#Aromatic Compound - 1
#Aromatic Compound - 1
#Aromatic Compound - 1
op kers
Class 11 T
By E ran culty
-JE Fa r
IIT enior emie .
S fP r es
o titut
Ins
CHEMISTRY
FOR JEE MAIN & ADVANCED
SECOND
EDITION
Exhaustive Theory
(Now Revised)
Formula Sheet
9000+ Problems
based on latest JEE pattern
Plancess Concepts
Topic Covered Tips & Tricks, Facts, Notes, Misconceptions,
Key Take Aways, Problem Solving Tactics
Alkyl Halides, Aryl Halides
and Aromatic Compounds PlancEssential
Questions recommended for revision
12. ALKYL HALIDES,
ARYL HALIDES
A N D A R O M AT I C
COMPOUNDS
ALKYL HALIDES
1. INTRODUCTION
When hydrogen atoms or atoms of alkanes are replaced by a corresponding number of halogen atoms, the
compounds are called halogen derivatives of alkanes.
They are classified according to the number of halogen atoms that replace hydrogen atoms in the alkane.
Monohalogen derivatives: They contain only one halogen atom.
E.g. CH3Cl Methyl chloride
CH3CH(Br)CH3 2-bromopropane
Monohalogen derivatives of alkane are called alkyl halides
Dihalogen alkanes contain two halogen atoms.
Trihalogen alkanes contain three halogen atoms.
Monohaloalkanes
The general formula is RX where R is an alkyl group and X is a halogen.
Common system: ‘Alkyl halides’ are the monohalogen derivatives of alkanes. These are named by naming the alkyl
group attached to halogen and adding the name of the halide. E.g. Methyl halide, Isobutyl halide.
The name of the alkyl group and halide are written as two separate words. The prefixes used to distinguish alkanes
like n-, iso-, sec-, tert, etc. are also written.
IUPAC system: Rules for naming haloalkanes that have branches in carbon chains:
The monohalogen derivatives of alkanes are called haloalkanes. The name of haloalkanes are written by prefixing
the word ‘halo’ (bromo or chloro or iodo or fluoro) to the name of the alkane corresponding to the longest
continuous carbon chain holding the halogen atom. E.g. Bromoethane E.g. Trichloromethane
(a) The longest continuous chain containing the carbon attached to halogen group is selected as the parent alkane
(principal chain or parent chain). While naming alkanes, all the rules that apply to alkane names should be followed.
(b) The carbon atoms are numbered in such a way that the halogen carrying carbon atom gets the lowest number.
(c) The position of the halogen atom and other substituents are indicated by numbers 1,2,3….etc.
E.g. 1-Iodo-2-methylpropane
Dihalo derivatives
(a) When two halogen atoms are attached to the same Carbon-atom, these are called geminal dihalides. Alkylidene
dihalides or alkylidene dihalides are also names used for such compounds. E.g. ethlydine dichloride
(b) When two halogen atoms are attached to adjacent Carbon-atoms, they are called vicinal dihalides. As they
are prepared from alkenes, they are named as the dihalide of the alkene from which they are prepared. E.g.
ethylene dichloride
Polyhalo derivatives: Polyhalo derivative are compounds with multiple halogen atom. These have important
application in agricultural industry.
Fully halogenated hydrocarbons are also called perhalohydrocarbons under a common system.
Nomenclature of aryl halides: Aryl halides are termed Haloarenes in IUPAC systems. ‘Halo’ (bromo or chloro or
iodo or fluoro) is prefixed before the name of the aromatic hydrocarbon. In case of disubstituted compounds, the
relative positions are indicated by (1,2), (1,3) or (1,4). Ortho, meta and para are also used to indicate the positions.
E.g. Chlorobenzene, Bromobenzene.
B.P(K)
400
Chlorides
Bromides
Room 300 Iodides
temperature
200
Gas
Gas
100
0
CH3X CH3CH2X CH3CH2CH2X
Figure 12.1: Boiling points of haloalkanes
Notice that three of these have b.ps’ below room temperature (taken as being about 20° C). These will be gaseous
at room temperature. All the other you are likely to come across are liquids.
Chem i str y | 12.3
PLANCESS CONCEPTS
(b) Boiling point of some isomers: The example shows that the boiling point fall as the isomers go from a
primary to a secondary to a tertiary haloalkane.
CH3
|
CH3 − CH2 − CH2 − CH − Br CH3 − CH2 − CH − CH3 CH3 − C − CH3
| |
Br Br
B.P.s' 375 K 364 K 346 K
To put it simply, this is the result of the fall in the effectiveness of the dispersion forces. The temporary dipoles are
greatest for the longest molecule. The attractions will also be stronger if the molecules can lie closely together. The
tertiary haloalkane is very short and fat, and won’t have much close contact with its neighbours.
The importance of bond strengths: The pattern in strengths of the four carbon-halogen bonds are:
Bond strength falls as you go from C-F to C-I(C-F being the strongest)
1 2 . 4 | Alkyl Halides, Ar yl Halides and Aromatic Compounds
PLANCESS CONCEPTS
You will find almost as many different values for bond strengths (or bond enthalpies or bond energies) as
there are different sources! Don’t worry about this-the pattern is always the same. This is why you have
got a chart here rather than actual numbers.
Saurabh Gupta (JEE 2010, AIR 443)
In order for anything to react with the haloalkanes, the carbon-halogen bond has got to be broken. As that gets easier
when you go from fluoride to chloride to bromide to iodide, the compounds get more reactive in that order. Iodoalkanes
are the most reactive and fluoroalkanes are the least. In fact, fluoroalkanes are non-reactive and thus, not considered.
The influence of bond polarity: Out of the four halogens, fluorine is the most electronegative and iodine the
least. This means that the electron pair in the C-F bond will be dragged most towards the halogen end.
Let’s look at the methyl halides as a simple example:
+ - + - + -
F Cl Br l
No polarity
One of the important set of reactions of haloalkanes is substitute reactions, which involves replacing the halogen
by something else. These reactions involve:
(a) The carbon-halogen bond breaking to give positive and negative ions. The ion with the positively charged
carbon atom then reacts with something either fully or slightly negatively charged. Or,
(b) Something either fully or negatively charged attracted to the slightly positive carbon atom and pushing off
the halogen atom.
The thing that governs the reactivity is the strength of the bonds which have to be broken. It is difficult to
break a C-F bond, but easy to break a C-I one.
Illustration 1: (a) Dipole moment of CH3F is 1.85 D and that of CD3F is 1.86D. (JEE MAIN)
(b) 8-Hydroxy quinoline can be sepated from 4-hydroxy quinolone by steam distillation.
4
Sol: (a) Both the compound has dipole moment as they do not have structural symmetry
5
but CD3F has higher dipole moment compared to CH3F, It is due to the large size of CD3F, but
6 3
D is less EN than H. ( µ = q × d) 7 2
(b) 8-Hydroxy quinoline can be sepated from 4-hydroxy quinolone by steam distillation as it 8 N1
Illustration 2: (a) The pK a of p-fluorobenzoic acid (I) is 4.14, whereas that of p-chlorobenzoic acid (II) is 3.99.
(b) Glycine exists as zwitterion, but PABA does not. (JEE MAIN)
Sol: (a) pKa is a quantitative measure of the strength of an acid in solution. The larger the pKa value, COOH
the more dissociation of the molecules in solution and thus the stronger the acid.
In p-Fluorobenzoic acid + R (resonance effect) is more due to more effective overlap of 2p of F
and 2p of C; combined effect of +R and –I, net e- donating by resonance is slightly more. So, it is
a weaker acid than p-chlorobenzoic acid. (2p)
:F:
(2p)
:
(I)
Chem i str y | 12.5
In case of p-chlorobenzoic acid +R (resonance effect )is very less, due to less effective overlap of COOH
3p of Cl and 2p of C. Combined effect of +R and –I; net e -withdrawing effect is more. So, it is a
‒
:
Glycine is an amino acid it contains both acidic and basic functional group thus (II)
(H N − CH − COOH←
2
→H N
3
⊕
)
− CH2 − COOΘ , the aliphatic ( −NH ) group is sufficiently basic to
2
(Dipolar or Zwitter Ion)
H2N COOH
whereas in PABA (p-amino benzoic acid; an aromatic acid, due to presence of electron donating group ( −COOH)
is not strong enough to donate H⊕ to a much weaker base ( Ar − NH2 ) . So, the dipolar ion is not formed.
-: O H -: C N - : O + + - +
:
: :
H H N
+H H
+
Nucleophiles are either fully negative ions, or have a strong –ve charge. Common nucleophiles are hydroxide ions,
cyanide ions, water and ammonia. Notice that each of these contains at least one lone pair of electrons either on
an atom carrying a full negative charge, or on a very electronegative atom carrying a substantial-charge.
1 2 . 6 | Alkyl Halides, Ar yl Halides and Aromatic Compounds
The nucleophilic substitution reaction –an SN2 reaction: We’ll discuss this mechanism by using an ion as a
nucleophile because it’s slightly easier. The water and ammonia mechanisms involve an extra step which you
can read about on the pages describing those particular mechanisms. We’ll take bromoethane as a typical
primary halogenoalkane. The bromoethane has a polar bond between the carbon and the bromine. We’ll
look at its reaction with a general purpose nucleophilic ion which we’ll call Nu-. This will have at least one
lone pair of electrons. Nu- could, for example, be OH- or CN-. The lone pair on the Nu- ion will be strongly
attracted to the +carbon, and will move towards it and begin making a co-ordinate (dative covalent) bond.
In the process, the electrons in the C-Br bond will be pushed even closer towards the bromine, making it
increasingly negative.
-
Br Br
+ Nu
Nu
The movement goes on until the –Nu is firmly attached to the carbon, and the bromine has been expelled as
a Br‒ ion.
Note: We haven’t shown all the lone pairs on the bromine here. These other lone pairs aren’t involved in the
reaction, and including them simply clutters the diagram to no purpose.
Things to notice: The Nu- ion approaches the carbon from the far side of the bromine atom. The large
bromine atom hinders attack from the side nearest to it and, being –ve would repel the incoming Nu- anyway.
This attack from the back is important if you need to understand why tertiary haloalkanes have a different
mechanism. There is obviously a point in which the Nu- is half attached to the carbon, and the C-Br bond is
half way to being broken. This is called a transition state. It isn’t an intermediate. You can’t isolate it - even for
a short time. It’s just the mid-point of a smooth attack by one group and the departure of another.
+
CH3 + : Nu → H3C − Nu
PLANCESS CONCEPTS
In exam, you must show the lone pair of electrons on the nucleophile (in this case, the Nu- ion). It
probably doesn’t matter whether you show them on the departing Br-ion or not.
Nu: C Br Nu C Br
Technically, this is known as Han SN2+reaction.
- S stands for substitution, N for nucleophilic, and the 2 refers to the
initial stage of the reaction thatHinvolves two species –the bromoethane
H and the Nu- ion.
Transition state
Mechanism: The step-wise mechanism needs to be drawn as shown with very clear details as it gives one a picture
of the molecule’s arrangement in space.
CH3 CH3 H
CH CH3 CH
H 3
3
Nu: C Br Nu:
Nu C
C Br NuNu C C Br + : Br
H + - H + - H
H H H HH
Transition state Transition state
Notice that the molecule has been inverted during the reaction-rather like an umbrella being blown inside-out.
The alternative mechanism: The reaction happens in two stages. In the first, a small proportion of the haloalkane
ionizes to give a carbocation and a bromide ion.
CH3 CH3
slow
CH3 C Br CH3 C+ + : Br
CH3 CH3
This reaction is possible because tertiary carbocations are relatively stable compared to secondary or primary ones.
Even so, the reaction is slow. However, once the carbocation is formed,, it will react immediately when it comes into
contact with a nucleophile like Nu-. The lone pair on the nucleophile is strongly attracted towards the +ve C, and
moves towards it to create a new bond.
CH3 CH3
+ : Nu fast
CH3 C CH3 C Nu
CH3 CH3
The speed of the reaction is governed by the ionization of haloalkane. Because this initial slow step only involves
one species, the mechanism is described as SN1 -substitution, nucleophilic, one species taking part in the initial
slow step.
A primary carbocation would be formed, and this is much more energetically unstable than the tertiary one formed
from tertiary haloalkanes-and therefore, much more difficult to produce.
This instability brings in a very high activation energy for the reaction involving a primary haloalkane. The activation
energy is much less if it undergoes an SN2 reaction.
(iii) Nucleophilic substitution in secondary haloalkanes: There isn’t anything new in this. Secondary haloalkanes
will use both mechanisms-some molecules will react using the SN2 mechanism and other, the SN1. The SN2
mechanism is possible because the back of the molecule isn’t completely cluttered by alkyl groups and so,
the approaching nucleophile can still reach the carbon atom. The SN1 mechanism is possible because the
secondary carbocation formed in the slow step is more stable than a primary one. It isn’t as stable as a tertiary
one though, and so the SN1 route isn’t as effective as it is with tertiary haloalkanes.
1 2 . 8 | Alkyl Halides, Ar yl Halides and Aromatic Compounds
SNi mechanism
(i) Reaction of SOCl2 with Secondary Alcohols: The SNi Mechanism: Walden noted that CH3 CH CH3
when (+)-malic acid treated with PCl5 , the product was (-) chlorosuccinic acid –a process
that proceeded with inversion of stereochemistry. When (+) malic acid was treated with Br
a secondary
thionyl chloride (SOCl2), the product was (+)-chlorosuccinic acid. This proceeds with
haloalkane
retention of stereochemistry.
How can we understand this?
O H Cl O HO H O Cl H
OH PCl5 OH SOCl2 OH
HO HO HO
O O O
(ii) Why Adding SOCl2 And Pyridine Leads To Inversion (via SN2): As it turns out, the stereochemistry of
this reaction can change to inversion if we add a mild base- such as pyridine.
O
Cl
O
: :
S O
: :
Cl Cl
Cl S Cl
Cl H S
:
O HO : H O HO H O O H
OH OH OH
HO HO HO
O O O
O : :
: :
Cl O Cl Cl
O O
:
H H
O OH OH
HO HO
OH
HO O O
O
Both reactions form the “chlorosulfite” intermediate. But, when pyridine (a decent nucleophile) is present,
it can attack the chlorosulfite, displacing chloride ion and forming a charged intermediate. Now, if the
leaving group departs, forming a carbocation, there’s no lone pair nearby on the same face that can
attack. In other words, by displacing chloride ion, pyridine shuts down the SNi mechanism.
Chem i str y | 12.9
PLANCESS CONCEPTS
SOCl2 plus alcohol gives retention of configuration, SOCl2 plus alcohol plus pyridine give inversion
of configuration (SN2)
O HO H O H Cl
OH SOCl2 OH
HO HO
Pyridine
O O
(+)-malic acid (+)-chlorosuccinic acid
inversion
PLANCESS CONCEPTS
Some substrates, whether they are sterically hindered or not, may prefer to undergo SN1 reactions if they
can dissociate into very stable carbocations in the presence of the solvent. In most cases, this involves
resonance-stabilized cations.
Examples of SN1 substrates that form stable carbocations
Br
Polar solvent + -
CH2 + Br
Cl
+
•• Nature of the nucleophile: Both SN1 and SN2 reactions prefer small nucleophiles. Large nucleophiles
have more difficulty accessing the electrophilic center in the substrate. They also have an increased
tendency to act as Bronsted bases, seeking acidic protons rather than electrophilic centers. This is due to
the lower activation energy of acid-base reactions compared to nucleophilic substitutions.
