtained from the reaction of CH3Br with
(i) C2H5OH (ii) (CH3)2NH and (iii) (Ar) 3P.
2. Supply formulas for the products for the following reactions
(i) CH3CH2CH2Br + (CH3)2CHONa ¾¾® (ii) Bromocyclopentane + NaI ¾¾®
(iii) CH3CH2CH2Cl + (CH3)2S ¾¾® (iv) ClCH2CH2I (one mole) + CN– (one mole) ¾¾®
:

O:
H Cl
– SN2 –
+ OH ——® C2H5 Br + : N—O : ——®
: :

(v) (vi)
H3C H
– 2–
: :

(vii) n–C3H7Br + [ S—C º N:] ——® (viii) C2H5I + [ : S SO 3] ——®

3. Account for the fact that the reaction of an alkyl halide with H 2O, or an alcohol always gives the neutral final products, while
reaction with NH3 or R¢NH2 gives the cations.
4. Explain that reaction between RF and NaCl is not feasible while reaction between RCl and NaF is feasible.
5. A typical nucleophilic substitution reaction of an alkyl halide takes place as
d+ d-
® H 3 C — Nu + Cl -
H 3 C — Cl + : Nu ¾¾
Does the rate of the reaction depend on the amount of d+ on the attacked C of alkyl halide ?
6. (a) Among the following pairs of compounds, which of the compounds would undergo SN 2 reaction faster?

Br I
(i) (A) and (B)

Br
(A) and (B)
(ii)
Br

Cl

(iii) (A) and (B) (iv) —CH 2Br (A) and —Br (B)

Cl
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(b) Among the following pairs, which would undergo S N 1 reaction faster ?

(A) and (B) —CH 2Cl (A) and —Cl (B)

(i) (ii)
Cl Cl

(iii) —CH2Cl (A) and —Cl (B) (iv) —Cl (A) and —Cl (B)

7. Each of the following two ethers can be prepared by nucleophilic substitution of alkyl halides in two different manners.
(a) 2-Ethoxypropane (b) 2-methoxy-2-methylpropane
Write down the chemical reactions for these two possible sets for each ether and explain which set gives quantitative yield in each case.

8.3.2 Elimination Reaction (Dehydrohalogenation)

In an elimination reaction, a halogen and a hydrogen atom are removed from adjacent carbon atoms to form a
double bond. This is sometimes called b-elimination and carried out by a strong base, viz. KOH in ethanol. For example,
alc. KOH
CH3CH2CHBrCH3 ¾¾¾¾¾ ¾® CH3CH = CHCH3
The order of reactivity of alkyl groups towards elimination is : 3° > 2° > 1°. In case, an alkyl halide can form two
alkenes, more substituted alkene (also known as Saytzeff product) is the major product and less substituted alkene (also known as
Hofmann product) is the minor product.
alc. KOH
CH3CH2CH2CHClCH3 ¾¾¾¾¾ ¾® CH 3 CH 2 CH = CHCH 3 + CH 3 CH 2 CH 2 CH = CH 2
(Major) (Minor)
Saytzeff product Hofmann product

However, remember that elimination reactions compete with substitution reactions. Elimination reactions dominate
over substitution when strong Bronsted base (e.g. NH2–, Me3CO–, –OC2H5 etc.) is used and alkyl halide is 3° or 2°.

Summary of substitution vs elimination

1. When the substrate is a 1° halide, SN2 predominates except when a hindered strong base like Me3CO– is used.
2. When the substrate is a 2° halide SN2 occurs with weak bases like I–, CN–, RCOO– etc., and E2 occurs with strong
bases like RO–.
3. When the substrate is a 3° halide, SN1 is favoured at low temperature and in solvolysis (when no strong base/
nucleophile is present and the solvent acts as a nucleophile/base) ; when a strong base (e.g. RO–) is used E2
predominates.

1. Arrange the following bases in decreasing order of reactivity for b-elimination NH2–, OH–, OR–, RCOO–, CN–, NO3–, (CH3)3CO –
.
2. Arrange the following compounds in decreasing order of ease of dehydrohalogenation.

Br I I I I
Br
(a) (b)

Br (A) (B) (C) (D)

(A) (B) (C)

3. Complete the following :

Br
–
OH – OC H
2 5
(a) ClCH2CHCl2 ¾ (ethanol)
¾ ¾ ¾¾® (b) ———®
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Cl –
2 5OC H
(c) ——–® A (Major) + B (Minor) (d) CH3CH2CH2Br + LiAlD4 ¾¾®
CH3
(e) Me 3CBr + HCOOH ¾¾® (f) Me 3CBr + HCOOH + HCOONa (trace) ¾¾®
(g) Me 2C = CHCl + NaNH2 ¾¾®
4. Give the expected product(s) in each of the following reactions. Mention the mechanism ( SN1 , SN2 , E1, or E2) followed by each
product.
CH3OH (CH3)3COH
(a) CH3(CH2)15CH2Br + CH3O– (b) CH3CH2CH2 Br + (CH3)3CO –
CH3 – CH OH 50°C, CH3OH
(c) CHBr + HS ———
3
® (d) (CH3CH2)3CBr + OH–
C2H5
25°C, CH OH CH OH
(e) (CH3CH2)3CBr 3
(f) CH3CHBrCH3 + OCH3– ¾ ¾3¾¾®
(g) CH3CH = CHCl + NH2– ¾¾®
5. Account for the fact that the reaction of 1-chloro-2-butene with CN– gives a mixture of two products.
-
CN
CH3CH = CHCH2Cl ¾¾¾ ® CH3CH = CHCH2CN + CH3CH(CN) CH = CH2.

8.3.3 Reaction with Metals

(a) Alkyl halides (1°, 2°, or 3°) react with metals generally in presence of diethyl ether (solvent) to form compounds
having C-metal bond (organometallic compounds). For example,
diethyl ether
R—X + 2Li ¾¾¾¾¾¾
® R - LI + LiX
Alkyllithium

diethyl ether
R—X + Mg ¾¾¾¾¾¾ ® R - MgX
Alkylmagnesium halide

Alkylmagnesium halides are commonly called Grignard reagents.

(i) Among alkyl halides, the order of reactivity is : I > Br > Cl > F ; since bromides are readily available and quite
reactive, these are most oftenly used
(ii) The reactivity of a metal with an alkyl halide depends on its reduction potential ; the more easily a metal is
reduced, the more reactive it is e.g. Mg > Zn.
(iii) The solvent used must be anhydrous because even a trace of water or alcohols react with metals to form
insoluble hydroxide or alkoxide salts that coat the surface of the metal and thus prevent it from reacting
with the alkyl halide. Moreover, organo-metallic compounds are strong bases and react rapidly with even
weak proton sources to form hydrocarbons.
(b) Organosodium compounds, formed in the same manner as above, are so reactive that as soon as these are
formed, they couple with their parent alkyl halides to form alkane as the final product (Wurtz reaction).
ether CH Cl
CH 3 Cl + 2Na ¾¾¾® [CH 3 Na] ¾¾¾¾
3
® CH3 CH 3 + NaCl
Methyl chloride ( - NaCl) Methylsodium Ethane

ether
or CH3Cl + 2Na + ClCH3 ¾¾¾® CH3CH3 + 2NaCl
Reaction between alkyl halide, aryl halide and sodium in presence of dry ether is known as Wurtz-Fittig reaction.
Na
C6H5Cl + 2Na + ClCH3 ¾¾¾
® C6H5CH3 + 2NaCl
(c) Ethyl chloride when heated with a sodium-lead alloy under pressure gives tetraethyl lead, TEL (an important
anti-knocking compound).
4C2H5Cl + 4Na/Pb ¾¾® (C2H5)4 Pb + 4NaCl + 3Pb
(d) Alkyl halides react with lithium to form alkyllithiums which react with copper halide to form higher alkane as
the find product (Corey-House synthesis, discussed in detail in chapter on Alkanes).
Li/Et O CuI R'X
RX ¾¾¾¾
2
¾
® RLi ¾¾¾
® R 2 CuLi ¾¾¾
® R -R'
(1° , 2° or 3° ) (1° halide)
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1. Give the products for the viable reactions.

Et2O
Et O THF —F + Mg ——®
(i) CH3Br + Li ¾¾¾
2 ® (ii) n-C 3H7Cl + Mg ¾¾¾® (iii)

(iv) n-C 3H7I + Zn ¾¾® (v) n-C 3H7Cl + Zn ¾¾®

2. Give the products when Mg/Et2O is treated with
(i) BrCH2CH2Br (ii) BrCH2CH2CH2Br (iii) BrCH2CH2CH2CH2Br.

8.3.4 Reaction of A l k yl H al i des w i th A romatic H ydrocarbons (Electrophilic Substitution in Benzene)

Benzene and other aromatic hydrocarbons react with alkyl halides, alkylene halides, and other halogen
derivatives in presence of anhydrous AlCl3 to form higher aromatic hydrocarbons.

CH3

AlCl
(a) + CH3Cl ——–3®

CH2
AlCl3
(b) 2 + CH2Cl2 ——–®

Diphenylmethane

AlCl
3C6H6 + CCl4 ¾¾¾¾
3 ® (C H ) CCl
(c) 6 5 3
Trityl chloride

CH(CH3)2 CH2CH2CH3

AlCl 3
(d) + CH3CH2CH 2Cl ——–® and not

Isopropylbenzene (Cumene)

Formation of cumene is due to more stability of the 2° carbocation as compared to 1°.

H
AlCl3 + 1, 2-hydride +
CH3CH2CH2Cl ——–® CH3—CHCH2 ————–® CH3—CH—CH3
shift
1° Carbocation 2° Carbocation
(less stable) (more stable)

Above reaction between alkyl halide and arenes can also be extended between alkyl halide and alkenes, e.g.
AlCl , -10° C
CH2 = CH2 + Me3CCl ¾¾¾¾¾¾
3
® Me3CCH2CH2Cl

Mechanism

AlCl CH2 = CH2 AlCl -

3
Me 3 CCl ¾¾¾¾ ® Me 3 C + Me3CCH2C+H2 ¾¾¾¾
4 ® Me CCH CH Cl + AlCl
3 2 2 3
( - AlCl 4- )
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1. Give mechanism involved in the following reactions.

Cl
+ AlCl3 ——® + AlCl3 ——®
(a) (b)
Cl

8.3.5 Reduction
Most alkyl halides may be reduced either via the Grignard reagent or directly with metal (usually zinc) and acid
or with LiAlH4 to produce an alkane.

(a) H 2 O (D2 O)
R—X + Mg ¾¾® R—MgX ¾¾¾¾¾® RH (or RD)

(b) R—X + Zn + HX ¾¾® R—H + ZnX2

In these reactions, zinc atoms transfer electrons to the carbon atom of the alkyl halide. Zinc is a good reducing
agent because it has two electrons in an orbital far from the nucleus, which are readily donated to an electron
acceptor.

(c) LiAlH 4
R—X ¾¾¾¾ ® R—H

Example 1 :
Arrange the following nucleophiles in order of decreasing nuclephilicity in aqueous solution.
OH - , C 6 H 5 O - , CH 3OH , CH 3S - , CH 3COO -

Solution :
Let us divide the nucleophiles into groups.
(i) Nucleophiles with a negatively charged atom, viz. S and O.
(ii) Neutral nucleophiles.
We know that in the polar aqueous solvent, the nucleophile with the negatively charged sulphur is the most
nucleophilic because of larger size of sulphur than oxygen. Further, the nucleophile with the neutral (oxygen) atom
is the poorest nucleophile. The three nucleophiles lying between them can be arranged on the basis of their conjugate
acids.
H2O, C6H5OH, CH3COOH
The three conjugate acids according to their acidic character is
CH3COOH > C6H5OH > H2O decreasing acidity
CH3COO– < C6H5O– < OH– increasing basicity
Thus the relative nucleophilicity is
CH3S– > OH– > C6H5O– > CH3COO– > H2O
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Example 2 :
(S)-CH3CHBrF + CH3ONa ¾¾® Product
Answer the following, regarding above reaction.
(a) Write down the structure of the product.
(b) Whether the product shows retention or inversion of configuration. Also mention the R or S designation of the
product.

Solution :
(a) Br Br
– + F CH3
CH3 O Na H
H C C CH3 H C
F
CH3
F OCH3 OCH3
(S)-1-Bromo-1-fluoroethane S

Priority order : Br, F, C and H

F, O, C, H
Here Br– ion is replaced because it is too weak base to be considered as basic ion, hence it is an excellent
leaving group. On the other hand, F– is the most basic of the halide ions, thus it is a terrible leaving group.
(b) Since the reactant is a 1° alkyl halide, it undergoes SN2 reaction involving inversion in configuration.
According to R, S-designation the product is S. It is due to change in priority orders of the groups attached on
C. Thus there is a change in priority order of F and also there is inversion in configuration with the result the
product belongs to S series. In case, there were no inversion in configuration, the product would have been R
instead of S.

Example 3 :
Give steps involved in the conversion of cyclohexane to cyclohexa-1, 3-diene.

Solution :
Br

Br , hv
2 alc. KOH NBS alc. KOH
———® ———–® ———————–® ————®
(Allylic bromination)
Br Cyclohexa-1, 3-diene

Example 4 :
Suggest the mechanism for the reaction.

AgNO
3
———® OH
CH2Cl

Solution :
+ +
Ag +
——® Å
——————® º
(ring expansion*)
CH2Cl CH2

HO
2 Å
——® OH2 ——® + OH
(– H )

* Change in ring size is favourable when a relief in ring strain occurs.

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Example 5 :
Give steps involved in the following reaction and give IUPAC name of the product.

n-C4H9Li Br
CBr4 + ———–®
Br

Solution :

halogen-metal exchange
CBr4 + n-C4H9Li ¾¾¾¾¾¾¾¾¾¾ ® n-C4H9Br + LiCBr3

LiCBr3 ¾¾® LiBr + : CBr2

Dibromocarbene

Br
+ CBr2 ——®
Br
7, 7-Dibromo
[4.1.0]–bicycloheptane

Example 6 :
Identify (A) to (F) in the following series of reactions.

Br alc. KOH NBS

Cyclopentane ——2® A ———–® B ——® C
hv
——® F
aq. KOH Na
———–® D ——® E

Solution :

Br Br
Br2, hn alc. KOH NBS
————–® ———–® ———–®
bromination (– HBr) (allylic
bromination)
(A) (B) (C)
—–®

aq. KOH

OH ONa
——®

(D) (E)
ONa Br O
Williamson
+ ————–®
synthesis
(E) (C) (F)
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Example 7 :
Identify X to Z in the following series of reactions.

H2SO4 BH / THF
3 HBr
Z ¬——– ————® X ——® Y
HO 2 2

Solution :

+
CH2
OH
OH
H SO BH /THF HBr 1, 2-hydride shift
¬ ———
2 4 3
————® ——® ——————–®
(b) H2O2 (a)

Z [X] 1° carbocation

Br
+

–
Br
¬ ——

3° carbocation [Y]
(more stable)

Explanation
(a) It is an example of hydroboration (recall that hydroboration takes place in anti-Markovnikov’s rule).
(b) It is an example of hydration (Markovnikov’s addition).

Example 8 :
Convert cyclohexanol to biphenylene.

Solution :
OH
H2SO4 NBS
———® ———————® —Br
(– H2O) allylic bromination

HBr (i) Li, (ii) CuI NBS

—OH ——® —Br —————–® ——®
(iii) Br—

2 H –Pt alc. KOH

——–® ——–————®
(– HBr)
H comes from 3°C
Br Br Biphenylene
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Example 9 :
Explain the formation of all products in the following solvolysis reactions.
OCOCH3
I OCOCH3
CH3COOH
(a) +
heat

CH2I CH3 OCH2CH3

CH3CH2 OH
(b) OCH 2CH 3 +
heat

Solution :
Alkyl halides in presence of polar solvents lose halide ions forming carbocations which then react with the nucleophile
in its original (provided it is quite stable) form as well as in the rearranged form.
(a) Nucleophilic attack on unrearranged carbocation :

O
I
heat + CH3C – OH

2° carbocation
Note : The doubly-bonded oxygen of acetic acid is more nucleophilic because the product so formed is resonance-stabilized.

.. + O
OH :OH :O – H
+ O – C – CH3
.O. = C – CH3 O – C+– CH3 O – C – CH3 I
–

(–HI)

Nucleophilic attack on rearranged carbocation :

H OCOCH3
H H
H + H
+ hydride (i) CH3COOH
shift H –
+ (ii) I
2° carbocation allylic 2° carbocation

(b) Nucleophilic attack on rearranged 3° carbocation :

H +
CH2I +
heat
CH2 CH3
hydride
– shift
(–I )
1° carbocation 3° carbocation
(unstable)

CH3 CH3
+
CH3CH2 OH OCH2CH3 OCH2CH3
H
Nucleophilic attack on carbocation obtained by ring expansion :
+
CH2 H OCH2CH3
+
CH3CH2OH

1° carbocation 2° carbocation
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Example 10 :
A solution of pure (R)-2-iodobutane, [a] = –15.9° in acetone is treated with radioactive iodide, until 1.0% of the
iodobutane contains radioactive iodine. The specific rotation of the recovered iodobutane is found to be –15.58°.
(a) Determine the percentage of (S)- and (R)-2-iodobutane in the product mixture.
(b) What inference you get about the mechanism of the reaction?

Solution :
-15.58
(a) Optical purity = ´ 100% = 98%
-15.90
Thus the product contains 98% of the (R)-enantiomer and 2% of racemic mixture, or 99% R and 1% S.
(b) The 1% of radioactive has produced exactly 1% of the S enantiomer. Each substitution must occur with
inversion indicating SN2 mechanism.

Example 11 :
Explain the following observations :
KBr(aq.)
(a) (R) - 2 - Bromobutane ¾¾¾¾® (R, S) - 2 - Bromobutane
KOH(aq.)
(b) ( R) - 2 - Butanol ¾¾¾¾¾
® No reaction
dil. acid
(c) (R) - 2 - Butanol ¾¾¾¾® (R, S) - 2 - Butanol

Solution :
CH3 2 CH3
– SN –
(a) Br H + Br H Br + Br
CH2CH3 2 CH2CH3
SN
(R)-2-Bromobutane (S)-2-Bromobutane

(b) OH– being a poor leaving group can't be replaced by other nucleophile, e.g. OH– in the present case.
(c) This is an SN1 reaction (weaks nucleophile H2O, ionizing solvent) and involves the formation of carbocation
which leads to racemization.

Example 12 :
Observe the following two reactions and explain the difference in the rate of reaction mentioned.
Br Br
| |
(a) KOH KOH
CH 3 CHCH 3 ¾¾¾® CH 2 = CHCH3 much faster than D 3 C - CH - CD 3 ¾¾¾® D 2 C = CH - CD 3
alcohol alcohol

Br Br
| |
(b) H 2 O/acetone H O/acetone
CH 3CHCH 3 ¾¾¾¾¾¾® CH2 = CHCH3 equal to D 3 CCHCD 3 ¾¾¾¾¾¾®
2 D 2 C = CHCD 3
heat heat

Solution :
(a) Here the elimination follows E2 mechanism (OH– is a strong base) which is one step (which is also rate
determining) i.e. the attack of base (OH–) and the elimination of H or D take place simultaneously. Now since
the C – D bond is slightly stronger than the C – H bond, reaction involving removal of H will be faster than
that which involves removal of D.
(b) Here the elimination follows E1 mechanism (strong base is absent, heat removes Br) which involves two
steps, the rate-determining step is the removal of Br as Br–. Elimination of H or D occurs in the second (fast)
step, hence it is quite immaterial whether H or D is eliminated. Hence the reaction rate will be same in both
reactions.
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Example 13 :
Give steps involved in the following conversion :

Cl OCH2COOH
Cl Cl Cl O Cl
(i) NaOH, heat
+ ClCH2COONa + +
(ii) H
Cl Cl Cl O Cl
Cl Cl
[A] [B]

Solution :
Formation of A :
– +
Cl O Na OCH2COOH
Cl Cl Cl
1 eq. NaOH, heat (i) ClCH2COONa
+
(SN reacton) (ii) H
Cl Cl Cl
Cl Cl Cl
[A]
Formation of B :
– +
O Na Cl Cl Cl
Cl Cl O
+ + 2NaCl
Cl Cl Cl Cl O Cl
+Na– O

[B]

Example 14 :
Propose mechanism and give the product formed when 2,4-dinitrochlorobenzene is treated with excess of hydrazine.
Draw all possible reasonating structures of the intermediate carbanion.

Solution :
+ +
Cl Cl NH2NH2 Cl NH2NH2
+ + –
NO2 .. – N O N O
:NH2NH2 :
O– O–
+ +
NO2 N N
O O– O O–
+ + +
Cl NH2NH2 Cl NH2NH2 Cl NH2NH2
+ H
N O N O NO2
–:
O– O–
.. –
+ + +
N N N
O O– –O
O– O O–
+
H — NHNH2 NHNH2
– NO2 .. NO2
–Cl :NH2NH2 +
+ NH3NH2

NO2 NO2
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8.4 Halogen Derivatives of Unsaturated Hydrocarbons

These are mainly of two types.

(i) Those unsaturated compounds in which halogen is attached to the sp2 hybridised carbon atom, e.g.

H2 C = CHCl CH 3 C(Br) = CH2

Vinyl chloride 2-Bromopropene

In this type of compounds, halogen atom is present on the doubly bonded carbon atom. Since such compounds
can show resonance which impart C—Cl bond a partial double bond character due to which it becomes short
and hence strong.
–
Å
H2C = CH—Cl
– ¬¾ ® H2C—CH = Cl
Thus such compounds do not undergo nucleophilic substitution and hence do not give precipitate on treatment
with alcoholic silver nitrate (similarity with halogenobenzenes ArX).
(ii) Those unsaturated compounds in which halogen atom is present on the sp3 hybridised carbon atom, e.g.

H 2 C = CH ¾ CH 2 ¾ Cl CH 3 CH = CHCH 2 ¾ I
Allyl chloride Crotyl iodide
(3 - Chloropropene) (1- Iodobutene - 2)

In this type of compounds, halogen atom and double bond are separated by —CH2—grouping discarding the
possibility of resonance. Hence such compounds behave like alkyl halides, i.e. they undergo nucleophilic
substitution and hence give precipitate with alcoholic silver nitrate solution.
Thus halogen compounds are of two types.
(a) Those which give precipitate with alcoholic AgNO3 solution.

CH2X
CH3—CH2—X CH2 = CH2—CH2—X

(b) Those which do not give precipitate with alcoholic AgNO3 solution.

Cl
Cl
CH2 = CH—X
CH3

8.4.1 Vinyl Halides

Among vinyl halides, vinyl chloride is the most important. It can be prepared by the following methods.
(i) HC º CH + HCl ¾¾® CH2= CHCl
–
OH /C 2 H 5 OH OH –/C H OH
(ii) CH2ClCH2Cl ¾¾¾¾¾¾¾ ® CH2 = CHCl ¬¾¾¾¾¾¾
2 5 ¾ CH3CHCl2
As mentioned above, halogen atom of vinyl chloride is inert to nucleophilic substitution.
However, like alkyl halides, vinyl chloride undergoes elimination reaction and also form Grignard reagent.
alc. KOH
CH2 = CHCl ¾¾¾¾¾
® CH º CH
Acetylene

THF as solvent
CH2 = CHCl + Mg ¾¾¾¾¾¾¾
instead of ether
® CH2 = CHMgCl
Vinylmagnesium chloride

Further, like alkenes it undergoes the usual addition reactions such as addition of hydrogen, halogens acids, etc.
and polymerisation.
CH2 = CHCl + HBr ¾¾® CH3CHBrCl (Markownikoff’s product)
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peroxide
CH2 = CHCl + HBr ¾¾¾¾¾ (anti-Markownikoff product)
® CH 2 Br ¾ CH 2 Cl
1-Bromo-2-Chloroethane

Cl Cl
benzoyl peroxide | |
nCH2 = CHCl ¾¾¾¾¾¾¾
(polymerisation)
® —(—CH2— CH ¾ CH 2 ¾ CH —)n—

Polyvinyl chloride (PVC)

Polyvinyl chloride is a plastic of great importance.

8.4.2 Allyl Halides

Allyl chloride can best be prepared by allylic chlorination of propene with chlorine at about 400°C.

° 400 C
Cl—Cl ¾¾¾¾® Cl

Cl2
Cl + H—CH2 —CH = CH 2 ——– ® [CH2—CH = CH2 ¬— ® CH2 = CH—CH 2] ¾¾¾ ® CH 2 = CH ¾ CH2 Cl + Cl
(–HCl)
Allyl chloride
Allyl free radical

Allyl bromide is best prepared by allylic bromination using N-bromosuccinimide (NBS) in presence of sunlight.
NBS functions as a bromine reservoir maintaining a low concentration of molecular bromine by reacting with HBr formed
initially as a side product.

O O

NBr + HBr ——® NH + Br2

O O
NBS Succinimide

hn
Br2 ¾¾® 2Br
Further steps are similar as described above.
Allyl iodide can be prepared by following methods.
(i) By heating allyl chloride with sodium iodide in acetone.

acetone
CH2 = CHCH2Cl + NaI ¾¾¾¾¾¾¾¾¾
(Finkelstein reaction)
® CH2 = CHCH2I + NaCl

(ii) By heating glycerol with hydrioidc acid or white phosphorus and iodine.

CH2OH CH2I CH2

3HI
CHOH CHI CH
(–I2 )

CH2OH CH2I CH2I

Glycerol Glyceryl triodide Allyl iodide

Allyl halides give the addition reactions of the double bond and also nucleophilic substitution reactions of alkyl
halides. Remember that allyl halides undergo nucleophilic substitutions much faster than the alkyl halides because of
resonance stabilisation of the allyl cation.

Å Å
CH 2 = CH—CH 2 ¬—® CH2—CH = CH 2
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8.5 Polyhalogen Compounds

The three polyhalogen compounds of methane are methylene chloride, chloroform and carbon tetrachloride.
Methylene chloride (CH2Cl2) is formed by controlled free-radical chlorination of methane. It is a colourless non-
polar liquid and undergoes typical SN2 displacement when treated with sodium hydroxide.
–
HO
H H H
–
H—–C—–Cl ¾¾® H—–C—–O—–H ¾¾® O = C + H2O + Cl
–
HO Cl H
Cl
Methylene chloride Chloromethanol Formaldehyde

Remember that the hydrolysis of methylene chloride is slower than that of methyl chloride. Low reactivity of
methylene chloride is believed to be due to the presence of two chlorine atoms having unshared pairs of electrons which
tend to repel the negatively charged nucleophile.
Higher alkanes can form two or more isomeric dihalogen derivatives, differing in relative positions of the two
halogen atoms, of which three are more important.
CH3CH2CH2CHCl2 and CH3CH2C(Cl2)CH3
1, 1-Dichlorobutane 2, 2-Dichlorobutane
(gem-Dihalides or Alkylidene halides)
CH3CH2CH(Cl) CH2Cl and CH3CH(Cl) CH(Cl)CH3 ClCH2CH2CH2CH2Cl
1, 2-Dichlorobutane 2, 3-Dichlorobutane 1, 4-Dichlorobutane
(vic-Dihalides or Alkylene halides) (a, w*-Dihalides or Polymethylene dihalides)

Vicinal and gem-dihalides resemble in their reaction with alcoholic KOH, but differ in reaction towards aq. KOH
and reaction with KCN followed by hydrolysis.

CH 2 Cl CH 3 CH 2 CH
(i) | or | alc. KOH || NaNH
2® |||
¾¾¾¾¾
® ¾¾¾¾
CH 2 Cl CHCl 2 CHCl CH

Ethylene chloride Ehtylidene chloride Vinyl chloride Acetylene

CH 2 Cl CH 2 OH
| aq KOH |
(ii) ¾¾¾¾®
CH 2 Cl CH 2 OH

Ethylene chloride Ethylene glycol

CH 3 CH3
aq. KOH
| ¾¾¾¾¾
® | ¾¾® CH 3 CHO + H2O
CHCl 2 CH(OH)2

Ethylidene chloride Ethanal

CH 2 Cl CH2 CN CH 2 COOH heat CH 2—CO

(iii) |
aq KCN
¾¾¾¾® | hydrolysis
¾¾¾¾¾® | ¾¾¾¾® O
( - H 2 O)
CH 2 Cl CH2 CN CH 2 COOH CH 2—CO

Ethylene chloride Succinic acid Succinic anhydride

* Symbol w represents the end carbon atom.

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CH 3 CH 3 CH 3 heat CH 3
| aq. KCN
¾¾¾¾®
hydrolysis
¾¾¾¾¾® | ¾¾¾¾® |
| ( - CO 2 )
CHCl 2 CH(CN) 2 CH(CN)2 CH 2 COOH

Ethylidene chloride Methylmalonic acid Propanoic acid

Remember that on heating, dicarboxylic acids having two —COOH groups on the same carbon atom give
monocarboxylic acids, while dicarboxylic acids having —COOH groups on C1 and C2 or on C1 and C3 give anhydrides on
similar treatment (Blanc rule).

1. Draw the structures of the various isomers of dibromoderivatives, and give their reaction with zinc dust and methanol.
2. Identify A to C with proper explanation, where necessary.

Br 2/CCl4 (i) KCN heat

¾¾¾¾® A ¾¾¾¾®
+ B ¾¾® C
(ii) H3O

3. Identify X, Y and Z in the following series of reactions

NaOH NaOH
X ¾¾¾¾ ® Y ¾¾¾¾
® CHCl3 + Z
(C 4 H 8 Cl2 ) Cl2

Write down structures of all structural isomers of X.

