SWEEPING REVISION

Hydrocarbon

Organic compounds containing carbons and hydrogens only.

Most of the fuels are hydrocarbons.

LPG — Liquified Petroleum Gas

CNG — Compressed Natural Gas

LNG — Liquified Natural Gas

Classification of Hydrocarbons

HYDROCARBON

Saturated Unsaturated Aromatic

Hydrocarbon Hydrocarbon Hydrocarbon

✓ Alkane ✓ Alkene ✓ Benzene

✓ Alkyne
Alkanes

Alkanes are saturated hydrocarbons.

General formula of alkanes is CnH2n+2.

Methane is the first member of this family and it is found in coal mines
and marshy places.

Alkanes under normal conditions are inert and cannot react with acids,
bases and other reagents, so these are called paraffins.
PREPARATION OF
ALKANES
 H2/Pt, Ni, Pd
CH2 = CH2
Raney Ni/250°C 200℃
Sabatier Senderens Reduction (Catalytic reduction)

O Zn–Hg/HCl (Clemmensen
reduction-acid sensitive) or
CH3 – C – R
NH2NH2/EtO–Na+
(wolf kishner reduction-base CH4
sensitive) CH3—CH3
R—CH2—CH3
Zn + Dil.HCl
Br–CH2–CH3
(Metal + acid)-reduction reaction

O
H3C – C – OH NaOH+CaO/∆
(Decarboxylation) (Sodalime)
 LiAlH4/Et2O
Br–R (1° & 2°)
(SN2)

Kolbes electrolysis
H3C – C – ONa
(Free radical reaction)
O CH4
CH3—CH3
R’’—R'
O
Hl/Red P.
H – C – CH3
(Radical reaction)

R''–X
R'2Zn
(SN2)
(Frankland reaction)
 O
Hl/Red P.
H – C – CH3 (Radical reaction)
2Na/Dry ether
2CH3–Br Wurtz reaction
(Not good for (Radical reaction/C-C coupling)
unsymmetrical Alkane)

Hl/Red P.
O CH3—CH3
(Radical reaction)
HO – C – CH3 R—R'

R'–X (R' 1°, 2°)

R2CuLi (Corey house synthesis)
(Good for both sym.
(SN2)
unsym. alkane)
H2 O
Al4C3 CH4
–4 Al(OH)3
(Hydrolysis reaction)
Physical Properties

(i) C1 to C4 gases, Neopentane is also gas, but n-pentane and isopentane

are low B.P. liquids.

(ii) Next members C5 to C17 are colourless liquids and above C17 are Waxy
white solids.

(iii) Density: The density of alkanes increases with increase in molecular

mass and becomes constant at 0.8 g/mL. Thus, all alkanes are lighter
than water.
Physical Properties

(iv) Solubility: Alkanes being non-polar and thus insoluble in water but
soluble in non-polar solvents.

Example

C6H6, CCl4, Ether etc.

Physical properties

(v) Boiling point:  Molecular mass (for n-alkanes)

1
∝
Number of side chain

i.e. Boiling point: Pentane < hexane < heptane

and
Boiling point: n–Pentane > Isopentane > neopentane
Physical Properties

(vi) Melting Point: M.P. of alkanes does not show the regular trend. Alkanes
with even number of carbon atoms have higher M.P. than their alkanes of
odd number of carbon atoms.

C C C C C
< C
C C C C C

Odd number of carbon Even number of carbon

✓ REFERENCE NCERT
Example
Which of the following has the lowest boiling point?
(A) (B)

(C) (D)

Solution

Ans. (C)
Example
Arrange the following in the decreasing order of their boiling points:

(i) C9H20 (ii) C8H18 (iii) (iv)

(A) (i) > (ii) > (iii) > (iv) (B) (iv) > (iii) > (ii) > (i)
(C) (i) > (ii) > (iv) > (iii) (D) (iii) > (iv) > (ii) > (i)

Solution

Ans. (A)
CHEMICAL REACTION
OF
ALKANE
 X2/h
CH3–CH2–X
(Free radical substitution reaction)
[F2 > Cl2 > Br2 > I2]
Cl2/h
CH3–CH2–Cl
(Free radical substitution
reaction)