- - - - - - - -
OH CH3O CH3 CH2 O CN RS R C C Br l
Small, strong nucleophiles that favor SN2 reactions are shown below. Most of them have a localized
negative charge. It is also better if they are weak bases, such as bromide and iodide ions, but they can
be strong bases such as hydroxide and alkoxide ions (conjugate bases of alcohols).
Weak, small nucleophiles that favor SN1 reactions are shown below. Notice that several of them are the
conjugate acids of strong nucleophiles. They are also typically neutral, but some have a delocalized
negative charge.
O
-
H2O CH3OH CH3 CH2 OH RSH NH3 F C -
H3C O
•• Leaving group: The nature of the leaving group has more of an effect on the reaction rate (faster or
slower) than it does on whether the reaction will follow an SN1 or SN2 mechanism. The most important
thing to remember in this regard is that good leaving groups are weak bases.
o Except for fluorine, all halogens are good leaving groups
o Groups that leave as resonance stabilized ions are also weak bases and therefore, good leaving
groups.
o Water is a good leaving group frequently used to prepare alkyl chlorides and bromides from alcohols.
The OH group in alcohols is not a good leaving group because it leaves as a hydroxide ion, which is a
strong base. However, if the hydroxyl group is protonated first with a strong acid, it can leave as a water
molecule, which is a good leaving group.
Sol: Reaction of alcohol with alkyl halide in the presence of base yields ether. This reaction is known as Williamson’s
Synthesis.
Na
I. n − Pr OH n−Pr Br
→ n − PrOΘ → Pr OPr ( A )
Na
II. MeOH → MeOΘ ( )
PhCH Br
2 → PhCH OMe B
2
NaOH
III. PhOH EtBr
→ PhOΘ → PhOEt ( C )
Chem i str y | 12.11
Na
IV. t − BuOH
EtBr
→ t − BuOΘ → t − Bu − OEt (D )
This reaction gives a poor yield because of the bulkiness of t-BuO-
Illustration 5: An aromatic compound ( A )( C7H8 O ) on reaction with Br2+H2O gives a white ppt. of compound
(B )( C7H5OBr3 ) . Compound ( A ) is soluble in NaOH. Compound ( C ) , an isomer of ( A ) , also gives the same
reaction and gives a white ppt. of compound (D )( C7H5OBr3 ) . Compound ( C ) is insoluble in NaOH. Identify
( A ) , (B ) , ( C ) and (D ) . (JEE ADVANCED)
Sol: OH OH
Br Br
Br2/H2O
CH3 CH3
(A)
Br
(B)
OCH3 OCH3
Br Br
Br2/H2O
(C)
Br
(D)
Illustration 6: Starting from C6H6 and C6H5OH, synthesize phenyl-2,4-dinitrophyneyl ether (B) (JEE ADVANCED)
Sol:
Cl Cl
NO2
Cl2
Path I : C6H6
FeCl3 Fuming
HNO2
NO2 -
PhO
(A)
-
OH O O
- NO2
OH
Path II :
Cl
NO2
(B)
O Nitration
1 2 . 1 2 | Alkyl Halides, Ar yl Halides and Aromatic Compounds
(b) Elimination reactions: We have seen that alkyl halides may react with basic nucleophiles such as NaOH via
substitution reactions.
H H
H
-O : : : :-
: :
: :
: :
: :
: :
: :
:
H + C Br H O C Br H O C + Br
H
H HH H
H
transition state
When a 2° or 3° alkyl halide is treated with a strong base such as NaOH, dehydrohalogenation occurs producing
an alkene-an elimination (E2) reaction.
KOH in ethanol
Br + KBr + H2O
-HBr
H
OH- + C C C=C + Br + HO-H
Br
The Nu: removes an H+ from a β-carbon, the halogen leaves forming an alkene
All strong bases, like OH, are good nucleophiles. In 2° and 3º alkyl halides, the α-carbon in the alkyl halide is
hindered. In such cases, a strong base will ‘abstract’ (remove) a hydrogen ion (H+) from a β-carbon, before it hits
the α-carbon. Thus, strong bases cause elimination (E2) in 2° and 3 alkyl halides and cause substitution (SN2) in
unhindered methyl° and 1° alkyl halides.
In E2 reactions, the Base to H σ bond formation, the C to H σ bond breaking, the C to C π bond formation, and
the C to Br σ bond breaking all occur simultaneously. There are no intermediate forms of carbocation. Reactions in
which several steps occur simultaneously are called ‘concerted’ reactions.
(i) Zaitsev’s Rule: Recall that, in elimination of HX from alkenes, the more highly substituted (more stable)
alkene product predominates.
Br
CH3CH2O- Na+
CH3CH2CHCH3 CH3CH=CHCH3 + CH3CH2CH=CH2
EtOH
2-butene 1-butene
major product minor product
(>80%) (<20%)
•• In cyclic structures, however, single bonds cannot rotate, in regards with the stereochemistry. See the
following example.
E.g. Trans-1-chloro-2-methylcyclopentane undergoes E2 elimination with NaOH. Draw and name the
major product.
H H3C
H3C H H
Na+ OH- + NaCl
H H3C
+ HOH H
H H E2 H
H H
Cl Non zaitsev product Little or no zaitsev (more stable)
is major product product is formed
3-methylcyclopentene 1-methylcyclopentene
PLANCESS CONCEPTS
•• Non basic, good nucleophiles, like Br − and l− will cause substitution not elimination. In 3° substrates,
only SN1 is possible. In Me and 1° substrates, SN2 is faster. For 2° substrates, the mechanism of
substitution depends upon the solvent.
•• Strong bases, like OH- and OR-, are also good nucleophiles. Substitution and elimination compete. In
3° and 2° alkyl halides, E2 is faster. In 1° and Me alkyl halides, SN2 occurs.
•• Weakly basic, weak nucleophiles, like H2O , EtOH, CH3COOH , etc., cannot react unless a C+ forms.
This only occurs with 2° or 3° substrates. Once the C+ forms, both SN1 and E1 occur in competition.
The substitution product is usually predominant
•• High temperatures increases the yield of elimination product over substitution product.
( ∆G =∆H − T∆S ) Elimination produces more products than substitution, hence creates greater
entropy (disorder).
•• Polar solvents, both protic and aprotic, like H2O and CH3CN, respectively, favor unimolecular
reactions (SN1 and E1) by stabilizing the C+ intermediate. Polar aprotic solvent enhance bimolecular
reactions (SN2 and E2) by activating the nucleophile.
Saurabh Gupta (JEE 2010, AIR 443)
1 2 . 1 4 | Alkyl Halides, Ar yl Halides and Aromatic Compounds
(iii) E1CB elimination: In any E1CB reaction, a base first removes a proton from the α carbon of the substrate
to give an intermediate carbanion (a species with a negatively charged carbon). This carbanion then
( )
loses the leaving group − : L to form alkene products (s). The E1CB mechanism usually occurs with
strong bases and with substrates where groups directly attached to the carbanion center can stabilize that
center’s negative charge.
- -
B: H C C L B H :C C L
- -
:C C L C = C :L
(iv) Elimination of X-X: Alkenes also form from the loss of both X’s of a 1,2-dihaloalkane.
X X Elimination
of
C C C=C
Both
X’s
These dehalogenation reactions do not involve bases. They use metals such as Mg or Zn that react with
the halogens (Cl, Br, and/or I) to form metal salts such as MgX2 or ZnX2 .Their mechanisms probably
involve formation of intermediate organometallic compounds on the metal surface that then eliminate
as +Mg ‒ X or +Zn ‒ X and X‒
Mg
BrCH2 CH2Br CH2=CH2+MgBr2
Ether
Zn
(CH3)3 C CHBr2 CH2Br (CH3)3 C CH2 CH=CH2+ZnBr2
Br
Zn
+ ZnBr2
Br
1ooalkyl
2oalkyl Cl
3 alkyl R X Br
alkenyl l
aryl
Mg Ether
or THF
R Mg x
l +Mgl
Mg
C - C Basic and nucleophilic
H H Ether H H
H H
Iodomethane Methylmagnesium iodide
Mg 2 → CH CH CH CH CH CH H O
CH3CH2CH2CH2CH2CH2Br → CH3CH2CH2CH2CH2CH2MgBr 3 2 2 2 2 3
Ether
Basic and
nucleophilic
2Li
CH3CH2 CH2CH2Br CH3CH2 CH2CH2Li + LiBr
Pentane
1-Bromobutane Butyllithium
Ether
2 CH3Br + Cul (CH3)2Cu- Li+ + Lil
Methyllithium Lithium dimethylcopper
(a Gilman reagent)
Ether
(CH3)3CuLi + CH3(CH2)8CH2l o
CH3(CH3)8CH2CH3 + Lil + CH3Cu
0C
Lithium 1-lododecane Undecane (90%)
dimethylcopper
Re dP
•• R − I + HI →
∆
R − H + I2
•• Zn−Cu/alc
R − CI + 2 H → R − H + HCl
Illustration 7: Identify all the possible alkenes that would be formed on the dehydrohalogenation of the following
organic halides with alcoholic KOH. Also, identify the major alkene.
i. 1-Chloropentane ii. 2-Chloropentane (JEE MAIN)
Sol: 4 2 4 2
4 Cl Alc. KOH
5 2 5 4
i. Cl Alc. KOH
2
1 + Me
5Me 3 1 Me
5 3 Me
Me 3 1 Me 3 1 + Me Me
Pent-1-ene Pent-2-ene
Pent-1-ene
(Minor) Pent-2-ene
(Major)
(Minor) (Major)
ii. Cl
Cl
5 4 2 Alc. KOH
Me Me + Me
5Me 4 3 2 1 Alc. KOH Me
Me Me + Me
Me 3 1 Me Pent-2-ene Pent-1-ene
Pent-2-ene
(Major) Pent-1-ene
(Minor)
(Major) (Minor)
Illustration 8: Predict the order of reactivity of the following compounds in dehydrohalogenation. (JEE MAIN)
Me
I. Me Cl II.
Cl
Me
Me
Me
III. Br IV. Me
Me Br
Br
V.
Me Me
Me
Sol: Stability of carbocation has the influence on reactivity towards dehydrohalogenation. The more stable the
carbocation, greater is the reactivity towards dehydrohalogenation.
Order of the Stability of carbocation: tert>sec>primary.
Find out the carbocation formed during each reaction and predict the order of reactivity accordingly.
Order of reactivity: (V) > ( III ) > ( II ) > ( IV ) > ( I )
+
I. Me Cl Me
o +
1C
Me
Me
+ +
o
2C
o + o
+
(1 C 2C )
Me Me Me
Me +
II. Cl +
Me Me Me
o + o
+
1C 3C
o
+ o
+
(1 C 3C )
Me
Me + Me Me
Br +
III.
Me Me Me
+
3 C+
o o
1C
o
+ o
+
(1 C 3C )
IV. Me Me +
(only 2oC )
Me Me
+
2 C+
o
Br
Me
Me
+ o +
(only 3 C )
V. Br
Me
Me Me Me
o
3C
1 H
2 -
EtO + EtOH
Cl Only one product
trans-1-Isopropyl-2-chloro
cyclohexane
Sol: Bulky group at equatorial position imparts stability to the ring. In order to undergo dehydrohalogenation
reaction the basic condition to be followed is that the two leaving group has to be in anti periplanar geometry. By
using this condition answer the question.
•• Here Bulky group has to be in equatorial position (down the plane) as to impart stability and Cl group should
also be at equatorial position (up the plane) for trans-configuration.
•• In Dehydrohalogenation reaction one important requirement is the orientation of the two leaving atom.
•• The two leaving atom has to be in Anti periplanar position.
•• Here there are two possibilities, H can be eliminated from C1 or it can be eliminated from C3.
•• On talking about H at C1, The H atom occupies axial position and Cl is in equatorial position. Thus the orientation
is Syn periplanar (Both upward) so the reaction is not feasible. Thus we only get one product.
1 2 . 1 8 | Alkyl Halides, Ar yl Halides and Aromatic Compounds
Me
(Cl) and group in trans-position
Me
1a 1 1
e Me 2
H Me
Cl
2 e 2 3
3 3
H a
H
•• H atom at C3 occupies equatorial position and Cl is also in equatorial position thus the orientation is anti, thus
we get the product.
Illustration 10: Explain the stereochemistry of the products from E2 dehalogenation with IΘ of the following.
E2-dehydrobromination of (a) R, R-2, 3-dibromobutane and (b) meso-(R,S)-2, 3-dibromobutane. ( JEE ADVANCED)
Sol: Draw the structure of the compound (a) and (b).In order to undergo dehydrohalogenation reaction the two
leaving group has to be in anti periplanar. In order to get this condition interchange the group accordingly. Br-
attacks the compound from the bottom side.
(a)
Br
(b)
Me Me
Me H H H
Me
Me
Br Br + Me
Br Br
H
cis or E-2-Bromo-2
butene (Note: cis or E)
:
B
(R,S)
Chem i str y | 12.19
(a) Alkane +Cl2 or Br2, heat or light replaces C-H with C-X but gives mixtures
i) Hard to control ii) Via free radical mechanism
(b) It is usually not a good idea to plan a synthesis that uses this method-multiple products
h
Initiation step Cl Cl 2 Cl
H3C H H Cl
Step 1
+ +
Propagation steps H3 C
Cl
(a repeating cycle)
+ Step 2 +
H3C Cl Cl Cl
H3C + CH3 H3C CH3
Termination steps Cl + CH3 Cl CH3
Cl + Cl Cl Cl
( )
30% 1ο Product
= 5%per(1ο )H
70%(2ο )Product
= 17.5%per(2ο )H
6 (1 ) H's
ο
4(2ο )H's
17.5%per(2ο )H
∴ = 3.5 : 1 relative Reactivity
5%per(1ο )H
1 2 . 2 0 | Alkyl Halides, Ar yl Halides and Aromatic Compounds
35 : 65
( )
65% 1ο Product
7.2%per(1
= ο
)H
35%(3ο )Product
35%per(3ο )H
9 (1 ) H's
ο
1(1ο )H's
35%per(3ο )H
∴ =5:1 relative reactivity
7.2%per(1ο )H
Relative Reactivity
1. Based on quantitative analysis of reaction products,
relative reactivity is estimated for RCH3
( )
R2CH2
Cl2 : 5 : 3.5 : 1for 3ο : 2ο : 1ο R3CH
R’ H + .Cl
2. Order parallels stability of radicals
3. Reaction distinction is more selective with bromine than Energy R’. + HCl
H H H H R H R’ Cl
H H R
C C C
R H R R R R C C C Reaction progress
R H R R R R
Primary < Secondary < Tertiary Primary < Secondary < Tertiary Figure 12.1: Energy profile diagram of different
1.0 3.5 5.0
alkyl halide
Reactivity Stability
h
+ Br2 + HBr
cyclohexene H H 3-bromocyclohexene
(80%)
An allylic hydrogen has been substituted for a bromine.
The bromine atom abstracts an allylic hydrogen because the allylic radical is resonance stabilized.
The radical then reacts with a bromine molecule to continue the chain.
abstraction of allylic H
H
H H
. H H Br
Br. . Br - H +
H
.
H
Br - Br
+ Br .