8.5. 1. Chloroform or Trichloromethane, CHCl3

It is the most important trihalogen derivative of alkanes and can be prepared by the following methods.
Sunlight
1. CH4 + 3Cl2 ¾¾¾¾¾¾¾¾¾¾
(controlled chlorination)
® CHCl3 + HCl

2. In laboratory and commercial scale, it is prepared by the distillation of ethanol or acetone with a paste of bleaching
powder in water. This reaction is an example of haloform reaction; bleaching powder supplies the necessary
chlorine and slaked lime (alkali) for the reaction.
CaOCl2 + H2O ¾¾® Ca(OH)2 + Cl2
Other steps involved in the reaction can be summarised below.
oxidation
(a) CH3 CH2 OH + Cl2 ¾¾¾¾¾ ® CH 3 CHO + 2HCl
Ethanol Ethanal

CH 3 CHO + 3Cl2 ¾¾® CCl 3 CHO + 3HCl

Ethanal Chloral

2CCl3CHO + Ca(OH)2 ¾¾® 2CHCl3 + (HCOO)2 Ca

Chloroform Cal. formate

(b) CH 3 COCH 3 + 3Cl2 ¾¾® CCl 3 COCH3 + 3HCl

Acetone Trichloroacetone

2CCl3CO.CH3 + Ca(OH)2 ¾¾® 2CHCl3 + (CH3COO)2Ca

3. In industry, chloroform is also prepared by the reduction of carbon tetrachloride.
Fe/steam
CCl4 + 2[H] ¾¾¾¾¾ ® CHCl3 + HCl
4. Pure chloroform is prepared by treating pure chloral hydrate (or chloral) with sodium hydroxide.
CCl3.CH(OH)2 + 2NaOH ¾¾® CHCl3 + HCOONa + H2O
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Properties : Chloroform is a colourless, heavy, sweet-smelling liquid (hence collected with water as lower layer), insoluble
in water but soluble in alcohol and ether. When exposed to air and sunlight, it oxidises to carbonyl chloride (phosgene),
a highly poisonous substance, used in warfare.
2CHCl3 + O2 ¾¾® 2COCl2 + 2HCl
To avoid its oxidation, chloroform is always stored in amber coloured bottles to cut off light. Moreover, bottles
are filled to the neck and well stoppered to exclude air.
Caution

Thus when chloroform is used as anaesthetic it must be tested for the presence of poisonous phosgene, for which
it is treated with aqueous AgNO3 solution—appearance of white precipitate of AgCl (HCl + AgNO3 ¾¾® AgCl) indicates
that some chloroform has decomposed to COCl2 and HCl and hence it is contaminated with the poisonous phosgene.

Further, a small amount of alcohol (~ 1%) is added to chloroform bottle which converts the toxic phosgene, if
formed, to harmless diethyl carbonate.
2C2H5OH + Cl 2 C = O ¾¾® (C2 H 5 O)2 C = O + 2HCl
Phosgene Diethyl carbonate

Other important reactions of chloroform can be summed up as below.

(i) Reduction. Different products are formed by different reducing agents, e.g. reduction with Zn and HCl, Zn and
alcoholic KOH and Zn and water gives methylene chloride, methyl chloride and methane respectively.
diffused
(ii) Chlorination. CHCl3 + Cl2 (gas) ¾¾¾¾®
sunlight
CCl4 + HCl

(iii) Nitration. Chloroform can be nitrated with concentrated nitric acid to form nitro-chloroform, commonly known as
chloropicrin which is a useful insecticide and lachrymatry substance.
HCCl3 + HONO2 ¾¾® O 2 NCCl 3 + H2O
Chloropicrin

(iv) Dehalogenation. Chloroform, when heated with silver powder, gives acetylene.
heat
HCCl3 + 6Ag + Cl3CH ¾¾¾ ® HC º CH + 6AgCl
(v) Hydrolysis. On warming with aqueous sodium hydroxide solution, it is hydrolysed to carbon monoxide and
sodium formate.
CHCl3 + 4OH– ¾¾® 3Cl– + HCOO– + 2H2O
CHCl3 + 3OH– ¾¾® 3Cl– + CO + 2H2O
Mechanism of alkaline hydrolyses of chlorform is different from that of other alkyl halides particularly methylene
chloride. Due to the presence of three strong electron-withdrawing chlorine atoms, hydrogen atom of chloroform
is highly acidic and hence the base (OH–) easily abstracts proton from chloroform rather than displacing its one
of the chlorine atoms by SN2 mechanism.

Cl Cl
¾ ¾
® Fast
¾¾®
–
¾ ¾¾® CCl2
–
+ Cl
®¾Cl
HO + H—–C® ¾¾® H2O + C¾¾Cl ¾¾®
¾ ¾ Dichlorocarbene
Cl
¾ Cl
Trichloromethyl carbanion

Existence of above steps in the mechanism of alkaline hydrolysis of chloroform gets support from the following
observations.
(a) Since removal of proton from CHCl3 (having three —Cl atoms) is easier than that from CH2Cl2 (having two —
Cl atoms), while CCl4 has no proton for elimination, CHCl3 undergoes alkaline hydrolysis much more rapidly
than CH2Cl2 and CCl4.
(b) When chloroform is hydrolysed in presence of D 2O and the reaction is stopped before completion, the
unreacted chloroform is found to contain deuterium. This indicates that the removal of proton takes place
in a fast and reversible step.
–
– –
HO + H—CCl3 ¾¾®
¾¾® CCl3 ¾¾®
¾¾® CDCl3 + OD
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(c)
The rate of reaction is slowed down by the addition of chloride ions. This indicates that step 2 and hence
step 1 is reversed by excess of Cl– and thus confirms that step 2 is a reversible step.
(d) When the alkaline hydrolysis of CHCl3 in presence of I– is interrupted, CHCl2I is also recovered along with
CHCl3 confirming the formation of : CCl2 and : CCl3– as intermediates and reversibility of both the steps.
Remember that CHCl3 does not react with I– ion in the absence of base.
Dichlorocarbene, formed above, undergoes hydrolysis to form carbon monoxide or sodium formate in the
following way.
Formation of carbon monoxide
Cl Cl
Cl + – –
– – H OH OH –
HO + C ¾¾® H—O—C ¾¾® H—O—C—H ¾¾¾¾® – O = C—H ¾¾® CO + Cl + H2O
(–H2 O, –Cl )
Cl
Cl Cl Cl
Formation of formate
Cl Cl
– –
OH – OH – –
H—C = O ¾¾® H—C—O ¾¾® H—C—O + Cl + H2O

O—H O
(vi) Reimer-Tiemann reaction. When alkaline solution of phenol is refluxed with chloroform at 60°C a mixture of o-
hydroxybenzaldehyde (salicylaldehyde) and p-hydroxybenzaldehyde is formed.
OH OH OH
CHO
heat
+ CHCl3 + 3KOH ¾ ¾+® +
H
Major
CHO
Minor
Since the o-isomer is only sparingly soluble in water and has low boiling point than the p-isomer, the two can be
separated by steam distillation very easily.
Mechanism of Reimer-Tiemann reaction
–
OH + CHCl ¾¾® H O + CCl ¾¾® Cl + CCl
– –
3 ¾¾® 2 3 2
Dichlorocarbene
– –
O O O
H CHCl2
+ CCl2 ¾¾® CCl
– 2
¾¾®
Electrophile
–
O
CHO
–
2OH –
¾¾® + 2Cl + H2O

(vii) Condensation with ketones. Chloroform reacts with acetone in alkaline solution to form chloretone, used as a
hypnotic (substance used to produce artificial sleep).
OH
NaOH
(CH3)2CO + HCCl3 ¾¾¾® (CH3)2C
CCl3
Chloretone
Mechanism
–
O OH
– H2O
(CH3)2C = O + CCl3 ¾¾® (CH3)2C ¾¾® (CH3)2C
CCl3 CCl3
(viii) Action of alcoholic potash and primary amines (Carbylamine reaction) with chloroform forms isocyanides, also
known as carbylamines which are easily detected due to their foul smell.
RNH2 + CHCl3 + 3KOH ¾¾® RNC + 3KCl + 3H2O
This reaction is used for the identification of primary amines.
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Relative reactivity of haloforms
CHI3 > CHBr3 > CHCl3 >> CHF3.
Thus iodoform is very much reactive as compared to chloroform which is evident from the following facts.
(i) Iodoform decomposes easily to free iodine, when it comes in contact with organic matter. This explains the
antiseptic use of iodoform.
(ii) Iodoform gives yellow precipitate of AgI on heating with silver nitrate, while chloroform does not give any
precipitate with AgNO3 solution.

1. Complete the following reactions :

H
(i) + CHCl3 + (CH3)3 COK ¾¾® (ii) + CBrCl3 ¾¾® (iii) + CHCl3 + NaOH ¾¾®

2. Explain the following : H

(a) Chloroform undergoes alkaline hydrolysis much more rapidly than CH2Cl 2 as well as CCl 4 .
(b) Alkaline hydrolysis of chloroform slows down in presence of sodium chloride.

8.5.2 Carbon Tetrachl ori de or Tetrachloromethane, CCl4

It is the most common per- halogenated aliphatic compound ; corresponding ethane derivative, C2Cl6 is a solid
compound known as artificial camphor. Carbon tetrachloride can be prepared by the following methods.
1. By the chlorination of chloroform or methane.
2. By chlorinolysis (cleavage by chlorine) of hydrocarbons.
400° C
CH3CH2CH3 + 9Cl2 ¾¾¾¾¾®
74-100 atm.
CCl4 + C2Cl6 + 8HCl­

3. By the action of chlorine on carbon tetrachloride.

AlCl , Fe or SbCl S 2 Cl 2
CS2 + 3Cl2 ¾¾¾¾¾¾¾¾
3 5
® CCl4 + Sulphur monochloride
as catalyst
Sulphur monochloride is separated by fractional distillation and treated with fresh carbon disulphide to form
carbon tetrachloride.
CS2 + 2S2Cl2 ¾¾® CCl4 + 6S
Properties : Carbon tetrachloride is a colourless, non-flammable, poisonous liquid, soluble in ethanol and ether. On
heating with steam at about 500°C, it undergoes oxidation to form carbonyl chloride (phosgene).
500°C
CCl4 + H2O (steam) ¾¾¾¾ ® COCl2 + 2HCl
It reacts with hydrogen fluoride in presence of SbCl 5 forming dichlorodifluoromethane, commonly known as
freon-12, a widely used refrigerant and propellant in aerosol sprays.
SbCl5
CCl4 + 2HF ¾¾¾¾ ® CCl2F2 + 2HCl
or 3CCl4 + 2SbF3 ¾¾® 3CCl2F2 + 2SbCl3
Like chloroform, it undergoes Reimer-Tiemann reaction to form o-hydroxybenzoic acid (salicylic acid).
OH OH
+ CCl4 + 4NaOH ¾¾® + 4NaCl + 2H2O
COOH
Carbon tetrachloride as a fire extinguisher : Carbon tetrachloride is used as an important fire extinguisher under the name
of pyrene. It gives dense, incombustible vapours which cover the burning substance and hence does not allow oxygen from
reaching the burning substance. However, after the use of pyrene the room should be well ventilated to remove phosgene
vapours (a toxic substance), formed by the oxidation of carbon tetrachloride. Other uses of CCl4 are as anthelmentic, fumigant,
solvents, laboratory reagent and in dry cleaning.

Freons cause destruction to ozone layer in the atmosphere, hence they are being replaced by other referigerants.
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EXERCISE 8.1 (MCQ - ONE option correct)

1. Which statement is correct regarding isomers of C4H9Cl ? 8. Which of the following statement is true ?
(a) It has three isomers : one 1°, one 2° and one 3° alkyl (a) Increased temperature favours elimination reactions over
chloride substitutions
(b) It has four isomers : two 1°, one 2°, and one 3° alkyl (b) Increased temperature favours substitution reactions over
chloride eliminations
(c) Increased temperature favours both substitution reactions
(c) It has four isomers : one 1°, two 2° and one 3° alkyl
as well as eliminations reactions to the same extent
chloride
(d) Increased temperature has no effect on the rate of substi-
(d) It has four isomers : two 1° and two 2°. tution/elimination reactions.
CH2Cl 9. Pick up the correct statement regarding following reaction
80% C H OH
2 5
2. can be classified as (CH3)3CCl ¾¾¾¾¾¾¾®X
20% H 2 O
Br
(a) Product X is (CH3)3COC2H5 and formed by SN 2 reaction
(a) an alkyl halide (b) vinyl halide (b) Product X is (CH3)3 COC2H5 and formed by S N 1 path-
(c) an allyl halide (d) all the three. way involving attack of the nucleophile (C2H5OH)
3. 1-Bromo-1-methylcyclohexane can be obtained by the addition (c) Product X is (CH3)3COC2H5 and formed by S N 1 path-
of HBr on way involving attack of the base (C2H5OH)
(d) Product X is (CH3)2C = CH2 formed by E2 pathway.
10. Which one of the following method gives good yield for prepar-
ing cyclohexanenitrile ?
(a) (b)
CN–
(a) —Cl ¾ ¾ ® —CN

I– CN–
(c) (d) both from (b) and (c). (b) — Cl ¾¾ ® —I ¾ ¾ ® —CN

(c) Both methods give equally good yield

(d) Neither of the two methods can be applied because each
4. + HBr ¾¾ ® X has its own drawback.
11. Pick up the major product in the following elimination reaction :
In the above reaction, X is Br (–HBr)
¾ ¾®
(a) (b) Br
Br (a)

Br
(b)
(c) (d) (c) Both will be formed in equal amounts
Br (d) Third product having rearranged skeleton will be formed.
Br
5. Which alkyl halide can’t be prepared by free radical halogena- 12. Reaction between phenol and alkaline chloroform to form o-
hydroxybenzaldehyde is said to be an example of electrophilic
tion of alkanes ?
substitution. Pick up the electrophile involved in this reaction.
(a) CH3Cl and CH3F (b) CHCl3 and CH3I
(c) CCl4 and CHBr3 (d) CH3F and CH3I. (a) HCHO (b) : CCl3
(c) : CCl22– (d) : CCl2.
6. Which of the following statement is correct ?
13. Which of the following compounds undergo alkaline hydrolysis
(a) The weaker the Bronsted basicity of X–, the better the leav-
most rapidly ?
ing group is X– and the more reactive is RX.
(a) CH2Cl2 (b) CHCl3
(b) The stronger the Bronsted basicity of X–, the better the (c) CCl4 (d) All at the same rate.
leaving group is X– and the more reactive is RX.
14. Alkaline hydrolysis of chloroform involves the formation of
(c) The weaker the Bronsted basicity of X–, the weaker the (a) : CCl2 (b) HCOCl
leaving group is X–, and the more reactive is RX. (c) Both (a) and (b) (d) None of the two.
(d) The weaker the Bronsted basicity, the weaker the leaving 15. Butanonitrile may be prepared by heating
group and the less reactive is RX. (a) propyl alcohol with KCN
7. The increasing order of basicities of X– is (b) butyl alcohol with KCN
(a) I– < Br– < Cl– < F– (b) I– < Br– < Cl– << F– (c) butyl chloride with KCN
(c) F– < Cl– < Br– < I– (d) F– < Cl– < Br– << I–. (d) propyl chloride with KCN.
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EXERCISES
16. Identify the main product in the reaction
SnCl4 + C2H5Cl + Na ¾¾®
(a) C2 H 5 C 2 H 5 (b) C2H5Na
(c) (C 2H5) 2Sn (d) (C 2 H5) 4Sn. (a) (b)
17. Vinyl chloride on treatment with dimethyl copper gives
(a) CH2 = CHCH3 (b) CH2 = CHCu
(c) CH2 = CHCH = CH2 (d) (CH2 = CH)2 Cu.
18. Which of the following will react with water ?
(a) CHCl3 (b) CCl3CHO
(c) CCl4 (d) ClCH2CH2Cl.
19. Ethylene chloride and ethylidene chloride are isomeric compounds. (c) (d)
Identify the statement which is not common to both of them
(a) Both of them are derivatives of ethane
(b) Both of them react with aqueous potash and give the same
product 26. In which of the following reaction, regioselectivity can be observed.
(c) Both of them react with alcoholic potash and give the same
product CH 3
(d) Both of them respond Beilstein’s test |
(a) alc.KOH/ D
CH 3 - C - CH 2 - Cl ¾¾¾¾¾¾ ®
20. CH3CHCl2 and CH2Cl.CH2Cl show which type of isomerism |
(a) Functional (b) Chain H
(c) Position (d) Metamerism
21. Which of the following give white precipitate of silver chloride
when boiled with alcoholic silver nitrate? CH 3
|
(a) Methyl chloride (b) Carbon tetrachloride (b) alc.KOH/ D
CH 3 - C - CH 3 ¾¾¾¾¾¾ ®
(c) Benzyl chloride (d) Vinyl chloride |
Cl
Cl

(i) Me N
22 ¾¾¾¾¾¾
3 ® major product is CH 3
(ii) AgOH, D
| alc.KOH/ D
(c) CH 3 - C - CH 2 - CH 3 ¾¾¾¾¾¾ ®
|
Cl
(a) (b)

CH 3
(c) (d) |
alc.KOH/ D
(d) CH 3 - C - CH 2 - Cl ¾¾¾¾¾¾ ®
23. How many products having 12 carbon are obtained in following |
CH 3
reaction ?

Na 27. Select the formula representing the major product of the following
14 Cl ¾¾¾
®
reaction.
(a) 3 (b) 4
Br H
(c) 10 (d) 12 CH CH OK/CH CH OH
H C– C CH3 ¾¾¾¾¾¾¾¾¾¾¾
3 2 3 2 ®
24. A compound ‘A’ of formula C3H6Cl2 on reaction with alkali can D
give ‘B’ of formula C3H6O or ‘C’ of formula C3H4. ‘B’ on oxidation CH3 CH2CH3
a compound of the foumula C3H6O2. ‘C’ with dilute H2SO 4
containing Hg2+ ion gave ‘D’ of formula C3H6O, which with
bromine and alkali gave the sodium salt of C 2H4O2. Then ‘A’ is H CH3 Br H
(a) CH3CH2CHCl2 (b) CH3CCl2CH3 (a) (b) C– C CH3
(c) CH3ClCH2CH2Cl2 (d) CH3CHClCH2Cl H2C
CH3 CH2CH3 CH2CH3
25. Identify the product (Y) in the following reaction.
2Br /CCl
(i) H - C º C - H ¾¾¾¾¾®
2 4 (X) H CH2CH3 Br H
(c) (d) H5C2O C– C CH3
AlBr
(ii) 4 + (X) ¾¾¾¾
3 ® (Y) + 4HBr
CH3 CH3 CH3 CH2CH3
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469
28. Compare the two methods shown for the preparation of
CH3
carboxylic acids :
H+ 2 Br , CCl
4
34. ¾¾¾ ®[F] ¾¾¾¾¾ ® C 4H 8 Br2 . How
Mg
Method -1 : R - Br ¾¾¾® (i) CO 2
R - MgBr ¾¾¾¾¾ 1424 3
+ ® RCO 2 H -H 2 O
Et 2 O (ii) H 3 O H3C OH 5 such products
are possible

NaCN (i) H /H 2O + many structures for F are possible?

Method - 2 : R - Br ¾¾¾¾ ® R - CN ¾¾¾¾¾¾ ® RCO 2H
D (a) 2 (b) 5
Which of the following statement correctly describes this (c) 6 (d) 3
conversion 35. What would be the product formed when 1-bromo-3-
chlorocyclobutane reacts with two equivalents of metallic
sodium in ether?

Br COOH Cl
(a) Both method 1 and method 2 are appropriate, for carrying
out this conversion. (a) (b)
(b) Neither method 1 nor method 2 are appropriate for carrying Br
out this conversion.
(c) Method 1 will work well, but method 2 is not appropriate. (c) (d)
(d) Method 2 will work well, but method 1 is not appropriate.
29. Isobutyl magnesium bromide with dry ether and ethyl alcohol 36. The reagent(s) for the following conversion,
gives :
Br ?
H H
(a) CH 3 CHCH 2 OH & CH 3CH 2 MgBr Br
| is/are
CH 3
(a) alcoholic KOH
(b) alcoholic KOH followed by NaNH2
(b) CH 3 CHCH 3 & MgBr(OC2H 5 )
| (c) aqueous KOH followed by NaNH2
CH3 (d) Zn/CH3OH
37. In CH3CH2CH2I, the C–I bond is formed by the overlapping
(c) CH 3 CHCH = CH 2 & Mg(OH)Br
| of
CH 3 (a) 2sp3 – 2pz orbitals (b) 2sp3 – 3pz orbitals
(c) 2sp3 – 4pz orbitals (d) 2sp3 – 5pz orbitals
(d) CH 3 CHCH 3 & CH 3 CH 2 OMgBr 38. Although hexafluoroethane (C2F6, b.p. –79ºC) and ethane (C2H6,
|
CH 3 b.p. – 89ºC) differ very much in their molecular weights, their
boiling points differ only by 10ºC. This is due to
30. During debromination of meso-2,3-dibromobutane, the major (a) low polarizability of F
compound formed is
(b) nearly similar size of F and H
(a) n-butane (b) 1-butene
(c) both (a) and (b)
(c) cis-2-butene (d) trans-2-butene
(d) Neither of the two
31. (CH3)3CMgCl on reaction with D2O produces :
39. Which of the following is not possible ?
(a) (CH3)3 CD (b) (CH3)3COD
(c) (CD3) 3CD (d) (CD3 )3COD (a) acetone
ICH 2 COOH + NaCl ¾¾ ¾¾® ClCH 2 COOH + NaI
32. A solution of (+) –2–chloro–2–phenylethane in toluene racemises
slowly in the presence of small amount of SbCl5 , due to the acetone
(b) ClCH 2 COOH + NaI ¾¾ ¾¾® ICH 2 COOH + NaCl
formation of
(a) carbanion (b) carbene (c) Both
(c) free-radical (d) carbocation (d) None
33. Identify the set of reagent / reaction conditions 'X' and 'Y' in the 40. Which of the statement(s) is/are true, regarding following
following set of transformations reaction?

X Y
CH 3 - CH 2 - CH 2 Br ¾¾® Product ¾¾® CH 3 - CH - CH 3 R R
| Nu – –
Br R' CBr R' CNu + Br
(a) X = dilute aqueous NaOH, 20°C;
R'' R''
Y = HBr/acetic acid, 20°C (i) The reaction involves the formation of transition state.
(b) X = concentrated alcoholic NaOH, 80°C; (ii) Higher the nucleophilic character of the nucleophile, faster
Y = HBr/acetic acid, 20°C will be the reaction.
(c) X = dilute aqueous NaOH, 20°C ; Y = Br2/CHCl3, 0°C (iii) The product is always optically inactive.
(d) X = concentrated alcoholic NaOH, 80°C; (a) (ii) (b) (ii) and (iii)
Y = Br2/CHCl3, 0°C (c) All the three (d) None of the three
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41. Predict the major products, P1 and P2 in the following two 45. Which of the following gives white precipitate when treated with
reactions silver nitrate solution ?
CH COO - CH 2 = CHCH2 Cl
(i) Me 2 CHBr ¾¾¾¾¾®
3 P1 (a) CHCl 3 (b)

(CH ) CO -
(ii) CH 3 (CH 2 )15 CH 2 CH 2Br ¾¾¾¾¾¾
3 3 ® P2 Cl
(a) P1 is Me2CHOCOCH3, P2 is CH3(CH2)15CH2CH2OCMe3 O2N NO2
(b) P1 is Me2CHOCOCH3, P2 is CH3(CH2)15CH = CH2 (c) C6H5 CH2 Cl (d)
(c) P1 is CH3 CH = CH2, P2 is CH3(CH2)15CH2CH2OCMe3
(d) P1 is CH3 CH = CH2, P2 is CH3(CH2)15CH = CH2
NO2
42. Nucleophilic substitution and elimination reactions of alkyl
halides oftenly compete each other, elimination reactions are
favoured under which conditon. 46. The number of stereoisomers obtained by bromination of
(a) By carrying out the reaction at high temperature trans-2-butene is
(b) By using sterically hindered nucleophile (a) 1 (b) 2
(c) By using strong but slightly polarizable base (c) 3 (d) 4
(d) All the above three 47. How many stereoisomers does this molecule have
43. Which of the following alkyl halide undergoes E2 mechanism CH3CH = CHCH2CHBrCH3 ?
most easily ?
(a) 6 (b) 12
(a) Me2 CH CH ( Br ) CH3 (b) Me3 C CH 2 Br (c) 16 (d) 4

CMe3 48. How many numbers of possible stereoisomers are there for 2, 3,
| 4-trichloropentonic acid ?
(c) Me3 C CH 2CH 2Br (d) Me 3C CHCH 2 Br (a) 8 (b) 12
44. Which of the following is major product in the following (c) 16 (d) 4
reaction ? 49. The configuration of the chiral centre and the geometry of the
double bond in the following molecule can be described by
OH -
I ¾¾¾®
F

HOOC C OH

(a) OH (b) OH C CH3

H3C C
H
O
(a) R and E (b) S and E
(c) OH (d) (c) R and Z (d) S and Z

EXERCISE 8.2

3. Which of the following occurs during the formation of CHCl3

DIRECTIONS for Q. 1 to Q. 20 : Multiple choice questions with from C2H5OH and bleaching powder?
one or more than one correct option(s). (a) oxidation (b) reduction
(c) hydrolysis (d) chlorination
1. Which of the following reagents can be used to prepare an alkyl 4. Which of the following statements are true about chloroform?
halide from an alcohol? (a) it is used as anaesthetic
(a) NaCl (b) HCl + ZnCl2 (b) it is used as a solvent
(c) it has sp2 hybridized carbon
(c) SOCl2 (d) PCl5
(d) it has a distorted tetrahedral shape
2. Which of the following compounds, on being warmed with iodine 5. Which of the following methods can be used for the preparation
solution and NaOH, will give iodoform? of acetylene?
(a) CH 3 CH 2OH (b) CH 3COCH 3 (a) CH 3 CHCl 2 + alc. KOH ¾¾ ®
(b) ClCH 2CH 2 Cl + alc. KOH ¾¾ ®
H3C
liq. NH
3
CHOH (c) ClCH 2CH 2 Cl + NaNH 2 ¾¾¾¾¾ ®
(c) (d) CH 3OH D
H3C (d) none of these
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6. The haloform test is given by
*
(a) formaldehyde (b) acetaldehyde (a) CH 3 - CH - C H - OC2 H 5 by S N 2 reaction (reaction
| |
(c) acetone (d) a-phenylethyl alcohol CH3 C2H 5
7. Which of the following can be used for the preparation of
takes place with inversion)
chloroform?

(a) CH 3 CH 2 .CO.CH 2 CH 3 *
(b) CH 3 - CH - C H - OC2 H 5 by S 2 reaction (reaction
| | N
(b) CH 3 .CO.C 2H 5 CH3 C2H 5

(c) CH 3 CH 2 .CO.C 3 H 7 mixture)

(d) CH 3 CHO CH3

| *
(c) CH 3 - C - CH 2 - C2 H 5 by S N1 reaction
H3C H |
OC2H5

reagent R (d) none is correct

8. ¾¾¾¾¾ ® product P
H Cl alcoholic4 HgSO
12. C3 H 6 Cl 2 ¾¾¾¾¾
® A ¾¾¾¾ ®B
KOH H 2 SO 4
Which are true statements about reagent R and product P :
B gives iodoform test. Hence A is :
(a) 1, 1 dichloropropane (b) 1, 2 dichloropropane
H3C OH

(c) 2, 2 dichloropropane (d) 1, 3 dichloropropane

(a) P is when R is aq. KOH in S N 2 reaction

H H 13. Cl
Cl
Cl
I II III
H3C
Which are correct statements :

(b) P is when R is t-BuOK (a) reactivity for S reaction is I < II < III
N1

(b) reactivity for S reaction is I < II < III

H N2

(c) reactivity for S reaction is I > II > III

N1
H3C
(d) reactivity for S reaction is I > II > III
N2
(c) P is —NH2 when R is NH3 14. The correct statement(s) about the compound

H H
Cl CH3
H3C H
(d) P is H3C— —COOH when R is KMnO4 Cl
given below is/are
9. CH3CH2OH can be converted into CH3CH2Cl by (a) The compound is optically active
(a) thionyl chloride (b) The compound possesses centre of symmetry
(b) sulphuryl chloride (c) The compound possesses plane of symmetry
(c) phosphorus pentachloride (d) The compound possesses axis of symmetry
(d) phosphorus oxychloride 15. In the reaction,
10. Product obtained from the reaction of chloroform with nitric acid
is used as : CHCl 3 + 4OH - ¾¾
® HCOO - + 3Cl - + 2H 2 O
(a) insecticide (b) war gas the intermediate species formed are
(c) anaesthetic (d) dye (a) CCl3– (b) : CCl2
11. Possible products of the following reaction can be : (c) CH(OH)3 (d) COCl2
16. Which of the following compounds will give haloform test ?
CH 3 - CH - * H - Br ¾¾¾¾
C
OC 2H 5
® (a) CH3COCH2I (b) CH3 – CHCl – CH3
| |
CH 3 C2 H 5 (c) C6H5COCH3 (d) CH3COOC 2H5
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17. Benzyl chloride (C6H5CH2Cl) can be prepared from toluene by (a) ethene; E1
chlorination with (b) ethene; E2
(a) SO2Cl2/peroxide (b) SOCl2 (c) ethyl methyl ether; SN2
(c) Cl2/hv (d) NaOCl (d) ethyl methyl ether; SN1
18. The correct statement(s) about the compound 22. What is the major product of the reaction below, and what is the
H3C(OH)CH – CH = CH – CH(OH)CH3(X) mechanism by which it is produced?
is/are (CH3CH2)3CBr + OH– ®
(a) The total number of stereoisomers possible for X is 6 temperature: 500°C; solvent: CH3OH
(b) The total number of diastereomers possible for X is 3 (a) (CH3CH2)3COH; SN1
(c) If the stereochemistry about the double bond in X is trans, (b) (CH3CH2)3COH; SN2
the number of enantiomers possible for X is 4 (c) CH3CH=C(CH2CH3)2; E2
(d) If the stereochemistry about the double bond in X is cis, the (d) CH3CH=C(CH2CH3)2; E1
number of enantiomers possible for X is 2
19. Pick up the reaction in which Hofmann elimination is the major
product.
PASSAGE 2
Br Me3COK Alkyl halides in presence of polar solvents lose halide ions forming
(a) ¾¾¾¾ ¾® +
75°C carbocations which then react with the nucleophile.

OCOCH3
(b) C 2 H5OK + I OCOCH3
Cl ¾¾¾¾® CH3 COOH
heat
+

(c) C H OK + I II
Cl ¾¾¾¾®
2 5

23. The carbocation formed by the loss of halide ion is

Br (a) 1° (b) 2°
( C2H5 ) N (c) 3° (d) allylic
(d) ¾¾¾¾¾
3
® + 24. Formation of two products is because

O
20. Which of the organic compounds will give white precipitate ||
with AgNO3 solution ? (a) CH 3 - C - OH has two nucleophilic sites

(a) C6 H5Cl (b) the carbocation formed initially rearranges to the more stable
carbocation
(b) NaCl
(c) Both of the two
+ (d) None of the end
(c) C6 H5 N H3Cl - 25. The product II is formed through a
(d) 2, 4, 6 - trinitrochlorobenzene (a) 2° carbocation (b) 3° carbocation
(c) allylic 2° carbocation (d) vinylic 2° carbocation

DIRECTIONS for Q. 21 to Q. 35 : Read the following passages and

answer the questions that follows : PASSAGE 3
Observe the following two reactions :

Br
PASSAGE 1 |
KOH
(a) CH 3 CHCH 3 ¾¾¾® CH 2 = CHCH 3 is much faster than
A characteristic of alkyl halides is their ability to undergo nucleophilic alcohol

substitution reactions with nucleophiles and elimination reactions with

bases, although reactants are often both nucleophiles and bases. Br
|
Depending on factors such as the relative strength of nucleophile versus KOH
D 3C - CH - CD 3 ¾¾¾® D2 C = CH - CD 3
base, steric effects, temperature, and carbocation stability, the reaction alcohol
mechanism and most abundant products of certain reactions involving
alkyl halides can be predicted Br
|
(b) H O/acetone
CH 3CHCH 3 ¾¾¾¾¾¾
2 ® CH 2 = CHCH 3 is equal to
heat
21. What is the major product of the reaction below, and what is the
mechanism by which it is produced?
Br
CH3CH2Br + CH3O– ® |
H O/acetone
D3 CCHCD 3 ¾¾¾¾¾¾
2 ® D2 C = CHCD 3
temperature: 50°C; solvent: CH3OH heat
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26. The reaction (a) follows 33. The product (X) and the related most probable mechanism of its
(a) E1 (b) E2 formation are respectively
(c) either of the two (d) E1CB
NH2
27. The difference in the two reactions of the set (a) is due to the fact
that CH2 – CH –
(a) these reactions follow E2 path
(b) the C–D bond is slightly stronger than the C–H bond (a) ; SN2
(c) both of the above statements
(d) these reactions follow E1 mechanism NO2
28. The two reactions in the set (b) follow equal rate because
(a) the reaction occurs in two steps
(b) O2N – – CD = CH – ; E1
(b) the rate determining step involves removal of Br as Br–
(c) both (a) and (b)
(d) in presence of acetone C–H and C–D bonds are cleaved at (c) O2N – – CH = CH – ; E2
the same rate
29. Which of the reactions of the set (b) follows E1 mechanisms?
(d) O2N – – CD = CH – ; E1cB
Br Br
| |
(a) CH 3 CHCH 3 (b) D3 CCHCD3 34. The correct information about formation of Y are
(a) Regioselective, nonstereospecific, nucleophilic addition
(c) Both (d) None
(b) Nonregioselective, nonstereospecific, electrophilic addition
(c) Regioselective, stereospecific, electrophilic substitution
(d) Regioselective, stereospecific, electrophilic addition
PASSAGE 4
Although both nucleophilicity and basicity depend upon the 35. The product Y and Z are where (Ar’ is – NO2) and
availability of electrons, they do not always parallel each other.
In going from left to right in a period, both basicity and (Ph is – C6H5)
nucleophilicity decrease. However, down a group nucleophilicity
(a) Ar' – CD – CH – Ph ; Ar' – CD – CH – Ph
increases while basicity decreases. In case, the nucleophilic centre
is the same, two things happen : (i) nucleophilicity parallels Cl OH OH OH
basicity and (ii) nucleophilicity decreases and the basicity
O
increases as the size of nucleophile increases.
(b) Ar' – CD – CH – Ph ; Ar' – CD – CH – Ph

30. Which of the following has the highest nucleophilicity ? Cl OH

(a) F– (b) OH– O
(c) CH3– (d) NH2– (c) Ar' – CD – CH – Ph ; Ar' – CD – CH – Ph
31. The weakest base among the following is OH Cl
(a) (CH3)3CO– (b) CH3CH2O–
(d) Ar' – CD – CH – Ph ; Ar' – CD – CH – Ph
(c) (CH3)2CHO– (d) C6H5O–
32. The most reactive nucleophile among the following is Cl Cl OD OH
(a) CH3 O– (b) C6H5 O–
(c) (CH3)2CHO– (d) (CH3)3CO–
DIRECTIONS for Q. 36 to Q. 40 : The following questions are
matching type questions. Match Column I with Column II

PASSAGE 5
36. Column I Column II
D F

CH – CH – CH3 CH2Cl
(A) (a) S
N1
C=C
(1) NaNH 2 (2) Chlorine water
¾¾¾¾¾® (X) ¾¾¾¾¾¾¾¾
® (Y) CH3 CH3
(Major) (Major)

NO2 CH3 CR2Cl

(B) (b) S
C=C N2
CH3 CH3
NaOD (60°C)
¾¾¾¾¾¾® (Z)
D2O (C) (CH3)3 CCl (c) E1
(Major)
(D) CH3CH2Cl (d) E2
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37. Column I Column II 42. Statement 1 : Alkyl halides, though polar, are immiscible with
(A) Carbon tetrachloride (a) Laboratory reagent water.

(B) Chloroform (b) Easiest hydrolysis Statement 2 : Alkyl halides (haloalkanes) are polar due to the
presence of polar C – X bond.
(C) Methylene chloride (c) Reimer-Tiemann reaction
43. Statement 1 : neo-pentyl bromide undergoes nucleophilic
(D) Phenol (d) Methanal
substitution reactions very fast.
38. Match the column-1 with column-II : Statement 2 : The reactivity of neopentyl bromide in SN1
Column-I Column-II mechanism is very fast.
(Reaction) (Products) 44. Statement 1 : Vinyl chloride is unreactive in nucleophilic
A. Chloroform reacts with HNO3 (a) Gammaxene substitution reactions.
to form an insecticide Statement 2 : Due to delocalization of electrons by resonance.
B. Silver acetate gets converted (b) Dichlorodiphenyl 45. Statement 1 : n-Butyl chloride reacts with aqueous sodium
into methyl bromide on trichloroethane hydroxide by SN2 mechanism while tert-butyl chloride SN1
reaction with Br2 in CCl4 mechanism.
C. Chrobenzene in the presence (c) Chloropicrin Statement 2 : The carbocation formed is a tertiary carbocation,
of conc. H2SO4, reacts with in case of tert-butylchloride whereas in the case of n-butyl
trichloroacetaldehyde chloride, the carbocation formed is a primary carbocation.

D. Benzene reacts with Cl2 in (d) Compound 46. Statement-1 : S N 2 reaction of an optically active aryl halide
presence of sun light containing oxygen.
with an aqueous solution of KOH always gives an alcohol with
(e) Borodiene
opposite sign of rotation.
Hunsdiecker reaction
39. Column-I Column-II Statement-2 : S N 2 reactions always proceed with inversion of
A. (CH3)3CCl (a) Hofmann product configuration.
B. CH3CH2CH2CH2Cl (b) Saytzeff product 47. Statement-1 : Grignard reagents are prepared in ether but not in
C. CH3CHClCH2CH3 (c) E1 benzene.
D. CH3CHFCH2CH3 (d) E2 Statement-2 : Grignard reagents are soluble in benzene.
40. Column-I Column-II 48. Statement-1 : Treatment of 1, 3-dichloropropane on reaction
with alc. KOH gives allene.
A. SN1 (a) Inversion
Statement-2 : It is nucleophilic elimination reaction.
B. SN2 (b) Carbocation
49. Statement-1 : Alkyl halides give elimination reaction with
C. E2 (c) Transition state
alcoholic KOH, but nucleophilic substitution with aqueous KOH.
D. E1 (d) Retention
Statement-2 : In alcoholic KOH, attacking ion is – OR which is
stronger base than OH–.

Instructions for Q. 41 to 49 : Following questions are Assertion and

Reasoning Type Questions : Instructions for Q. 50 to 52 : Following questions are Integer Type
Note : Each question contains STATEMENT-1 (Assertion) and Questions :
STATEMENT-2 (Reason). Each question has 5 choices (a), (b), (c),
(d) and (e) out of which ONLY ONE is correct. 50. The number of structural and configurational isomers of a bromo
(a) Statement-1 is True, Statement-2 is True; Statement-2 is a correct compound, C5H9Br, formed by the addition of HBr to 2-pentyne
explanation for Statement-1. respectively are
(b) Statement-1 is True, Statement-2 is True; Statement-2 is NOT a
correct explanation for Statement-1. HCl/ ZnCl2
51. CH3 H Product
(c) Statement -1 is True, Statement-2 is False. (i)
Ph – CH – C – CH2 – CH3 Product
(d) Statement -1 is False, Statement-2 is True. (ii) SOCl2
OH Product
(e) Statement -1 is False, Statement-2 is False.
(Optically pure (iii) PCl5
single stereoisomer)
41. Statement 1 : 3-bromocyclohexene is less reactive than 4-
bromocyclohexene in hydrolysis with aqueous NaOH. Find the sum of total number of isomeric chlorides obtained in
Statement 2 : Reactions of the given halides with aqueous these reactions (consider only the major products)
NaOH is expected to proceed via SN1 mechanism. 52. The total number of alkenes possible by dehydrobromination of
3-bromo-3-cyclopentylhexane using alcoholic KOH is
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EXERCISE 8.3 (Subjective Problems)

1. Write IUPAC names for : 8. Suggest a suitable mechanism for the following transformation.
(i) allyl iodide (ii) tert-amyl bromide
(iii) neopentyl chloride OH
H2 O
— CH2Cl ¾ ¾ ® —CH2OH +
Br

Cl + CH2 = CH—CH2—CH2OH
(iv) (v)
Cl 9. Give the possible products when the following alkyl halides are
Cl
treated with sodium ethoxide.
(a) (CH3)2CHCHClCH3
Br
CH3
2. (a) can be prepared from two alkenes. Name
Br
them (b)
(b) Prepare n-butyl iodide from butene-1.
3. How will you prepare (a) allyl iodide, and (b) allyl fluoride
from propene ?
BrH2C CH3
4. (a) Assign structure to the hydrocarbon (molecular weight =
72) which gives a single monochloride and two isomeric (c)
dichlorides on photochlorination.
(b) Assign structure to the hydrocarbon (M.W. = 70) which
gives a single monochloride and three isomeric dichlorides 10. Name the chief product obtained by the reaction of n-C 4H4Br
on photochlorination. with
5. Arrange the following species in increasing order of their fugicity (a) Zn, H+ (b) Li, then CuI, C2H5Br
(leaveability). (c) NaI in presence of (CH3)2CO
– – (d) Mg, ether, and then D2O (e) CH3COOAg
H2O, OH–, CH3OH, O CH3, O COCH3, H–, CN–, R–, ArSO2O– (f) Li, CuI.
. 11. Arrange the following alkyl bromide in decreasing order toward
6. Arrange the following alkoxide ions in order of decreasing order SN 2 reactivity.
of SN 2 reactivity :
(a) 1-Bromo-3-methylbutane, 2-bromo-2-methylbutane, 3-
bromo-2-methylbutane
Me 3CO –, MeO–, MeCH2O–, Me2CHO–, and . (b) 1-Bromobutane, 1-bromo-2, 2--dimethylpropane, 1-
O– bromo-2-methylbutane, 1-bromo-3-methylbutane
12. Arrange the following alkyl bromides in decreasing order toward
7. Explain the following :
S N 1 reactivity.
(a) Although CH3 —O—CH2Cl is a primary alkyl halide, it
undergoes S N 1 reaction. 2-Bromo-2-methylbutane, 1-bromopentane, 2-bromopentane
13. Give the principal product obtained by the free radical
(b) AgNO3 increases the rate of solvolysis in S N 1 reactions. bromination of each of the following :
(c) Ethyl alcohol is added to water during solvolysis of alkyl
halides by water.
(a) (b)
(d) Account for the trend observed in relative rates for the
formation of alcohols in the following alkyl halides with
H2O/C2H5OH at 25°C.
(c)
MeBr (2140) : MeCH2Br (172) ; Me2CHBr (4.99) ; Me3CBr
(1010)
14. Explain the following :
(e) PHO– is a weaker nucleophile than RO –.
(i) Bromine is less electronegative than chlorine, yet the dipole
(f) An SN 2 solvolysis (where solvent is the nucleophile) moments of CH3Cl and CH3Br are very similar.
appears to follow a first order rate law, rather than a (ii) Carbon-carbon bond dissociation energy of ethane and
second order one. propane are different.
(g) 4-Bromo-2-pentene forms a racemic product on treatment (iii) Dry gaseous hydrohalic acids and not their aqueous
with sodium iodide. solutions are used to prepare alkyl halides from alkenes.
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(iv) Iodoform gives precipitate with silver nitrate on heating, 17. Isopropyl bromide reacts with hydroxide ion, in 80% ethanol at
while chloroform does not. 55°C, according to the following kinetic equation
(v) On treatment with base, CH3CH2I loses HI easily than Rate in moles L–1 S–1 = 4.7 × 10–5 [RX] [OH–] + 0.24 × 10–5
CD3CH2I loses DI [RX]
(vi) The carbocation F3C+ is stable while F3C—CH2+ is not Determine the percentage of isopropyl bromide reacting by SN 2
stable.
mechanism when [OH–] is :
15. Categorise the following compounds
(a) 0.001 molar (b) 0.1 molar and
(i) bromobenzene (ii) tert-butyl bromide
(c) 1. 0 molar
(iii) n-hexyl chloride (iv) n-hexyl iodide
18. Optically pure (S) – (+)-CH3CHBr C2H5 has specific rotation
(v) benzyl bromide (vi) carbon tetrachloride of + 36°. A partially racemized sample of this bromide with
(vii) sec-butyl chloride. specific rotation of + 30° is treated with dilute NaOH to form
On the basis of their reactivity with alcoholic silver nitrate in the an alcohol (R) – (–) – CH3CHOHC2H5 of specific rotation –
following three categories. 5.97° ; whose optically pure form has a specific rotation of –
(a) react rapidly at room temperature 10.3°.
(b) react rapidly only on heating Write the equation for the reaction using projection formula
(c) inert even on heating. and calculate
16. Calculate the rate of reaction between CH3I and CN–, when (i) the percent optical purity of reactant and product
they react by the SN 2 process in a solution in which the (ii) the percentage of racemization and inversion
(iii) the percentage of the front side and backside attack.
concentration of each is 0.1 mol dm–3 (0.1 molar), given that
the rate at 0.01 molar concentration is 5.44 × 10–9 mol dm–3 s–1. Can we increase the percentage of inversion by changing the
condition of the reaction ?
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EXERCISE 8.1

1 (b) 6 (a) 11 (a) 16 (d) 21 (d) 26 (c) 31 (a) 36 (b) 41 (b) 46 (a)

2 (d) 7 (b) 12 (d) 17 (a) 22 (a) 27 (c) 32 (d) 37 (d) 42 (d) 47 (d)

3 (d) 8 (a) 13 (b) 18 (b). 23 (a) 28 (c) 33 (b). 38 (c) 43 (a). 48 (a).

4 (c) 9 (b) 14 (c) 19 (b) 24 (a) 29 (d) 34 (d) 39 (a) 44 (b) 49 (c)

5 (d) 10 (b) 15 (d) 20 (c) 25 (b) 30 (b) 35 (d) 40 (d) 45 (d)

Cl Cl
Cl
1. Cl
1-Chlorobutane (1°) 1-Chloro-2-methylpropane (1°) 2-Chlorobutane (2°) 2-Chloro-2-methylpropane (3°)

2. Alkyl halide because Cl is attached to sp 3 hybridised C, vinyl halide because Br is attached to sp 2 hybridised carbon, allyl halide
because Cl is attached to sp 3 hybridised carbon which in turn is attached to the sp 2 hybridised carbon.

Br

3. HBr HBr
¾ ¾ ¾¾ ¾ ¾ ¾ ¾ ® ¬ ¾¾ ¾ ¾¾ ¾ ¾¾ ¾
Markownikov’s addition Markownikov’s addition

4. It is an electrophilic addition and involves the formation of carbocation. Here 2° carbocation undergoes 1, 2-hydride shift to form the
more stable benzylic carbocation.

H Br
Å
+ –
H Å Br
¾¾ ® ¾¾® ¾¾®

(2° Carbocation) (Benzylic carbocation)

5. RCl and RBr can be prepared by free radical halogenation of alkanes, but RF and RI can’t be prepared because fluorination is so fast
that explosion occurs, while iodination is slowest and produces HI a strong reducing agent which causes the reaction to proceed
backward.
6. Weaker a Bronsted base, more will be its stability than its conjugate acid, and hence more will be the tendency of the base to be removed
and thus more will be reactivity of the RX.
7. Among halides, fluoride ion is the smallest ion, so it provides minimum volume for spreading of electrons and thus electrons are easily
available. Further, F has no d orbital while Cl has d orbital so delocalisation in Cl– further increases and thus its basicity (availability
of electrons for protonation) decreases much more than F –.
8. Increased temperature increases the rates of both substitutions and eliminations. However, increased temperature favours eliminations
over substitutions because elimination reactions have higher free energies of activation than substitutions since the former involve more
changes in bonding (i.e. more bonds are broken and formed).
9. 3° Halide does not undergo SN 2 reaction because of bulky alkyl group present on C bearing the leaving group. Ethyl alcohol is a weak
base but good nucleophile, hence (CH3)3C+ formed as intermediate is attacked by the nucleophile, C 2H5OH (remember it is an
example of solvolysis). Elimination reaction is not possible because C 2H5OH is a weak base.
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10. Iodide ion is excellent nucelophile as well as a leaving group, while Cl– is a poor leaving group as compared to I –. So in the two step
method, both steps are fast and hence the two step route is preferred as compared to first which proceeds at a slower rate (poor yield).

Repulsion between
methyl groups
CH3 H Ch3 CH3
Br + +
–H +
11. ¾¾– ® ¾¾ ®
(–Br ) H
(a) (Hofmann product) (b) (Saytzeff product)

Thus here, Saytzeff product (having more alkyl groups on the doubly bonded carbon atoms) is not stable due to steric repulsion
between bulky methyl groups.
12. Dichlorocarbene is a neutral bivalent electron deficient species having two non-bonding electrons on the carbon atom. It is formed by
the loss of Cl– from trichloromethyl carbanion.

Cl –
Cl Cl
OH – –
H—C—Cl ¾¾ ®
¾¾® C—Cl ¾¾® C—Cl + Cl
Cl Cl

13. Hydrogen of CHCl3 is acidic than that of CH2Cl2 because the former has three —Cl (electronegative groups) while CH 2Cl2 has two,
hence it is easily eliminated by alkali ; CCl4 has no hydrogen atom, so it will not react with alkali.
14. See mechanism of alkaline hydrolysis of chloroform.
15. During reaction of an alkyl halide with KCN, one carbon atom is introduced by KCN in the form of —CN, hence alkyl halide should
be propyl chloride.
CH3CH2CH2Cl + KCN ¾¾® CH3CH2CH2CN + KCl
16. 4C 2H5Cl + SnCl4 + 8Na ¾¾® (C2H5)4 Sn + 8NaCl

- +
diethyl
17. CH2 = CHCl + (CH 3 )2 Cu Li ¾¾¾¾
® CH2 = CHCH3
Lithium dimethylcuprate ether

–
O OH
OH2
18. Cl3 C—C = O ¾ ¾ ® Cl3C—C + ¾ ¾ ® Cl3 C—C
O—H OH
H H H
H Chloral hydrate

Å –
Å NMe3OH
Cl NMe3Cl

22. (a) (i) Me N AgOH D

¾¾¾¾¾
3 ® ¾¾¾¾
® ¾¾®

Hoffmann's elimination

OH -
24. (a) CH 3 - CH 2 - CHCl 2 ¾¾¾® CH 3CH 2 CHO or CH 3 C º CH
(A) (B) (C)

[O]
CH 3 - CH 2 - CH = O ¾¾¾
® CH 3 - CH 2 - COOH
(B)

O
P
Dil.H 2SO 4 Br2 /NaOH
CH 3 - C º C - H ¾¾¾¾¾® CH 3 - C - CH 3 ¾¾¾¾¾¾ ® CH 3COONa
(C) (D)
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25. (b)

(i) H - C º C - H + 2Br2 ¾¾
® CHBr2CHBr2 (X)

Br Br
CH
(ii) 2 + AlBr (Y) + 4HBr
¾¾¾¾¾¾¾¾¾
2 ®
Friends craft reaction
CH
Br Br

Br H Br C2H5 H C2H5
27. (c) Base
H C– C CH3 ¾¾
® H C–C CH3 ¾¾¾® C= C
CH3 CH2CH3 CH3 H CH3 CH3

28. (c) Since alkyl halide is 3°, so in presence of NaCN it will follow E2 path rather SN2, so method 2 is not appropriate.

C H OH
29. (b) (CH3)2 CHCH2MgBr ¾¾¾¾¾
2 5 ® (CH3)2 CHCH3 + MgBr(OC2H5)
30. (d) Debromination is a trans-elimination reaction.
meso- 2, 3-Dibromobutane on debromination gives trans-2-butene.

31. (a) (CH3 )3 C - MgCl + D 2O ¾¾

®(CH3 )3 C - D + Mg(OD)Cl

32. (d) Occurrence of racemization points towards the formation of carbocation as intermediate, which being planar can be attacked from
either side.

Cl
|
SbCl
C6H 5 - C - CH 3 ¾¾¾¾¾
5 ® Cl -
|
- ( -SbCl6 ) ¾¾¾
® ( + ) - + ( -) -
H
(+)

33. (b) Dehydrobromination by strong base (alc. NaOH) followed by Markownikoff addition of HBr.

CH 3 CH 2 CH =CH 2 + CH 3 CH =CHCH 3
CH3 Butene-1 Butene-2
34. (d) H+ (cis - and trans )
® E5555555555555555555555555555555F
¾¾¾
OH F
CH 3

Br2 * HCH Br
CH 3 CH 2 CH =CH 2 ¾¾¾ ® CH 3 CH 2 C 2
Butene-1 |
Br
( + ) - and (–) enantiomer

Br
¾¾¾
2®

CH3
® H Br
Br2
¾¾¾
H Br
CH3
meso
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35. (d) It is an example of intramolecular Wurtz reaction.

Cl Cl

Na Na
ether
+ NaCl
–
Br

Br– is a better leaving group than chloride. In this reaction alkali metal (Na) is electron donor.

Alc.KOH
NaH 2
36. (b) BrCH2 – CH2Br ¾¾¾¾¾
® CH2 = CHBr ¾¾¾¾ ® CH º CH

Elimination of HBr from CH2 = CHBr requires a stronger base because here, Br acquires partial double bond character due to
resonance.

37. (d) Carbon belongs to 2nd period, while iodine belongs to 5th period, hence the C-I bond in CH3CH2CH2I must be formed by the
overlapping of 2sp3 orbital of C with the 5pz orbital of iodine.

38. (c) Small difference in boiling points of C2F6 and C2H6 is due to the fact that (i) the F atom is only slightly larger than H, and (ii) F has
low polarizability

39. (a) Sodium chloride is far less soluble in acetone than NaI, hence reaction (b) is possible, but not (a)

40. (d) tert-Alkyl halides undergo S reactions, hence they involve the formation of quite stable carbocations, and not the transition state.
N1
In S reactions, the nucleophile is not involved in rate determining (first) step, hence its stronger or weaker nature does not influence
N1
the reaction rate. In S 1, the product has more percentage of the inverted configuration than the retained configuration, i.e. only
N
partial racemization takes place, hence the product will be having some optical activity.

41. (b) (i) Weak bases like CH3COO–, Cl– etc. favours substitution rather elimination.

(ii) Sterically hindered base favours elimination reaction, no matter the alkyl halide is primary.

42. (d) (a) Elimination reactions have higher free energies of activation than substitution reactions because they involve a greater change in
bonding, i.e., more number of bonds are broken and formed than in substitution reactions. Now the increase in temperature
although increases the number of molecules crossing the barrier in both reactions, the proportion of such molecules is significantly
higher in elimination reaction leading to increased rate of elimination reaction.

(b) The sterically hindered nucleophile will inhibit the formation of transition state leading to substitution reaction, hence the alkyl
halide will mainly undergo elimination reaction .

(c) Use of strong and slightly polarizable base, e.g. NH -

2 ion favours elimination reaction.
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EXERCISE 8.2
1 (b, c, d) 2 (a, b, c) 3 (a, c, d) 4 (a, b, d) 5 (a, b, c)
>1 CORRECT 6 (b, c, d) 7 (b, d) 8 (a, b) 9 (a, c) 10 (a, b)
OPTION 11 (a, c) 12 (a, b, c) 13 (a, d) 14 (a, d) 15 (a, b)
16 (a, b, c, d) 17 (a, c) 18 (a, d) 19 (a, c, d) 20 (c, b)
PASSAGE 1 21 (c) 22 (a)
PASSAGE 2 23 (b) 24 (b) 25 (c)
PASSAGE 3 26 (b) 27 (c) 28 (c) 29 (c)
PASSAGE 4 30 (c) 31 (d) 32 (a)
PASSAGE 5 33 (d) 34 (d) 35 (b)
36 (A)-a, b ; (B) a, c ; (C) a, c ; (D) b, d
37 (A) - a, c, (B) - a, b, c, (C) - d, (D) - a, c
MATCH THE
FOLLOWING 38 (A)-c, d ; (B) d ; (C) b ; (D) a
39 (A)- c ; (B) d ; (C) b, d ; (D) a, d
40 (A)-a, b, d ; (B) a, c ; (C) c ; (D) b
41 (d) 42 (b) 43 (c) 44 (a) 45 (a)
A/R
46 (d) 47 (c) 48 (a) 49 (a)
INTEGER 50 2&4 51 4 52 5

Sol. (33-35) 51. 4

CH3
F HCl/ ZnCl2
NaNH2 Ph – C – CH2 – CH2– CH3
D – CH – CH – O2N – – CD = CH – (i) SN1
E1cB (X) Cl
Major (±)mixture (two products)
(2) Cl2/ H2O
CH3 H CH3 H
NO2 SOCl2
Ph – CH – C – CH2 – CH3 Ph – CH – C – CH2 – CH3
(ii) SN1
NaOD OH Cl
O2N – – CD– CH – O2N – – CD – CH –
D2O Retention (one product)
O Cl OH
(Z) (Y) CH3 Cl
PCl5
33. (d) 34. (d) 35. (b) Ph – CH – C – CH2 – CH3
46. (d) A is false, because aryl halides do not undergo nucleophilic (iii) SN2
H
substitution under ordinary conditions. This is due to Inversion (one product)
resonance, because of which the carbon–chlorine bond Total no. of products is 4.
acquires partial double bond character, hence it becomes 52. 5
shorter and stronger and thus cannot be replaced by Total no. of alkenes will be = 5
nucleophiles. However (R) is true.
47. (c) The correct reason is : Grignard reagents are soluble in ether Br
but not in benzene
50. 2&4 H3C CH2 CH2 C CH2 CH3
Addition of HBr to 2-pentyne gives two structural isomers
(I) and (II)
alc.KOH
HBr
CH3 - C º C - CH 2 CH 3 ¾¾¾
®
CH3C(Br) = CHCH 2 CH3 + CH 3CH = C(Br)CH 2 CH 3 H3C CH2 CH2 C CH CH3
(I) (II)
Each one of these will exist as a pair of geometrical isomers. (E & Z)
Thus, there are two structural and four configurational
isomers.