H H H
Cyclohexene allylic radical allylic bromide
Chem i str y | 12.21
3. From Alcohols
anhydrous
(a) Preparation of alkyl chloride: R − OH + HCl
ZnCl ∆
→ R − Cl + H2O
2,
anhydrous ZnCl
(i) 2 → CH CH − Cl + H O
CH3CH2 − OH + HCl( g) 3 2 2
Note: Tertiary alcohols react with HCl(g) even in the absence of anhydrous ZnCl2.
conc.H SO
(b) Preparation of alkyl bromides: R − OH + HBr →2 4
reflux
R − Br + H2O
conc.H SO
(i) CH3CH2 − OH + HBr →2 4
reflux
CH3CH2 − Br + H2O
reflux
(c) Preparations of alkyl iodides: R − OH + HI → R − I + H2O
reflux
CH3CH2 − OH + HI → CH3CH2 − I + H2O
3R − OH + PCl3 → 3R − Cl + H3PO3
Pyridine
R − OH + SOCl
reflux
→ R − Cl + SO + HCl
CCl
4. Borodine Hunsdiecker Reaction: RCOOAg + Br2 → 4
reflux
R − Br + CO2 + AgBr
Mechanism
RCOOAg R C O + Ag
O
Step 1 : R C O+Br Br R C O Br + Br
O O
Step 2 : Initiation
R C OBr R C O + Br
O O
Step 3 : Propagation
R C O R + CO2
O
Step 4 : Propagation
R + R C O Br R Br + R COO
O
1 2 . 2 2 | Alkyl Halides, Ar yl Halides and Aromatic Compounds
5. Finkelstein Reaction
3 CH OH or
R − Cl + NaI → R − I + NaCI
NaCl
acetone
acetone
R − Cl + NaBr → R − Br + NaCl.
The reverse reactions, is not possible because NaCl and NaBr are insoluble in CH3OH or acetone.
Illustration 11: Identify all the possible products. Give the major products and rank the products in decreasing
order of reactivity with NBS.
Me Me
NBS + h
Products
(
Sol: Reactivity order: 3ο allylic > 2ο allylic > 1ο allylic )
(I) > (II) = (III) > (IV) o
2 allylic
Me Me Me Me
NBS + h
o
1 allylic Allylic
bromination Br
o
3 allylic
(I)
o
2 allylic Major
Br
+
Me Me Me Me
+
(III) Br (II)
Br
+ Me
(IV)
Chem i str y | 12.23
Illustration 12: Identify all the possible products. Give the major products and list them in decreasing order of
reactivity with Me3COCl.
Me
Me3COCl
Products
Me Me h
Me3COCl
Me
Products
Me h
( )
Me
Sol: Reactivity order: 3ο allylic > 2ο allylic > 1ο allylic Me Me3COCl
Me Me +h
Me Me3COCl
Allylic
Me
o
2 allylic +h chlorination
Me
Allylic
o
o
2 allylic
1 allylic Cl chlorination
Me
Me
o
1 allylic Cl + Cl Me
Me Me Me Me
(I) + Cl (II)
Me Major Me Minor
Me
(I) (II)
Major Minor
Illustration 13: which of the following will solvolyse faster in SN1 and why?
CH3 H
H CH3
H and Br
Br H
(A) (B)
Sol: Compound with Substituents on equatorial position are more stable than Diaxial compound. Less stable
compound undergoes the reaction faster.
•• The rate of SN1 reaction depends on the difference in energy of the ground state and the transition state.
•• In compound (A) both H occupies equatorial position whereas in compound (B) both H occupies axial position
•• Compound (A) will solvolyses faster than (B).
•• Diaxial compound (A) is less stable than diequatorial compound (B) and thus (A) solvolyses faster.
Illustration 14: Indicate whether the following are SN1, SN2, E1, or E2.
60ο C
1. ( CH3 ) CBr + C2H5OH → ( CH3 ) C− OC2H5 + ( CH3 ) C = CH2
3 3 2
(Major ) (Major )
2. CH3CH2CH2Br + LiAlH4 →
3. CH3CH2CH2Cl + IΘ →
Θ
6. CH3CHBr − CH3 + OH (Ethanol) →
4. ( CH3 )2 C = CH2 ,E2,3 halide, and CN- is a strong base, so elimination is predominant over SN1.
ο
7. ( CH3 )3 C − OH,SN1, H2O is not basic enough to remove a proton to give elimination reaction.
Illustration 15: The order of leaving group ability for the following is: 1. −OAc 2. −OMe 3. −OSO2Me 4. −OSO2CF3
Sol: Acidic and leaving group order: CF3SO3 − > MeSO3 − > AcO− > MeO − .
Base
A. (A)
Me
OH Br Base A. Me
A. (A) + OH
Cl
OH Br
Me
Br C2H5O
B. (B) B. Me
S 1 + OH
Br C2NH2O F
B. 1
(B)
SN Me
O Me C. Me
+ OH
A. (A) B. (B)
O Me Me
Sol: A. O (A) B. (B) F Me
A. Me
+ OH
O Cl
D. + OH
Me
Illustration 17: Give the major products of
B. the
Mefollowing elimination reactions. Br
+ OH
F
Me
Me Me
C. Me E. Me Cl + CH3O
A. Me
+ OH + OH
Cl
F Me
Me
Me
Me
B. Me
+ OH D. + OH
F F. Me O + CH3X
Me Br
C. Me Me
+ OH Me Me
F Me Me E2
E. Me Cl + CH3O G. N Me + OH
Me
O
Me O O
S O Ph + OH
I. S Ph + OH
I.
F. Me O + CH3X
Me Me Chem i str y | 12.25
Me Me
Me
Me Ph Ph
Ph Ph
H H CH3
Me J. H H CH3
E2 J. E1
G. N Me + OH H3C N
N
E1
H3C
Me O CH3
Me O CH3
OH + Me
H / Me
H. Me
E1 Me CH3OH
Me Me CH3OH
K. Ph
K. Ph E1
Cl E1
Cl
Me
O Me
O
I. S Ph + OH
Me Me
Sol: E2
Ph elimination
Ph follows Hofmann rule and produces Hoffmann product (less substituted alkene-less stable)
H H CH3
E1
J.
elimination follows Zaitsev’s rule
E1 and produces Zaitsev’s product (more substituted alkene –more stable)
H3C N
O Me
CH (E2, Saytzeff)
A. Me
3
E. CH3OΘ (nucleophilic cannot attack) 3ο C having high e‒ density, hence elimination takes place giving alkene.
Me
Me
Me Cl + OCH3 Me
Me
Me Me
Me Cl + OCH3 Me
Me
Me
Me
( )
F. Williamson synthesis ( CH3 ) CΘ NuΘ attacks on 1ο C atom. (SN2)
3
Me O + CH3 X Me O Me
Me Me
Me Me
Me O + CH3 X Me O Me
Me Me
G. Hofmann elimination, less-substituted alkene because the leaving group ( CH3 ) N⊕ departs as uncharged
3
species.
1 2 . 2 6 | Alkyl Halides, Ar yl Halides and Aromatic Compounds
Me
Me Me
N
+ (CH3)3N
Me H Me
OH
OH +
H /
H. +
Me Me E1
Major Minor
Saytzeff Alkene
O O
O O
I. S Ph + OH Ph
S
Me
Me Me Me
Ph Ph Ph Ph
H H CH3
J.
E1 H3C H
H3C N
O CH3
Me Me
Me CH3OH CH3
K. Ph Ph CH
Cl E1 CH3
Me OCH3
ARYL HALIDES
1. INTRODUCTION
Aryl halides are compounds where halogen is directly attached to an aromatic ring. They have the general formula
ArX, where Ar is phenyl substituted phenyl or a group derived from some other aromatic system e.g.
Br Cl l COOH
Cl
NO2
CH3
An aryl halide is not just any halogen compound containing an aromatic ring C6H5 − CH2 − Cl is not an aryl halide
for the halogen is not attached to the benzene ring.
The properties of aryl halides are entirely different from that of Alkyl halides.
Chem i str y | 12.27
Reduction HNO2/HX
o
0C
diazonium salt
(i) Sandmeyer Reaction + -
NNX Cl
Cu2Cl2 + N2
+
(ii) Gattermann Reaction
-
N NCl Cl
Cu/HCl + N2
The Gatternann reaction is a modification of Sandmeyer reaction. In Sandmeyer reaction, cuprous halides are used which
are unstable and difficult to handle, however in Gattermann reaction copper power and hydrogen halide are used.
Cl Cl Br Br
FeCl3;Dark
FeCl ;Dark FeCl3;Dark
FeCl3;Dark
(i)
(a) (a) + Cl2 + Cl2 3 (ii)
(b)
+ HCl + HCl (b) + Br2 + Br2 + HBr + HBr
310-320
310-320 K K Room Room
Temp Temp
l
(iii) + l2 + Hl
This reaction is reversible due to the formation of HI which is a strong reducing agent. To get iodobenzene, HI must
be removed from the reaction mixture. To achieve this some oxidising agent like HIO3,HNO3 or HgO is used.
Illustration 18: Starting from C6H6 and C6H5OH , synthesize phenyl-2, 4-dinitrophenyl ether (B). (JEE ADVANCED)
Sol: The Cl of (A) undergoes aromatic nucleophilic displacement because it is activated by two ( −NO2 ) groups.
Cl Cl
NO2
Cl2
Path I : C6H6
FeCl3 Fuming
HNO3
NO2 PhO
(A)
OH O O
NO2
OH
Path II :
Cl
NO2
(B)
O Nitration
1 2 . 2 8 | Alkyl Halides, Ar yl Halides and Aromatic Compounds
(a) Aryl halides are colourless liquids and colourless solids with a characteristic odour.
(b) The boiling point of aryl halide follows the order ArI > ArBr > ArCl > ArF
(c) The melting point of p-isomer is more than o- and m-isomer.
Structure and Reactivity of Aryl Halide and Vinyl Halides: Chlorobenzene is a resonance hybrid of 5 resonating
structures.
:
:
: : : : : : :
Cl +Cl +Cl +Cl Cl
- -
-
I II III IV V
Contribution by II, III and IV give a double bond character to the carbon-chlorine bond. Hence C-Cl bond in
chlorobenzene is strong. As a result, aryl halides are less reactive compared to the corresponding alkyl halide
towards nucleophilic substitution reaction.
Similar is the case with vinyl halides.
+
:
: :
CH2 = CH Cl CH2 CH = Cl
(a) Therefore attempts to convert aryl halides into phenols, ethers, amines with the usual nucleophilic reagents
and conditions are unsuccessful. e.g R-Cl+aq.NaOH → ROH+NaCl
Cl
+ aq NaOH No reaction
(b) The carbon-halogen bonds of aryl halides and vinyl halides are usually short.
(c) Dipole moments of aryl and vinyl halides are usually small
:
:
Cl Cl
3
2
Cl sp Center
sp
Center(d) In chlorobenzene, the chlorine atom is attached to a sp2hybridized carbon atom whereas in alkyl chloride, the
chlorineCH
atomCH
is attached
Cl to a sp3 hydridized carbon atom.
3 2
The sp2 hybridized carbon atom is more electronegative than the sp3 hybridized carbon atom, thereby the
release of electrons to chlorine atoms is less in chlorobenzene and more in alkyl chloride.
:
:
Cl Cl
3
Cl resonatingspstructure
Center
2
sp (e) The of chlorobenzene indicate that the benzene ring carries a –ve charge at o- and
Center p-positions w.r.t. chlorine atom. Thus the benzene ring definitely takes part in electrophilic substitution
reactions.
CH3 CH2 Cl
Chem i str y | 12.29
-+
OK OH
Like NO2, certain other groups have been found to increase the reactivity of chloro benzene if present at ortho or
para to chlorine atom. These groups are,
⊕
− N(CH ) , − CN, − SO H, H− COOH, − CHO, − C − R
33 3 ||
O
Cl ONa OH
Cl OH
NO2 NO2
(i) Na2CO3
o
130 C
(ii) dil.HCl
NO2 NO2
Cl OH
NO2 NO2 NO2 NO2
H2O; warm
NO2 NO2
NH3, Cu2O
o + HCl
200 C
20-30 atm
Aniline
1 2 . 3 0 | Alkyl Halides, Ar yl Halides and Aromatic Compounds
Here again the presence of NO2 groups at ortho or para position w.r.t. Cl group increases the reactivity.
Cl NH2
NO2 o
NO2
NH3; 170 C
NO2 NO2
Cl CN
+ CuCN + CuCN
475 K
Cl OCH3
Cu Salt
+ CH3ONa o + NaCl
220 C
Mechanism: The nucleophilic aromatic substitution reaction can be well explained by a bimolecular mechanism.
Cl : Nu-
Cl Nu
slow -
Step 1 (Intermediate)
Cl NO2
Nu
-
: :
+ : Cl
:
-
Step 2
Product
Equivalent to
Cl Nu Cl Nu Cl Nu Cl Nu
- -
X X X
NH2
+ NH3
H Benzyne
Addition
-
NH2 NH2
-
NH2 NH2
+ H - NH2 + NH-
2
-
2.
Electrophilic Substitution Reaction: Halogens are unusual in their effect on electrophilic substitution
reactions: They are electron withdrawing yet ortho and para-directing.
To understand the influence of halogens, let us consider the intermediate formed when an electrophile attacks
the halobenzene at ortho, meta and para positions.
X X X
Y Y Y
Ortho attack
H H H (A)
X X X X
Y H H Y H Y
X X X
Y Y Y
In A, B and C if one considers the inductive effect i.e. (-I effect) of X then A and B would be unstable because the
(+) charge comes on the carbon atom carrying the halogen atom X. The structure C will be most stable and the (+)
charge does not come on the carbon atoms carrying the halogen atom X.
We should therefore expect that halogen atoms attached to the benzene ring would be meta. While directing for
electrophilic substitution reactions, the existence of halonium ions have shown that halogen can share a pair of
electrons and can accommodate a positive charge. When this idea is applied to the present problem the carbocations
formed when an electrophile attacks at ortho or para position i.e. (A) and (B) would be stabilized as below. Whereas
the carbocation formed when the electrophile attacks the meta position on halo benzene i.e. C would be destabilized.
:
: :
X : :
X
Y Y
(A)
H H Charge delocalized
: :
X
:
: :
X
Charge delocalized
(B)
H Y
H Y
1 21.
. 3 2Halogenation
| Alkyl Halides, Ar yl Halides and Aromatic Compounds
Cl Cl 1. Cl
Halogenation
Cl
The inductive effect causes electrons withdrawing deactivation-Clthe resonance effect tends Cl to oppose theClinductive
FeCl2;Dark
effect for attack at 2ortho and para position, and hence
+ Cl + makes the deactivation less for orthoCland para than for
Cl2
FeCl2;Dark
meta. This shows reactivity is controlled by the inductive effect, and+orientation is controlled by resonance
+ effect.
Reactions Cl Cl
1.
1. Halogenation 2.
Halogenation
2. Nitration Nitration
2. Nitration
Cl Cl Cl ClCl Cl Cl Cl Cl
Cl NO2
FeCl2;Dark NO2 + H2SO4
+ Cl2 + H2SO4 + + HNO3 +
+ HNO 3 + o
60 C
o
60 C
Cl NO2
3. Sulphonation (C)
3. Sulphonation
2. Nitration Cl NO2 Cl Cl
3. Sulphonation
Cl
Cl
Cl
Cl
Cl
Cl
SO3H
NO2 + H2SO4 +
+ H2SO4 SO H
+ HNO3
o + 3
+ H2SO60
4
C + SO3H
NO2
3. Sulphonation
Cl Cl Cl SO3H
SO3H
4. Friedel Crafts Reaction
+ H2SO4 +
(a)
(A) Alkylation
SO3H
Cl Cl Cl
anhyd
R
AlCl3
+R-X +
(b)
(B) Acylation R
O
Cl Cl Cl
anhyd
C-CH3
AlCl3 +
+ CH3COCl or CH3C-O-C CH3
O O
C=O
(c)
(C) Benzoylation CH3
O
Cl Cl Cl
anhyd
C-C6H5
AlCl3 +
+ C6H5COCl or C6H5-C-O-C-C6H5
O O
C=O
C6H5
Chem i str y | 12.33
5. Miscellaneous Reactions
(c ) Ullmann's reaction
l
Cu powder
Biphenyl
Chlorobenzene does not undergo Ullmann’s reaction but if a deactivating group is attached to chlorobenzene then
the substituted chloro benzene can take part in Ullmann’s reaction.
Cl NO2
NO2
Cu powder
NO2 NO2
NO2
NO2
SN2 SN1
Reaction RX + Nu ‒‒ > RNu + X Same
Mechanism Concerted Two steps
Intermediate None Carbocation
Kinetics Second-order First order
Stereochemistry Complete inversion Nonspecific
Nucleophile Important Unimportant
Leaving Group Important Important
Alkyl Group CH3 > 1° > 2° > 3° 3° > 2° > 1° > CH3
(steric hindrance) (carbocation stability)
Occurrence CH3, 1°, some 2° 3°, some 2°
Solvent Effects Variable (Poloreproteic) Polar, protic
1 2 . 3 4 | Alkyl Halides, Ar yl Halides and Aromatic Compounds
PLANCESS CONCEPTS
Elimination Mechanisms
Table 12.2: Difference between E1 and E2
E2 E1
Reaction RX + Base-->C=C Same
Mechanism Concerted Two steps
Intermediate None Carbocation
Kinetics Second-order First order
Stereochemistry Anti periplanar Nonspecific
Base Important Unimportant
Leaving Group Important Important
Alkene Produced Zaitsev Rule Same
SN1 SN 2 E1 E2
CH3X No Good nucl. No No
1° (RCH2X) No Good nucl., weak base No Strong base, weak nucl.
E2 SN2 E2 No reaction
2ο (R 2CHX )
E2 SN1 E2 S N2
3ο (R 3CX )
Illustration 19: Write the structure of carbocation produced on treatment of a compound (A)(Ph2CHC(OH)Me2)
with SbF5/SO2. (JEE MAIN)
Sol: It is formed by protonation and subsequent elimination of H2O, followed by H+ ion transfer to form a more
stable carbonium ion.
H OH H
H
Ph C C Me Ph C C Me
-H2O
Ph Me Ph Me
H
Ph C C Me
Ph Me
Illustration 20: Which of the following has the greater Ka value (JEE Advanced)
OH OH
D D
I. II.
Illustration 21: Which of the carbonyl groups in (A) and (B) protonate more readily in acid solution and why?
(JEE Advanced)
A. H3CO COCH3
B. O2N COCH3
Sol: Protonation of (A) takes place more readily than (B), since protonated (A) is more resonance stabilised than
protonated (B).
OH
MeO C COCH3
OH
Illustration 22: (JEE MAIN)
O2N C COCH3
Cl
(B) Less stable
O2N NO2
I. + NaOH (A)
NO2
NO2
NO2
MeONa
II. (B)
MeOH,
I. + NaOH (A)
NO2
NO2
MeONa
II. (B)
MeOH,
CF3
III. NaNH3
(C)
Liq. NH3
Cl
Br
Me OMe KNH2
IV. (D)
Liq. NH3
Sol: (I) [due to three e‒ -withdrawing (NO2) groups (C ‒ Cl) bond is weakened.
(III) [Due to e‒ -withdrawing (‒CF3) groups, (C ‒ Cl) bond is weakened, so SN reaction takes place.]
(IV) No. reaction since there is no H at o-position that can form benzyne.
NO2
KCN,
II. (H)
C2H5OH
Br
CN
Sol: I. (F) O
O (G) II. (H)
Diels-Alder
Br
Chem i str y | 12.37
Me
Me
Illustration 24: Br
Br
NaCN,
NaCN,
I.I. (J)(J)
CC2H
H5OH
2
OH 5
NO
NO22
NO22
NO
Br
Br22,Fe
,Fe (i)(i)KCN
KCN
II.II. (K)
(K) (L)(L)
(ii)
(ii)HH
2OO
2
Me
Me
(JEE ADVANCED)
Me NO2
Br CN COOH
CN Br Br Br
Me Me Me
Illustration 25: When a trace of KNH2 is added to a solution of chlorobenzene and potassium triphenyl methide
((Ph)3 CΘK ⊕ ) in liquid NH3, a rapid reaction takes place to yield a product of formula C25 H20. What is the product?
What is the role of KNH2 and why is it needed? (JEE ADVANCED)
Sol: C25H20 suggests that the product is tetraphenylmethane, Ph4C. KNH2 is used to produce benzyne which
combines with Ph3 C‒K+ to give the final product.
Cl
CPh3
CPH3
KNH2 Ph3C NH3
NH3 + NH2
+H +
1 2 . 3 8 | Alkyl Halides, Ar yl Halides and Aromatic Compounds
1. PHENOL
This process (to derive phenol) is carried out by the aerial oxidation of cumene to hydroperoxide, which is then
decomposed by acid into phenol and acetone (by product).
Me Me
Me +H2SO4 O2
or o
OH 130 C
Cl (100% yield)
+ Anhyd, AlCl3
Me Me
Me
or Me O - OH
OH
+ BF3
Me Me Cumene
hydroperoxide
Electrophile in all is Me Me
Attacking point OH
Me
H2SO4
o
100 C
+ O
Me
Phenol Acetone
(c) Carbocations formed during the reaction rearrange to yield more stable carbocation.
(d) It is often accompanied by the rearrangement of alkyl group attached to the nucleus e.g., 1, 2, 4-trimethyl
benzene rearranges to give mesitylene in friedal craft reaction.
Me Me
Me
AlCl3 + HCl
+ AlCl3 + HCl
or HAlCl4
Me Me
Me
(e) The presence of e¯-withdrawing groups (m-directing group) in the ring hinders the Friedal craft reaction,
e.g., nitrobenzene and acetophenone do not undergo this reaction. On the other hand, if a strong activating
group (e¯-donating group) is present in either of the above two compounds, reaction takes place, e.g., o-nitro
anisole can undergo this reaction.
(f) The presence of (NH2), (NHR) and (NR2) groups also inhibits the reaction. This is because these groups
become powerful e¯-withdrawing groups reacting with Lewis acid or with protoic acid when the compounds
containing these are placed in friedal craft reaction mixtures.
+ AlCl3
(I)
Lewis acid
NH2 NH2
(II) +H
(g) Friedal craft reaction reactivity order of the following compounds is:
Me
Me Me Me Me Me Me
D D T T
D T
Here, again no. (C–H), (C–D), or (C–T) bond break in the first R.D.S. (See mechanism), so primary isotope effect does
not take place. So the rate of reaction of the above is almost same.
1 2 . 4 0 | Alkyl Halides, Ar yl Halides and Aromatic Compounds
Me Me Me
Me3C-Cl+AlCl3 COPh
PhCOCl+AlCl3
Me3C-OH+AlCl3
Me
Me Me
COPh CMe3 Me
PhCl+ AlCl3 COPh
+
SO3H SO3H
t-Butyl o-Benzoyl
benzene toluene
Me
COPh
Desulphonation
o-Benzoyl H2SO4+steam+H2O
toluene or
o
HCl/H2O at 150 C
To avoid the oxidation of aniline and phenol by nitration, the amino and (–OH) groups are protected by acetylation
or benzoylation. The acetyl or benzoyl group is finally removed by hydrolysis to give o-and p-isomers.
Acetylation can be done by any of the following three acetylating reagents.
(a) (CH3CO)2O + Glacial acetic acid
(b) (CH3CO)2O + Conc. H2SO4
(c) CH3COCl + Pyridine
The benzoylation of alcohol, phenol, aromatic or aliphatic amine with benzoyl chloride (C6H5COCl) and NaOH is
called Schotten-Baumann reaction.
Chem i str y | 12.41
Example:
Py.
(i) ROH + ClCOCH3 ROCOCH3 + HCl
PhCOCl
+NaOH ROCOPh + NaCl + H2O
(ii)
(ii) NH - CO - Ph NH2 NH2 - CO - CH3
Benzoylation Acetylation
(CH3CO)2O + CH3COOH
Benzanilide Aniline Acetanilide
(N-Phenyl benzamide)
NHCOCH3 NHCOCH3
Conc. HNO3
NO2
+ Conc. H2SO4
+
Nitration, 288 K
NH2 NH2
NO2
H / H2O +
-AcOH
NO2 (Minor)
(Major)
SOCl2 Anhyd. Zn + Hg S or Se
o-HOOC – C6 H4 – CH2 – Ph (B) (C) (D) (E)
(A) AlCl3 + HCl 600ºC
Sol:
O
COOH H
SOCl2 Cl
(A) (B)
Anhycl. AlCl3 Intramolecular
F.C.
O
Zn-Hg+HCl
Clemmensen
n
(D) recl (C)
( > C=O - CH2-)
o
S or Se, 600 c
Aromatisation
(A) (B)
O
Zn-Hg+HCl
Clemmensen
(D) reduction (C)
( > C=O - CH2-)
o
S or Se, 600 c
Aromatisation
Anthracene
5. DIRECTIVE/INFLUENCE
: :
: :
: :
> C> O R> C> O C R> C> NH2
O O O O
Ester Anhydride Amide
−R > −Ar > −CH =CH2 −F > −Cl > −Br > −I (Due to − I effect)
..
−CH2 X > −SR > N= O − S
. .− R
||
O
Chem i str y | 12.43
PLANCESS CONCEPTS
All o¯, p-directing groups except halogens and groups in (iv) are activating groups.
All those substituents which are more reactive than benzene (standard for comparison) are activating.
Second group
CH3
CH3 CH3
NO2
Nitration
+
Toulene
NO2
CHO CHO
Nitration
-CHO is
m-directing NO2
Third group: The position of a third group entering the benzene ring is determined by the nature of two groups
already present there.
Case I: When both the groups belong to Class I, the directive influence of each group is in the order as given in
Table. (When both the groups belong to Class I): Reactivity of (–CH3) > (–Cl).
i. CH3
CH3 CH3
Cl Cl O2N Cl
Nitration
+
NO2
Case II: When both the groups belong to Class II, the third group is introduced only with difficulty. The directive
influence of each group is in the order as given in Table. (When both groups are of Class II): Reactivity of (–CN)
> (–CHO)
i. CN CN CN
CHO CHO CHO
Nitration
+
NO2 NO2
Nitration
Nitration
Case III: When groups belongs to Class I and Class II, the directive influence of the group belonging to Class I takes
precedence. (When both groups are of Class I and Class II):
(– CH3) group of Class I directs the substitution.
i.
CH3 CH3 CH3
CH3 CH3 CH3
NO2 Cl NO2 NO2
NO2 Halogenation Cl NO2 NO2
Halogenation +
+
Cl
o-Compound Cl
o-Compound
Two isomers
Two isomers
CH3
ii. CH3 CH3 CH3
CH3 CH3
Cl
Halogenation Cl
Halogenation +
+
NO2 NO2 NO2
NO2 NO2 NO2
Cl
m-Compound Cl
m-Compound
CH3
CH3
Cl
Cl
+
+
NO2
NO2
Three isomers
Three isomers
Fourth Group: When a trisubstituted substance is converted to a tetrasubstituted product, adjacent compound
(i.e., 1, 2, 3-derivative) gives two, the unsymmetric compound (i.e., 1, 2, 4-derivative) gives three, and the symmetric
compound (i.e., 1, 3, 5-derivative) gives only one tetrasubtituted product.
For Example:
CH3 CH3 CH3
CH3 Cl CH3 CH3
A. Chlorination
+
CH3 CH3 Cl CH3
1, 2, 3-Trimethyl benzene
(Adjacent) Two isomers
Chem i str y | 12.45
6. RELATIVE REACTIVITIES
All the activating groups render the benzene ring more reactive and the deactivating groups less reactive than
benzene towards SE reaction. If a substituent contains a pair of non-bonded e¯’s on the atom directly attached
to the benzene ring, and these e¯s being in conjugation with the π e¯s of the benzene ring are delocalized into
the
.. ring
.. through
.. π - orbital overlap, then it is called electron donation by resonance or π donation, for example,
OH,
..
− NH
.. 2
, − Br
..
: , etc. They also withdraw e¯s inductively due to the greater electronegativity (EN) of the atom
attached to the benzene ring than the EN of H. This is called σ -withdrawing or inductive electron withdrawing.
:
NH3 Me NH3
-donation
Donate e ’s into the ring by resonance ( π donation) and withdraw e ’s from the ring inductive ( σ withdrawing).
But they donate e ’s into the ring less effectively than the very strong activating groups. It means that they are less
effective e¯ donors by resonance, since they can donate e ’s by resonance in two opposite competitive directions,
i.e., into the ring and away from the ring (cross conjugation) and this net resonance effect is decreased. Despite this,
e donation by resonance is more than e withdrawal by inductive effect ( σ withdrawal). That is why these groups
are moderately activating. (–CH=CH2), (–CH=CH–R), (–CH=CR2), and aryl (Ar¯) groups are weakly activating groups.
They can donate and withdraw e s by resonance but are slightly more e¯ donating than e¯ withdrawing. In case of
three isolated rings, the central ring (A) acts as e¯ donating by resonance, since it is bonded to two activating Ph
group and it can donate e¯s on either side of the ring.
A A
Benzene
(e donation by resonance by ring A on either side)
Alkyls [(–CH3), (–C2H5), and –CH (CH3)2] are weakly activating groups. An alkyl group is a weak e¯ donor inductively
( σ donation) and simultaneously e¯ donor by hyper conjugation.
The halogens are weakly deactivating groups because they donate e¯’s to the ring by resonance ( π donation) and
withdraw e¯’s inductively ( σ withdrawal). The deactivating characteristic is due to the high EN of halogens, yet they
are o¯, p-directing due to e¯ donation by resonance (X =–F, –Cl, –Br, –I).
Illustration 27: Given the decreasing order of the relative reactivity towards SE reaction of the following compounds.