H3C CH2 CH C CH2 CH3

or
(E & Z)

H3C CH2 CH2 C CH2 CH3

or
(Only 1)
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EXERCISE 8.3
1. (i) CH2 = CH CH2I is 3-iodo-1-propene (ii) (CH3)2C(Br)CH2CH3 is 2-bromo-2-methylbutane
(iii) (CH3)3 CCH2Cl is 1-chloro-2, 2-dimethylpropane (iv) 4-(1-bromoethyl)-3-chloro-2, 2, 7-trimethyloctane
(v) trans-1, 3-Dichlorocyclobutane.

and
2. (a)
2-Methylpentene-2 2-Methylpentene-1

CH 3
|
NaI
(b) CH3CH2CH = CH2 CH CH 2C H Br CH3CH2CH2CH2Br ¾ ¾¾¾
¾® CH3CH2CH2CH2I
1°
2
acetone

NaI
Cl 2 , hn
3. (a) CH3CH = CH2 ¾¾¾¾ ® ClCH2CH = CH2 ¾¾¾¾
acetone
® ICH2CH = CH2 + NaCl ¯

Cl 2 , hn AgF
(b) CH3CH = CH2 ¾¾¾¾ ® ClCH2CH = CH2 ¾¾¾ ® FCH2CH = CH2 + AgCl ¯
4. (a) Hydrocarbon (MW = 72) should contain 5 C atoms, hence its molecular formula is C5H12. Since it forms only one monochloro
derivative, its all 12 hydrogen atoms should be equivalent which is possible only in (CH3)4C. Thus its monochloro and two
isomeric dichloro derivatives are
(CH3)3CCH2Cl ; (CH3)3CCHCl2 and (CH3)2C(CH2Cl)2
(b) Hydrocarbon of MW 70 should again have 5 carbon atoms, thus it should have molecular formula of C 5H10. Which indicates the
presence of 1° of unsaturation. No alkene with five C’s has all equivalent H’s, hence the compound should be cycloalkane, i.e.
cyclopentane. Its monochloro and isomeric dichloro products are
Cl Cl —Cl
—Cl
Cl
Cl
Cl
5. Weaker a base, better is its leaveability (basicity in turn can be known by knowing acidity of the respective conjugate acid, remember
that weaker a base stronger is its conjugate acid). Thus first of all write down conjugate acids of different bases and then arrange them
in decreasing acidity.
+
Conjugate acid. H3O+, H2O, CH3 O H2, CH3COOH, H2, HCN, RH, ArSO2OH

+ +
Decreasing acidity. H 3 O, CH 3 O H 2 > ArSO 2 OH > HCN, CH 3 COOH > H 2 O, CH 3 OH > H 2 , RH
very strong acids Strong acid Weak acids feeble acids Weakest acids

Remember that only conjugate bases of very strong acids are weak enough to be good leaving groups. Thus
H–, R– < CH3O–, OH– < CN–, CH3COO– < ArSO2O– < H2O, CH3OH
(Increasing fugicity or decreasing basicity of the parent species)

6. Remember that the S N 2 reactivity is susceptible to steric hindrance by the nucleophile as well as R’s around the site of displacement.
Hence as the number of R’s accumulate on the C bonded to O –, the nucleophile becomes bulkier and its backside approach to the
reaction site is retarded, causing a decline in the rate of SN 2 reaction. Thus the order will be
H
MeO– > MeCH2 O– > > Me2CHO– > Me3CO–
O–
Note that both A and B belong to R2CHO– type, but the R’s of A form the sides of the ring and are ‘‘tied back’’ away from the —O.
This arrangement permits a more facile approach than by Me 2CHO–.
7. (a) The carbonium ion from chloromethyl methyl ether is resonance stabilized. Remember that stability of R+ is determining factor
between S N 1 and SN 2 reactions.
.. + .. ..
ClCH2— O . . —CH3 ¬¾® C H 2 — O ..
—CH3 ¬¾® CH2 = O —CH3
+
(b) Ag+ has a stronger affinity for X– than a solvent molecule ; the precipitation of AgCl accelerates the dissociation of X–. This is an
example of electrophilic catalysis. Remember that Lewis and Bronsted acids (Ag+, AlCl3 and strong HA) or weak Lewis base
(e.g. H2O) catalyses S reaction.
N1
(c) Water is a poor solvent for alkyl halides and ethyl alcohol is added to aid the reaction in their solution.
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(d) The first three halides react mainly by the S pathway and their rate decline as Me’s replace H’s on the attacked C, because of
N2

steric hindrance. A change to the S N1 pathway accounts for the sharp rise in the reactivity of Me 3CBr.

(e) In PhO–, the pair of electrons on oxygen is involved in resonance and thus nucleophilic character of PhO– decreases. No such
resonance is possible in case of alkoxide ion.
(f) In S solvolysis, the concentration of solvent (one of the components) is very large, hence reaction follows the pseudo first order
N2
rate law.
(g) It is a 2° halide, hence follows S pathway which gives racemic mixture.
N1

I
+ – |
I
CH3—CH = CH—CH(Br)—CH3 ¾¾® CH3—CH = CH— C HCH 3 ¾¾® CH3CH = CH CHCH 3

(+) or (–) ( ±)

(b)
+ + +
H2O H2O –H
8. —CH2Cl ¾ ¾1 ® —CH2 ¾¾ ® —CH2OH2 ¾¾ ® —CH2OH
*SN
(a)

(b) (a)

+ OH
CH2—CH2—CH = CH 2 Ch2 + +
CH ( i) H2O
½ CH2 º ¾ ¾ ¾®
(i) H2 O, CH2
+
(ii) –H
+
(ii) – H

HOCH2 —CH2—CH = CH2

*Sterically hindered C bearing —Cl and weak base favours S reaction.

N1

H Cl H
2° hadide +
9. (a) CH3—C—–C—CH3 ¾¾ ¾¾®
1 CH3—C—–C—CH 3
SN
CH3 H CH3 H
2° Carbocation

1, 2-hydride shift

H OC2H5
+ –
–H + OC2H5
(CH3)2C = CHCH3 ¬ ¾ ¾ CH3—C—–C—CH3 ¬ ¾¾ ¾ CH3—C—CH2CH3
(Major)
CH3 H CH3
3° Carbocation (Major)

H H OC2H5
–
elimination + OC2H5
CH3—C = CHCH3 ¬ ¾¾ ¾ ¾¾ CH3 —C—–C—CH3 ¾ ¾ ¾® CH3 —C—–C—CH3

CH3 CH3 H CH3 H

(Major) 2° Carbocation (Minor)
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CH3 CH3 CH3 CH3

H OC2H5
Br +

2° halide + 1, 2-hydride
(b) ¾¾ ¾ ® ¾¾ ¾ ¾¾ ® ¾¾ ¾ ® +
1 shift
(SN )
2° Carbocation 3° Carbocation (Major)

¾®
CH3 CH3
OC2 H5
+

Minor

+
CH2 Br 1 CH2 CH2 CH3
SN 1, 2-methyl
(c) ¾¾ ¾ ¾¾ ® ¾ ¾ ¾¾ ¾ ® +
due to steric shift
CH3 hindrance CH3
1° Carbocation 3° Carbocation

– CH2CH3
OC2H5
¾¾ ¾ ¾® + —CH2CH3
OC2H5
1
via SN via elimination

10. (a) CH 3 CH 2 CH 2 CH 3 (b) CH 3 CH 2 CH 2 CH 2 CH 2 CH 3 (c) CH 3 CH 2 CH 2 CH 2 I

n-Butane n-Hexane n-Butyl iodide

O
||
(d) CH 3 CH 2 CH 2 CH 2 D (e) n-C4 H 9 O C ¾ CH 3 (f) (n-C4 H 9 )2 CuLi
1-Deuteratedbutane Methyl pentanoate Lithium di-n-butylcopper

11. Steric factors are controlling. The usual SN 2 order is 1° > 2° > 3°. In case all halides are 1°, rate decreases with increase in branching on
the carbon attached to — CH2Br.

CH 3 CH 3 CH 3
| | |
(a) CHCH2 CH 2 Br > CH 3 CHCHBrCH 3 > CH 3 ¾ C ¾ CH 2 CH 3
1° 2° |
Br
3°

CH 3 CH 3 CH 3
| | |
(b) CH3 CH2 CH 2 ¾ CH 2 Br > CH 3 CHCH 2 ¾ CH 2 Br > CH 3 CH 2 CH ¾ CH 2 Br > CH 3 ¾ C ¾ CH 2 Br
1° 1° 1° |
CH 3
1°

12. Polar factors are controlling, the more stable the cation being formed in the initial ionization, the faster the reaction. The usual order is
3° > 2° > 1°

CH 3
|
CH 3 CH 2 ¾ C ¾ CH 3 CH 3 CH2 CH 2 CH ¾ CH 3 CH 3 CH2 CH 2 CH 2 ¾ CH 2 Br
| > | > 1°
Br Br
3° 2°
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13. We know that the order of reactivity of hydrogen atoms is 3° > 2° > 1°.
Br
Br
(a) (b) (c)
Br
14. (i) TheC¾Br bond is longer than the C¾Cl bond, therefore while the change in e in the dipole moment expression (m = e × d) is smaller
for the bromine than for the chlorine compound, the distance d is greater.
(ii) Write down the products obtained on homolytic C—C bond cleavage in the two cases.
· · · ·
H 3 C ¾ CH 3 ¾¾® H3 C + C H3 ; H 3 CCH 2 CH 3 ¾¾® CH 3 C H 2 + C H 3
Ethane Two methyl radicals Propane Ethyl Methyl
radical radical

Now observe the relative stability of the products in the two cases : more the stability of the product, easier will be its formation and
thus lesser will be the energy required to break that C—C bond. In present case, ethyl radical (formed in propane) is more stable than
methyl radicals (formed in ethane), hence less energy will be required to break C—C bond in propane than in ethane.
(iii) Dry hydrogen halides are stronger acids and better electrophiles than the H 3O+, formed in aqueous solution of hydrogen halides.
Furthermore, H2O is a nucleophile that can react with R+ to give ROH.
(iv) Carbon-iodine bond is weak (bond energy 45.5 Kcal mol–1) than the carbon-chlorine bond (bond energy 66.5 Kcal mol–1), hence
C—I breaks up easily to give I– ions than the C—Cl bond.
(v) This reaction is an E2 reaction ; and involves the cleavage of the C—H (or C—D) bond in the rate determining step.
Now the C—H bond, being weaker, breaks rapidly than the stronger C—D bond, hence
CH3CH2I loses HI faster than the CD3CH2I loses DI.
+
(vi) In F3C— C H2, carbon bearing three electronegative atoms develops partial positive charge.
Such species having similar charge on the adjacent carbon atoms will be unstable.
+
On the other hand, in F3 C , the unshared electron pair in the p-orbital of each of the fluorine can delocalize to electron deficient carbon
+
(p-p overlapping) with the result the carbocation F3 C is stabilised.
15. The more stable the carbocation, more reactive will be the corresponding alkyl halide. Further the C—I bond is weak, it will be quite
reactive in case when iodine is present on sp 3-hybridised carbon, than the C—Cl or C—Br.
+ +
(a) tert-Butyl bromide and benzyl bromide will be most reactive because their corresponding carbocations (Me 3 C and C6H5 C H2) are
quite stable. n-Hexyl iodide is also very reactive because of weak C—I bond and the carbocation is not destabilised.
(b) n-Hexyl chloride and sec-butyl chloride.
+
(c) Inert even on heating. Bromobenzene (C6H5+ is very unstable) and CCl4 ( C Cl3 is unstable because of —I effect of chlorine atoms).
16. We know that rates are proportional to the products of the concentrations of the reactants, thus

Rate (0.1 mol dm -3 ) (0.1 mol dm -3 )

-3 -1
=
5.44 ´ 10 -9
mol dm s (0.01 mol dm -3 )(0.01 mol dm -3 )
\ Rate = 5.44 × 10–7 mol dm–3 s –1.
17. The given rate expression indicates that the rate is made up of two parts

Rate = 4.7 ´ 10 –5 [RX][OH – ] 0.24 ´ 10 -5 [RX]

1444424444 3 + 1442443
S 2 S 1
N N

S
N2
Hence, Percentage due to S = ´ 100
N2 S N 2 + S N1

4.7 ´ 10 -5 [RX][OH – ] 4.7 [OH - ]

= ´ 100 = ´ 100
4.7 ´ 10 -5 [RX][OH – ] + 0.24 ´ 10 -5 [RX] 4.7 [OH - ] + 0.24

Thus, percentage due to S at various OH– concentrations can be calculated as below.

N2

4.7 ´ 0.001
(a) When [OH–] = 0.001, % S = 4.7 ´ 0.001 + 0.24 ´ 100 = 1.9%
N2

4.7 ´ 0.1
(b) When [OH–] = 0.1, % S N 2 = 4.7 ´ 0.1 + 0.24 ´ 100 = 66.2%

4.7 ´ 1.0
(c) When [OH–] = 1.0 , % S = ´ 100 = 95.1% .
N2 4.7 ´ 1.0 + 0.24
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18. According to given statement

C2H5 C2H5
NaOH
CH3 Br ¾¾ ¾ ® HO CH3

H H
(S) (R)

[a]Actual + 30° – 5.97°

[a] for optically pure + 36° – 10.3°
+ 30°
(i) % of optical purity of the bromide = ´ 100 = 83%
+ 36°

- 5.97°
% of optical purity of the alcohol = ´ 100 = 58%
- 10.3°
(ii) Percentage of inversion is calculated by dividing the percentage of optically active alcohol of opposite configuration by that of
reacting bromide, i.e.
58
% inversion = ´ 100 = 70%
83
\ % racemisation = 100%—70% = 30%
(iii) We know that inversion involves only backside attack, while racemization results from equal backside and frontside attack. The
percentage of backside reaction is the sum of inversion and one-half of the racemization ; while percentage of frontside attack is
the remaining half of the percentage of racemization. Thus
1
% Backside reaction = 70% + (30%) = 85%
2
1
% Frontside reaction = (30%) = 15%
2
The inversion takes place in S reaction, thus more the rate of S reaction higher will be inversion. The S rate can be increased
N2 N2 N2
by increasing the concentration of the nucleophile, i.e. OH–.
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9.1 Methods of Preparation 9.5 Arylalkyl Halides

9.2 Physical Properties EXERCISES

9.3 Chemical Properties SOLUTIONS

9.4 Nucleophilic Aromatic Substitution

Aryl halides are the compounds having halogen atom directly attached to the aromatic ring. They are represented
by the general formula AR—X where Ar may be phenyl, substituted phenyl or other aromatic system e.g. naphthyl.
All compounds containing aromatic ring and a halogen atom should not be considered as aryl halides e.g.
benzyl chloride (C6H5CH2Cl) is not an aryl halide because chlorine is not directly attached to the ring ; rather benzyl
chloride and other related compounds resemble alkyl halides in structure and properties too.
The carbon-halogen bonds of aryl halides are both shorter and stronger than the carbon-halogen bonds of RX, and
in this respect as well as in their chemical behaviour, they resemble vinyl halides (H2C = CH—X) more than alkyl halides.
: :

CH2—X:
: :

X:
: :

: :
: :

CH2 = CH—X: R—CH2—X: CH2 = CH—CH 2—X:

Aryl halides Vinyl halides Alkyl halides Allyl halides Benzyl halides

2 3
Halogen attached to sp hybridised C, Halogen attached to sp hybridised C, delocalisation
C—X bond is shorter and stronger because of electrons on halogen is not possible, hence
of partial double bond character due to C—X bond does not acquire double bond
delocalisation of electrons on halogen character, hence it is weaker and reactive.

The strength of the C—X bonds causes aryl halides to react very slowly in reactions in which cleavage of C—X
bond is rate-determining, i.e. nucleophilic substitution. However, we will study certain examples of such reactions that do
take place at reasonable rates either at high temperatures or by mechanisms, distinctly different from the classical S N1 and
SN2 pathways.
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1. Write down all isomers of an aromatic compound of the formula C 7H7Cl. Comment on the C—Cl bond strength of the various
isomers.

9.1 Methods of Preparation

Methods used for the preparation of alkyl halides are not applicable for the synthesis of aryl halides, e.g. alkyl
halides are most readily prepared from the corresponding alcohols ; while aryl halides are not prepared from the
phenols. The reason being the stronger Ar—OH bond in phenols because of partial double bond character of the C—O bond and/
or sp2 hybridization of the carbon bearing —OH group. Important methods are given below.
1. By direct halogenation of arenes. Aryl chlorides and bromides are conveniently prepared by treating the corresponding
arene with chlorine (or bromine) at low temperature and in the presence of halogen carrier (Fe, FeCl3, AlX3 etc.). The
reaction is an example of electrophilic aromatic substitution and has already been discussed.

Cl Cl Cl
Cl
Fe Fe/Cl
2
+ Cl2 ¾¾® ¾¾¾® +

Cl
NOTE THAT

(i) fluorination is difficult to control.

(ii) iodination is too slow to be useful.

2. By the decomposition of diazonium salts. Arene diazonium salts are obtained by treating aromatic amines with
nitrous acid at 0—5°C. The diazonium salts decompose easily on heating with cuprous chloride or cuprous
bromide in presence of haloge acids to form the corresponding chloride or bromide (Sandmeyer reaction).

HONO CuCl
Ar—NH2 ¾¾¾¾® Ar—N2+ ¾¾¾® Ar—Cl or Ar—Br
0° C or CuBr

Aryl fluorides are obtained by treating the diazonium salt with fluoroboric acid (HBF4) or its salt by to form
sparingly soluble arenediazonium fluoroborate. The solid so obtained is carefully heated after drying to form
aryl flouride (Balz-Schiemann reaction).
heat
Ar—N2+X– + HBF4 ¾¾® Ar—N2+BF4– ¾¾¾ ® Ar—F + N2 + BF3
Aryl iodides are obtained by treating the diazonium salt with aqueous potassium iodie.
Ar—N2+X– + KI ¾¾® Ar—I + N2 + KX
NOTE

Preparation of aryl halides from diazonium salts is more important than direct halogenation of arenes due to
following reasons.
(i) Fluorides and iodides can be easily prepared.
(ii) Halogenation gives a mixture of ortho and para isomers which are difficult to separate, while it is not so in
method involving diazonium salt.

3. Hunsdiecker method. Silver salts of aromatic acids are heated with chlorine or bromine.
C6H5COOAg + Cl2 ¾¾® C6H5Cl + CO2 + AgCl
CuCl
4. Industrial method for chlorobenzene. 2C6H6 + 2HCl (g) + O2 (air) ¾¾¾¾
heat
2®
2C6H5Cl + 2H2O
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1. Give steps invovled in the preparation of o-nitrochlorobenzene and p-nitrochlorobenzene from benzene.

9.2 Physical Properties

(i) Aryl halides resemble alkyl halides in many of their physical properties like insolubility in water and denser
than water. Insolubility in water is due to their incapability of forming hydrogen bonds.
(ii) Aryl halides are less polar than alkyl halides because in
aryl halides, halogen is present on sp2 hybridised carbon —Cl —Cl
which is more electronegative than the sp3 hybridised carbon
Chlorobenzene Chlorocyclohexane
of alkyl halides or halocyclohexane. Consequently, the (C—Cl bond is less polar (C—Cl bond is more polar
electronegativity difference between C and Cl is low in aryl and shorter in length) and longer in length)
m = 1.7 D m = 2.2 D
halides than in alkyl halides.
Further due to possibility of resonance in chlorobenzene, the C—Cl bond becomes shorter and hence dipole
moment of chlorobenzene is less than that of chlorcyclohexane.
(iii) The isomeric dihalobenzenes have nearly the same boiling points, yet the melting points of the isomers show a
considerable difference, the para isomer has 70—100°C higher melting poing than the ortho and meta isomers.
This is due to the fact that the para isomers, being symmetrical, are better packed in the crystal lattice. This
explains why only the para isomer crystallises on cooling a solution containing ortho and para isomers. Further,
due to strong intracrystalline forces, the higher-metling para isomer is less soluble in a given solvent than the
ortho isomer.

9.3 Chemical Properties

1. Formation of organometallic compounds. Aryl halides react with magnesium in presence of dry ether to form
the corresponding arylmagnesium halides (Grignard reagents).
ether
ArX + Mg ¾¾¾ ® Ar MgX
Aryl iodides are the most reactive, while aryl fluorides the least.
Remember that (a) ArX is less reactive than RX in forming Grignard reagents, and (b) tetrahydrofuran is used as
a solvent for ArCl.
Aryllithiums are obtained by treating an ethereal solution of aryl halides with lithium metal.
ether
C6 H 5 X + 2Li ¾¾¾ ® C6H5Li + LiX
(X = Cl, Br)

ether
C6H5X + 2Li ¾¾¾® LiX + C6 H5 : Li ¬¾¾® C6H5– : Li+
Phenyllithium

Aryllithium compounds may also be obtained by the halogen-metal exchange when aryl halides are treated
with n-butyllithium.

Br Li

+ n-C4H9Li ¾¾® + n-C4H9Br

Cl Cl
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2. Wurtz-Fittig and Fittig reactions.
ether
(a) C6H5X + 2Na + XC2H5 ¾¾¾ ® C6H5C2H5 + 2NaX
ether
C6H5Cl + 2Na + ClCH2C6H5 ¾¾¾ ® C6 H 5 CH 2 C 6 H 5 + 2NaCl
Diphenylmethane

ether
(b) C6H5Cl + 2Na + ClC6H5 ¾¾¾¾¾¾®
Fittig reaction
C 6 H 5 C 6 H 5 + 2NaCl
Diphenyl

3. Ullmann reaction.
heat in a
2C6H5I + 2Cu ¾¾¾¾¾® C6H5C6H5 + 2CuI
sealed tube

Aryl chlorides and bromides respond Ullmann reaction only when an electron-withdrawing group is present in
ortho or para position.

NO2 NO2
NO2
heat
2 —Cl + 2Cu ¾¾® + 2CuCl

4. Reaction with chloral. When chlorobenzene is heated with chloral in presence of conc. H2SO4, a powerful
insecticide DDT (p, p¢-dichlorodiphenyl trichloromethane).

Cl—
Conc. H SO
2 4
+ OHCCCl3 ¾¾¾¾¾® Cl—
Chloral
Cl— CHCCl3

Chlorobenzene Cl—

D.D.T.

IUPAC name of DDT is 2, 2'-bis (p-chlorophenyl)1, 1, 1-trichloroethane.

5. Electrophilic aromatic substitution. Aryl halides undergo the typical electrophilic substitution reactions in
the ortho and para-positions, though less readily than benzene because halogens deactivate the benzene nucleus
due to its high electro-negativity. However, inspite of deactivating nature, halogens are o, p-directing due to + M
and + E effects (difference from other o, p-directing groups which are activating). Its mechanism has already been
discussed.
6. Reactions of the side chain of aryl halides. Side chain, if present, may undergo (i) halogenation in presence of
light (free radical substitution), and (ii) oxidation.

Cl Cl Cl
COOH CH2R CHClR
KMnO4 Cl2
¬¾¾¾ ¾¾¾¾¾¾®
in hot and light

9.4. Nucleophilic Aromatic Substitution

Aromatic nucleophilic substitution are those reactions in which a leaving group is displaced along with its
bonding electrons from a ring carbon atom by a nucleophile.

X Nu

+ Nu ¾¾® + X
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However, aryl halides (like vinyl halides) do not undergo nucleophilic substitutions under ordinary conditions
(difference from alkyl halides which undergo these reactions very easily). For example, aryl halides (e.g. chlorobenzene) do
not react with nucleophiles like OH–, OR–, NH3, CN– etc. Under ordinary conditions, low reactivity or inert nature of aryl
halides towards nucleophilic substitution is due to the fact that the non-bonding pair of electrons on the halogen are in
conjugation with the ring causing resonance stabilisation of the compound by delocalisation of electrons.

: Cl : : Cl : Cl : Cl : Cl :

:
¬¾® ¬¾® ¬¾® ¬¾®

I II III IV V
Resonance stabilization of chlorobenzene

¬¾® H2C—CH = Cl

: :
H2C = CH—Cl
: :

:
VI VII
Resonance stabilisation of vinyl chloride

1. Which halogen best delocalizes electron density to the benzene ring ?

Possibility of resonance in aryl halides and vinyl halides produces following important results.
(a) Stabilisation of the molecule by delocalisation of electrons.
(b) The carbon-halogen bond acquires double bond character (structures III, IV, V and VII) and thus becomes shorter
and stronger than a single bond present between carbon-halogen in alkyl halides. Both these factors reduce
reactivity of the halogen.
Low reactivity of aryl halides and vinyl halides than alkyl halides can alternatively be interpreted in terms of
hybridisation of the carbon atom bearing halogen. In alkyl halides, the carbon hearing halogen is sp3-hybridised. In aryl
and vinyl halides, carbon is sp2-hybridised ; and thus the carbon-halogen bond is shorter (due to more electronegative
nature of sp2 carbon than that of sp3) and stronger. Thus halogen derivatives can be categorised in two main groups on the
basis of reactivity of the halogen atom.
(i) Those in which halogen is present on sp3-hybridised carbon atom, such halogens are highly reactive. For example,

CH2—X :
: :
: :

: :

R—CH2—X : H2C = CH—CH2—X:

Alkyl halides Aryl substituted Allyl halides
alkyl halides

(ii) Those in which halogen is present on sp2-hybridised carbon atom, such halogens are relatively inert. For example,
:

: X: CH3
: :

X:

H2C = CH—X :
: :

Aryl halides Vinyl halides

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+
However, aryl halides having electron-attracting substituents* (like —NO2, —CN, — N Me3, —SO3H, —COOH, —
CHO, —COR), in ortho and para positions undergo nucleophilic substitution very easily. Further, greater the number of
such groups in o-and p-positions, more rapid is the reaction and less vigorous conditions are needed. For example,

Cl OH Cl OH
7% NaOH, 350°C 15% NaOH, 160°C
¾¾¾¾¾¾¾® ; ¾¾¾¾¾¾¾®
Pressure

NO2 NO2

Cl OH
Cl OH O2N NO2 O2N NO2
H2O, Warm
NO2 Na2 CO3, 130°C NO2 ¾¾¾¾¾®
¾¾¾¾¾¾®
;
NO2 NO2
NO2 NO2 2, 4, 6-Trinitrophenol (Picric acid)
2, 4, 6-Trinitrochlorobenzene

Similar effects are observed when other nucleophilic reagents e.g. NH3, CH3ONa are used.

Cl NH2 Cl NH2
NH3, Cu2O
NO2 NH3, 170°C NO2
¾¾¾¾¾¾® ; ¾¾¾¾¾®
200°C, pressure
NO2 NO2
Thus the relative rate of nucleophilic substitution for the various chlorobenzenes is

Cl Cl Cl Cl
NO2 O2N NO2
< < <
NO2 NO2 NO2
Since electron-withdrawing groups activate toward nucleophilic substitution, electron-releasing groups
deactivate, the various groups can be categorised in three groups for nucleophilic substitution.
(i) Strongly electron-releasing groups, —NH2 and —OH deactivate strongly.
(ii) Moderately electron-releasing groups, e.g. —OR deactivate moderately.
(iii) Weakly electron-releasing groups (like —R group) deactivate moderately.
Relative reactivity of halogens toward nucleophilic substitution. In contrast to nucleophilic substitution in
alkyl halides, where alkyl fluorides are exceedingly unreactive, aryl fluorides undergo nucleophilic substitution readily
when the ring bears an o- or p-nitro group.

F OCH3
NO2 CH3OH NO2
+ KOCH3 ¾¾¾® + KF
85°C

NO2 NO2
1-Fluoro-2,4-dinitrobenzene
(Sanger’s reagent)

Indeed, the order of leaving-group reactivity in nucleophilic substitution is opposite to that observed in aliphatic
substitution; in aromatic nucleophilic substitution fluoride is the most reactive and iodide the least.
Ar—F > Ar—Cl > Ar—Br > Ar—I (Relative reactivity of halogens in SN2Ar).
The unusually high reactivity of aryl fluorides (although having a strong C—F bond) is due to very high
electronegativity of fluorine due to which it can disperse the negative charge of the intermediate carbanion most easily
leading to increased rate of formation of the intermediate carbanion (see mechanism discussed just after this).
Mechanism. Nucleophilic aromatic substitution takes place by two mechanisms (i) Bimolecular mechanism is
applicable to reaction of aryl halides, having electron withdrawing group, with the usual nucleophiles like NaOH,
CH3ONa etc. (ii) Benzyne mechanism is applicable when aryl halides are treated with strong base like NH2– or with usual
nucleophiles like NaOH, NH3, CH3ONa etc. under drastic conditions.

* Note that all these groups are deactivating and meta-directing towards electrophilic substitution.
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9.4.1 Bimolecular Displacement Mechanism (Addition-Elimination Mechanism)

It has two steps.
(i) Addition of nucleophile (slow step). Resonating structures III, IV and V of chlorobenzene indicate that C1, C3 and
C5 are relatively electron-deficient. Further among these three, C1 is most electron-deficient because it has strongly
electron-withdrawing group. Hence the nucleophile will undoubtedly attack on C1 to form carbanion.
Cl Z Cl Z Cl Z Cl
Z: H H
+ :
slow
¾¾® ¬¾® ¬¾® :

:
H
A resonance stabilised cyclohexadienyl carbanion

(ii) Expulsion of halide ion from the carbanion (fast step) to form the product, having a stable benzenoid nucleus.

Z Z
Cl

fast
– ¾¾®

: :
+ :Cl:

Comparison of intermediate in biomolecular

nucleophilic aliphatic substitution (S N 2) and Z Cl
bimolecular nucleophilic aromatic substitution
d– d–
(SN2Ar). Recall that in aliphatic SN 2 reactions, Z C Cl –
there is no intermediate, actually a transition state
is formed in which a carbon bonded to five atoms Transition state in aliphatic SN2 Intermediate in aromatic
is present which is unstable. On the other hand, (Note the pentavalent carbon) nucleophilic substitution
in nucleophilic aromatic substitution, the (Note the tetrahedral carbon)

intermediate is an actual compound which is quite stable because of delocalization of the negative charge.

1. Compare bimolecular aromatic nucleophilic and electrophilic substitution reactions with aliphatic SN2 reactions in terms of (a)
number of steps and transition states, (b) character of intermediates.

Effect of substituents on nucleophilic aromatic substitution (Relative reactivity in nucleophilic aromatic

substitution).
We have seen that in SNAr (aromatic nucleophilic substitution) reactions, a carbanion is formed as an intermediate,
so any substituent that increases the stability of the intermediate carbanion and hence the transition state leading to its
formation will enhance the SNAr reaction.
To compare the rates of substitution in chlorobenzene, chlorobenzene having electron-withdrawing group, and
chlorobenzene having electron-releasing group, we compare the structures carbanion I (from chlorobenzene), II (from
chlorobenzene containing electron-withdrawing group) and III (from chlorobenzene containing electron-releasing group).

Z Cl Z Cl Z Cl

– – –

I
G G
II III
G withdraws electrons, neutralises G releases electrons, intensifies
(disperses) –ve charge of the ring, –ve charge, destabilizes carbanion,
stabilises carbanion, facilitates SN retards SN reaction (deactivation)
reaction ( activation effect)
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Common groups that activate SN Ar reactions are —NMe3+, —NO2, —CN, —SO3H, —COOH, —CHO, —COR
and —X ; while the corresponding deactivating groups are —NH2, —OH, —OR and —R. Note that SN Ar activating
groups are deactivating groups for electrophilic aromatic substitution, while the S N Ar deactivating groups act as activating
groups for electrophilic aromatic substitution.
Ortho- and para-Nitrochlorobenzenes are more reactive than the m-isomer. This is again due to more stability
of the intermediate carbanion from o- and p- than that from meta.