(a) I. Benzene, II. Phenol, III. Aniline, IV. Chlorobenzene
(b) I. Acetanilide, II. Aniline, III. Acetophenone, IV. Benzene
(c) I, 1,3-Dimethyl benzene, II. 1, 4-Dimethyl-benzene, III. Toluene, IV. Benzene,
V. 1,3, 5-Trimethyl benzene (JEE ADVANCED)
1 2 . 4 6 | Alkyl Halides, Ar yl Halides and Aromatic Compounds
Sol: (A) (III) > (II) > (I) > (IV) (PhNH2> PhOH > PhH > Ph-Cl)
Reactivating of –NH2 > – OH > – H > – Cl
(B) (II) > (I) > (IV) > (III)
O O
:
(C) (V) > (II) > (I) > (III) > (IV)
(C) (V) > (II) > (I) > (III) > (IV)
Me Me Me Me
Me Me Me
Me
(H.C. Effect)
Illustration 28: Indicate by an arrow the position(s) where SE reaction takes place in the following:
(JEE ADVANCED)
O
(A) (B) ||
Ph − NH − C − Ph
O (I) NO2
|| (H) COOH
(C) (D) (E)
Ph − NH − C − CH3 OH O2N
Sol: Electrophilic Substitution takes place at position where electron density is maximum. Depending upon the
group present and their influence (ortho,meta,para) predict the site of SE
(A) 2
3
1
4
6 5
1, 4-diphenyl benzene
or
p-terphenyl
SE reaction takes place at the place indicated by the arrows in the central ring, since it is joined to two activating
phenyl rings.
(B) O
:
NH C B
Benzanilide
Chem i str y | 12.47
Ring (A) bonded to (–NH–) is activated. So SE reaction takes place at o¯ and p-position of ring (A) but p-product is
major, since o-positions will be sterically hindered. Ring (B) is bonded to group and is deactivated.
(C) : O
NH C CH3
Acetanilide
Same explanation as in (b), p-product is major.
(D) COOH
OH
The (–COOH) group is deactivating and m-directing, (–OH) is activating, and o-and p-directing class I (–OH) decides
orientation.
(E) NO2
NO2
No reaction because of two strongly deactivating (–NO2) groups.
However, the (–NO2) group is m-director; if suitable conditions are employed then (–NO2) directs at m-position.
+ OMe Slow
R.D.S.
(Na )
Arenanion O2 or K3[Fe(CN)6]
OMe OMe
:
+H + H2O
ArSN reactions are possble with ArX and ArOTs, aromatic halides and tosylate (-Ts = p-Toluene sulphonyl group
O
Me S ). Both –X and (–OTs) are good leaving groups, especially when EWG (e¯-withdrawing groups),
O
such as (–NO2) and (–C ≡ N), are present at ortho and/or para to the reacting C atom e.g.,
1 2 . 4 8 | Alkyl Halides, Ar yl Halides and Aromatic Compounds
Cl OH
Aq. NaOH
(I)
Aq. NaOH. 623K
300 atm
Cl OH
O2N NO2 O2N NO2
Aq. NaOH
(II)
or H3O ,
NO2 NO2
PLANCESS CONCEPTS
Greater the number of these EWG at o-and/or p-position, faster is the reaction and lesser vigorous are
required. This is also called addition-elimination reaction (since Nu⊕ adds and –X eliminates)
NH2 Br OH
NO2 NO2 NO2
NH3 Aq. Na2CO3
475 K, 60 atm 373 K
SCH2Ph OC2H5
PhCH2SNa C2H5ONa
NO2 NO2
NHEt
NO2 EtNH2
NO2 NO2
NO2
Step 1: Slow R.D.S: In this reaction, first the elimination of HCl occurs and then the addition of NH2 takes place, so,
this ArSN reaction is called elimination-addition reaction.
14
When chlorobenzyne (I) with C is treated with NaNH2 in liquid NH3, half of the product has an (–NH2) group
14 14
attached to C (C*) as expected, but the other half has an (– NH2) groups attached to the carbon adjacent to C
(C*). This observation proves the formation of a benzyne intermediate which has two equivalent C atoms to which
the (–NH2) group can be attached. Benzyne has an additional π -bond formed by sideway overlap of sp2 orbitals
alongside the ring. These orbital’s that form π - bond cannot overlap with the aromatic π -system because they are
not coplanar. The new π -bond is weak because of the poor overlap and hence benzyne is very reactive.
NH3
:
Cl Cl * *
:
* NH2 * -Cl * NH2
+
-H
H NH3
Benzyne
* * NH3
+ Redistribution
NH3 of H atoms
The diphenyl is sterically hindered because of bulky ortho substituents, therefore phenyl rings cannot be coplanar,
and the energy barrier for rotation of (C1 – C1) σ -bond is very high for inter-conversion of enantiomers. The
enantiomers are isolable at room temperature. This type of stereoisomerism is due to restricted rotation about a
single bond. Such a process in which stereoisomers can be isolated is called atropisomerism and the isomers so
formed are called atropisomers.
1 2 . 5 0 | Alkyl Halides, Ar yl Halides and Aromatic Compounds
O2N
NO2
Me
In this case, free rotation about the single bond is possible and each ring has vertical plane of symmetry. Hence, it
does not show optical isomerism. (A) + CBrCl3
h
(C) Me COOH
Cl
[O] Soda lime
NaNH2
KMnO4/OH and (B) ? ?
Liq. NH3
Et
Me
Illustration 30: Complete the following reactions: (JEE ADVANCED)
O
NO2
Me
h (i) OH
(A) + CBrCl3 (C)
(ii) K3[Fe(CN6)],
NO2
Cl
NaNH2
(B) ? ?
Liq. NH3
Et
Me
O
NO2
Sol: (A) Reaction proceeds by free radical mechanism because in the presence of light, radicals are formed. (C – Br)
bond is weaker than (C – Cl) bond and hence (C – Br) bond breaks to give Br–.
(i) OH
(C)
(ii) K [Fe(CN6)],
CBrCl3 h Br 2+ CCl3 3
NO
Attack by
CCl3 on toluene occurs at the Me side chain and not in the ring because (C – H) bond of Me is weaker
than (C – H) bond of the ring. Moreover, benzyl radical is more stable than aryl radical.
CH3
Br CCl3
CHCl3 CH2
CH2+ HBr
CBrCl3
CCl3 + CH2Br
h
(Br)
Path (A) is favourable because the formation of CHCl3 is more stable than the formation of HBr. It is because (C – H)
bond in CHCl3 is stronger than (H – Br) bond.
Chem i str y | 12.51
Cl
NaNH2
Me
:
Et
O
(Nucleophile)
Me Me
Et Et
NH3
O : O
(C) It is an example of ArSN (addition-elimination) reaction due to the presence of strongly EWG [two (–NO2)
Θ
groups]. H atom at o- and p- to (–NO2) group will be most activated and is attacked by nucleophile OH at these
positions. K3 [Fe(CN)6] is an oxidising agent to remove proton from the complex
NO2 NO2
OH
Na
NO2 NO2
H OH
NO2
K3[Fe(CN6)]
OMe 2
(ii) NaNH
?
1. Excess of NaOH2.NH3
+ ? (G)
Liq.NHO3 2. H3O
Br Et Me
O
Sol: These reaction are example of intermolecular friedal craft alkylation reaction.
(i) 1 1
2 H 2 1, 2-H
3 3 shift
4 4
Me Me
5 Me
6
1 1
H 2
Cr3O3 2
Aromatisation Intramolecular 4 3
4 3
F.C. reaction
Me Me
Me Me
(B)
o
3C
(More stable)
Me Et
1-Ethyl-1-Methyl
napthalene
(C)
3 3
2 2
NH2 4
(ii) 4
Strong base -H 5 5
Br H 1 Br -Br
:
1
H 6
6
O OMe O OMe COOMe
(F)
(G)
Illustration 32: Indicate the position where ArSN reaction will take place and explain why. (JEE ADVANCED)
PhONa
O2N I Br (B)
(i)
(A)
PhONa
O2N I Br (D)
(ii)
(A) NO2
PhONa
O2N I Br (D)
( iii )
(E) OMe
PhONa
HO3S I NO2 Br (H)
(iv)
(G)
O2N I
(ii)
NO2
(-NO2 at p) (NO2 at m) Chem i str y | 12.53
Sol: ArSN (addition-elimination) reaction takes place in the ring which contains
PhO strong EWG
NOat
2 +o- or
I / and p to the
eliminating group.
NO2
OPh OPh
:
O2N I MeO I
(i)
:
( iii )
OMe
I + PhO NO2
p-OMe = -I m-OMe
and +R and = only -I
OPh + R > -I Net Net e- with
e- donating drawing
O2N I
(ii)
PhO + I OMe
NO2
(-NO2 at p) (NO2 at m)
MeO
PhO NO2 + I
NO2
OPh
OPh
O
:
MeO I
HO S I NO2
:
( iii )
(iv)
O OMe
o-SO3H = -I o-NO2-, -R, -I of NO2
net e- = -I
and -R,p-OMe > -Im-OMe
of SO3H
withdrawing
and +R and (EN of=Nonly
> S)-Ibut
is greater
+ R > -I Net
-R of SO3H >with
Net e- - R of
e- donating drawing
NO2 (more resonance
st. of SO3H); net e-
withdrawing
PhO is
+ less
I OMe
than -SO3H
MeO
PhO SO3H + O2N I
OH
CH2Br CH2MgBr Me
Mg H3O
Illustration 33: ether + Me - CHO + Compound (B)
(A)
Compound (B) is an isomer of (A). Compound (B) shows positive iodoform test and gives o-toluic acid. What is (B)?
Explain its formation. (JEE ADVANCED)
Sol: (B) is an isomer of (A) and shows iodoform reaction, therefore, the side chain must contain either
O
C CH3
or
CH
OH
CH3
group.
1 2 . 5 4 | Alkyl Halides, Ar yl Halides and Aromatic Compounds
(I) (II)
But (I) is not an isomer of (A) (molecular formula C9H10O), (II) is an isomer of (A). Hence, compound (B) is (II).
Formation of (II): It involves the rearrangement. The (CH3CHO) group is attached to o-position of the ring, due to the
polarisation of (Me-HC=O Me-CH-O) in which o-position of the ring behaves as the nucleophilic centre.
H H
+ CH = O CH = O CHOMgBr CH OMgBr
Me Me Me Me
Me OH
H3O Me
B (II)
POINTS TO REMEMBER
H H H SO SO3H NO2
SO3/H2SO2 4 4HNO3
Hor H SO , H2SO4 SO3H
2 SO43/H2SO4
SO3H
(c) Sulfonation Hor H SO ,
2 SO43/H2SO4
or H2SO4,
(d) Friedel – Crafts Alkylation – Substitution of methyl (Me) or ethyl (Et) need Lewis acid catalyst.
H R
RX (R = Me, Et)
AlCl3
Chem i str y | 12.55
Why does R have to be Me or Br ? Longer alkyl chains attach at most substituted carbon.
H X
AlCl3
(e) Friedel-Craft Acylation – Substitution of acyl group (RC = O) for H : Need Lewis acid catalyst.
O
O (Acyl halide)
H CR
RCX ketone
AlCl3
CR CH2R
2. Clemmensen reduction Zn(Hg)
HCl
O
3. Wolf-Kishner reduction
CR CH2R
N2H4
OH/
O O
O O
R 1. KMnO4, OH- COH
5. Carboxylic acid
R - COH
1. H+ 4, OH
2. KMnO
Carboxylic acid
2. H+
O
R O
COH
K2Cr2O7
R COH Dicarboxylic acid
KH2Cr2O
2SO
6. R 47 COH Dicarboxylic acid
H2SO4 O
R COH
O
1 2 . 5 6 | Alkyl Halides, Ar yl Halides and Aromatic Compounds
Flow Chart:
CuCl2
+N2
Cu/HCl
+N2
Cl
FeCl3, Dark
+Cl2 +HCl
310-320 K
Chem i str y | 12.57
Elimination reaction
E1 E2 E1CB
Reactivity of Aryl Halide:
Halogenation
Nitration
Fridal craft
Alkylation/
Acylation /
Benzylation
Solved Examples
+ HBF4 +
BF4
Since the reaction is reversible; as more stable the Resonating structures of m-, o-, and p-xylenes are.
σ -complex more will be the equilibrium on the right,
i.e., the more basic is the arene.
Chem i str y | 12.59
Me
H Me H Me H Me H Me
+ HBF4 +
Me Me Me Me Me
m-Xylene
(I) (II) (III) (IV)
Me
H Me H Me H Me H Me
Me Me Me Me Me
+ HBF4 +
o-Xylene
(V) (VI) (VII) (VIII)
Me
H Me H Me H Me H Me
+ HBF4 +
Me Me Me Me Me
p-Xylene (IX) (X) (XI) (XII)
m- o- p- Br Br Br
Xylene Second 1 mol of
method Mg/ether
Example 2:
(i) CO2
Br MgBr Br COOH
(ii) H3O
Br COOH
(A)
? (B) This involves friedal craft acylation of chlorobenzene.
Chloro groups directs acyl group at para position which
on chlorination in presence of light gives the product.
Br Br
1 2 . 6 0 | Alkyl Halides, Ar yl Halides and Aromatic Compounds
Cl Wurtz reaction.
Me
Cl Cl
Me3C H CH2 C Br
Cl2+h -NaBr
Acidic Me Me
H atom
Cl
Me3CH +CH2 = C Me
O O Me
p-isomer Isobutane Isobutene
(Major)
+ HN ?
the presence of d-orbital in Cl [2p(C) -3d(Cl)] overlap.
Θ Piperidine
Conjugate base CF3 is not resonance stabilized due to
the absence of d-orbitals in F. Sol:
H
+ HN
Θ ⊕
:
JEE Advanced/Boards Since the benezene ring does not contain any EDG
(activiting group) and vinyl ( −C = CH2 ) group is a
Example 1: weakly activating (and o, p-directing), SE reaction with
Me Br‒ is very slow. Hence, Br2 first adds to the double bond
Me ONa to form major contributing stable structure (I) (due to
the retention of aromaticity), leading to the product (II).
PhCHBr2
Me
?
Ph Ph
CH = CH2 + Br Br
HBr Me3CONa
? ? ? Br + CH CH2Br
Sol: (I)
Br
H
:
H 2Na/Hg in ether
Me3CO Ph3C Cl Ph3CNa CH CH2Br
: :
Ph C Cl Me3CO PhCCl -NaCl
Cl -Elimination
Deep red colour
Ph C PhCCl Ph
Carbene
Ph
(II)
Cl -Elimination
-HCl Ph Ph HOH
Carbene ROH
Cl -Hcl Ph3CH + RONa
Example 3: Ph3CH + NaOH
Ph Ph Ph Ph
Ph Ph Ph Ph
Me3CO Ph3C Cl
Me3CO 2Na/Hg in ether
Chlorotriphenyl Deep red colour
Ph OCMe3 Ph Cl methane
Ph OCMe3 Ph Cl Colour is H2O
discharged or
HBr ROH
HBr
Ph Ph Ph Ph
Ph Ph Ph Ph
+ Sol: Strong reducing agent, such as Na/Hg amalgam,
Br
Br + converts Ph3C-Cl to the sodium salt, very stable
Br
Br
Ph3 CΘ (triphenyl methyl or trityl anion) because of
Ph Ph
delocalisation of negative charge to three Ph rings. The
(( ((
Ph Ph
Three-membered ring Triphenylcyclo
Three-membered ring
attains aromaticity Triphenylcyclo
propenium bromide strongly basic carbanion accepts H+ from either weakly
attains aromaticity propenium bromide acidic H2O or ROH giving colorless Ph3CH.
:
2Na/Hg in ether
The absence of β − H atom suggests α -elimination via Ph3C Cl Ph3CNa
-NaCl
the formation of carbine intermediate which forms ring Deep red colour
with ( C ≡ C )
OMe HOH
ROH
Ph3CH + RONa
LiNMe2
(A) Ph3CH + NaOH ?+?