Z Cl Z Cl Z Cl
Resonating structures of the
¬¾® ¬¾® intermediate carbanion from
the p-isomer

NO2 NO2 NO2

Especially stable (because –ve charge
on C bearing —NO2 is neutralised most)

Z Cl Z Cl Z Cl
NO2 NO2 NO2
¬¾® ¬¾® From the o-isomer

Especially stable
(–ve charge on C
bearing —NO2 group)

Z Cl Z Cl Z Cl

¬¾® ¬¾® From the m -isomer

NO2 NO2 NO2

Similarly, we can see that deactivation by an electron-releasing group is strongest when it is ortho or para to the
halogen.
The activating effect of a number of electron-withdrawing groups (like —NO2, —CN, —COOH, —COR, —NO
etc.) toward nucleophilic substitution can also be accounted by resonance, this is in addition to explanation by inductive
effect. For example, the intermediate carbanions from p-and o-isomer are especially stable due to structures II and IV respectively
than that from the m-chloronitrobenzene or chlorobenzene itself.

– –
Z Cl Z Cl Z Cl O Z Cl +
O
+
– N N
–
¬¾® ; O ¬¾® O
–
+ +
N N

–O O –O O–
I II III IV
Especially stable (oxygen Especially stable
readily accommodates
negative charge)

1. Write resonance structures to account for activation in SN2Ar from delocalization of the charge of the intermediate carbanion by —
CN and —NO groups present in para-position.
2. Nitrosogroup, —NO activates ortho and para positions toward nucleophilic as well as electrophilic aromatic substitution. Explain.
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Comparision of SN1, SN2 (observed in R—X) and SN2 (observed in Ar—X).
(i) In SN1, the leaving group departs the molecule before the entering group, thus a full positive charge is developed
on carbon. Hence such reactions are favoured by electron release.
(ii) In alkyl SN2, the leaving group and entering group departs and enters respectively simultaneously and thus no
charge develops on carbon. Hence these reactions are insensitive to electronic factors.
(iii) In Ar SN2, the leaving group departs the molecule in the last and thus a negative charge is developed on the
molecule. Hence such reactions are favoured by electron withdrawal
:Z
+ ¾¾®
R—X ¾¾¾¾
– ® R R—Z SN1
(– X )

:Z
R—X ¾¾® [d– Z------R------Xd–] ¾¾® R—Z + X– SN2

Z X Z
X
:Z – – SN2Ar
¾¾® ¾¾® + X

9.4.2 Benzyne Mechanism (Elimination-Addition Mechanism)

Unactivated aryl halides (aryl halides not having electron- Cl KNH2 NH2
withdrawing group) when treated with strongly basic nucleophiles, such ¾¾¾¾®
liq. NH3
as amide ion or with usual nucleophiles under drastic conditions undergo
substitution by an elimination-addition (benzyne) mechanism. Chlorobenzene Aniline
The most important requirement for this mechanism is the presence of an ortho hydrogen atom. The reaction is
initiated by a two-step elimination of HX generating a highly reactive intermediate called benzyne (dehydrobenzene)
which then readily reacts with nucleophile to regenerate aromatic system.
Elimination step.

Cl Cl
–
+ :NH2 ¾¾¾® ¾¾® + Cl
(—NH3) :
H
Carbanion Benzyne

Addition step.

NH2 NH2
NH3 (solvent) –
+ :NH2 ¾¾® ¾¾¾¾¾® + NH2
:
Carbanion

The above mechanism involving benzyne intermediate is proved by isotopic method. Labelled chlorobenzene (a
chlorobenzene molecule in which carbon bearing chlorine is labelled i.e. it is C14 carbon), when treated with amide ion,
two different anilines are formed nearly in equal amounts : (i) aniline having —NH2 group on the usual carbon (C12) and
(ii) aniline having —NH2 group on the labelled carbon (C14).

NH2
*

14
Aniline having C –NH2
Cl
* –
NH2 *
NH3

Chlorobenzene Benzyne
14
having C –Cl *

NH2
12
Aniline having C –NH2
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Formation of benzyne as an intermediate also explains why m-chlorotoluene gives all the three isomers (o-, m-
and p-) of methylanilines.
CH3 CH3 CH3
–
NH2
NH2
CH3 ¾® ¾¾® +
NH3
– NH2
NH2 3-Methylbenzyne o-Methylaniline m-Methylaniline
NH3 CH3 CH3 CH3
Cl –
NH2
¾® ¾¾® +
NH3
NH2
NH2
4-Methylbenzyne m-Methylaniline p-Methylaniline

Structure of benzyne. Aromatic compounds related to benzyne are known

as arynes. The triple bond in benzyne is somewhat different from the usual
triple bond of an alkyne. In benzyne, one of the p components of the triple
Degree of overlap
bond is similar to that of other p bonds of benzene, i.e. it is formed by the 2
of the two sp orbitals
p-p-overlap of the two concerned carbon atoms and hence it is a part of the is very poor because
delocalized p system of the aromatic ring. However, the second p bond of they lie in the plane
the triple bond of benzyne is formed from overlapping of two sp2 hybridized of the ring.
orbitals. This p bond lies in the plane of the ring, and does not interact with
the aromatic p system. Since the contributing sp2-orbitals are not oriented
properly for effective overlap, this p bond is relatively weak.
Absence of linearity of the C—C º C—C unit due to benzene ring and weak nature of one of the p bonds of the
triple bond make benzyne a strained and highly reactive species.

1. Explain the following :

(i) When a mixture containing equal amount of bromobenzene and o-deutereobromobenzene is treated with sodamide, the unreacted
mixture contains more amount of o-deutereobromobenzene.
(ii) m-Bromoanisole when treated with sodamide gives mainly m-anisidine.

9.5 Arylalkyl Halides

Arylalkyl halides resemble alkyl halides, in their preparation as well as reactions, rather than aryl halides.

Preparation
1. By direct halogenation with chlorine or bromine in presence of light and in absence of halogen carrier.

CH3 CH2Cl CHCl2 CCl3

Cl2 Cl2
¾¾® ¾¾® ¾¾®
boil
Toluene Benzyl chloride Benzal chloride Benzo trichloride

Recall that side chain halogenation of ethylbenzene and other higher alkylbenzenes gives mainly one isomer.

CH2CH3 CHClCH 3 CH2CH2Cl

Cl2, heat
¾¾¾¾® +
light
1-Chloro-1-phenyl- 2-Chloro-1-phenyl-
ethane (91%) ethane (9%)
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This is due to more stability of the corresponding (benzyl) radical

CHCH3 CH2CH2

Benzyl radical (More stable) b-Phenylethyl radical (1°)

(due to delocalisation of odd electron)

Note that although chlorination of ethylbenzene gives 1-chloro- (major) as well as 2-chloro-(minor) products,
bromination of ethylbenzene gives exclusively 1-bromo-1-phenylethane.

CH2CH3 CHBrCH3

Br2, heat
¾¾¾¾®
light

1-Bromo-1-phenylethane
(only product)

This can be explained on the basis of selectivity reactivity principle. Chlorine, being more reactive, is less selective
and hence gives another product although in less quantity; while bromine, being less reactive, is more selective,
hence will replace more selectively a-hydrogen atom giving exclusively 1-bromo-1-phenylethane.
2. Like alkyl halides (but not aryl halides), arylalkyl halides can be prepared by the action of PCl5 or SOCl2 on
benzyl alcohol.
C6H5CH2OH + PCl5 (or SOCl2) ¾¾® C6H5CH2Cl + HCl + POCl3 (or SO2)
Benzal chloride can directly be prepared by the action of PCl5 on benzaldehyde.
C6H5CHO + PCl5 ¾¾® C6H5CHCl2 + POCl3
Properties. As already mentioned and explained in the beginning, arylalkyl halides, e.g. benzyl chloride, resemble
alkyl halides closely in their chemical properties and thus differ from aryl halides, e.g. chlorobenzene and vinyl halides.
Actually benzyl halides are more reactive than alkyl halides which is due to resonance stabilisation of the benzyl cation.

CH2 CH2 CH2 CH2

¬¾® ¬¾® ¬¾®

Resonating structures of benzyl cation.

Important reactions of benzyl chloride are summarised below.

1. Nucleophilic substitution reactions.

Q
C6H5CH2Cl + : N u ¾¾® C6H5CH2Nu + Cl–

Q
(Where : N u = OH–, NH2–, CN–, OC2H5– etc.)
Benzal chloride and benzotrichloride undergo alkaline hydrolysis to form benzaldehyde and benzoic acid
respectively (industrial methods).
–H O
Ca(OH)2
C6 H 5 CHCl 2 ¾¾¾¾¾ ® C6 H5 CH(OH)2 ¾¾¾¾
2
® C6 H 5 CHO
Benzal chloride Unstable Benzaldehyde

Ca(OH)2 – H 2O
C 6 H 5 CCl 3 ¾¾¾¾¾ ® C6 H5 C(OH)3 ¾¾¾¾ ® C6 H 5 COOH
Benzo trichloride Unstable Benzoic acid
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2. Reaction with certain metals
dry
(i) C6H5CH2Cl + 2Na + ClH2CC6H5 ¾¾¾® C 6 H 5 CH 2 CH 2 C 6 H 5 (Wurtz reaction)
ether Dibenzyl

dry
(ii) C6H5CH2Cl + 2Na + ClC6H5 ¾¾¾® C6H5CH2C6H5 (Wurtz-Fittig reaction)
ether
Dipenylmethane

(iii) C6H5CH2Cl + 2Cu + ClCH2C6H5 ¾¾¾¾¾

-
® C6H5CH2CH2C6H5 (Ullmann reaction)
( Cu2 Cl2 )

THF 2 6 5 ClCH C H
(iv) C6H5CH2Cl + Mg ¾¾¾ ® C6H5CH2MgCl ¾¾¾¾¾¾ ® C 6 H 5 CH 2 CH 2 C 6 H 5
Dibenzyl

Zn/Cu
(v) C6H5CH2Cl + 2[H] ¾¾¾¾¾ ¾
(Reduction)
® C6 H 5 CH 3 + HCl (Reduction)
Toluene

3. Friedel-Craft reaction.
Like alkyl halides, it reacts with benzene to form alkyl-benzenes (difference from chlorobenzene which does not
undergo Friedel-Craft reaction because of unstability of the C6H5+ cation)

CH2C6H5

anhydrous
+ ClCH2C6H5 ¾¾¾¾¾®
AlCl3
Diphenylmethane

4. Aromatic electrophilic substitution reactions.

Due to presence of benzene nucleus, benzyl chloride undergoes electrophilic substitution mainly in the o- and p-
positions, but with significant (10—15%) amount of the m-isomer. Formation of m-isomer is due to the presence
of Cl in —CH2Cl which decreases the electron-releasing power of the parent —CH3 group.

CH2®–Cl CH2Cl CH2Cl CH2Cl

Cl
cold, dark
+ Cl2 ¾¾¾¾¾¾® + +
halogen carrier
Cl
10–15%
Cl
85–90%

Thus we can explain the increased percentage of the m-isomer during electrophilic substitution, with the increase
in number of Cl atoms in the —CH3 group.

Cl
Cl
CH3 CH2®–Cl CH Cl C Cl
Cl

% of m-isomer 2–5% 10–15% 30–35% 60–65%

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5. Halogenation in the side chain.
Halogenation, when carried out in presence of sunlight or UV rays, takes place in the side chain (free-radical
halogenation).

CH2Cl CHCl2 CCl3

high temp. Cl2

+ Cl2 ¾¾¾¾¾® ¾¾¾®
light light

Benzyl chloride Benzal chloride Benzotrichloride

6. Oxidation of the side chain.

On oxidation, the side chain along with the halogen atom is oxidised to either —CHO or —COOH group
depending upon the nature of the oxidising agent.

CHO CH2Cl COOH

Pb(NO3) 2 HNO3
¬¾¾¾¾ ¾¾¾®

Benzaldehyde Benzoic acid

(—Cl lost) (—Cl lost)

Recall that —Cl present on the benzene nucleus is inert to oxidation and hence it will be present in the oxidised
product.

Cl Cl
CH3 COOH
HNO3
¾¾¾®

o-Chlorotoluene o-Chlorobenzoic acid

(—Cl present)

Thus oxidation along with reaction with alcoholic silver nitrate can be used for differentiating between —Cl
present on nucleus and on the side chain.

CH2Cl Cl

alc. AgNO
3 alc.
¾¾¾¾® ; ¾¾¾® No AgCl
AgNO3
(White)
Benzyl chloride Chlorobenzene
(—Cl on side chain, reactive) (—Cl on nucleus inert)
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EXERCISE 9.1 (MCQ - ONE option correct)

1. IUPAC name of DDT is 8. Which of the following will not undergo nucleophilic substitu-
(a) p, p¢-dichlorodiphenyl trichloroethane tion ?
(b) 4, 4¢-dichlorodiphenyl trichloroethane
(c) 2, 2-bis (p-chlorophenyl)-1,1,1-trichloroethane
(d) 2, 2¢-bis (p-chlorophenyl)-1,1,1-trichloroethane.
2. Which of the following statement is true regarding the following
reaction

(a) It is an example of aromatic electrophilic aromatic substi-

tution.
(b) It is an example of aliphatic nucleophilic substitution
(c) Both (a) as well as (b) are true
(d) None of the two is correct.
3. Which of the reaction is not possible ?
AlCl
(i) C6H6 + C2H5Cl ¾ ¾¾¾
3
® C6H5C2H5 + HCl
AlCl
(ii) C6H6 + C6H5Cl ¾ ¾¾¾
3
® C 6H5C6H5 + HCl (a) II, III and IV (b) II and IV
AlCl 3 (c) III and IV (d) only IV
(iii) C6H6 + CH2 = CHCH2Cl ¾ ¾¾¾®
9. Which chlorine is more reactive, in the compound drawn on
C6H5CH2CH = CH2 + HCl
side, toward nucleophilic substitution ?
(a) (ii) and (iii)
(a) Cla (b) Clb
(b) (ii)
(c) Clc (d) all are equal reactive.
(c) (iii)
10. Which of the following carbanion is more stable ?
(d) All the three reactions are possible.
4. Aromatic nucleophilic substitutions are activated by
(a) electron-withdrawal (b) electron-release
(c) by both (a) and (b) (d) no definite relation.
5. Arrange the following compounds in decreasing order of their (a) (b)
reactivity with sodium methoxide in methanol at 50°C.

(c) Both are equally stable

(d) Neither of the two is possible.
11. Which of the following is an example of nucleophilic aromatic
substitution ?

NO NO
(a) II > III > IV > I (b) II » IV > III > I
(c) II » III > I > IV (d) II » IV » III > I. + KOH(aq) ¾¾ ® + Me2NH
(a)
6. Reaction of chlorobenzene with sodamide in presence of liquid
NMe 2 OH
ammonia involves the formation of

(a) (b)
(b)

(c) (d) All the three.

(c)
7. Benzyne has four p bonds, how many of them are identical ?
(a) 2 (b) 3
(c) 4 (d) None of the four. (d) All the three.
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12. Which of the reactions can form benzyne ? 17. Chlorobenzene can be prepared by reacting aniline with

(a) hydrochloric acid

I. (b) cuprous chloride

(c) chlorine in presence of anhydrous aluminium chloride

Br (d) nitrous acid followed by heating with cuprous chloride

THF
II. + Mg 18. Benzyl chloride (C6H5CH2Cl) can be prepared from toluene by
heat
F chlorination with

(a) SO 2 Cl2 (b) SOCl2

Br
+ Li (c) Cl2 (d) NaOCl
III.
F
Cl
(a) I (b) II and III
19. HNO3 Cl2 NH2NH2
(A) (B) (C)
(c) All the three (d) None of the above. H2SO4 FeCl3, D

13. In the reaction of p-chlorotoluene with KNH2 in liquid NH3, the

major product is (C) is :
(a) o-toluidine (b) m-toluidine

(c) p-toluidine (d) p-chloroaniline. NO2 NO2

14. Which of the following statement is true regarding the reaction
(a) (b)
of 2, 6-dimethylchlorobenzene with aqueous NaOH ?
Cl NHNH2
(a) It reacts only at high temperature NHNH2 Cl
(b) It does not react even at high temperature because it has
two electron-withdrawing groups.

(c) It does not react even at high temperature because it has NO2 NO2
no ortho hydrogen.

(d) None of the above is correct. (c) (d)

NH NHNH2
15. Which of the following method should be used for preparing NH NHNH2
ethylphenyl ether ?

I. C6H5Cl + CH3CH2ONa ¾¾® C 6H5OCH2CH3

20. When p-chlorotoluene is treated with amide ion in liquid NH3,
II. C6H5ONa + CH3CH2Br ¾¾® C 6H5OCH2CH3 the major product is
(a) Method I (b) Method II
(a) p-toluidine (b) m-toluidine
(c) Both (d) None.
(c) o-toluidine (d) N-methylaniline
16. o-Chlorotoluidine can undergo
21. An aromatic compound has molecular formula C7H7Br. Give the
(i) electrophilic aromatic substitution
possible isomers and the appropriate method to distinguish them.
(ii) nucleophilic aromatic substitution
(a) 3 isomers; by heating with AgNO3 solution
(iii) nucleophilic aliphatic substitution
(b) 4 isomers; by treating with AgNO3 solution
(iv) free radical substitution
(c) 4 isomers; by oxidation
(a) only (i) (b) (i) and (iv)

(c) (i), (ii) and (iv) (d) all the four. (d) 5 isomers; by oxidation
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22. The major product of the following reaction is 24. When m-chloronitrobenzene is treated with sodamide in presene
of liquid ammonia, main product is

Me Br (a) o-Nitroaniline (b) p-Nitroaniline

F (c) m - Nitroaniline (d) All the above

Q Å 25. Which of the following statement is true re garding
Ph S Na
¾¾¾¾¾¾¾
dimethylformamide
® benzyne ?

NO2 (a) It has one type of p bonds

(b) It has two types of p bonds ; one is formed by the overlap
of p - p orbitals and other by sp2 - p
Me SPh Me SPh
(c) It has two types of p bonds ; one is formed by the overlap of
F F p - p orbitals and other by sp2 - sp2
(d) It does not have benzene ring
(a) (b)
26. Predict the product, if any, for the following reaction
NO2 NO2
Cl
Br Cl –
Me Me SPh aq. OH
Product
SPh SPh
Cl
(c) (d)

NO2 NO2
OH Cl
Cl OH
14 Cl
23. + NaOH(aq.) 400ºC
Product is (a) (b)

Cl Cl

14 14 OH
(a) (b) Cl
OH Cl

(c) Both (d) No reaction (c) (d) No reaction

OH

EXERCISE 9.2

3. Aryl halides are less reactive towards nucleophilic substitution

DIRECTIONS for Q. 1 to Q. 9 : Multiple choice questions with one
reaction as compared to alkyl halides due to :
or more than one correct option(s).
(a) The formation of less stable carbonium ion
3 3 HNO / AgNO (b) Resonance stabilization
1. Organic compound A ¾¾¾¾¾¾¾ ® white ppt. A can be :
(c) Longer carbon-halogen bond
(a) NH4Cl (b) Cl (d) sp2 hybridized carbon attached to the halogen.

A
4. —Cl ¾¾®
(c) Cl (d) CH2Cl

A can be :
2. Which of the following give (gives) white precipitate when boiled
with alcoholic silver nitrate? (a) NH3
(a) Chlorobenzene (b) alcoholic KOH
(b) Benzyl chloride
(c) Et3 N
(c) Alkyl chloride
(d) KNH2
(d) Vinyl chloride
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NH2 NH2
Me
.. NO2
NO2
5. N NaOH
A
D (a) (b)
H2N O2N NO2
Br OH
NO2 NH2
H2SO4/D

NO2 NO2
B
H2N NH2 H2N NH2
Which of the following is/are correct? (c) (d)
NO2
Me NO2
NO2 ..
(a) Product A is N 9. p-Chlorotoluene when treated with strong NaOH at 340°C gives
(a) o-cresol (b) m-cresol
OH OH
(c) p-cresol (d) All of these

O
NO2 INSTRUCTION for Q. 10 to 15 : Read the passages given below and
(b) Product B is NH answer the questions that follow.
Br Me

(c) Product A is formed by aromatic nucleophilic substitution PASSAGE 1

There are two (A and B) chlorine containing organic compounds; one of
reaction
which (A) does not react with aqueous NaOH, while the second (B)
NH Me easily reacts with sodium hydroxide. Compound (B) can be easily
NO2
obtained by treating compound (A) with a mixture of conc. HNO3 and
(d) Product B is O H2SO4 . compound (B) is a useful intermediate in the synthesis of
Br picric acid (2,4,6- trinitrophenol).
6. Aryl halides are less reactive towards nucleophilic substitution
reaction as compared to alkyl halides due to : 10. Compound A can be
(a) C6H5Cl (b) C6H5CH2Cl
(a) The formation of less stable carbonium ion
(c) CH2 = CHCH2CH2Cl (d) o-CH3C6 H4Cl
(b) Resonance stabilization
11. Compound B can most likely to be
(c) Longer carbon-halogen bond
Cl Cl
(d) The inductive effect
(e) sp2 hybridized carbon attached to the halogen. NO2
(a) (b)
7. Which of the following statement is false regarding following
NO2
reaction ?
Cl
Cl NO2
1 NO2
6 2 heat
+ NH3 pressure (c) (d) Any of the three
5 3
4
NO2
Cl
12. Reaction of 2,4- dinitrochlorobenzene with aquous NaOH to from
(a) No reaction is possible because —Cl is present on benzene 2, 4-dinitrophenol is an example of
ring. (a) SN1 (b) SN2
(c) Ar SN2 (d) benzyne
(b) A nucleophilic substitution will take place in which both
—Cl will be replaced by two —NH2 groups. PASSAGE 2
(c) A nucleophilic substitution will take place in which only Although chlorobenzene is inert to nucleophilic substitution, it gives
—Cl attached on C1 will be replaced by —NH2. quantitative yield of phenol when heated with aq. NaOH at high
(d) A nucleophilic substitution will take place in which only temperature and under high pressure. Phenol, so formed, is a weaker
—Cl attached on C4 will be replaced by —NH2. acid than the carboxylic acid; hence it dissolves only in strong bases like
NaOH, but not weak like NaHCO3. It reacts with acid chlorides and
8. Identify the final possible product(s) in the following series of
acid anhydrides in the absence of AlCl3 to form esters. As far as
reactions.
electrophilic substitution in phenol is concerned, the –OH is an activating
Cl group, hence its presence enhances the electrophilic substitution in the
o- and p-positions.
HNO3 + H 2SO4 NH Condensation with formaldehyde is one of the important property of
C6 H 2Cl 2 N 2 O 4 ¾¾¾¾ 3
140° C
® C6 H 6 N 4 O 4
phenol. The condensation may take place in presence of acids or alkalis
120° C
Cl and leads to the formation of bakelite, an important industrial polymer.
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13. Phenol undergoes electrophilic substitution more readily than
benzene because Instructions for Q. 18 to 23 : Following questions are Assertion and
(a) the intermediate carbocation is a resonance hybrid of more Reasoning Type Questions :
resonanting structures than that from benzene Note : Each question contains STATEMENT-1 (Assertion) and
STATEMENT-2 (Reason). Each question has 5 choices (a), (b), (c),
(b) the intermediate is more stable as it has positive charge on
(d) and (e) out of which ONLY ONE is correct.
oxygen, which can be better accommodated than on carbon
(a) Statement-1 is True, Statement-2 is True; Statement-2 is a
(c) in one of the canonical structures, every atom (except correct explanation for Statement-1.
hydrogen) has complete octet (b) Statement-1 is True, Statement-2 is True; Statement-2 is
(d) the –OH group is o, p–directing which like all other o,p- NOT a correct explanation for Statement-1.
directing groups is activating (c) Statement -1 is True, Statement-2 is False.
14. Phenol undergoes electrophilic substitution more readily in presence (d) Statement -1 is False, Statement-2 is True.
of alkali than the phenol itself because (e) Statement -1 is False, Statement-2 is False.
(a) of the formation of a more stable carbocation as an
intermediate 18. Statement 1 : The dipole moment of chlorobenzene is lower
(b) of the formation of a more stable carbanion as an than that of cyclohexyl chloride.
intermediate Statement 2 : Benzene molecule (or ring) is flat (planar) with
all carbon and hydrogen atoms lying in the same plane while in
(c) of the formation of a more stable neutral intermediate
cyclohexyl chloride the ring of cyclo hexane is not planar.
(d) in presence of alkali, a stronger electrophile is produced 19. Statement 1 : Benzyl bromide when kept in acetone it produces
15. Condensation of phenol with formaldehyde is an electrophilic benzyl alcohol.
substitution, in which Statement 2 : The reaction follows S 2 mechanism.
N
(a) CH2 = O as such is the electrophile in both acidic as well as
20. Statement 1 : The presence of nitro group facilitates
basic medium nucleophilic substitution reactions in aryl halides.
(b) CH2 = O is the real electrophile in acidic medium while in Statement 2 : The intermediate carbanion is stabilized due to
+
basic medium C H 2 - O - is the real electrophile the presence of nitro group.
+ 21. Statement-1 : Bromobenzene upon reaction with Br2/Fe gives
(c) CH 2 = O H and CH2 = O are the electrophiles in acidic and 1,4-dibromobenzene as the major product.
basic medium respectively. Statement-2 : In bromobenzene, the inductive effect of the
+ bromo group is more dominant than the mesomeric effect in
(d) CH2 = O and C H 2 - O - are the electrophiles in acidic and
directing the incoming electrophile.
basic medium respectively. 22. Statement-1 : Aryl halides undergo nucleophilic substitution
with ease.
Statement-2 : Carbon-halogen bond in aryl halides has partial
double bond character.
Instructions for Q. 16 to 17 : Following questions are Multiple 23. Statement-1 : 4-Nitrochlorobenzene undergoes nucleophilic
Matching type Questions : substitution more readily than chlorobenzene.
Statement-2 : Chlorobenzene undergoes nucleophilic
substitution by elimination-addition mechanism while 4-
16. Column I Column II
nitrochlorobenzene undergoes nucleophilic substitution by
(A) CH2 = CH CN (a) Electophilic addition addition-elimination mechanism.
(B) CH2 = CHCH2Cl (b) Nucleophilic substitution

(C) (c) Electrophilic substitution Instructions for Q. 24 to 26 : Following questions are Integer Type
Cl Questions :

(D) CH = CH2 (d) Nucleophilic addition 24. How many of the following compounds will give white
precipitate with aqueous AgNO3.
17. Column I Column II
(A) C 6 H 5 Cl + NaNH 2 (a) Addition-elimination
mechanism
Cl Cl
Cl Cl
(B) + NaOH (b) Elimination-addition Cl O

NO2
mechanism
Cl Cl
Ph Ph
(C) C6H5CHCl2 can be (c) C6 H5CH3 Cl
Ph — C — C — Ph
prepared
Cl OH Cl
O2N 25. IUPAC name of DDT is 2,2-bis (p-chlorophenyl)-1,1,1-
NO2
trichloroethane. How many reactive chlorine atoms are there in
(D) (d) C6H5CHO the compound?
26. How many methylanilines are formed when 3
NO2
methylchlorobenzene is treated with sodamide in liquid ammonia.
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EXERCISE 9.3 (Subjective Problems)

1. Give structures and names of products of the reaction (if any)

when bromobenzene is treated with
(i) hot 50% aqueous NaOH (ii) Cl2 and Fe
(iii) boiling alcoholic KOH (iv) sodium ethoxide
(v) fuming sulphuric acid (vi) boiling aq. NaCN (i)
(vii) I2 and Fe (viii) C6H6 and AlCl3
(ix) CH3CH2Cl and AlCl3 (x) NH3, copper powder
(xi) Cu at 200°C (xii) sodium acetylide.
2. (a) Identify (A) to (J) in the following reactions.

(i) A (ii)

3. Give the main product(s) obtained in each of the following

reactions.
(i) 2, 3-Dibromopropene with aq NaOH
(ii) B (ii) p-Bromobenzyl bromide with aq. ammonia
(iii) 3, 4, 5-Trichloronitrobenzene with one mol of sod.
methoxide
(iv) p-Bromochlorobenzene with magnesium in presence of
ether
(v) a-[o-chlorophenyl) ethyl bromide with alcoholic KOH
(iii) C (vi) p-Bromotoluene with one mol of chlorine on heating
(vii) o-Bromobenzotrifluoride with sodamide in liq. NH3
(viii) 2, 3, 4, 5, 6-Pentadeutereobromobenzene with sodamide
CF3 in liq. ammonia.
Cl 4. Give necessary steps involved in each of the following conver-
NaNH2/Liq. NH3 D
(iv) (Major) sions.
(i) Toluene to m-bromobenzoic acid
(ii) Toluene to p-bromobenzoic acid
(iii) Benzene to 3, 4-dibromonitrobenzene
(iv) Benzene to 2, 4-dinitroaniline
(v) Benzene to p-bromostyrene.
E
(v) (Major) 5. Categorise the following organic halides
Bromobenzene, tert-butyl bromide, n-hexyl chloride, n-hexyl io-
dide, benzyl bromide, sec-butyl chloride and carbon tetrachlo-
ride
towards their reaction with alcoholic silver nitrate in either of
the three groups.
(vi) F (a) Those which react rapidly at room temperature
(b) Those which react readily only when heated
(c) Those which are inert even to hot alcoholic silver nitrate.
6. Arrange the compound in each set in order of reactivity toward
the indicated reagent.
(i) Chlorobenzene, 3-chloronitrobenzene, 2-nitrochloro-
(vii) G benzene, 2, 4-dinitrochlorobenzene, and 2, 4, 6-
trinitrochlorobenzene toward NaOH
(ii) Benzyl chloride, chlorobenzene and ethyl chloride toward
KCN
(viii) H (iii) 2, 4-Dinitrochlorobenzene, p-nitrochlorobenzene, m-
nitrochlorobenzene and chlorobenzene toward sodium
ethoxide
(iv) Bromobenzene, p-bromotoluene, p-dibromobenzene, tolu-
ene toward fuming sulphuric acid
(v) 1-Bromobenzene, 3-bromo-1-butene and 4-bromo-1-
(ix) I butene toward alcoholic silver nitrate
(vi) 2-Bromo-1-phenylethene, a-phenylethyl bromide and b-
phenylethyl bromide toward alcoholic silver nitrate.
(b) Write down the various possible products that can be 7. Write the most stable resona nce structure for the
obtained from the following reactions. cyclohexadienyl anion formed by reaction of methoxide ion
with o-fluoronitrobenzene.
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8. Account for the following order of reac tivity toward (iv) Reaction between 2, 4, 6-trinitroanisole with sodium
nucleophiles. ethoxide or between 2, 4, 6-trinitrophenetole with sodium
methoxide gives the same product.
(v) In the preparation of 2, 4-dinitrochlorobenzene from
chlorobenzene, excess of acids is removed by aqueous
NaHCO3 but not by aqueous NaOH.
(vi) When p-iodotoluene is treated with aqueous NaOH at
340°C, a mixture of p-cresol and m-cresol in nearly equal
amounts is obtained. However, at 250°C, the same be-
9. Explain the following : comes slow and yields only p-cresol.
(i) p-Nitrobenzenesulphonic acid can be prepared from the (vii) When o-deuteriofluorobenzene is treated with sodamide
reaction of p-nitrochlorobenzene with NaHSO 3 or Na2SO3 in liquid ammonia it mainly gives fluorobenzene and only
but benzenesulphonic acid can’t be formed from a small amount of aniline. On the other hand, similar
chlorobenzene by this reaction. reaction with o-deuteriobromobenzene mainly gives ani-
(ii) Crude m-dinitrobenzene can be separated from the o- and line.
p-isomers by washing with aqueous sodium sulphite. (viii) A hydrocarbon, C25H20, is formed when one mole each of
(iii) Although amides can be hydrolysed by either aqueous chlorobenzene and Ph3C: – K+ are reacted with a small
acid or aqueous alkali, hydrolysis of p-nitroacetanilide is amount of potasamide in liquid ammonia.
best carried out in acidic solution.

EXERCISE 9.1
1 (c) 6 (d) 11 (d) 16 (c) 21 (c) 26 (a)
2 (c) 7 (b) 12 (c) 17 (d) 22 (a)
3 (b) 8 (d) 13 (c) 18 (c) 23 (c)
4 (a) 9 (a) 14 (c) 19 (a) 24 (c)
5 (b) 10 (a) 15 (b) 20 (a) 25 (c)

1. Observe the structure. It is a derivative of ethane whose one carbon atom is having two p-chlorophenyl groups.
CH3

AlCl3 AlCl
2. + CH3Cl ¾¾¾® ; CH3Cl + C6H6 ¾ ¾¾
¾3
® CH3C6H5 + HCl

In this reaction CH3Cl in presence of AlCl3 is an electrophile, hence the reaction is an electrophilic aromatic substitution. Simultaneously,
benzene is acting as a nucleophile and displaces —Cl along with its bonding electrons from CH 3Cl to form C6H5CH3, hence the reaction
may also be considered an aliphatic nucleophilic substitution in which —Cl is replaced by C 6H5–.
3. Chlorine in C6H5Cl can’t be displaced easily because of strong C—Cl bond nature due to its double bond character due to resonance.
4. Nucleophiles are electron-rich species, and attack electron deficient sites, thus any factor which reduces electron density of benzene
nucleus will activate the ring towards nucleophilic substitution.
5. The reaction is an example of nucleophilic aromatic substitution which involves the formation of carbanion as intermediate. The
carbanion from o- and p-chloronitrobenzenes are more stable than that from the m-isomer which in turn is more stable than that from
chlorobenzene, devoid of electron-withdrawing —NO2 group.
Z Cl Z Cl
NO2
®–
–
No especially stable carbanion is
possible in case of m -isomer.
–
®–

NO2
Especially stable Especially stable
6. Consult benzyne mechanism for nucleophilic substitution.
7. One of the p bonds of the triple bond is formed by overlapping of sp 2-sp 2 hybridised orbitals, hence it will be different from the
remaining three which are formed by p-p overlap.
8. In IV, no hydrogen or deuterium is present in the position ortho to fluorine.
9. Chlorines present in o- and p-positions activate the ring toward nucleophilic substitution ; so Cla which is ortho and para to the other two
chlorines, Clb and Clc, will be most reactive.
10. Methoxy group is electronegative so it can help in dispersing the negative charge, the effect is more pronounced on the carbon atom
adjacent to it.
11. In (a), (b) and (c), —NMe2, —OCH3 and —Cl respectively are the leaving groups while OH–, OH– and SO32–are the corresponding
nucleophiles.
12. Chlorobenzene under drastic conditions undergo nucleophilic substitution via benzyne mechanism. o-Bromofluorobenzene forms
benzyne when treated with Mg or Li.
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507
Br MgBr
Mg
¾¾ ® ¾¾ ® + Mg(F)Br

F F
Br Li
2Li
¾¾ ® ¾¾ ® + LiF

F F
Recall that order of reactivity of aryl halides toward Mg or Li is ARI > ArBr > ArCl > ArF.
13. Following intermediates will be formed in the addition step of NH2– on benzyne.
CH3 CH3 CH3 CH3
¯ ¯
–
:NH
2 NH
¾¾ ¾® or ¾¾ 3®

:
–
:– NH2
Less stable
NH2 NH2
More stable
(because –ve charge
is easily neutralised)
14. With no hydrogen in ortho position to Cl, benzyne formation is not possible.
15. C6H5Cl does not undergo nucleophilic substitution due to stable C — Cl bond, while in C 6H5O–Na +, it is the bond between O and Na
(polar bond) that breaks up easily forming the desired product.
CH2Cl CH3 CH3
Cl Cl Cl
Cl2, heat, light Cl2, FeCl3
16. ¬¾ ¾ ¾¾ ¾ ¾ ¾¾¾¾¾¾®
(free radical (electrophilic
substitution) substitution)

Cl
CH3
NH2
NaNH2
¾¾ ¾ ¾¾ ¾ ¾¾ ®
nucleophilic
arom atic substitution
Cl NO2 NO2 NO2
19.(a) HNO3 Cl2 NH2–NH2
H2SO4 FeCl3, D (SN–Ar)
(Nitration) (Chlorination) Cl
Cl
Cl Cl NHNH2
(A) (B) (C)
Cl NH2 NH2
NH2 NH2 liq. NH3
20.(a)
liq. NH3
–NH2

CH3 CH3 CH3 CH3

(Stable) (p-toluidine)
Br CH3 CH3 CH3
Br
21.(c) , , ,

Br Br
22. (a) The product (a) will be formed.
Nucleophilic substitution of an alkyl halide is easier as compared to that of an aryl halide.
æ O ö
PhS– is a strong nucleophile and dimethyl formamide ç || ÷ is a highly polar aprotic solvent. These reagents favour SN2
è H C NMe 2 ø
reactions at 2° benzylic carbon.
In a SN2 reaction, the major product formed is inversion product.
Me Br Me SPh
F F
PhSNa ∗
¾¾¾¾↑
DMF

NO2 NO2
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14 Cl 14 14 OH 14
–
23.(c) NaOH(aq.) OH
high temp.
+
(–HCl) OH
Benzyne
NO2 NO2 NO2
–
24.(c) or
(–NH3)
Cl
I II
I is more likely to be formed because hydrogen ortho to the –NO 2 group is more acidic than that of para, hence removed. Further I can
form two nitroanilines as explained below.
NO2 NO2 NO2 NO NO 2 2

:– NH2 –
: NH 3 –
or Thus + NH2
:–
NH2 NH2 NH2
I III IV
(more stable)
–ve charge easily
dispersed
25.(c) One of the p bonds in benzyne is formed by the overlap of two sp2 orbitals. This p bond is in place of two s C – H bonds formed by the
overlap of sp2 orbital of C with s orbital of H. Since this additional p bond of the triple bond lies in the plane of the ring and hence does
not interact with the aromatic p system. Thus we can say that benzyne has a benzene nucleus with aromatic sextet and an additional
p bond which does not form a part of the sextet.
26.(a) Although ordinarily chlorine present on benzene nucleus is difficult to be replaced, however if it has electron-withdrawing group in the
o- and p-position it is easily replaced. In the present case Cl (electronegative group) present on C2 and C4 are ortho and para respectively
to Cl present on C1, hence the latter can be replaced by OH–. Note that other two chlorines (at C2 and C4) are meta to one chlorine, so
these are not replaced.
Cl OH
1
2 Cl – Cl
aq. OH

3
4
Cl Cl

EXERCISE 9.2
1 (b, d) 2 (b, c) 3 (b, d) 4 (a, b, c, d) 5 (b, c)
>1 CORRECT OPTION
6 (b, e) 7 (a,c, d) 8 (a, d) 9 (b, c)
PASSAGE 1 10 (a) 11 (c) 12 (d)
PASSAGE 2 13 (c) 14 (c) 15 (c)
MATCH THE 16 (A) - a, d ; (B) - a, b ; (C) - c ; (D) –a, c
FOLLOWING 17 (A) - (b), (B) - (a), (C) - (c, d), (D) - (a)
18 (a) 19 (c) 20 (c)
A/R
21 (c) 22 (d) 23 (b)
INTEGER 24 5 25 3 26 3
6.(b, e) Aryl halides are stable due to resonance stabilization. •• Br ••
The resonating structures
+ + +
Cl Cl Cl

– – (–I effect, + M effect)

However, + M > –I hence halogens are said to be o, p- directing
– (due to + M effect) but deactivating group (due to –I effect)
groups giving mainly p-substituted product.
stabilise the aryl halide. These structures include a double 22.(d) Aryl halides undergo nucleophilic substitution with difficulty.
bond between C and Cl which is shorter and thus stronger 23.(b) Correct explanation : As compared to chlorobenzene, the
than the usual C – Cl single bond. The sp2 hybridised carbon, intermediate carbanion resulting from 4-nitrochlorobenzene
being electronegative, makes the C – Cl bond shorter and is stabilized by –R-effect of the NO2 group.
stronger. AgNO3
24. 5 + AgCl
7.(a,c,d) Recall that the —Cl group present in the o- and p- positions to
the electron-withdrawing group is activated toward
Å
nucleophilic substitution, hence only —Cl present on the o- Cl Antiaromatic
and/or p-position to the —NO2 group will be replaced.
AgNO3
21.(c) When halogen is present directly on the benzene nucleus it + AgCl
produces two opposing effects namely + M (activating effect)
and –I (deactivating) +
Cl (Aromatic)
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509
Ph Ph Ph Ph
AgNO3 AgNO3
+ AgCl Ph – C – C – Ph Ph – C – C – Ph + AgCl
Å
Å OH Cl OH
Cl
O O Ph
AgNO3
Ph – C – C – Ph
Å OH Ph
Cl Aromatic Å

EXERCISE 9.3
1. No reaction in (i), (iii), (iv), (vi), (vii), (viii), (x) and (xii)
(ii) o- and p-BrC6H4Cl (v) o- and p-BrC6H4SO 3H
(ix) o- and p-BrC6H4CH2CH3 (xi) Biphenyl.
CF 3

2. (a) (i) (ii) (iii)

CH3
C (Electrophilic
arom. substitution)
CF 3 CH3
NH2
CH2CN
(iv) (v) (vi)

NH 2
D* (due to E** (due to –
–I effect of CF3) F (CH2CN is better
+ I effect of CH3) –
COOH nucleophile than NH 2 ,
due to resonance)

(vii) (viii) (ix)

G (oxidation
of the side chain)

Note :

CH3 CH3 CH3 CH3 CH 3

NH2
(b) (i) + (ii) + +

NH2 NH2
NH2 NH2
3. (i) CH2 = C ¾ CH2 NaOH
¾ ¾¾¾® CH2= C ¾ CH 2 Recall that allylic halogen is more
| | | | reactive than vinylic
Br Br Br OH

(ii)
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p - Halogen / o - halogen wrt to

(iii) —NO 2 gp. is more reactive
than the m - halogen

(iv) Aryl bromides are more

reactive than ArCl

Benzylic halogen is more

(v) reactive than arylic

In presence of light,
(vi) substitution (free radical)
occurs in the side chain

(vii)

(viii)

4. (i) Toluene to m-bromobenzoic acid. Since the two groups are m- to each other, first we must first introduce m-directing group of
the two groups, i.e., —COOH.

(ii) Toluene to p-bromobenzoic acid. Here the two groups are para to each other, so first group must be introduced in the para
position.

(iii) Benzene to 3, 4-dibromonitrobenzene

(a)

(b)

Note that the route (a) is preferred because, here the entry of the third group (Br) is directed by both the existing groups (Br and NO 2)
in the parent compound.
(iv) Benzene to 2, 4-dinitroaniline

(v) Benzene to p-bromostyrene

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5. The more stable the R+, the more reactive is RX (ArX).
(a) Following compounds react rapidly with alcoholic AgNO 3 at room temperature.
(i) tert-Butyl bromide-due to a stable (3°) R+.
(ii) Benzyl bromide—due to stable C6H5CH2+.
(iii) n-Hexyl iodide—due to weak C—I bond and more insolubility of the AgI formed, although n-hexyl chloride reacts with
alcoholic AgNO3 rapidly only on heating.
(b) Following compounds react readily with alcoholic AgNO 3 only on heating.
(i) sec-Butyl chloride—due to 2° R+ which is less stable than the 3° R+.
(ii) n-Hexyl chloride—although 1° R+, it can go substitution by slower SN2 pathway.
(c) Following compounds do not react at all with alc. AgNO3
(i) Bromobenzene—an aryl halide, Ar+ is very unstable.
(ii) Carbon tetrachloride —CCl3+ is unstable because of electron-withdrawing effect of the three chlorine. Moreover, there is too
much steric hindrance towards SN2 attack.
6. First write down the structure of the various compounds and observe the nature of halogen in each compound.
(i) This is an example of aromatic nucleophilic substitution of the —Cl group which is facilitated by the presence of electron-
withdrawing groups preferably in the o- and p-positions. Further, more the number of such groups, higher will be the reactivity.

(ii) This is an example of nucleophilic substitution which follows the order.

C6 H 5CH 2Cl > CH 3CH 2Cl > C6 H 5Cl
Benzylic chlorine 1° Chlorine Arylic chlorine
(iii) Same as above.

(iv) This is an example of aromatic electrophilic substitution which is facilitated by the presence of electron-releasing groups and
retarded by electron-withdrawing groups present preferably in the o-and p-positions.

(v) It is an example of nucleophilic substitution.

CH 3CHBrCH = CH 2 > BrCH 2CH 2CH = CH 2 > C6 H 5 Br
Allylic bromine 1° Bromine Aryl bromine
(vi) It is an example of nucleophilic substitution
C6 H 5CHBrCH 3 > C6 H 5 CH 2 CH 2 Br > C6 H 5CH = CHBr
Benzylic bromine 1° Bromine Vinylic bromine
7. This structure is most stable because the negative charge is present on the more electronegative atom and positive charge on the less
electronegative atom.

8. Relative reactivity is attributed to the relative stability of the intermediate formed in the addition
step of each of reactant.

9. (i) The reaction is an example of nucleophilic aromatic

substitution which is possible when —NO2 group is
present in the p-position to the —Cl group, because
—NO2 stabilizes the carbanion. Sodium sulphite
produces the nucleophile, SO32–.
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Note that here the sulphonating reagent (Na2SO3 or SO32–) is completely different from the reagent used in ordinary sulphonation, i.e. SO3.

(ii) In o- and p-dinitrobenzenes, since one —NO 2 activates the other,

they undergo nucleophilic aromatic substitution to form water soluble
benzenesulphonates (—NO2 group is a leaving group). The m-isomer
does not react and thus remains insoluble.

(iii) In presence of alkali, p-nitroaniline formed after hydrolysis may undergo nucleophilic aromatic substitution to form p-nitrophenol
(here —NH2 is the leaving group).

(iv) Both reactions are nucleophilic aromatic substitution and involve a common intermediate carbanion.

(v) To minimize nucleophilic substitution by OH– that would convert some of the product into 2, 4-dinitrophenol.
(vi) At 340°C, reaction proceeds, at least partly, via benzyne.

At 250°C, reaction proceeds by aromatic bimolecular substitution to give only p-cresol.

(vii) This reaction involves benzyne as an intermediate in which halogen is to be eliminated as an anion. F – is a much poorer leaving
group than Br–, hence formation of benzyne intermediate will be very slow in fluoro compound than in bromo compound.

(viii) Benzyne formed from chlorobenzene adds Ph3C:– and then H+ from ammonia to form Ph4C.
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10 .1 Definition and Nomenclature 10 .5 Limitations in the Use of Grignard Reagents

10 .2 Preparation of Organolithium and Organomagnesium 10 .6 Organozinc Reagents for Cyclopropane Synthesis

Compounds
10 .7 Organocadmium Compounds
10 .3 Reactions of Organolithium and Organomagnesium
Compounds 10 .8 Organocuprates (Gilman reagents)

10 .4 Grignard Reagents as Synthetic Agent EXERCISES

SOLUTIONS

10.1 Definition and Nomenclature

Organometallic compounds are compounds that contain a carbon-metal bond. The nature of the carbon-metal
bond may be ionic, partly ionic or primarily covalent depending upon the nature of the metal.
Carbon, a group 14 element is neither strongly electropositive nor strongly electronegative. Its electronegativity
on the Pauling scale is 2.5 which is slightly more than hydrogen (2.1) and hence C—H bond is not very polar. When carbon
is bonded to an atom which is more electronegative than carbon, viz O or Cl, the electron distribution in the bond makes
carbon slightly positive and the more electronegative atom slightly negative. Conversely, when carbon is bonded to a more
electropositive atom, such as a metal, the electrons in the bond are more strongly attracted towards carbon with the result
carbon becomes slightly negative.

d+ d– d– d+
C—–X C—–M
X is more electronegative than carbon X is less electronegative than carbon

A species having negatively charged carbon is referred to as a carbanion. In general, the percentage of ionic
character of the C—M bond depends largely upon the electronegativity of the metal, i.e. lesser the electronegativity (or
greater the electropositivity) of the metal more will be the ionic character of the C—M bond. Thus the ionic character of the
C—M bond follows the order :
C—K > C—Na > C—Li > C—Mg > C—Al > C—Zn > C—Cd > C—Hg
Electronegativity of the metal 0.8 0.9 1.0 1.2 1.5 1.6 1.8 1.9
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Thus carbon-sodium and carbon-potassium bonds are largely ionic ; carbon-lead, carbon-zinc, carbon-cadmium
and C-mercury are essentially covalent ; and carbon-lithium and carbon-magnesium lie between these two extremes.

– + d– d+
—C : M —C : M —C—M

Primarily ionic (M = Mg or Li) Primarily covalent

(M = Na or K) (Mg = Zn, Cd or Hg)

The reactivity of organometallic compounds increases with the increase in ionic character of the C—M bond.
Thus alkylsodium and alkylpotassium compounds are highly reactive and are among the most powerful bases. They react
explosively with water and burst into flame when exposed to air. Organomercury and organolead compounds are less
reactive, they are often volatile and are stable in air.
Organometallic compounds of lithium and magnesium are neither too reactive nor inert, hence these are of great
importance in organic synthesis. Since C—Li and C—Mg bonds are polar, organolithium and organomagnesium
compounds have significant carbanionic character and it is the carbanionic character of such bonds that is responsible for their
importance as synthetic reagents.

Nomenclature. (i) Organometallic compounds are named as substituted derivatives of metals.

CH3Li CH2 = CHNa (CH3CH2)2Mg (CH3)3 CLi
Methyllithium Vinylsodium Diethylmagnesium tert-Butyllithium or
1, 1-Dimethylethyllithium
(ii) When the metal has a substituent other than alkyl group, the substituent is treated as if it were an anion and
hence named separately.
H

CH3MgBr MgBr ICH2ZnI

Methylmagnesium Cyclohexylmagnesium Iodomethylzinc
bromide bromide iodide

10.2 Preparation of Organolithium and Organomagnesium Compounds

1. Organolithium compounds are prepared by the reaction of organic halides with lithium metal in presence of
solvents like diethyl ether, tetrahydrofuran (a cyclic ether) or hydrocarbons like pentane and hexane.
(C H ) O
R—X, CH2 = CH—X or Ar—X + 2Li ¾¾¾¾¾
2 5 2
® R—Li, CH2 = CHLi or ArLi + LiX
(i) The order of reactivity of halides is RI > RBr > RCl > RF (fluorides are seldom used). Bromides are readily
available and quite reactive, these are used most often.
(ii) Solvent used should be anhydrous because even a trace of water or alcohol reacts with lithium to form insoluble
hydroxide or alkoxide that coats the surface of the metal and prevents it from reacting with the alkyl halide.
Moreover, organolithium compounds are strong bases, as soon as these are formed they react rapidly with even
weak proton sources like H2O or ROH to form hydrocarbons.
(iii) Most organolithium compounds slowly attack ethers by bringing about an elimination reaction.
d- d+
R : Li + HCH 2 CH 2 OCH 2 CH 3 ¾¾® RH + CH2 = CH2 + LiOCH2CH3
Ether (solvent)

Due to this reason, organolithium compounds are not usually stored but are used immediately after their
preparation.

1. Give equations showing the formation of

(a) sec-Butyllithium (b) Isopropenyllithium (c) Benzylsodium.
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2. Organomagnesium halides (discovered by the French chemist, Victor Grignard, Nobel prize winner in chemistry
in 1912), commonly called Grignard reagents are the most important organometallic reagents. These are prepared
by the reaction of an organic halide and magnesium metal (turnings) in an ether solvent.
ether
RX + Mg ¾¾¾® RMgX
35° C

(R may be methyl, 1°, 2°, or 3° alkyl, a cycloalkyl, alkenyl, or aryl group)

(i) The solvent (usually diethyl ether or tetrahydrofuran) plays a crucial role in the
formation of a Grignard reagent. The magnesium atom of a Grignard reagent is R
surrounded by only four electrons, it needs two more pairs of electrons to form X
an octet. Solvent molecules provide these electrons by coordinating to the metal.
Mg
Coordination allows the Grignard reagent to dissolve in the solvent and thus
prevents the Grignard reagent from coating the magnesium shavings, which

:
R2O :

:
: OR2
would make them unreactive.
Tetrahedral arrangement around Mg

(ii) The order of halides reactivity is RI > RBr > RCl > RF. However, alkyl bromides are most widely used because
they react more readily than alkyl chlorides and are less expensive than alkyl iodides.
(iii) Alkyl halides are more reactive than aryl and vinyl halides. Indeed, aryl and vinyl chlorides do not form
Grignard reagents in diethyl ether, a solvent of low b.p. 35°C. These are, however, prepared by using
tetrahydrofuran, a solvent of higher b.p., 65°C.
THF
CH2 = CHCl + Mg ¾¾¾
® CH2 = CHMgCl
60° C
(iv) Allyl and benzyl halides are so reactive that they readily couple with their Grignard reagents (as soon as they
are formed) to form diallyl or dibenzyl. Hence, it is difficult to prepare Grignard reagents of allyl halides and
benzyl halides.

1. Write down the reaction and the structure of the Grignard reagent formed by the following organic halides.
(a) Allyl chloride (b) 1-Bromocyclohexene (c) p-Bromofluorobenzene.

10.3 Reactions of Organolithium and Organomagnesium Compounds

1. Organolithium and organomagnesium compounds as Bronsted bases. (Reactions with compounds containing
acidic hydrogen atom). Due to their carbanionic character, organolithium compounds and Grignard reagents
are very strong bases. Thus they can abstract proton from any species more acidic than the hydrogen atoms of an
alkane or alkene ; viz. terminal alkynes and any compound that has a hydrogen attached to an electronegative
atom such as O, N, or S. In these reactions, a proton is transferred to the negatively polarized carbon of the
reagent to form a hydrocarbon. This is the reason, that Grignard reagents are not prepared in presence of
compounds containing —OH, —SH or —NH groupings.
CH3CH2CH2CH2Li + HOH ¾¾® CH3CH2CH2CH3 + LiOH
Stronger base Stronger acid Weaker acid Weaker base
C6H5MgBr + HOCH3 ¾¾® C6H6 + CH3OMgBr
Phenylmagnesium Methanol Methoxymagnesium
bromide bromide
CH3CH2MgBr + H3N ¾¾® CH3CH3 + MgBr(NH2)
CH3CH2MgBr + HC º CCH3 ¾¾® CH3CH3 + BrMgC º CCH3
Ethylmagnesium Propyne Propynylmagneisum
bromide bromide
(Stronger base) (Stronger acid) (Weaker acid) (Weaker base)
From above reactions, it is clear that for every active hydrogen atom in the compound one molecule of alkane
(22.4 litres at NTP) is produced which can be measured easily. This principle is used in the estimation of groups
containing active hydrogen atom such as —OH, —NH2, —SH etc. (Zerewitnoff method).
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2. Organolithium and Grignard reagents as nucleophiles. Grignard reagents are not only strong bases, they are
also powerful nucleophiles. In fact, reactions in which Grignard reagents act as nucleophiles are by far the most
important. Grignard reagents act as nucleophiles by attacking saturated and unsaturated carbon atoms.
(A) Grignard reagents as nucleophile for a saturated carbon atom, e.g. oxiranes (epoxides).

d– d+ d+ d+ Et O H
+
2
RMgX + H2C—–CH2 ¾¾ ® R—CH2—CH2 ¾ ¾ ® R—CH2CH2OH
2+ – A 1° alcohol

: :
O
d– –OMgX
Oxirane

Grignard reagents react primarily at the less-substituted ring carbon atom of substituted oxiranes because
compartively it is more electrophilic.
(i) Et2O
C6H5MgBr + H2C—–CHCH3 ¾ ¾ ¾+ ® C6H5 CH2CHCH3
(ii) H
O OH
A 2° alcohol
(B) Grignard reagents as nucleophile for an unsaturated carbon atom, viz.
½ ½
— C = O, — C = S, —C º N, etc.
(i) Grignard reagents are nucleophilic and add to the electrophilic carbon atom of the carbonyl group, forming
a new carbon-carbon bond.
+
d– d+ d+ d– – 2+ – H3 O 2+ – –
C == O: ¾¾® ¾ ¾ ¾ ¾ ¾ ® R—C—OH
:

: :

R—MgX + R—C—O: MgX (HCl + H2O)

+ Mg X HO

Alcohol
The type of alcohol (1°, 2° or 3°) produced depends on the nature of the carbonyl compound used. Note that
the two substituents present on the carbonyl carbon stay in the product, an alkyl group from the Grignard
reagent attaches on the carbonyl carbon and carbonyl oxygen is converted to hydroxy group. Thus
formaldehyde (HCHO) gives 1° alcohols.

H +
diethyl 3 HO
CH3MgBr + C = O ¾ ¾ ¾ ® CH3CH2OMgBr ¾¾ ® CH3CH2OH
ether
H Ethanol

MgCl H CH2OH
(i) diethyl ether
+ C=O ¾ ¾ ¾ ¾ ¾+ ¾ ®
H (ii) H3O
Cyclohexyl- Cyclohexylmethanol
magnesium chloride

H (i) diethyl ether

CH3(CH2)3C º CMgBr + C = O ¾ ¾ ¾ ¾ ¾+ ¾ ® CH3(CH2)3C º CCH2OH
(ii) H3O
H 2-Heptyn-1-ol

Aldehydes other than formaldehyde give secondary alcohols.

CH3 CH3
CH3 +
diethyl H3O
CH3CH2MgBr + C = O ¾ ¾ ¾ ® CH3CH2C—OMgBr ¾ ¾ ® CH3CH2CHOH
ether
H 2-Butanol
H (2° alcohol)

Ketones give tertiary alcohols.

CH3 CH3
CH3 Et2O NH4Cl
CH3CH2MgBr + C = O ¾ ¾® CH3CH2C—OMgBr ¾ ¾ ¾ ® CH3CH2C—OH
H2O
CH3
CH3 CH3
2-Methyl-2-butanol (3° alcohol)
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(i) diethyl ether

CH3MgCl + ¾¾¾¾¾¾®
(ii) NH4 Cl/H2 O

O H3C OH
Cyclopentanone 1-Methylcyclopentanol
(3° alcohol)

Since 3° alcohols are susceptible to acid-catalysed dehydration, a solution of NH4Cl in water is often used
for hydrolysing the intermediate because it is acidic enough to convert ROMgX (a strong base) formed in
the product to ROH, thus avoiding dehydration of the tert-alcohol.
Addition of Grignard reagent on a, b-unsaturated carbonyl group
If carbonyl group is conjugated with a double bond, Grignard reagent gives nucleophilic addition on the
double bond.
– +
O O Mg X
+
RMgX HO
CH2 = CH — C — H ¾ ¾ ¾ ® R — CH2 — CH = C — H ¾ ¾3 ¾ ®

O —H O
tautomerisation
ˆˆˆˆˆˆˆˆˆˆ
†
R — CH2 — CH = C — H ‡ˆˆˆˆˆˆˆˆˆˆ R — CH 2 — CH 2 — C — H
(ii) Organolithium reagents react with carbonyl groups in the same way as Grignard reagents, however they
are somewhat more reactive than Grignard reagents.

1. Give necessary steps involved in the following conversions.

(i) to OH (ii) Sodium acetylide to 1-ethynylcyclohexanol.

OH

(iii) ¾¾ ®
Li

(iii) Grignard reagents react with other functional groups having CO as part in their structures in the same
manner to form different products. For example,
(a) One mole of alkyl formates i.e. methyl or ethyl esters of formic acid react with two moles of the Grignard
reagents to form secondary alcohols as the final product.