Ether
Example 2:
Ph3C Cl
2Na/Hg in ether Cl
Example 4:
Chlorotriphenyl Deep red colour
methane
OMe
Br2 + FeBr3 Colour is H2O KOH
(B)+(C)+(B) (B) ?
(A) LiNMe2
(B) Ph or
Br2 + FeBr3 (A) ? + discharged
?
Styrene Ether ROH
(B)+(C)+(B)
Styrene Cl
Sol: Br Br Br
Br Br Br
Br Br Br Br Sol:
(B) It is an example
KOH of ArSN (elimination-addition)
?
Br2 Br Br Br Ph via benzyneintermediate, since strong Electron
reaction
+ +
FeBr3
Br2
Br withdrawing group o or/and p-to the eliminating group
+ + is not present. Thus, ArSN (addition-elimination) is not
FeBr3 Br Br possible.
Br Br
1 2 . 6 2 | Alkyl Halides, Ar yl Halides and Aromatic Compounds
Θ Example 5:
: NMe2 Group in (LiNMe2) acts as a base to remove
1
H SN Cr2O3 or V2O5
Me CH2 O CH2
ortho-H atom to the eliminating group.
(B) (C)
(A) or Mo2O3
Me
: :
:
:
O N O 773 K, 10-20 atm
Since the rearranged product has increased conjugation
with the ring, it is a thermodynamically controlled Me CH2 O CH2 ON O
product (T.C.P) and is the result of an equilibrium- Sol: Nitrite
controlled Reaction. 1 1
2 2
Hence, the starting material is the kinetically controlled H 1, 2-H shift
product (K.C.P). 4
3
4
3
Me Me
The conversion of K.C.P. to T.C.P is due to the removal of 5 Me
α -H atom by base, and α -H atom is acidic due to the 6
1
1
2
-I effect of (Ph-) group. Cr2O3
2 H
Intramole- 4 3
(A) Aromati- 4 3 Me
cular F.C. Me
sation
OMe OMe Me reaction
(B) Me
o
3 C
LiNMe2 Li
Me2NH+ (More stable)
Me Et
:
Cl Cl 1-Ethyl-1-methyl
naphthalene
OMe (C)
OMe
CH2 CH2
OH
: :
Ph CH2 CH=CH2 -H O Me O Me O
:
( (
2
EtO -H
CH CH=CH2
Me O OEt
CH CH=CH2
Example 7: Catalytic dehydrogenation of methyl
cyclohexane, obtained from petroleum, gives a liquid
H2 O
Ph CH=CH2 CH2 which on treatment with chlorosulphonic acid at 370 K
+H yields a mixture of two isomers (A) and (B), C7H7SO2Cl. The
major isomer (A) reacts with ammonia to form (C), which
Ph CH=CH CH3 on oxidation with permanganate gives compound (D). On
heating, compound (D) gives a well-known sweetening
(E). The minor isomer (B) also reacts with ammonia to give
Chem i str y | 12.63
(( ((
SO2Cl
(B) (F)SO2NH2
(B) (F) Chloramine-T
Cl Shifting of
3 2 1
Chloramine-T
An antiseptic Ph CH2 CH2 CH2 double bond
An antiseptic
1.2% soln for
1.2% soln for
mouthwash) Br
mouthwash)
1-Bromo-3-phenyl propane
Ph H Ph CH3
C C + C C
H trans CH3 H cis H
(D) (E)
(More stable)
JEE Main/Boards
Q.2 Which one of the following has the highest dipole Q.13 Write the mechanism of the following reaction:
moment why? BOH−H O
2 → nBuCN
nBuBr + KCN
(i) CH2Cl2 (ii) CHCl3 (iii) CCl4
Q.3 What are ambident nucleophiles? Explain with an Q.14 Out of C6H5CH2Cl and C6H5CHClC6H5, which is
example. more easily hydrolyzed by aqueous KOH?
Q.4 Write the equation Wurtz-fittig reaction. Q.15 The treatment of alkyl chlorides with aqueous KOH
leads to the formation of alcohols but in the presence
of alcoholic KOH, alkenes are major products. Explain.
Q.5 p-Dichlorobenzene has higher m.p. and solubility
than those of o-and m-isomers. Discuss.
Q.16 Identify and indicate the presence of chirality,
if any in the following molecule. How many stereo
Q.6 An alkyl halide, (X) of formula C6H13 Cl on treatment
isomers are possible for those containing chiral center?
with potassium tertiary butoxide gives two isomeric
alkenes (Y) and (Z). (C6H12). Both alkenes on hydrogenation
give 2, 3-dimethybutane. Predict the structures of (X), (Y) Q.17 Give two example of molecules which contain
and (Z). chirality centers but process a chiral structure?
Q.7 What happens when and complete equation? Q.18 Write the equation of elimination with mechanism?
(i) n-butyl chloride is treated with alcoholic KOH. Q.19 (i) Why are haloalkanes more reactive towards
(ii) Bromobenzene is treated with Mg in the presence nucleophilic substitution reaction than haloarenes?
of dry ether. (ii) Which of the following two substance undergo SN1
(iii) Chlorobezene is subjected to hydrolysis. reaction faster and why?
(iv) Ethyl chloride is treated with aqueous KOH. Q.20 Identify and indicate the presence of center of
(v) Methyl bromide is treated with sodium in the chirality, if any in the following molecules. How many
presence of dry ether. stereoisomers are possible for those containing chiral
center?
(vi) Methyl chloride is treated with KCN.
(i) 1, 2-dichloropropane
Q.8 What is meant by chiral or asymmetric carbon (ii) 3-bromo-pent-1-ene
atom?
Q.11 Predict all the alkenes that would be formed by Q.24 Write the difference between SN1 and SN2
dehydrohalogenation of the following halides with reaction?
sodium ethoxide in ethanol and identify the major alkene:
(i) 1-Bromo-1-methylcyclohexane Q.25 Explain nucleophilic substitution reaction in aryl
halides?
(ii) 2-chloro-2- methylbutane
(iii) 2,2,3-Trimethyl-3-bromopentane. Q.26 How will you bring about the following
conversions?
Q.12 Gives the uses of Freon 12,DDT, carbon
(i) Bromoethane to cis-hex-3-ene
tetrachloride and iodoform.
Chem i str y | 12.65
Q.32 Explain SN1 Mechanism with example. (A) t-butyl ethyl ether (B) 2, 2-dimethylbutane
(C) 2-methylprop-1-ene (D) Isopropyl n-propyl ether
Q.33 What are arenes? How are they classified? Discuss
briefly the isomerism and nomenclature of arenes.
Q.4 The fire extinguisher ‘pyrene’ contains.
(A) Carbon dioxide (B) Carbon disulphide
Q.34 Discuss of structure of benzene laying emphasis
on resonance and orbital structure. (C) Carbon Tetrachloride (D) Chloroform
Q.35 CH3 HCO3H Q.5 The final product (Z) is the following sequence of
X reactions
KMnO2,
Y HNO
2 →(X)
CH3CH2 NH2
SOCl
3 → (Z) is
2 →(Y) NH
Q.36 Justify the Statement: Benzene is highly Q.6 Consider the following reactions:
unsaturated compound but behaves like a saturated
compound. 1. CH3CH2CH2Cl+I‒ →
2. (CH3)3 C-Br+ ethanolic KCN →
Q.37 Discuss briefly the mechanism of electrophilic 3. CH3CHBrCH3+aqueous KOH →
substitution reactions in benzene.
4. CH3CHBrCH3+alcoholic KOH →
Q.38 Explain the directive influence of various The most likely products is these reactions would be
substituent and their effect on reactivity of arenes.
(A) 1. CH3CH2CH2l 2. (CH3 )3 C− CN
Q.7 Aryl halides are less reactive towards nucleophilic (i) CH3CH2CH2Cl (ii) CH3CH2 CHClCH3
substitution reaction as compared to alkyl halides due to (iii) (CH3)2CHCH2Cl (iv) (CH3)3CCl
(A) The formation of less stable carbonium ion
(A) (i)>(ii)>(iii)>(iv) (B) (iii)>(iv)>(ii)>(i)
(B) Resonance stabilization
(C) (i)>(iii)>(ii)>(iv) (D) (iv)>(iii)>(ii)>(i)
(C) Longer carbon-halogen bond
(D) sp2-hybridized C attached to the H Q.12 In the reaction:
KCN [H]
Q.8 In the following reaction: A → B → C2H5NH2
Br
AgNO
l 2→
StepII Q.13 C2H5I X . Here X is
→(CH ) C H − CH− CH Br (Major product)
32 2
O
Which of the following sets of reagents can be used for
step I and step II? (A) C2H5-O-N=O (B) C2H5 - N
O
Step I Step II
1. HBr HBr and peroxide (C) C2H5-N=O (D) C2H5-N=N-C2H5
(B) 2, 4-Dinitrochlorobenzene o
600 C
Q.22 Z .Z may be
(C) 4-Nitrochlorobenzene
(D) 3- Nitrochlorobenzene
(A)
(A)
Q.16 o-Chlorotoluene reacts with sodamide in liquid
NH3 to give o-toluidine, and m-toluidine. This proceeds
through an Intermediate (B)
(B)
Q.17 The final product D in the above sequence of Q.23 Which of the following is used for aromatization
reactions is of n-hexane?
(A) AlCl3
2 NBS Alc.KOH Pd/C
+ A B C D
-H2
(B) Na in liquid NH2
OH
Q.18 1, 3-Dichloropropane reacts with Zn and NaI and Q.24 CH=CH CH3 CHCH3CH3
gives (major product)
+
(A) Propane (B) Propane H2O/H
Q.21 Which xylene gives only one monobromo Q.2 What would be the product formed when 1-Bromo-
derivative? 3-chloro cyclobutane reacts with two equivalents of
metallic sodium in ether (2005)
(A) Ortho (B) Para
Cl
(C) Meta (D) None of these (A) (B)
Br
(D)
(C)
1 2 . 6 8 | Alkyl Halides, Ar yl Halides and Aromatic Compounds
Q.3 Aryl halide are less reactive towards nucleophilic Q.9 The synthesis of alkyl fluorides is best accomplished
substitution reaction as compared to alkyl halide due by: (2015)
to (1990)
(A) Free radical fluorination (B) Sandmeyer’s reaction
(A) The formation of less stable carbonium ion
(C) Finkelstein reaction (D) Swarts reaction
(B) Resonance stabilization
(C) Longer carbon-halogen bond Q.10 In the reaction (2015)
CH3Br C2H5
Q.12 2- Chloro -2 – methyl pentane on reaction with
sodium methoxide in methanol yields : (2016)
(A) (B)
Br CH3
C2H5CH2C CH2 C2H5CH2 C CH3
CH3 C2H5CH2C OCH3
CH3 CH3
CH3
CH2Br (i)
(A) (ii)
(B) (iii)
(C)
CH2Br
(A) All of these (B) (i) and (iii)
(C) (D)
CH3 (C) (iii) only (D) (i) and (ii)
CH3
Chem i str y | 12.69
JEE Advanced/Boards
CH3
CH3 H3C CH3 Q.7 Propose a mechanism for the following reaction
(B) H3C CH3Li C
H3C CH3 OH
Br H3C CH3
Br
CH3
CH3 CH3 H2O
H3C AlBr3
(C) H3C Br
H3C
Br Br
Br
OH Q.8 What products would be formed when each of the
(D) Ag+ following compounds reacts with N-bromosuccinimide
Br H2O in CCl4 in the presence of light.
Br
CH3
CH3
CH3 OH H3C CH3 (A) (B)
(E) H3C CH3 H+ CH3 CH3
OH CH3 O CH3
CH3
H H H H (C)
CH3 (D)
H-
(F) H
Br H3C CH3
H3C H3C CH3
1 2 . 7 0 | Alkyl Halides, Ar yl Halides and Aromatic Compounds
Q.9 (a) p-Methoxylbenzyl bromide reacts faster than CCl4; all three are soluble in cold conc. H2SO4. Compound
p-nitrobenzyl with ethanol to from an ether product. a gives a precipitate when treated with AgNO3 in NH3
Explain why. (aq), but compound B and C do not. Compound A and
B both yield hexane when they are treated with excess
(b) In the following reaction the relative rate is 3,300
H2 in the presence of platinum catalyst, under these
faster when X = F than I. explain.
conditions C absorbs only one molar equivalent of H2
and gives a product with the formula C6 H12. When A is
X
NO2 N
oxidized with basic KMnO4 and the resulting solution
NO2
acidified, the only organic product that can be isolated
+
N is CH3(CH2)3CO2H. Similar oxidation only CH3CH2CO2H
+ X- and C gives only HO2C(CH2)COH. What are structures
NO2 H of A, B and C.
NO2
(c) Identify A, B, C, D and E in the following Q.15 Explain elimination reaction in halo arene.
Br
Q.16 Compound A (C8H12Cl) exists as a racemic form.
Compound A does not decolorise either Br2/CCl4 or
(CH3)3COK+ Cold dil. KMnO4
A B dilute aqueousKMnO4. When A is treated with Zn/
HCO3H
C CH3COOH, two fractions B and C both with molecular
O, H2O BaO, formula C8 H16 are obtained fraction B consists of a
racemic form and can be resolved. Fraction C can’t be
D E
Q.17 For each reaction below, fill in the structure of Q.19 Convert with equation.
the expected product, showing stereochemistry where
(i) Benzene to p-nitrochlorobenzene
appropriate. Then indicate the type of reaction and/or
mechanism involved. (ii) Benzene to aniline
(iii) Benzene to m- nitrochlorobenzene
Br
(A)
H2CO [H] (iv) Benzene to dipehnyl
H 25
o
H H HCl
Ph + + etc.
(E) H2C
CH3
OH H2C
CH3
OH Cl
H3C
Ph N+ HCl
only
OH H2C Cl
H3C CH3
O-
Br
1 2 . 7 2 | Alkyl Halides, Ar yl Halides and Aromatic Compounds
Q.24 Optically active 2-iodobutane on treatment with Q.31 The freezing point constant of C6H6 is 4.90 and
Nal in acetone gives a product which does not show its melting point 5.51ºC. A solution of 0.810 g of a
optical activity. Explain why? compound (A) when dissolved in 7.5 gms of benzene
freezes at 1.59ºC. The compound (A) has C = 70.58%.
Q.25 An organic compound ‘A’ having molecular Compound (A) on heating with sodalime gives another
formula C4H8 on treatment H2SO4 gives ‘B’. ’B’ on compound (B) which on oxidation and subsequent
treatment with conc. HCl and anhydrous ZnCl2 gives acidifications gives an acid (C) of equivalent weight 122.
‘C’; and on treatment with sodium ethoxide gives back (C) on heating with sodalime gives benzene. Identify
‘A’ identify the compounds ‘A’, ‘B’ and ‘C’ and write the (A), (B) and (C) and explain the reactions involved.
equations involved.
Q.32 When bromo benzene is mono chlorinated,
two isomeric compounds (A) and (B) are obtained.
Q.26 (W) and (X) are optically active isomers of C6H9Cl.
Monobromination of (A) gives several isomeric products
(W) on treatment with one mole of H2 is converted
of formula C6H3ClBr2. While monobromination of (B) yields
to an optically inactive compound (Y), but (X) gives
only two isomeric (C) and (D). Compound (C) is identical
an optically active compound (Z) under the same
with one of the compound obtained from the bromination
conditions. Give structure of (Y) and configuration
of (A). However (D) is totally different from any of the
of(W), (X) and (Z) in Fischer projections.
isomeric compounds obtained from bromination of (A).