O O—MgX
ether —MgX(OC H )
RMgX + H — C— OC2H5 ¾ ¾ ¾ ® R—C—H ¾ ¾ ¾ ¾ ¾2 ¾5 ®

OC2H5
Unstable
O OMgX OH
+
RMgX H3O
R—C—H ¾¾¾® R—C—H ¾ ¾¾ ® R—C—H
Aldehyde
(more reactive than ester) R R
A 2° alcohol

(b) One mole of methyl or ethyl esters of acids other than formic acid, viz. methyl acetate reacts with two
moles of the reagent to form 3° alcohol as the final product. Ketones formed initially are not isolated but
reacts with the second mole of the Grignard reagent to form 3° alcohol as the final product.
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O OMgX
ether —MgX(OCH )
RMgX + R¢ —C —OCH3 ¾¾¾® R—C—OCH3 ¾ ¾ ¾ ¾ ¾ ¾3 ®

R¢

O OMgX OH
RMgX NH4Cl
R—C—R¢ ¾¾¾® R—C—R¢ ¾¾¾® R—C—R¢
H2O
Ketone
(more reactive R R
than ester) A 3° alcohol

(c) Reaction with acid chlorides, acid anhydrides and acid amides give first ketones and finally tert-
alcohols.

–
O O—MgX R
(i) RMgX
RMgX + R¢ —C—Cl ¾ ¾ ® R¢ —C—Cl ¾ ¾ ¾ ¾ ® R¢ —C = O ¾¾¾¾¾® R¢—C—OH
(—MgXCl) (ii) NaCl/H2O
Acid chloride
R R R
Ketone A 3° alcohol

O – +
OMgX O O OH
R¢ —C +
H3O (i) RMgX
RMgX + O R¢ —C—O—C—R¢ ¾ ¾¾ ¾ ¾ ¾ ® R¢—C ¾ ¾ ¾ ¾ ¾ ¾ ® R¢ —C—R
—Mg(X)OCOR¢ (ii ) NH4Cl/H2O
R¢ —C
R R R
O
Acid anhydride

– Å
O O OMgX
– Å RMgX
RMgX + R¢ —C—NH2 ¾ ¾ ® R¢—C—NHMgX ¾ ¾ ¾ ® R¢—C—NHMgX
(– RH) – Å
Acid amide
R

+
OH R
H3O (i) RMgX
¾¾¾¾¾¾¾® R¢ —C—OH ¾ ¾ ¾ ® R¢—C = O ¾ ¾ ¾ ¾ ¾ ¾ ® R¢—C—OH
(—2MgXOH, —NH3) (– H2O) (ii ) NH4Cl/H2O
R R R

(d) Grignard reagents react with CO2 and CS2 exactly in the same way forming carboxylic acids and
dithionic acids respectively.
O O O
|| || ||
H 3 O+
RMgX + C = O ¾¾® R¾ C ¾ OMgX ¾¾¾¾ ® R¾ C ¾ OH
S S S
|| || + |
|
H3 O
RMgX + C = S ¾¾® R¾ C ¾ SMgX ¾¾¾¾ ® R¾ C ¾ SH
Dithionic acid

1. Give as many combinations as possible for the synthesis of 2-phenyl-2-butanol using Grignard reagent as one of the reactants.
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519
(iv) Grignard reagents as nucleophile for the carbon atom of the nitrile group, C º N. These reactions are used for the
preparation of aldehydes (from HCN) and ketones (from RCN).
CH 3 CH 3 CH 3
| + ½ ½
H3 O H2O
(a) CH3MgX + H—C º N ¾¾® H— C = NMgX ¾¾¾¾ ® H ¾ C = NH ¾¾¾ ® H ¾ C = O + NH3
Aldimine Ethanal

CH 3 CH 3 CH 3
| H3 O + ½ H 2O
½
(b) CH3MgX + CH3—C º N ¾¾® CH3— C = NMgX ¾¾¾¾ ® CH3¾ C = NH ¾¾¾ ® CH3¾ C = O + NH3
Ketimine

10.4 Grignard Reagents as Synthetic Agent

The ease of its preparation and reactivity of Grignard reagent make it very important synthetic reagent. Nearly
every type of organic compound starting from alkane upto other organometallic compounds can be prepared.

Class of organic compound Starting materials

1. Alkanes RMgX + HOH(ROH, NH3 etc.) ¾¾® RH
2. Higher alkanes RMgX + XR¢ ¾¾® R—R¢ + MgX2 (SN reaction)
3. Higher alkynes RMgX + IMgC º CCH3 ¾¾® RC º CCH3
4. Primary alcohols (i) RMgX + CH2O ¾¾® RCH2OH
Methanol can’t be prepared by this method
O
(ii) RMgX + CH2— CH2 ¾¾® RCH2CH2OH

Ag H3 O +
1
(iii) RMgX + 2 O2 ¾¾® ROMgX ¾¾¾¾ ® ROH
R
5. Secondary alcohols (i) RMgX + R¢CHO ¾¾® CHOH
R¢
R
(ii) 2RMgX + HCOOR¢ ¾¾® CHOH
(2 moles) R
R
6. Tertiary alcohols (i) RMgX + R2¢CO ¾¾® R¢—– COH
R¢
R
(ii) 2RMgX + R¢COOCH3 ¾¾® R —– C—OH
(2 moles)
R¢
7. Aldehydes RMgX + HC º N ¾¾® RCHO
R
8. Ketones RMgX + R¢C º N ¾¾® CO
R¢
9. Carboxylic acids RMgX + CO2 ¾¾® RCOOH
Dry ice
10. Thioalcohols RMgX + S ¾¾® RSMgX ¾¾® RSH
11. Nitriles (i) RMg + ClCN ¾¾® RCN + MgXCl
Cyanogen chloride
(ii) RMgX + (CN)2 ¾¾® RCN + MgXCN
Cyanogen
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12. Amines RMgX + ClNH 2 ¾¾® RNH2

Chloramine

13. Other organometallic (i) 2RMgX + ZnCl2 ¾¾® R2Zn + 2MgXCl

compounds (ii) 4RMgX + 2PbCl2 ¾¾® R4Pb + Pb + 4MgXCl

1. Write the structure of the product formed by the reaction of propylmagnesium iodide with each of the following compounds :
(i) Methanal (ii) 2-Butanone (iii) Cyclopentanone
(iv) Benzaldehyde (v) Dry ice (vi) Butanenitrile
(vii) Pentyne-1, followed by reaction with cyclohexanone (viii) Benzoyl chloride.
2. Identify A to C in the following reactions :
O C2H5
+
H Mg (i) [B]
(i) CH3CH2MgBr + ¾¾ ® [A] (ii) C6H5Br ¾¾¾ ® C 6H5MgBr ¾¾¾® C6H5 —C—C6H5
THF + (ii) H
OH
NaNH2 (i) Cyclopentanone
(iii) HC º CH ¾¾ ¾® HC º CNa ¾¾¾+¾ ¾ ¾¾¾ ® [C]
(ii ) H

10.5 Limitations in the Use of Grignard Reagents

Extraordinary reactivity of Grignard reagent as a nucleophile and a base are also responsible for its certain
limitations.
(i) Due to powerful basic nature of Grignard reagents, we cannot prepare a Grignard reagent from a compound
containing an —OH, —NH—, —SH, —COOH, or —SO3H group. Even, if a Grignard reagent were to form, it
would immediately react with the acidic group.
(ii) Since Grignard reagents are powerful nucleophiles, we cannot prepare a Grignard reagent from any organic
halide containing a carbonyl, epoxy, or cyano group. Any Grignard reagent formed would react with the unreacted
starting material.
(iii) The nitro (—NO2) group oxidizes a Grignard reagent, so alkyl halides having —NO2 group can’t be converted
into Grignard reagent.
(iv) A compound to be reacted with a Grignard reagent should CHO COCH3 COCH3
also not contain either of the above mentioned groups
because in such cases Grignard reagent would be
decomposed by these groups (—NO2, —NH2, —COOH, etc.)
before reacting with the main functional group, the carbonyl NO2
group in the following examples. NH2 COOH
This means that we can prepare Grignard reagents effectively from alkyl halides or analogous organic halides
containing C—C double bonds, internal triple bonds, ether linkages, and —NR2 groups.

Protecting groups : An alkyl halide containing an alcoholic –OH group can be converted to Grignard reagent by
first protecting the –OH group by converting it to a tert-butyldimethylsilyl ether which is inert to Grignard reagent. The
protecting group is finally liberated by treatment with fluoride ion.

CH3 CH 3 CH3
| | |
(C 4 H9 )4 N + F -
R-O-H + Cl Si - C(CH 3 )3 ¾¾
® R - O - Si - C(CH 3 )3 ¾¾¾¾¾¾¾
® R - O - H + F - Si - C(CH 3 )3
| | THF |
CH3 CH 3 CH3
tert -Butylchlorodimethylsilane
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Example 1 :
Which of the following reaction is feasible?
OH
Br CHC6H5 MgBr
(i) Mg, ether +
CH3 CHO, H3O OH
(a) (ii) C6 H5 CHO
(b)
N + N
H (iii) H3 O H
O
HO CH2CH3
(i) CH3CH2MgB r
(c) +
(ii) H3O
OH OH
Solution :
(a) As Grignard reagent is formed, it would instantaneously react with the NH present in other molecules of
the same substance.
(b) The reagent used (CH3CHO and H3O+) must be numbered, viz. (i) and (ii), otherwise it indicates that the
Grignard reagent is exposed to acidic medium which will decompose it to alkane.
(c) The Grignard reagent will immediately react with the –OH part of the reagent.
So none of the three options is feasible.

Example 2 :
When 1-bromo-2-butene is treated with magnesium metal in dry ether, a Grignard reagent is formed. Addition of
water to this Grignard reagent gives a mixture of 1-butene and 2-butene. Further, 3-bromo-1-butene under similar
treatment gives the same products. Explain.
Solution :
+
MgBr
CH3CH = CHCH2Br .–.
1 Bromo 2 butene CH3CH = CHCH2 CH3CH = CHCH3
H2O 2- Butene
or

CH3CHBrCH = CH2 CH3CH2CH = CH2

.-. 1- Butene
3 Bromo 1 butene CH3CHCH = CH2
+
MgBr
Allylic carbanion

Example 3 :
Give steps involved in the following transformation using Grignard Synthesis.
OH
Br

HOH2 C HOH2C
Solution :
Since Grignard reagents decompose the alcoholic –OH group, the latter is first protected by converting it to a tert-
butyldimethylsilyl ether.
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Br
Br CH3
ClSi(CH3)2C(CH3 )3 |
imidazole
(CH3 )3 C - Si - O - H 2 C
|
HOH2C
CH3

OH
OH
CH3
(i) Mg, ether | + –
(Bu4)2N F
(CH 3 ) 3 C - Si - O - H 2 C
(ii) (CH3 )2CHCHO |
+ CH3 HOH2C
(iii) H3O

10.6 Organozinc Reagents for Cyclopropane Synthesis

Zinc reacts with alkyl halides in a manner similar to that of magnesium.

ether
RX + Zn ¾¾¾ ® RZnX
Organozinc reagents are less reactive toward aldehydes and ketones than Grignard reagents and organolithium
compounds. An organozinc compound important in organic synthesis, is iodomethylzinc iodide, ICH2ZnI. It is prepared by
the reactions of zinc-copper couple with diiodomethane is ether.

ICH 2 I diethyl ether

+ Zn ¾¾¾¾¾¾ ® ICH 2 ZnI
Di-iodomethane Cu Iodomethylzinc iodide

Iodomethylzinc iodide is very important in synthesising cyclopropanes. It reacts with alkenes to give
cyclopropanes (Simmons-Smith reaction). In this reaction methylene is transferred from iodomethylzinc iodide to the double
bond converting latter to cyclopropane derivative.

diethyl
R R
R2C = CR2 + ICH2ZnI ¾ ¾ ¾ ¾ ® + ZnI2
ether
R R

CH I , Zn(Cu)
¾ ¾ 2¾2 ¾ ¾ ¾ ®
diethyl ether

Cyclopentene Bicyclo [3.1.0] hexane

The reaction is stereospecific, addition of —CH2 takes place in syn manner.

1. Identify the starting material in each case which can be converted into following cyclopropane derivatives by reaction with
iodomethylzinc iodide.

CH3
(i) (ii)
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10.7 Organocadmium Compounds

These are quite similar to organozinc compounds and best prepared by the reaction of Grignard reagents with
cadmium chloride
2CH3MgBr + CdCl2 ¾¾® (CH3)2Cd + 2MgBrCl
These reagents have linear geometry (metal is sp hybridised). Chemically, they are similar to dialkylzincs but are
less reactive. When treated with acid chlorides, they form the corresponding ketones.
(C2H5)2Cd + 2CH3COCl ¾¾® 2C2H5.CO.CH3 + CdCl2
Since cadmiumalkyls are less reactive, they do not react with ketones, hence cadmium alkyls are considered
useful for the synthesis of ketones.

10.8 Organocuprates (Gilman reagents)

other or THF
2CH 3 Li + CuI ¾¾¾¾¾¾
® (CH 3 )2 CuLi + LiI
Gilman reagent

Gilman reagents are useful in synthetic chemistry. They react with alkyl halides (except alkyl fluorides) and
replace the halogen by one of the alkyl groups of the Gilman reagent.

H Br H CH2CH3
ether
(i) C=C (CH 3 CH 2) 2 CuLi ¾ ¾ ¾
¾® C=C
H3C CH3 H3 C CH3 + CH 3 CH 2 Cu + LiBr

I CH3
ether
(ii) + (CH 3 ) 2 CuLi ¾ ¾ ¾
¾® + CH 3 Cu + LiI

ether
(iii) CH 3CHCOCH 3 + (CH 3 )2 CuLi ¾¾¾® CH 3 CHCOCH 3 + CH 3 Cu + LiBr
| |
Br CH3

CH3
I æ CH3ö C CH3
ç | ÷
CH2 |
(iv) + ç CH 2 C —÷ CuLi ¾ ¾
ether
¾
¾® + CH 2 = C Cu
ç ÷
CH3 ç ÷ CH3
è ø2
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EXERCISE 10.1 (MCQ - ONE option correct)

1. IUPAC name of HC º CNa is 14. Reaction of CH3MgBr with acetone and hydrolysis of the resulting
(a) sodium acetylide (b) ethynylsodium product gives
(c) sodium acetylene (d) both (a) and (b). (a) CH3CH2CH2OH (b) CH3CH2CH2CH2OH
2. Predict the nature of P in the following reaction : (c) (CH3)2CHOH (d) (CH3)3COH.
O 15. To prepare 3-ethylpentan-3-ol, the reagents needed are
(a) CH3CH2MgBr + CH3COCH2CH3
C6H5MgBr + C2H5CH—–CH2 ¾ ¾® P (b) CH3MgBr + n-C 3H7COCH2CH3
(c) C2H5MgBr + C2H5COC2H5
C2 H 5 OH
| (d) n-C 3H7MgBr + CH3COC2H5.
|
CH MgBr
(a) C6H5 CH.CH 2 OH (b) C6H5CH2 CHC2 H 5 (c) 16. 3
Ethyl ester ¾¾¾¾¾
® P. The product P will be
excess
both (a) and (b) (d) None of the two.
3. Which can be other reactant for synthesising methyl alcohol from C2H5 CH3 C2H5 C2H5
Grignard reagent ? (a) (b)
(a) Formaldehyde (b) An oxirane C2H5 OH C2H5 OH
(c) Oxygen (d) Any of the three.
4. 3-Phenyl-3-pentanol can be prepared from a Grignard reagent H3C CH3 C2H5 H
and other component which can be (c) (d)
(a) 3-Pentanone (b) Ethyl benzoate CH3 OH CH3 OH
(c) Ethyl phenyl ketone (d) Any of the three.
(i) CO 2
5. Identify the nature of main product(s) in the following reaction: 17. C6H5MgBr ¾¾¾¾
® P. Here P is
(ii) H 3 O +
(i) diethyl ether
CH3MgBr + CH3COCH2CH2OH ¾¾¾¾¾¾¾
® In the above reaction, P is
(ii) NH 4 Cl/H 2 O
(a) C6H5CHO (b) C6H5COOH
(a) CH4 (c) C6H5OH (d) C6H5COC 6H5.
(b) CH3CH3 CN
(c) 3-Methylbutane-1, 4-diol
(d) Both (a) and (c). +
3 HO
6. Which of the following is an organometallic compound ? 18. + CH3MgBr ¾ ¾ ® A ¾ ¾ ® B . Here B is
(a) Lithium methoxide
OCH3
(b) Lithium acetate
(c) Lithium dimethylamide CHOHCH3 CHO
(d) Methyllithium.
7. The addition of the Grignard reagent, CH3MgBr to acetaldehyde (a) (b)
is a nucleophilic addition to the carbonyl group. The nucleophile
in this reaction is OCH3
+ COCH3 COOH
(a) CH3CHO (b) C H3
(c) Br – (d) : CH3–
8. (CH3)3CMgCl on reaction with D2O produces (c) (d)
(a) (CH3)3CD (b) (CH3)3COD OCH3 OCH3
(c) (CD3) 3CD (d) (CD3)3COD. 19. Ketones are best prepared by which reaction?
9. Grignard reagent is not prepared in aqueous medium but (a) RCOCl + RMgX (b) RCN + RLi
prepared in ether medium, because (c) RCOCl + R2Cd (d) All the three
(a) the reagent is highly reactive in ether
(b) the reagent becomes inactive in water O
||
(c) the reagent reacts with water 20. (i)PhMgCl (1eq)
Et - C - OET ¾¾¾¾¾¾¾®
(ii)H2 O
(d) none of three is correct.
10. Reaction of Grignard reagent with formaldehyde followed by True about product of above reaction is
acidification gives (a) One of the product will give positive iodoform test
(a) an aldehyde (b) a primary alcohol (b) Product will give CO2 on heating
(c) a carboxylic acid (d) a ketone. (c) Product will give only one oxime with NH2OH
11. Reaction of elemental sulphur with Grignard reagent followed (d) Product will give achiral alcohol with EtMgBr followed by
by acidification leads to the formation of hydrolysis
(a) mercaptan (b) sulphoxide O O
+
(c) thioether (d) sulphonic acid. 21. PhMgBr CH2MgBr H /H2O
12. 1-Phenylethanol can be prepared by the reaction of benzaldehyde Product
(1 eq.) (1 eq.) (1 eq.)
with O
(a) methyl bromide The product formed in the reaction is :
(b) ethyl iodide and magnesium OH OH
(c) methyl iodide and Mg O O
(a) Me Ph (b)
(d) methyl bromide and aluminium bromide.
O Me—C—C—Ph
13. Which of the following compounds on reaction with CH3MgBr
will give a tertiary alcohol ? OH
(a) C6H5CHO (b) C 2H5COOCH3 O O
Me—C—COOH
(c) C2H5COOH (d) CH3CH—–CHCH3 . (c) (d)
Ph—C—C—Me
O Ph
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Cl CH3
H
(b) CH3 – CH2 – C = C (single stereoisomer)
(i) Mg (1 eq.)/ Et2O
D
22. (ii) D2O (excess) CH3 H
Br CH3 – CH – C – CH3
Major product is (c) (single stereoisomer)
CH2D Cl D
(d) A racemic mixture of (CH3)2CH–CHD–CH3
O
+
H3O
(a) (b) 25. CH3 – C – CCl3 + CH3MgBr (excess) A B
B is
Br CH2D
OH O
CH2D
(a) CH3 – C – CCl3 (b) CH3 – C – CH3

CH3
(c) (d) None of these
OCH3
CH2D
(c) CH3 – C – CCl3 (d) None of these
O

COOH (i) Ca(OH)2 Ph–C–O–O–H CH3

23. P1 P2
COOH (ii) D
26. O2N COCl + R
(i) MeMgBr (excess) HÅ
P3 P4 (Cyclic compound)
(ii) H2O
P4 is : O2N COCH2CH3
O The reagent R may be
O
(a) (b) CH3CH2MgBr CH3CH2Li
I II
Me OH Me OH (CH3CH2) 2Cd (CH3CH2) 2CuLi
III IV
(c) O (d) O (a) I or II (b) I or II or III
(c) III or IV (d) Any of the four
27. Ethyl magnesium bromide when treated with methanal forms an
CH3 addition product which when hydrolysed with water in presence
H
HBr/R2O2 of acids forms propanol. What would be the major product when
24. (i) CH3 – C = C (P) the above reaction is carried out in the following sequence ?
D
(i) H O +
(ii) P (dextrorotatory)
CH3 MgBr
The end product is : CH3 CH 2 Mg Br ¾¾¾¾¾
3
®
(ii) HCHO
CH3
(a) CH3CH 2CH 2OH (b) CH3CH 2CHO
(a) CH3 – C – CH2D OH
(c) CH3CH3 (d) |
CH3 CH3 CHCH3

EXERCISE 10.2

DIRECTIONS for Q. 1 to Q. 11 : Multiple choice questions with 4. Solvent used during preparation of organolithium compounds
one or more than one correct option(s). should be completely dry because
(a) lithium forms insoluble hydroxide
1. Grignard reagents easily react with (b) the organolithium compound formed will react with water
(a) carbonyl compounds (b) esters (c) the solvent is protonated and thus becomes inactive
(c) carbon dioxide (d) hydrogen cyanide (d) solvent is insoluble in water
2. Which of the following statement(s) is(are) true? 5. Which of the following statement(s) is/are true?
(a) Sodium forms ionic organometallic compounds (a) Methylmagnesium iodide is a powerful Bronsted base
(b) Sodium does not form any organometallic compound (b) Methylmagnesium iodide is a powerful Lewis base
(c) Mercury forms ionic organomercury compounds (c) Methylmagnesium bromide is a powerful nucleophile
(d) Mercury forms covalent organomercury compounds (d) Methylmagnesium bromide is a weak nucleophile
3. The solvent used in preparing organometallic compounds belongs 6. An organic halide containing which of the following group does
to which series of organic compounds? not form easily the corresponding Grignard reagent
(a) An ether (b) Hydrocarbon (a) C = C (b) –NO2
(c) A cyclic ether (d) Dry alcohol (c) –N(CH3) 2 (d) –SH
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7. Which of the following reaction(s) is(are) not feasible? 13. The second step of each of the above reactions is an example of
(a) acid-base reaction
OH
(b) nucleophilic addition
Br CHC6H5 (c) nucleophilic substitution
(i) Mg, ether (d) none of these
(a) 14. The Grigrand reagent formed in each of the above reactions are
(ii) C6H5CHO
N + N stable due to
H (iii) H3O H (a) electronegativity of Br (b) resonance
(c) presence of MgBr (d) unstable
MgBr
+
CH3CHO, H3O OH
(b) PASSAGE 2
Grignard reagents (organomagnesium halides) were discovered
O by the French chemist Victor Grignard in 1900. He was awarded the
HO CH2CH3 Nobel Prize for his discovery in 1912. Grignard reagents behave as if
(i) CH3CH2 MgBr they were carbanions.They have extensive use in organic synthesis.
(c) + They are usually prepared by reacting an organic halide with magnesium
(ii) H O
OH 3
OH in an anhydrous ether solvent as follows
(d) All the three are feasible RX + Mg ® RMgX
8. Methyl magnesium iodide may react with where R is a suitable organic group and X is I, Br, or Cl
(a) 1 mole of ethyl formate
(b) 2 moles of ethyl formate 15. Grignard reagents are
(c) no reaction with ethyl formate I. Strong acids II. Strong bases
(d) zinc chloride III. Strong electrophiles IV. Strong nucleophiles
9. Isobutyl magnesium bromide with dry ether and absolute alcohol (a) I is correct (b) II is correct
gives (c) I & III are correct (d) II & IV are correct
16. In the preparation of a Grignard reagent, the reason why the ether
(a) CH 3 CHCH 2 OH (b) CH 3 CHCH 2CH 2 CH 3 solvent must be anhydrous is that
| |
CH3 CH3 (a) hydrogen ions from any water present would immediately
react with any Grignard reagent produced
(c) Mg(OH)Br (d) CH 3 CH 2 OMgBr (b) grignard reagents are insoluble in water
10. Primary alcohols can be obtained from Grignard reagent by (c) water is necessary for Grignard reagents to ionize
reacting with (d) water is the universal solvent
17. Which of the following are suitable organic reactants for
CH3
synthesizing Grignard reagents?
(i) (ii) I. C3H7I II. CH3OCH2Br
O O III. HSCH2CH2I IV. CH3COCH2Br
(a) I and II (b) II and III
(c) III and IV (d) I and IV
(iii) (iv)
O O
PASSAGE 3
(a) (i) (b) (i) and (iii) H
(c) (i), (ii) and (iii) (d) All the four Cl2
11. 2-Phenylbutanol-2 can be prepared by which of the following Me – C – Me hv
A(major product)
combinations ? Me
(a) C6H5COCH3 + C2H5MgBr
(b) C2H5COCH3 + C6H5MgBr (i) Mg/ Et2O H
Å

(c) C6H5COC2H5 + CH3MgBr O

B D
C (Product without rearrangement)
(d) C6H5COC6H5 + C2H5MgBr (i) O3,
(ii) (ii) Zn/ H2O

INSTRUCTION for Q. 12 to 20 : Read the passages given below and D+ E

answer the questions that follow.
18. Select the correct statement
PASSAGE 1 (a) D is a bicyclo compound and doesn’t give aldol
Observe the following reactions and answer the questions condensation with NaOH
(b) D is a bicyclo compound and it givs aldol condensation
Mg
(i) CH 3 CH = CHCH 2 Br ¾¾¾
® CH 3 CH = CHCH 2 MgBr with NaOH at two different a-positions.
dry ether (c) E is an open chain compound and doesn’t give aldol
H O condensation with NaOH
¾¾¾
2 ® Alkene
(d) E is an open chain compound and will give aldol
MgBr condensation with NaOH
Br
| | 19. How many enantiomeric pairs are formed when C is treated with
Mg
(ii) CH 3 CHCH = CH 2 ¾¾¾
® CH 3 C HCH = CH 2 NBS
dry ether (a) 3 (b) 2
H O (c) 1 (d) None of these
¾¾¾
2 ® Alkene
20. How many deuterium atoms are present in the compound which
is formed when compound D is kept with dil. KOD for long time
12. The alkene formed in reaction (i) is and then heated ?
(a) but-2-ene (b) but-1-ene (a) 1 (b) 2
(c) both (d) none (c) 3 (d) 4
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Instructions for Q. 21 to 22 : Following questions are Multiple Instructions for Q. 26 to 29 : Following questions are Integer Type
Matching type Questions : Questions :

26. How many moles of Grignard reagent can react with one mole of
21. Column I Column II following compound.
(A) CH3MgBr + epoxide (a)Zerewittnoff estima-
tion O
(B) C6H11MgCl + CH2O (b)2° alcohols
C–Cl
(C) Solvent in preparing RMgX (c) Pentane
(D) n-C5H11MgBr + NH3 (d)1° alcohols COOEt
22 Column I Column II
(A) RMgX + Methyl ester (a)Ketones
HO
(B) RMgX + Acid anhydrides (b)3° alcohols
(C) Most reactive organometallic (c) Me2CuLi C–Me
H
compound
(D) Gilman reagents (d)CH2=CHCH2MgBr O
27. Calculate number of molecules of Girgnard reagent consumed
Instructions for Q. 23 to 25 : Following questions are Assertion and by 1 molecule of following compound.
Reasoning Type Questions :
H
Note : Each question contains STATEMENT-1 (Assertion) and
STATEMENT-2 (Reason). Each question has 5 choices (a), (b), (c),
(d) and (e) out of which ONLY ONE is correct. O
(a) Statement-1 is True, Statement-2 is True; Statement-2 is a correct O O
explanation for Statement-1. O
(b) Statement-1 is True, Statement-2 is True; Statement-2 is NOT a
correct explanation for Statement-1. HO NO2
(c) Statement -1 is True, Statement-2 is False.
(d) Statement -1 is False, Statement-2 is True. O O
(e) Statement -1 is False, Statement-2 is False.
CH3MgBr (excess)
23. Statement-1 : Grignard reagents are prepared in ether but not O O
(ether)
in benzene.
Statement-2 : Grignard reagents are soluble in benzene. 28.
24. Statement-1 : Hydroxyketones are not directly used in Grignard HO NHCH3
reaction. O
Statement-2 : Grignard reagents react with hydroxyl group.
25. Statement-1 : All the iron-carbon bond distances in ferrocene are Find the number of CH3MgBr molecules used by the given
equal. reactant, to react completely.
Statement-2 : The p electrons in the cyclopentadienyl group of 29. How many total possible Grignard reagent can give 3-
ferrocene are delocalised. methylpentane on treatment with H Å .