Give structures of (A), (B) and (D) with explanation.
Q.27 A white precipitate was formed slowly when
Br
AgNO3 was added to a compound (A) with molecular
formula C6H13Cl. Compound (A) on treatment with hot C2H5
Cu Powder
alcoholic KOH gave a mixture of two isomeric alkenes Q.33 (A)
(B) and (C) having formula C6 H12. The mixture of (B) and
(C) on ozonolysis furnished four compounds.
Write the structure of A and explain its stereochemistry
(i) CH3CHO; (ii) C2H5CHO;
(iii) CH3COCH3; (iv) (CH3)2CHCHO. Q.34 + CH3COCl
AlCl3
A
What are (A), (B) and C? NO2
Q.28 Primary alkyl halide C4H9Br (a) reacted with alcoholic Zn-Hg Br2/Fe
B C
KOH to give compound (b). Compound (b) is reacted HCl
with HBr to give (c) which is an isomer of (a). When (a) is
reacted with sodium metal it gives compound (d), C8H18 Me
which is different form the compound formed when Q.35 Nitration of with HNO3 in acetic acid
n-butyl bromide is reacted with sodium. Give the structural
formula of (a) and write the equations for all the reactions. solvent at 45ºC occurs 25 times faster than nitration
Aq.NaOH
Q.4 CH − CH CH Br →X
Q.39 Write the Mechanism of nitration of benzene and 3 2 2
toluene. Al O Cl / H O
2 3 Y
X → 2 2 →
Heat
CH2CH2CH2Br
Exercise 2 (A) Identify ‘z’ in
NO2 (A) i < ii < iii (B) i < iii < ii (C) iii < i < ii (D) iii < ii < i
CH CH2CH3
(D) O N
(A) 2
Br Cl (D) O2N Cl Q.6 List the hydrogen halide acids in decreasing
order of reactivity in the following reaction:
NO2 R-OH+HX → RX + H2O
(A) HI>HBr>HCI>HF (B) HBr>HI>HCI>HF
(B) Cl (C) (CH3)2N Cl (C) HI>HCI>HBr>HF (D) HI>HF>HBr>HI.
(C) Formation of (CH3)3 CBr from (CH3)3 C+ is a slow step Q.14 When propane is heated with excess of Cl2 at
(D) Formation of (CH3)3 C is a fast step
+ 573-673 K under 75-100 atm. Pressure, the products
obtained are
Q.8 SN1 reactions occur through the intermediate (A) CH3CH2CH2Cl + CH3CHClCH3
formation of (B) CCl4+C2Cl6
(A) Carbocations (B) Carbanions (C) CH3CH2CHCl + CH3CHClCH2Cl
(C) Free radicals (D) None of these (D) CHCl3 + CH3CH2Cl
Q.9 SN1 reactions are favored by Q.15 Which of the following is used as a camphor
substitute?
(A) None polar solvents
(B) Bulky groups on the carbon atom attached to the (A) C2Cl6 (B) CHCl3 (C) CCl4 (D) CF2Cl2
halogen atom
(C) Small groups on carbon atom attached to the Q.16 Freon used as a refrigerant is
halogen atom (A) Acetylene tetrachloride
(D) None of these
(B) Trichloroethylene
(C) Dichlorodifluoromethane
Q.10 The main product formed when ethylbenzene
reacts with chlorine in presence of UV light is (D) Ethylene dichloride
(A) 1-Chloro-1-phenylethane
(B) o-Chloroethylbenzene Q.17 n-Propyl bromide on treatment with ethanolic
potassium hydroxide produces
(C) 2-Chloro-1-phenylethane
(D) p-Chloroethylbenzene (A) Propane (B) Propene
(C) Propyne (D) Propanol
Q.11 + CH2Cl2
Anhyd.
AlCl3
A. A is Q.18 Chlorobenzene can be prepared by reacting
aniline with
Excess
(A) Hydrochloride acid
(B) Cuprous chloride
(A) CH2Cl (B) CHCl2
(C) Chlorine in presence of anhydrous aluminum
chloride
(C) (D) CH2 (D) Nitrous acid followed by heating with cuprous
chloride
Comprehension Type
Multiple Correct Choice Type
There are several factors which decide the fate of
substrate in presence of nucleophile (or base). One of Q.39 When nitrobenzene is treated with Br2 in the
them is nature of solvent. presence of FeBr3, the major product formed is
In mildly basic, neutral or acidic solution primarily m-bromonitrobenzene. Statements which are related
substitution takes place. This will occur via SN2 to obtain the m-isomer are
mechanism for 1° alkyl halides and via SN1 mechanism (A) The electron density on meta carbon is more than
for 3° alkyl halides. When 2° alkyl halides react with that on ortho and para positions
(-) charge nucleophile in polar protic solvents, the SN2
mechanism is followed when 2° alkyl halides react with (B) The intermediate carbonium ion formed after initial
H2O or ROH as solvent SN1 mechanism is followed. attack of Br+ at the meta position is least destabilished
In strongly basic solutions primarily elimination takes (C) Loss of aromaticity when Br+ attacks at the ortho
place with 2° and 3° alkyl halides moderate or strong and para positions and not at meta position
basic solutions arise when followed are present NaOH, (D) Easier loss of H+ to regain aromaticity from the meta
KOH, NaOEt. When we use strong and sterically position than from ortho and para positions
hindered base, KOtBu, even 1° alkyl halides given
elimination products primarily.
Q.40 Benzene can undergo
Na+N− (A) Substitution (B) Addition
Q.36 CH3 − C H − CH3 3
Acetone
→ A; product A is
| (C) Elimination (D) Oxidation
Br
(A) CH3CH = CH2 (B) CH3‒CH2‒CH2‒N3
Q.41 C7H7Cl i) KMnO4 Cl
ii) Sodalime,
(C) CH3 − C H =
CH3 (D) CH2 CH2
| N
N CH2 N
3 (A) CH2Cl (B) Cl CH3
KOH Cl Cl
Q.37 CH3CH2CH2Br → B; product
product BB isis
t BuOH
(C) CH3 (D) CH3
(A) CH3CH = CH2 (B) CH3CH2CH2OH
In the above reactions, compound (A) is
(C) CH3 − C H −CH3 (D) CH3 − C H −CH3
| |
A
OH OtBu Q.42 Ph C CH3 → Ph–CH2–CH3
O
CH A could be:
3
| –
Na+N3− (A) NH2NH2, glycol/OH (B) Na(Hg)/conc. HCl
Q.38 CH3 − CH − C H − CH3
H2O/Acetone
→
|
Br (C) Red P/HI (D) CH2 CH2 ; Raney Ni–H2
CH CH SH SH
3 3
| |
(A) CH3 − CH − C H − CH3 (B) CH3 − CH − CH =
CH2
|
N3
Chem i str y | 12.77
Previous Years’ Questions Q.4 The major product of the following reaction is
H3C Br
Q.1 Identify the set of reagents/reaction conditions X
and Y in the following set of transformations (2002)
F
PhSNa
X Y
CH3 − CH2 − CH2Br → Pr oduct → dimethyl formamide
CH3 − C H − CH3
| NO2
Br
(A) X = dilute aqueous NaOH, 20°C,
H3C SPh H3C SPh
Y = HBr/acetic acid, 20°C,
(B) X = concentrated alcoholic NaOH, 80°C, F F
(A) (B)
Y = HBr/ acetic acid, 20°C,
(C) X = dilute aqueous NaOH, 20°C, Y = Br2/CHCl3, 0°C
NO2 NO2
(D) X = concentrated aqueous NaOH, 80°C,
Y = Br2/CHCl3, 0°C H3C Br H3C SPh
C2H5O-
+ C2H5l NO2 NO2
anhy. C2H5OH
(A) C6H5OC2H5 (B) C2H5OC2H5 Q.5 The compound used as refrigerant are (1990)
(C) C6H5OC6H5 (D) C6H5l (A) NH3 (B) CCl4
(C) CF4 (D) CF2Cl2 (E) CH2 F2
Q.3 The following compound on hydrolysis in aqueous
acetone will give: (2005)
Q.6 Match the following
CH3 CH3 CH3
MeO
CH3 CH3 CH3
NO2 Column I Column II
MeO NO2 (A) CH3-CHBr-CD3 on treatment (p) E1 reaction
H Cl CH3
with alc. KOH gives CH2=CH-CD3
H Cl CH3
It mainly gives as a major product.
CH3 CH3 CH3
(B) Ph-CHBr-CH3 reacts faster (q) E2 reaction
CH3 CH3 CH3
(K) MeO NO2 than Ph-CHBr-CD3
(K) MeO NO2
H OH CH3 (C) Ph-CH2-CH2Br on treatment (r) E1CB reaction
H OH CH with C2H5OD/C2H5O- gives Ph-
CH3 CH3 CH33 CD=CH2 as the major product.
CH3 CH3 CH3 (s) First order reaction
(L ) MeO NO2 (D) PhCH2 CH3CH2 Br and PhCD2
(L ) MeO NO2 CH2 Br react with same rate.
OH H CH3
OH H CH
CH3 CH3 CH33 Q.7 Which of the following is the correct method for
(M) MeO CH3 CH3 CH3 NO2 synthesizing methyl-t-butyl ether and why?
Q.9 What would be the major product in each of the aqueous Br2 (3.0 equivalents)
2 →X (i) Na NH
CH3CH2C ≡ CH (A) P (B) Q (C) R (D) S
(ii) CH3CH2Br
H2 /Pd−BaSO 4
X Akaline
→ Y →Z (2002) Q.16 The major product in the following reaction is
KMnO 4
(2014)
O 1. CH3MgBr, dry ether, 0 C
o
C
CH3CH2
H
CH2CH3 Q.17 The acidic hydrolysis of ether(X) shown below is
fastest when (2014)
Q.13 Which of the following molecules, in pure form, is
(are) unstable at room temperature? (2012)
acid
OR OH + ROH
(A)
(A) (A) (B) (B)
(B)
Q.19 The number of hydroxyl group(s) in Q is (2015) Q.21 Among the following, reaction(s) which gives(give)
tert-butyl benzene as the major product is(are) (2016)
+ aqueous dilute KMnO4(excess)
H H
P Q
HO heat o
0C Br
H3C CH3 Cl
(A) (B)
NaOC2H5 AlCl3
PlancEssential Questions
JEE Main/Boards JEE Advanced/Boards
Exercise 1 Exercise 1
Q.2 Q.4 Q.6 Q.7(iii, v) Q.3 (B, D, E) Q.5 (E) Q.8 (B, D) Q.10
Q.9(iii) Q.11 Q.16 Q.18 Q.14 Q.17 (C, E) Q.19 (vi, ix) Q.21
Q.19 Q.22 Q.24 Q.25 Q.24 Q.27 Q.29
Q.27 Q.32
Exercise 2
Exercise 2 Q.1 Q.3 Q.11 Q.14
Q.4 Q.5 Q.8 Q.10 Q.19 Q.25 Q.33 Q.38
Q.14 Q.16 Q.17 Q.22 Q.40
Q.24
Previous Years’ Questons
Previous Years’ Questions Q.3 Q.4 Q.6 Q.10
Q.3 Q.6
1 2 . 8 0 | Alkyl Halides, Ar yl Halides and Aromatic Compounds
Answer Key
JEE Main/Boards
Exercise 1
Q.6
CH3CH3 CH3CH3 CH3CH3
CH3 C CH CH3 -HCl CH2 = C CH CH3+CH3 C=C CH3
(Y) (Z)
Cl
H2
CH3 CH CH CH3
CH3 CH3
Exercise 2
Single Correct Choice Type
JEE Advanced/Boards
Exercise 1
Q.5
CH3
OH
(A) H3C (C) H2C
(B) CH3
CH3 CH3
CH2
l
Br
(D) (E)
Chem i str y | 12.81
Q.8
Br Br Br CH3
Br CH
3
Q.10 (a)
O O
Cl
H Cl
(D) CN
(E) (F)
O O OH
O
OH OH OH
(H) (I)
(G)
OH O HO
(c)
OH
OH
(A) (B)
OH O
OH COOH
COOH
(C) (D) (E)
1 2 . 8 2 | Alkyl Halides, Ar yl Halides and Aromatic Compounds
Q.11
OH
Br OH
D(=B)
Q.12
CH CH3
(A) H3C (B) H C (C)
3
Q.13 CH2
(A) H3C Br (B) H3C
CH
(C) H3C Br (D) H3C
Br
Q.14
Br Br H2C
(C) H 3 C CH3 (D) CH2
Cl CH3
CH3
A= B=
Q.16 CH3 CH3
H3C
Ph H
H
(E2) (Singlet carbene cycloaddition)
CH3
(C) (Hofmann E2) (D) H
(Saytzeff E1)
H3C
N CH2
H3C CH3 H CH3 Chem i str y | 12.83
H3C
Ph H
H
(E2) (Singlet carbene cycloaddition)
(E) (F)
H
H3C Ph
H3 C
Q.18
CH3
O
H3C Ph
(I) (II) (III) O
H3C CH3
NO2
Q.20
OMgBr
O CH3
CH3MgBr CH3 HOH
+
[H ]
(A) O (B) O
CH3
CH3 OC
Ozonolysis OH-
CH3
Intermolecular
aldol condensation
(B) (D)
CH3
Br
(E)
Q.23
O
O H3C C2H5
O
- C2H5 O O
O
O
C2H5 O O
H5C2 H5 C 2
1 2 . 8 4 | Alkyl Halides, Ar yl Halides and Aromatic Compounds
Q.26 The given statements suggest that (W) and (X) are as follows:
CH2CH3 CH2CH3 CH2CH3
H2
H Cl H Cl or CHCl
CH3 CH3
H2
H CH2Cl H CH2Cl or
CH=CH2 CH2CH3
Q.29
OH
Br MgBr
Mg CH3CHO C CH3
Ether H
(A) (B)
HBr
OH
Br CH3
H HO C CH3
Br 2
CH3 CH3 H
Q.30 (1) The compound (X) has two isomers(Y) and (Z).
(2) The compound (X) has C, H and Cl atoms.
(3) % of Cl in (X) =71.72% ∴ Empiricial formula of (X) is CH2Cl
Exercise 2
Single Correct Choice Type
Comprehension Type
Q.31 C Q.32 A Q.33 D Q.34 A Q.35 A Q.36 A
Q.37 A Q.38 B
Chem i str y | 12.85
Solutions
JEE Main/Boards
Exercise 1
2-chloro-3-methylbutane
Sol 1: (i)
Alkyl 2º
Cl
(ii) 3-chloro-4-methylhexane
Cl
Alkyl 2º
(iii) 1-Iodo-2,3-dimethylbutane
I
Alkyl 1º
Br
2-Bromo-3-methyl butane
(v)
Alkyl 2º
Br
1 2 . 8 6 | Alkyl Halides, Ar yl Halides and Aromatic Compounds
(vi) Br
1-Bromo-2-ethyl-3-methylbutane
Alkyl 1º
2-Chloro-2-ethyl butane
(vii)
Alkyl 3º
Cl
Cl
(viii) 3-Chloro-5-methyl hex-2-ene
Vinyl 2º
4-Bromo-4-methyl-pent-2-ene
(ix) Alkyl 3º
Br
Cl
Sol 2:
Sol 3: Ambident nucleophile have 2 or more than 2 sites to donate electron to the electrophile
−
O
Eg. C ≡ N : here C and N both are nucleophiles.
Sol 5: P-Dichlorobenzene
Sol 6:
Sol 7:
S N1
SSNN2
2
(vi)
S N2
Sol 8: sp3 hybridized carbon which have u different valency is a chiral or asymmetric carbon atom.
1 2 . 8 8 | Alkyl Halides, Ar yl Halides and Aromatic Compounds
Sol 9:
S N2
Sol 10: (i) CH3Br < CH3I → better leaving group
(i)
(ii)
(iii)
S N2
Sol 13:
Sol 15:
O
−
But Alc. KOH gives elimination reaction because O H is not polarized so it can directly attack. H2O is formed
Sol 16: Intermolecular substitution reaction is known as SN1 mechanism in which both nucleophile is in same
molecule.
E.g. Darzen Process
R—OH + SOCl2 R —Cl + SO2 + HCl
Sol 19: (i) Halo alkanes have σ -bond so it is easily cleared but in haloarenes π -bond electrons get resonates so
there will be π -bond character which requires high energy
Sol 20:
Sol 21: It is not necessary that a compound which have optically active carbon atom is wholely a optically active
compound.
Sol 22:
1 2 . 9 0 | Alkyl Halides, Ar yl Halides and Aromatic Compounds
Sol 23:
(ii) (iii)
Sol 28: In chlorobenzene, ortho-para is preferable position because when electrophile attacks on ortho or para
position, it forms a stable intermediate.
In chlorobenzene due to resonance of e‒ s of Cl the C—Cl bond is getting less polarized while in cyclohexyl chloride
there is no such effect seen
(ii) Alkyl halides are not soluble in water because they are unable to form hydrogen bonds with water.
Sol 30:
H H
FeCl3 FeCl3
+ Cl2 + HCl + Cl2 + HCl
Br Br
Sol 31: Properties
1. They are
+ Clless reactive
FeBr3 than haloalkanes
+ HBr
FeBr3
2 + Cl2 + HBr
2. They can undergo replacement of halogen by hydroxyl group
H ONa OH
dil. HCl
+ NaOH
3. Replacement by group.
H NH2
Sol 32: Intermolecular substitution reaction is known as SNi mechanism in which both nucleophile is in same
molecule.
Eg. Darzen Process
R—OH + SOCl2 → R —Cl + SO2 ↑ + HCl
Sol 33: Arenes: Compounds with pleasant smell and they are called aromatic compounds.
They contain benzene having ring of six carbon atoms. Later on, it was found that many compound having these
benzene rings do not have pleasant smell.
Arenes are benzene substituted compounds. So, the nomenclature is based on the position of group substituted
which are named as ortho, meta, para.
Sol 34: or
Resonance
hybrid
1 2 . 9 2 | Alkyl Halides, Ar yl Halides and Aromatic Compounds
Each carbon atom is sp2 hybridised. Each carbon has 3 sp2 hybrid orbitals lying in 1 plane at angle. There is one
unhybridised p-orbital which participates in side ways overlapping to form pπ ‒ pp bond. 2 hybridised orbital do
axial overlapping with C atoms to form C – C σ bond and 1 to form C – H σ bond.
Sol 35:
Sol 36: Benzene is highly unsaturated because it is having 3C = C bond but because of its extra resonance stability, it
is inert toward addition reaction & nucleophilic substitution but undergoes electrophilic substitution, like saturated
alkanes.
Sol 37:
Y Y Y Y
H
+ + E + H +
+ E
E
E H
Ortho Meta Para
Sol 38: Substitution is influenced by the group already present in benzene ring. There are 2 types of groups
- Activators (O/P) directors - Deactivators (m-directors)
O
OH OH OH
NO2 COCH3 C CH3
HNO3
+
HNO3
H2SO4
NO2 NO2
Exercise 2
Single Correct Choice Type
Sol 2: (D) Hydrolysis of 3º alkane is preferable by SN1 mechanism because of the carbocation stability(D)
Sol 3: (C)
Sol 5: (C)
Sol 7: (B)
Sol 8: (D) HBr will give step (I) while Br2 will give 2Br groups in step (I) only.
1º alkyl halide so SN2 substitution(B) peroxide will cause allyl substitution
Sol 9: (B) More electron density than high nucleophilicity. More electron density than high more +I effect, high
e‒ density.
1 2 3
1 2 . 9 4 | Alkyl Halides, Ar yl Halides and Aromatic Compounds
Benzyne intermediate
Both optically active isomer so reacemic mixture. Planar carbocation attack can be from both up and down.
Sol 1: (A) CH3Cl have one Cl atom which is more electronegative so it will have highest dipole moment.
Sol 3: (B, E) Aryl halide are less reactive towards nucleophilic substitution reaction as compared to alkyl halide due
to following reasons
(B) Resonance stabilization
(E) sp2-hybridized carbon attached to the halogen.
Sol 5: (C E)
The main product of this reaction is nitroethane but ethylnitrite is also formed as a side product along with silver bromide.
Sol 6: (B, D) New carbon-carbon bond formation take place in Friedel Craft’s alkylation following mechanism
involve
Chem i str y | 12.97
Here new C—C bond formed between carbon of benzene ring and alkyl group.
Similarly, in Reimer-Tiemann reaction.
O
CH2 Br COOH C
[O]
Sol 8: (D)
O
CH3 COOH C
O
NH2 N2Cl CN
NaNO2/HCl CuCN/KCN
+ N2
0-5oC
OH
Sol 11: (B) 1. NBS/h OH-
2. H2O/K2CO3 +
Br
CH3 CH3
+
Sol 12: (A) CH3 CH2 CH2 C CH3
CH3ONa
CH3 C CH2 CH2 CH3
Cl OMe
C2H5 CH2 C CH2 + C2H5CH C CH3
CH3 CH3
1 2 . 9 8 | Alkyl Halides, Ar yl Halides and Aromatic Compounds
JEE Advanced/Boards
Exercise 1
Sol 1:
Sol 2: Vinyl chlorides eg. have double bond character in C—Cl bond because
of which it requires high energy to cleave that bond and substitute the reset one but in alkyl chlorides gives SN AE
mechanism or S 1 because reaction they form stable carbocation.
N
Sol 3: (A)
(B)
(C)
Chem i str y | 12.99
(D)
(E)
(F)
Sol 4:
X X X
E
E+
+ + H+
H H H
NO2
HNO3
+
NO2
E2 elimination reaction
Sol 5: (a)
(b)
1 2 . 1 0 0 | Alkyl Halides, Ar yl Halides and Aromatic Compounds
(c)
(d)
(e)
+ - OMe
NO2 NO2
Sol 7:
S N1
Chem i str y | 12.101
Sol 9: (a)
Carbon (1) has more eΘ density than (2) so bond of C1—Br is weaker than C2—Br so it get cleaned easily.
(b)
F creates make better nucleophile site due to its light electronegativity than I
1 2 . 1 0 2 | Alkyl Halides, Ar yl Halides and Aromatic Compounds
(C)
(CH3)3CO-K+
Sol 11:
S N1
∴ A →
C →
1 2 . 1 0 4 | Alkyl Halides, Ar yl Halides and Aromatic Compounds
Sol 13:
Br Br PPt
Br
Sol 14:
- u
- u
(A)
(B)
X X OMe OMe
-
+ OMe
Sol 16:
Cl CH3
CH3
A= B=
CH3 CH3
CH3 CH3
C= D=
CH3 CH3
(B)
1 2 . 1 0 6 | Alkyl Halides, Ar yl Halides and Aromatic Compounds
(C)
(D)
(E)
E1
(F)
(ii)
(iii)
(ii)
(iii)
1 2 . 1 0 8 | Alkyl Halides, Ar yl Halides and Aromatic Compounds
(iv) (v)
H
(vi) H H
H (vii)
H H
2 H2SO4
+ Cl3CHO
Chloral Cl DDT Cl
(viii) (ix)
Sol 20:
∴
Chem i str y | 12.109
Sol 21:
Sol 22: (i) Vinyl chloride do not undergo SN reaction because of double bond character due to resonance.
(ii)
can’t go SN2 because satirically hindered site and for SN1 also it is not a stable carbocation initially.
(iii)
Because intermediate of (I) is resonance stabilized while (II) there is only +I effect.
Ag. SN1
(iv) SN1 3º halides undergo SN1 mechn became SN2 is restricted till less satirically hindered
Cl NaOH
Sol 23:
Sol 24:
Sol 25:
S N2
E2
Chem i str y | 12.111
Sol 26:
Sol 27:
Sol 28:
1 2 . 1 1 2 | Alkyl Halides, Ar yl Halides and Aromatic Compounds
Sol 29:
Sol 30:
Chem i str y | 12.113
Sol 31:
COOH
Sol 32:
Cl
Sol 33:
1 2 . 1 1 4 | Alkyl Halides, Ar yl Halides and Aromatic Compounds
Stereochemistry :
Sol 34:
Sol 35:
o
45
+ HNO3
CH3COOH
56.5% 3.5%
40.0%
since –CH3 group is electron donating group it will activate the ring and rate of reaction will be more for toluene
than benzene –CH3 group show +I effect so it will be distance dependent and it is –o/–p director.
Ortho position will be more activated than para.
% product : (ortho > para) >> meta
Sol 36:
Chem i str y | 12.115
Sol 37: t-butyl benzene is very much reaction than benzene due to strong +I og t-butyl group. Value for nitration
at Para position is the withiest due to big size of butyl group which Coues stearic hindrance at or the position
Sol 38:
+
Sol 39: HNO3 + 2N2SO 4 → NO2 + 2NSO − 4 + H3O +
H NO2
+
+ NO2
Exercise 2
Single Correct Choice Type
Sol 1: (D)
1 2 . 1 1 6 | Alkyl Halides, Ar yl Halides and Aromatic Compounds
Sol 2: (A) Most electron deficient side will attract OH– towards it and –NO2 group show –M-effect (A)
Sol 3: (A)
Sol4: (A)
Sol 5: (B) Stable group have high livability tendency A <<< B (Resonance) (B)
Sol 7: (B)
Sol 12: (C) Other alcohols are poisonous for our body. So, silver nitrate precipitate out them as nitrates.
Chem i str y | 12.117
Sol 13: (B) CCl3NO2 (Chloropicrin) because it forms phosgene (COCl2) after reaction phosgene is harmful for our body.
573−673 K
Sol 14: (B) + Cl2
75 −100 atm
→ CCl4 + C2Cl6
At such high p & T , it cleaves the C—C bond and chlorinate all valency of carbon.
Sol 15: (A) Computer substitute is C2Cl6 because it has same odour (A)
⊖
more e deficient
Sol 22: (A) They do not form H-bonds because of electron donating alkyl group. and also because of very bond
blooding.
1 2 . 1 1 8 | Alkyl Halides, Ar yl Halides and Aromatic Compounds
OH
Sol 23: (B) Chloral → CCl3–CHO CCl3—C
OH
It is a alkyl halide according to IUPAC nomenclature.
Sol 24: (A) Because chloride attached carbon has less electron density so it attaches to the other one against
markonikoff’s rule.
OH
⠤
Na N3–
+
H2O
Br N3
OH
Sol 25: (C) In presence of sunlight chloroform forms phosgene which is harmful for our body. (Poisonous gas).
⠤ ⊖ ⊖
Na N3–
+
H2O
⊕
⊖ ⊖
⊕
Better leaving group
1
so go via SN path
Sol 26: (D) Chlorobenzene undergoes resonance so C–Cl bond have some double-bond character it will get hard
to hydrolysis it.
Sol 27: (B) It extinguishes five because it inhibits the chemical reactions not because of its non-polar nature solvent.
Sol 28: (A) Inductive effect increases electron density on carbon so it will be easy for Cl-atom to leave the site so
bond will get weakened.
Sol 29: (C) Vinyl group’s carbon area sp2 hybridised and thus are more electronegative than sp3 so they will not donate
electron and more important reason is resonance factor electron and more important reason is resonance factor.
⠤
H2C — C— Cl:
⠤
H
Cl
Sol 30: (A)
Cl2
+
hν Cl
78% 72%
Comprehension Type
Sol 31: (C) Polar solvent so via SN2 reaction –N3 will get substitute on 2º alkyl halide
Sol 32: (A) Strong sterecially
hindered base gives elimination products.
S N1
Chem i str y | 12.119
⊖
CN– C ≡ N: two donating site
∴ ambident nucleophile
Step 2:
Sol 2: (A)
S N2
Sol 4: (A) Nucleophile PhS– substitute the Br– through SN2 mechanism with inversion of configuration at α − C .
Sol 5: (D, E) The compound used as refrigerant are CF2Cl2 , CH2 F2.
Sol 6: A → q; B → q; C → r; D → p, s
Alc. KOH
(A) CH3–CHBr–CD3
E2
→ CH =CH–CD
2 3
E2 reaction is a single-step reaction in which both deprotonation from β − C and loss of leaving group from α − C
occur simultaneously in the rate-determining step. C–D bond is stronger than C–H bond, C–H is preferably broken
in elimination.
(B) Ph–CHBr–CH3 reacts faster than Ph–CHBr–CD3 in E2 reaction because in later case, stronger C–D bond is to be
broken in the rate determining step.
C H OD
(C) Ph–CH2–CH2Br
2 5
−
→ Ph–CD=CH2
C2H5O
1 2 . 1 2 2 | Alkyl Halides, Ar yl Halides and Aromatic Compounds
C H O−
I
2 5 →
(D) Both PhCH2CH2Br and PhCD2CH2Br will react at same rate in E1 reaction because C–H bond is broken in fast non
rate-determining step. Also E1 reaction follow first order kinetics.
Sol 7:
Alc. KOH
Sol 8: C6H5 CH2 CH C6H5 → C6H5—CH=CH—C6H5
E2
Sol 10:
Chem i str y | 12.123
+
CH3 CH2 C CH2 CH2 CH3
CH3
*
H2C CH2 CH CH2CH3 (d & l)
Cl CH3
+
* *
H3C CH CH CH2 CH3 (d & l)
Cl CH3
+ Cl
H3C CH2 C CH2 CH3
CH3
+
H3C CH2 CH CH2 CH3
CH2Cl
Sol 14: (B) SN2 reaction are through back attack of attacking Nu‒ and not on the basic of stability of carbocation.
1 2 . 1 2 4 | Alkyl Halides, Ar yl Halides and Aromatic Compounds
SO3H Br
(Q)
OH OMgX
Sol 16: (D) Cl CH3MgX, dry ether, 0oC Cl aqueous acid
CH3 CH3 CH3
CH3 O CH3
Sol 17: (C) When two phenyl groups are replaced by two para methoxy group, carbocation formed will be more
stable.
Br - Br -
Br
CH3 C CH = CH2 CH3 C = CH CH2 Br
CH3 CH3
(K.C.P) (K.C.P)
+
H H
H -H2O
HO +
H2O
CH3 CH3 + CH CH3 CH3
3 CH3
1,2 methyl shift
OH
CH3 Aq.dilute
o
KMnO4(excess)O C +
HO OH -H +
OH CH3 CH3
CH3 CH3 CH3
Chem i str y | 12.125
CH3
Br Br CH2 CH2 CH2 Br AlCl3
(A) + Cl
CH2 + H Br
H Br CH3
CH3 H2SO4
(B) +
H2SO4
(B) +
BF3.OEt2
(C) + OH