EXERCISE 10.3 (Subjective Problems)

1. (a) Give the products for the viable reactions. 6. Suggest as many as possible ways by which following alcohols
THF can be prepared by using a Grignard reagent.
(i) CH3CH2CH2Cl + Mg ¾¾¾
® (i) 2-Hexanol (ii) 2-Phenyl-2-butanol.
Et O 7. What combination of ester and Grignard reagent should be used
(ii) —F + Mg ¾ ¾
2
® to prepare following alcohols.
(iii) n-C 4H9I + Zn ¾¾® OH OH
(iv) n-C 4H9Cl + Zn ¾¾®. |
(b) Discuss the role of metal reactivity in the viability of the (i) C6H5 . C(CH 2 CH 3 )2 (ii) (C6H5) 2C
reaction. 8. Predict how many moles of a Grignard reagent can be consumed
2. Give the product formed from the reaction of Mg/Et2O with by one mole of the compound drawn on side. Give also structure
(i) BrCH2CH2Br (ii) Br(CH2)3Br of the final product.
(iii) Br(CH2)4Br. O
3. Explain the following. O
(i) Vinyllithium is recommended rather than vinylmagnesium
(ii) BrCH2C º CH cannot be converted into corresponding 9. Although oxira ne ( oxa cyclopropane) and oxetane
Grignard or organolithium reagent. (oxac yclobutane) reac t with Grignard reagents and
4. Write product (products) formed by the reaction of organolithiums to form alcohols, tetrahydrofuran
ethylmagnesium bromide with each of the following. (oxacyclopentane) is so unreactive that it is used as a solvent in
(i) D2 O (ii) Acetophenone the preparation of these reagents. Explain.
(iii) Cyclohexanone (iv) Cyclopentadiene
(v) Butyne-1, followed by CH3CHO and then H3O+.
5. Butyllithium is commercially available, give reactions for O O O
converting it into lithium diethylamide and lithium 1-hexanolate.
Oxirane Oxetane THF
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EXERCISE 10.1
1 (d) 6 (d) 11 (a) 16 (c) 21 (c) 26 (c)
2 (b) 7 (d) 12 (c) 17 (b) 22 (d) 27 (c)
3 (c) 8 (a) 13 (b) 18 (c) 23 (a)
4 (d) 9 (c) 14 (d) 19 (c) 24 (c)
5 (a) 10 (b) 15 (c) 20 (d) 25 (d)
2. When Grignard reagent attacks on an oxirane, alkyl or aryl group 16. In the reaction an ester is treated with excess of CH3MgBr (a
attacks on the less substituted carbon atom. Grignard reagent), so the product can be either a 2° alcohol
3. Formaldehyde will give as alcohol having one carbon atom more (when ethyl ester is HCOOC2H5) or a 3° alcohol (when ethyl
than that of the alkyl group of Grignard reagent. Simplest oxirane ester is RCOOC2H5) having at least two methyl groups (from
(ethylene oxide) will increase two carbon atoms ; while reaction excess of CH3MgBr). Only option C has at least two methyl
of oxygen will form alcohol corresponding to the alkyl group of groups.
Grignard reagent. 17. Recall that dry ice (solid CO2) give caboxylic acids, when treated
1 with Grignard reagents.
H 3O 4
CH3MgBr + O2 ¾¾® CH3OMgBr ¾¾¾¾ ® CH3OH. 18. Recall that cyanides when treated with Grignard reagents give
2 ketons.
4. 3-Phenyl-3-pentanol (a 3° alcohol) can be prepared from Grignard
reagent and a ketone or an ester. Possible combinations will be O OH
P |
C6H5 20.
(i) Ph MgCl
Et - C - OEt ¾¾¾¾¾® Et - C - OH ¾¾¾¾®
(ii) H 2O | (- H 2O)
CH3CH2—C—CH2CH3
Ph
OH Et
3-Phenyl-3-pentanol |
EtMgBr
(a) Et - C = O ¾¾¾¾® Et - C - OH
CH 3 CH 2 . CO . CH 2 CH 3 + C6H5MgBr, or | |
Pentanone-3
Ph Ph
(b) C6 H 5 COOC 2 H 5 + 2CH3CH2MgBr
O O O O
Ethyl benzoate
PhMgBr MeMgBr
C6H5 21. Ph—C—C—OMgBr
¾¾® CH3CH2—C—CH2CH3 or, O
OMgBr OH
OH +
H /H2O
(c) C6 H 5 . CO . CH 2 CH 3 + CH3CH2MgBr Ph—C—C—OMgBr Ph—C—COOH
Ethyl phenyl ketone
5. Grignard reagent would react as a base with the acidic hydrogen Me O Me
rather than reacting at the carbonyl group as a nucleophile for Cl
which excess of Grignard reagent must be used (1 mole for react-
ing with the —OH group and the second mole for > CO group). (i) Mg (1 eq.)/ Et2O
6. Only methyllithium has C—M bond.
7. Electronegativity of C is more than that of Mg hence carbon of 22. (ii) D2O (excess)
methyl will be electron rich, i.e. it acts as a nucleophile.
8. (CH3)3 CMgCl + D2O ¾¾® (CH3)3CD + MgCl(OD). Br
9. Grignard reagents are strongly basic in character due to O O
carbanionic nature, hence it will react with water, a weak acid.
10. Formaldehyde reacts with RMgX to form 1° alcohols. O OH O
23. OH
+
H3 O
11. RMgX + S ¾¾® RSMgX ¾¾¾¾ ® RSH + MgXOH.
P1 P2 P3
OH CH3
|
HBr/ R2O2
12. 1-Phenylethanol C6H5. CH CH3 is a 2° alcohol so it can be pre- 24. CH3 – C = CHD CH3 – C – CHD
pared from benzaldehyde and Grignard reagent,
CH3MgX (CH3I + Mg). CH3 H Br
13. Tertiary alcohols are formed by treating Grignard reagents ei-
(P) dextro
ther with ketones or excess of an ester other than formate which
will give 2° alcohol. CH3 H
14. Same as above. CH3MgBr
15. Write down the formula of the required compound, examine the SN2 CH3 – CH – C – CH3
nature of functional group and then recollect its preparation
from Grignard reagents. So here, the component should be diethyl D
ketone and ethylmagnesium bromide. (single stereoisomer)
26. Organomagnesium and organolithium compounds can’t be
OH
prepared from the alkyl (or aryl) halide having –NO2 group. On
| the other hand, organocopper and organocadmium compounds,
CH3CH2 — C — CH2CH3 do not react with the –NO2 group.
|
27. H+
C2H5 CH 3 CH 2MgBr ¾¾¾
® CH 3 CH 3
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EXERCISE 10.2
1 (a, b, c, d) 5 (a, c) 9 (b, c)
>1 CORRECT 2 (a, d) 6 (b, d) 10 (b)
OPTION 3 (a, b, c) 7 (a, b, c) 11 (a, b, c)
4 (a, b) 8 (a, b, d)
PASSAGE 1 12 (c) 13 (a) 14 (b)
PASSAGE 2 15 (d) 16 (a) 17 (a)
PASSAGE 3 18 (c) 19 (d) 20 (b)
Match the 21 (A) - b, d, (B) - d, (C) - c, (D) - a, c
Following 22 (A) - a, b, (B) - a, b, (C) - d, (D) - c
A/R 23 (c) 24 (a) 25 (a)
26 7 27 6 28 6
INTEGER
29 4

24.(a) R is the correct explanation of A.

11.(a,b,c) is a 3° alcohol ; the first three 26. one mole for –COCH3
two moles for –COOEt
two moles for –COCl
combinations can be applied for its preparation. one mole for – C º CH
Sol. 18-20 : one mole for –OH
H Total 7 moles.
Cl2 27. 6
Me – C – Me hv
Me2CH – CH2 – Cl
H
A(Major)
Me
[1] C
(i) Mg/ Et2O
O C

(ii) O
O O
O
OMgCl [1]
CH2CHMe2 HO NO2 [3]

[1]
B 28. 6;
Å O O 2MeMgBr
H ,D

CH – CHMe2 CH2 – CHMe2 CH3MgBr (excess)

O O
(ether)
+ 1
C But it will give only O N HCH3
one product on ozonolysis
O
O3, 1 1
Zn / H2O 1
D 7 molecules of MeMgBr.
D
O O
MgX
* * |
dil. KOD
+ Me2CH–CHO 29. C - C - C- C - C - MgX C - C - C- C - C
D |
E | *
D NaOH C C
Me2CH–CH2OH ( ± )(2)enantiomers 4 Chiral compounds
+
Me2CH–COONa MgX C–C–C–C–C
|
18.(c) 19.(d) 20. (b)
23.(c) The correct reason is : Grignard reagents are soluble in ether C- C- C - C- C
| C
but not in benzene C MgX
achiral compound achiral compound

EXERCISE 10.3
1. (a) (i) CH3CH2CH2MgCl (THF is a better solvent than Et2O (iv) No reaction.
for RCl’s) (b) The reactivity of a metal depends on its reduction potential;
(ii) No reaction the more easily a metal is reduced, the less reactive it is,
(iii) n-C 4H9ZnI e.g. Mg > Zn.
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2. (i) H2C = CH2 (elimination of vic halogens) (b) CH3CH2CH2CH2CHO + CH3MgBr
CH2 Pentanal
¾¾® CH3CH2CH2CH2CH(OH)CH3
(ii) 2-Hexanol
CH 2—–CH 2
(iii) BrMg(CH2)4MgBr. Here intermolecular cyclization does not OH
occur because a 4-membered ring is not formed as readily |
as a 3-membered ring. (ii) 2-Phenyl-2-propanol, CH 3. C ¾ CH 3 . It is a 3° alcohol,
3. (i) Vinyl halides, especially chloride, react sluggishly with Mg. |
Further, n-C 4H9Li is easily available in the market it can C6 H 5
used for preparing vinyllithium from vinyl chloride (metal- hence it can be prepared by the reaction of Grignard reagent
halogen exchange method). and ketone. Two possible combinations are
CH2 = CHCl + n-C 4H9Li ¾¾® CH2 = CHLi + n-C 4H9Cl
Remember that the compound bearing metal to the more OH
electronegative carbon is more stable, thus in the above |
reversible reaction, CH2 = CHLi is more stable than n- (a) C6H5MgBr + CH3.CO.CH3 ¾¾® CH3— C ¾ CH 3
C4H9Li. |
(ii) Grignard reagent formed will instantaneously react with C6 H 5
the terminal acidic hydrogen. OH
Mg |
BrCH2C º CH ¾¾¾
® [BrMgCH2C º CH]
(b) CH3MgBr + C6H5.CO.CH3 ¾¾® CH3— C ¾ CH 3
BrCH C º CH
2
¾¾¾¾¾¾® CH3C º CH + BrCH2C º CMgBr |
4. (i) CH3CH2MgBr + D2O ¾¾® CH3CH2D + MgBr(OD) C6 H 5
(ii) CH3CH2MgBr + C6H5.CO.CH3 (c) Since the product (a 3° alcohol) has two similar alkyl
CH 2 CH 3 groups (methyl), it can also be prepared by reacting
| 1 mole of ester (C6H5COOCH3) with two moles of
(i) diethyl ether alkyl magnesium halide (CH3MgI).
¾¾¾¾¾¾¾ ® C 6H5. C.CH 3
(ii) NH 4Cl/H 2 O | C6H5COOCH3 + 2CH3MgI
OH CH 3
(iii) CH3CH2MgBr + |
O
¾¾® C6 H 5 ¾ C ¾ OH
CH2CH3 |
(i) diethyl ether
¾ ¾¾ ¾ ¾¾ ® CH 3
(ii) NH4Cl/H2 O
OH Methyl benzoate 2-Phenyl-2-
1-Ethylcyclohexanol propanol
7. (i) Note that the 3° alcohol is having two ethyl groups, so
(iv) CH3CH2MgBr + these should be introduced via Grignard reagents
Cyclopentadiene
CH3CH2MgBr, hence the other component should be an
ester of benzoic acid.
C6H5COOCH3 + 2CH3CH2MgBr
¾¾ ® CH3CH3 + BrMg— Methyl benzoate
CH 2 CH 3
(v) CH3CH2MgBr + HC º CCH2CH3
|
¾¾® CH3CH3 + BrMgC º CCH2CH3 (i) diethyl ether
¾¾¾¾¾¾¾ ® C6 H 5 ¾ C ¾ CH 2 CH 3
OH (ii) NH 4 Cl/H 2 O |
| OH
(i) CH 3 CHO
¾¾¾¾¾¾ + ® CH3. CH.C º CCH 2 CH 3 3-Phenyl-3-pentanol
(ii)H 3 O
Hex-3-yn-2-ol
(ii) Here the Grignard reagent is C6H5MgBr and ester is alkyl
5. n-Butyllithium is a strong base and hence can abstract proton cyclopropanecarboxylate.
from compounds having —OH, —NH2 or —SH. C 6 H5
(CH3CH2)2NH + CH3CH2CH2CH2Li 2C6H5MgBr + —COOC2H5 ¾ ¾®
C 6H 5
Diethylamine Butyllithium OH
(Stronger acid) (Stronger base) 8. Compound has two functional groups that can react with the
¾¾® (CH3CH2)2NLi + CH3CH2CH2CH3 Grignard reagent, viz. oxirane and ketonic group, each will be
Lithium diethyl Butane
taking one mole of the reagent.
amide (Weaker base) (Weaker acid)
CH3(CH2)4CH2OH + n-C 4H9Li O HO H3C
Hexanol-1 O CH3MgI O
¾¾ ¾¾®
¾¾® CH3(CH2)4CH2OLi + n-C 4H10
Lithium1-hexanolate Butane
6. First of all draw structure for the compound to be synthesised HO H3C
CH3MgI CH3
and examine the functional group in it. Then apply your memory ¾¾ ¾¾®
that from which functional group this functional group can be OH
introduced 4-Methylpent-1, 4-diol
(i) 2-Hexanol, CH3.CH(OH).(CH2) 3CH 3, is a secondary
alcohol, hence the two main reactants are Grignard reagent 9. The three- and four-membered rings are strained, and hence
and an aldehyde other than formaldehyde. The two possible they open on reaction with RMgX or RLi. THF, on the other
pairs for this are hand, has an unstrained five-membered ring hence it is
(a) CH3CHO + BrMgCH2(CH2)2CH3 highly resistent to be attacked by RMgX or RLi.
Ethanal Butylmagnesium bromide
¾¾® CH3CH(OH).CH2(CH2)2CH3
2-Hexanol
 www.crackjee.xyz
HYDROCARBONS AND HALOGEN DERIVATIVES
PAST YEAR QUESTIONS JEE ADVANCED/IIT-JEE (2013 - 2017)
MCQs with One Correct Answer H Br Br H
1. Isomers of hexane, based on their branching, can be divided (c) H2C (d) H C
CH3 CH 3
into three distinct classes as shown in the figure. 2
[JEE Adv. 2014] CH3
and 4. Among the following, reaction(s) which gives(give)
and tert-butyl benzene as the major product is(are)
[JEEAdv. 2016]
(I) (II) Br Cl
(a) (b)
NaOC2H5 AlCl3

OH
(c) (d)
(III) H2SO4 BF3OEt2
The correct order of their boiling point is 5. The correct statement(s) for the following addition reactions
(a) I > II > III (b) III > II > I is(are) [JEE Adv. 2017]
(c) II > III > I (d) III > I > II
H3C H
MCQs with One or More Than One Correct Br 2/CHCl 3
1. Among P, Q, R and S, the aromatic compound(s) is/are M and N
(i)
[JEE Advanced 2013-I] H CH3
Cl H3C CH3
Br 2/CHCl 3
(ii) O and P
AlCl3 NaH
P, Q H H
(a) O and P are identical molecules
(b) (M and O) and (N and P) are two pairs of diastereomers
O (c) (M and O) and (N and P) are two pairs of enantiomers
(NH 4) 2CO3 HCl
R, S (d) Bromination proceeds through trans-addition in both
100–115 °C the reactions
O O 6. For the following compounds, the correct statement(s) with
(a) P (b) R respect to nucleophilic substitution reaction is(are)
(c) Q (d) S [JEE Adv. 2017]
2. In the following reaction, the major product is Br Br
[JEE Adv. 2015]
CH3
(I) (II)
CH2 CH3
H2C 1 equivalent HBr
CH3
H3C—C — Br Br
CH3 CH3
CH3 CH3
(a) H2C (b) H3C (III) (IV)
Br
Br (a) I and III follow SN1 mechanism
(b) I and II follow SN2 mechanism
CH3 CH3 (c) Compound IV undergoes inversion of configuration
(d) The order of reactivity for I, III and IV is : IV > I > III
(c) (d) Br
H2C Br H 3C Comprehension Based Questions
3. Compound(s) that on hydrogenation produce(s) optically PASSAGE - I
inactive compound(s) is (are) [JEE Adv. 2015] Schemes 1 and 2 describe sequential transformation of alkynes M
H Br H Br and N. Consider only the major products formed in each step for
(a) (b) CH3 both the schemes.
H 3C CH 3 H 2C
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A-2

2. The correct statement with respect to product Y is

1. NaNH 2 (excess)
2. CH3CH 2I (1 equivalent) [JEE Adv. 2014]
H X Scheme-1 (a) It gives a positive Tollen's test and is a functional isomer
3. CH3I (1 equivalent)
HO M 4. H2, Lindlar’s catalyst of X
(b) It gives a positive Tollen's test and is a geometrical
isomer of X
1. NaNH 2 (2 equivalent)
OH (c) It gives a positive iodoform test and is a functional
isomer of X
2. Br
Y Scheme-2 (d) It gives a positive iodoform test and is a geometrical
H + isomer of X
3. H 3O, (mild)
N 4. H2, Pd/C Integer Value Correct Type
5. CrO3
1. In the following monobromination reaction, the number of
1. The product X is [JEE Adv. 2014] possible chiral products is (JEE Adv. 2016)
H3CO CH2CH2CH3
H Br Br2 (1.0 mole)
300°C
(a) CH3
H H (1.0 mole)
(enantiomerically pure)
H
2. Among the following, the number of aromatic compound(s)
H is (JEE Adv. 2017)
(b)
H3CO
CH3CH2O

(c)
H H
H

(d) H
CH3CH2O

PAST YEAR QUESTIONS JEE MAIN/AIEEE (2013 - 2017)

1. Which compound would give 5 - keto - 2 - methylhexanal region 4
upon ozonolysis ? [JEE M 2015]
CH3 region 3
CH3 region 2

(a) (b) H3C region 1

CH3

CH3
CH3
(a) region 3 (b) region 4
CH3 (c) region 1 (d) region 2
(c) (d)
3. At 300 K and 1 atm, 15 mL of a gaseous hydrocarbon requires
CH3 375 mL air containing 20% O2 by volume for complete
2. The hottest region of Bunsen flame shown in the figure combustion. After combustion the gases occupy 330 mL.
below is : [JEE M 2016] Assuming that the water formed is in liquid form and the
volumes were measured at the same temperature and
pressure, the formula of the hydrocarbon is: [JEE M 2016]
 www.crackjee.xyz
A-3

(a) C4H8 (b) C4H10

NH2 NHCOCH3
(c) C3H6 (d) C3H8
4. The reaction of propene with HOCl (Cl2 + H2O) proceeds
through the intermediate: [JEE M 2016] (c) (d)
(a) CH 3 – CH ( OH ) - CH 2+
10. The increasing order of the reactivity of the following halides
(b) CH3 – CHCl - CH 2+ for the SN1 reaction is [JEE M 2017]
CH3CHCH2CH3 CH3CH2CH2Cl
(c) CH3 – CH + - CH 2 – OH |
Cl (II)
(d) CH3 – CH + - CH 2 – Cl
(I)
5. Compound (A), C8H9Br, gives a white precipitate when
p-H3CO–C6 H4–CH2Cl
warmed with alcoholic AgNO3. Oxidation of (A) gives an
(III)
acid (B), C8H6O4. (B) easily forms anhydride on heating.
(a) (III) < (II) < (I) (b) (II) < (I) < (III)
Identify the compound (A). [JEE M 2013]
(c) (I) < (III) < (II) (d) (II) < (III) < (I)
CH2Br C2H5 11. Which of the following , upon treatment with tert-BuONa
followed by addition of bromine water, fails to decolourize
(a) (b)
the colour of bromine? [JEE M 2017]
Br
O C6H5
CH3
(a) (b)
Br Br
CH2Br
O
CH2Br O
(c) (d) (c) (d)
CH3 Br Br
CH3
12. 3-Methyl-pent-2-ene on reaction with HBr in presence of
peroxide forms an addition product. The number of possible
6. In SN2 reactions, the correct order of reactivity for the
stereoisomers for the product is : [JEE M 2017]
following compounds: [JEE M 2014]
(a) Six (b) Zero
CH3Cl , CH3CH 2Cl , (CH3 )2CHCl and ( CH3 )3CCl is:
(c) Two (d) Four
(a) CH3Cl > ( CH3 ) 2CHCl > CH3CH 2Cl > ( CH3 )3CCl 13. The major product obtained in the following reaction is :
Br
(b) CH3Cl > CH 3CH 2 Cl > ( CH3 ) 2 CHCl > ( CH3 )3CCl

(c) CH3CH 2 Cl > CH3Cl > ( CH3 ) 2 CHCl > ( CH3 )3CCl H
C6H5 t-BuOK
(d) ( CH3 )2CHCl > CH3CH 2Cl > CH3Cl > ( CH3 )3CCl D
C6H5
7. The major organic compound formed by the reaction of
(a) (±)C6H5CH(OtBu)CH2C6H5 [JEE M 2017]
1, 1, 1-trichloroethane with silver powder is: [JEE M 2014]
(a) Acetylene (b) Ethene (b) C6H5CH = CHC6H5
(c) 2 - Butyne (d) 2 - Butene (c) (+)C6H5CH(OtBu)CH2C6H5
8. The synthesis of alkyl fluorides is best accomplished by : (d) (–)C6H5CH(OtBu)CH2C6H5
[JEE M 2015] 14. Which of the following molecules is least resonance
(a) Finkelstein reaction (b) Swarts reaction stabilized? [JEE M 2017]
(c) Free radical fluorination (d) Sandmeyer's reaction
9. Which of the following compounds will form significant
amount of meta product during mono-nitration reaction ? (a) (b)
[JEE M 2016] O
OH OCOCH3

(c) (d)
(a) (b) N O
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A-4

SOLUTIONS
PAST YEAR QUESTIONS JEE ADVANCED/IIT-JEE (2013 - 2017)

MCQs with One Correct Answer

1. (b) Greater the extent of branching, lesser is the boiling point of the hydrocarbon, so order of b.p is III > II > I.
MCQs with One or More Than One Correct
Cl
Å –
AlCl – Å
1. (a, b, c, d) ¾¾¾®
3
AlCl4 ; ¾¾¾
®
NaH
Na + H 2 ­

Aromatic
(P) Aromatic
(Q)

NH3 100º -115ºC

¾¾¾¾¾
–2H O
®
from (NH 4)2CO3 2
O O O NH OH HO OH
:

2 N N
| |
H H
Aromatic
D (R)
(NH4)2CO3 2NH3 + CO2 + H2O

O OH
|| |
HCl Å
¾¾¾
® Cl
–

Aromatic
(S)
Note : P has 2 p electrons, while Q, R & S have 6 p electrons each. Hence all the 4 are aromatic.
2. (d)

Å Å
Å (Major)
3. (b, d)
H Br H Br
H2/Ni
(A) H2/Ni (B)
* (Optically inactive)

H2/Ni
(C) H2C H3C (D) H 2C CH3 H 3C CH3
H2/Ni
CH3 * CH3
CH3 CH3
4. (b, c, d)
Br
–
AlCl3 + 1, 2 H +
+ Shift
NaOEt
Cl

+ BF 3 1, 2 H
–
H + +
+ O–H Shift
H
 www.crackjee.xyz
A-5

5. (b, d)
(b) Bromination proceeds through trans-addition in both the reactions.
M and N are identical, hence, M and O and N and P are two set of diastereomers.
(d)
Br
CH 3
H
CH 3 H Br
H Br
CH 3 H H Br
a
Br—Br CH 3 H CH 3 CH 3
Br
b (N)
CH3 CH3
H
a
–
H Br
b
trans-2-Butene trans-Bromonium ion H CH 3 CH 3
Br Br H
Br
Br H
CH 3 H CH3
(M)
M and N are same
(meso-2, 3-Dibromobutane)

Br
CH 3
H CH 3 H Br
H Br H
CH 3 Br H
c
Br—Br CH3 H CH 3 CH 3
Br
(O)
d
H H
CH 3
c
CH3 Br
d H CH 3
cis-2-Butene cis -Bromonium ion CH3
Br Br H
Br H Br
H CH 3 CH 3
(P)
II and III are enantiomers
rac-2, 3-Dibromobutane
6. (a, b, c)
C
|
(a) I is Br (1° benzylic halide) and C – C – Br (3° alkylhalide). Follow S 1.
N
|
C
(b) I and II follow SN2 also, as both are 1° halide.
(c) Compound (IV) undergoes inversion of configuration due to presence of chiral carbon atom.
 EBD_7088
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A-6

Comprehension Based Questions

CH 3CH2 I
NaNH2 + – C– Na+
H Na O (1 eq.)
1. (a) HO

CH3 I C H2
+– C H3CO H3CO
(1 eq.) Lindlar
Na O
catalyst
H H
(X), C7H14O
OH
NaNH2 Br
2. (c) H C–Na+

O–Na+ (i) H + OH CrO3

C O
(ii) H2 , pd/C

(Y), C7H17O

Integer Value Correct Type

3 4 5
CH2CH2CH3 CH2CH2CH3 CH2CH2CH3 CH2CH3 CH2CH3
3 3
2 Br2(1.0 mole) 2 H Br Br H
1. (5) H Br H Br + Br Br + +
300°C H Br H Br
1
CH 3 CH2 – Br CH3 CH3 CH3
1
(1.0 mole) (Chiral) (Achiral) (Chiral) (Chiral)
(enantiomerically pure)
5
CH3 CH3 CH2 – Br
4 4
H Br Br H H H
+ H H + H H + H H
H Br H Br H Br
CH3 CH3 CH3
(Achiral) (Chiral) (Chiral)

2. (5)
Non-aromatic Anti-aromatic Non-aromatic Anti-aromatic Aromatic Aromatic Aromatic

Aromatic Aromatic

PAST YEAR QUESTIONS JEE MAIN/AIEEE (2013 - 2017)

1. (d) When 1, 3-dimethylcyclopentene is heated with ozone O O
and then with zinc and acetic acid, oxidative cleavage || ||
leads to keto - aldehyde. CH3 — C— CH 2 — CH 2 — CH— C— H
|
CH3 CH3 CH3
O 5- keto – 2 – methylhexanal
1O - 78° C 2. (d) Region 2 (blue flame) will be the hottest region of
¾ ¾ ¾3¾ ¾ ¾ ¾
® O C–H
2 - Zn- CH 3 COOH Bunsen flame shown in given figure
æ 4x + y ö y
CH3 CH3 3. (d) CxHy(g) + ç ÷ O2(g) ® xCO2(g) + H2O(l)
è 4 ø 2
 www.crackjee.xyz
A-7

20 group which, because of its positive charge, directs

Volume of O2 used = 375 ´ = 75 ml the entering group to the meta-position instead of ortho,
100
\ From the reaction of combustion and para. Å
: NH NH3
4x + y 2
1 ml CxHy requires = ml O 2
4
æ 4x + y ö Conc. HNO
¾¾¾¾¾® 3
15 ml = 15 ç ÷ = 75 Conc. H SO
è 4 ø 2 4
So, 4x + y = 20
x= 3 – NH2 gp : o, p-directing – NH3+ gp : m-directing
y= 8 10. (b) Since S N 1 reactions involve the formation of
carbocation as intermediate in the rate determining
C3H8 step, more is the stability of carbocation higher will be
the reactivity of alkyl halides towards SN1 route.
Since stability of carbocation follows order.
Å Å
CH2 – CH – CH3 CH3 – CH2 – CH 2
Å Cl More stable intermediate
4. (d) CH2 = CH – CH3 + Cl – Å
Å < CH3 – CH – CH2 – CH3
CH2 – CH – CH3
Å
Cl < p – H3CO – C6H4 – CH 2

Å OH Hence correct order is II < I < III

CH2 – CH – CH3 CH2 – CH – CH3
Cl Cl OH 11. (a)
CH2Br
5. (d) Alcholic AgBr
AgNO3 white ppt
O O
CH3 tert - BuONa
(a) ¾¾ ¾ ¾ ¾
®
Oxidation
HNO3
Br O-tBu
(fails to decolorise the
colour of bromine)
COOH CO due to unsaturation
D
O
COOH CO
6. (b) Steric congestion around the carbon atom undergoing C6H5
the inversion process will slow down the SN2 reaction, C6H5
(b) tert - BuONa
hence less congestion faster will the reaction. So, the ¾¾¾¾¾
®
order is Br
CH3Cl > (CH3)CH2 – Cl > (CH3)2CH – Cl > (CH3)3CCl (it decolorises
bromine solution)
Cl
|
7. (c) 2Cl - C - CH3 + 6Ag¾¾ ® CH 3C º CCH 3 + 6AgCl
| O O
Cl (c) tert - BuONa
¾ ¾ ¾ ¾ ¾®
1, 1, 1-trichloroethane 2-butyne
Br
8. (b) Alkyl fluorides are more conveniently prepared by
heating suitable chloro – or bromo-alkanes with organic (it decolorises bromine
solution)
fluorides such as AsF3, SbF3, CoF2, AgF, Hg2F2 etc.
This reaction is called Swarts reaction.
CH 3 Br + AgF ¾¾® CH 3 F + AgBr O O
2CH 3CH 2 Cl + Hg 2 F2 ¾¾
® 2CH 3CH 2 F + Hg 2Cl 2
9. (c) Nitration takes place in presence of concentrated (d) ¾ -¾
¾ tert BuONa
¾ ¾®
HNO3 + concentrated H2SO4. Br
(it decolorises bromine
In strongly acidic nitration medium, the amine is solution)
converted into anilinium ion (– NH3+); substitution is Products formed in option (b), (c) & (d) decolorises bromine
thus controlled not by – NH2 group but by – NH3+ solution due to presence of double bond.
 EBD_7088
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A-8

12. (d) If two chirality centres are created as a result of an 13. (b) Elimination reaction is highly favoured if
addition reaction four stereoisomers can be obtained (a) Bulkier base is used
as products.
(b) Higher temperature is used
CH3 CH3 Hence in given reaction biomolecular elimination
HBr
C = C ¾¾ ¾®
–H O reaction provides major product.
2
H C2H5
Br H
cis-3, methyl pent-2-ene
C6H5 t-BuOK
Br CH3 C6H5
| | 1, 2 elimination
CH3 – CH – CH – CH2 – CH3 H H
* *
2, Bromo, 3-methyl pentane
(2 chiral centre) OtBu
CH3 CH3
C6H5
+ t-BuOH + Br
H Br Br H C6H5

H CH3 H3C H
O

C2H5 C2H5
14. (d) is nonaromatic and hence least reasonance
(I) (II)
CH3 CH3

Br H Br stabilized whereas other three are aromatic.

H
H CH3 H3C H

C2H5 C2H5
(III) (IV)