CH3—CH3 Br2/h
CH3–CH2–Br
R—H (Free radical substitution reaction)

I2/h
HlO3/HNO3
CH3–CH2–I
(Free radical substitution)

HNO3
R–NO2
H2SO4/400°C
 H2SO4 + SO3
R–SO3H
(Free radical substitution reaction)

SO2Cl2/h
CH3–CH2–Cl
(Free radical substitution reaction)

CH3—CH3 Pyrolysis 773K

CH2 = CH2 + CH4
R—H (Free radical substitution reaction)

573 K/O2
CH3–CH2–OH
Cu tube
(Oxidation reaction)
Mo2O3/O2
CH3–CHO
(Oxidation reaction)
 (Oxidation reaction)
(CH3COO)2Mn/O2
CH3–COOH

Incomplete
CH4 Combustion Reaction
C(s) + 2H2O (l)
CH3—CH3

Combustion Reaction
CO2 + H2O
Aromatization:
Cr2O3/Al2O3
773 K (FRSR)

Cr2O3/Al2O3
CH3
773 K, 10-20 atm

Isomerization

Anhy.AlCl3
HCl

Oxidation at 3° H
CH3 CH3
KMnO4
H3C–C–H H3C–C–OH

CH3 CH3
Isomerisation

Unbranched chain alkanes on heating with AlCl3 + HCl, are converted

into branched chain alkanes.

CH3
AlCl3 + HCl
CH3—CH2—CH2—CH3 CH3—CH—CH3

n-Butane Isobutane

Branched chain alkanes converted to more branched alkane.

Reaction with Steam

Methane reacts with steam at 1273K in the presence of a nickel

catalyst to form carbon monoxide and dihydrogen. This method
is used for industrial preparation of hydrogen gas.

Ni
CH4 + H2O CO + 3H2
1273 K
Pyrolysis

When alkanes are heated to 500-700°C, then they are decomposed

into lower hydrocarbon. (liquid hydrocarbon is converted into gaseous
hydrocarbon) In the petroleum industry, it is also termed as cracking.
Cracking is used for the manufacture of petrol, petrol gas/oil gas etc.

It involves free radical elimination.

Example


CH3 — CH3 ⎯⎯→ CH2 = CH2 + H2

CH2 = CH2 + CH4


CH3CH2CH3
CH3 — CH = CH2 + H2
Example
Which of the following reactions of methane is complete combustion?
Cu/523K/100atm.
(A) 2CH4 + O2 2CH3OH
Mo2 O3
(B) CH4 + O2 HCHO + H2O
Δ
(C) CH4 + O2 C(s) + 2H2O(l)
(D) CH4 + 2O2 CO2(g) + 2H2O(l)

Solution

Ans. (D)
PREPARATION
OF
ALKENE
Alkenes

Alkenes are unsaturated hydrocarbons.

General formula of alkenes is CnH2n.

Alkenes are also known as olefins (oil forming) since the first member,
ethylene or ethene (C2H4) was found to form an oily liquid on reaction
with chlorine.
 H2SO4/∆ or
R–CH–CH3
H3PO4/ or Al2O3/
OH (E1)

X
Alc. KOH
R–CH2–CH2
–HX
(X:Cl, Br,I) → Saytzeff's Rule (E2) R—CH=CH2
X X R—CH=CH–R
Zn dust
R–CH–CH2 ∆
(E2)

⊕⊖ ⊖⊕ Kolbe’s electrolysis
KOOC COOK
(Free radical reaction)
R’—C—C—R
 H2/Pd-CaCO3
H3C–C≡C–CH3 (cis Alkene)
Lindlar Catalyst
or P-2 Catalyst (Ni2B)
(Hydrogenation, syn addition)

Na/Liq. NH3
H3C–C≡C–CH3 Birch Reduction CH2=CH2
(trans Alkene) CH3—CH=CH–CH3
(Anti-addition) (Cis/trans)
O H
Pyrolysis/
R–C–O–CH2–CH–R
(Ei)
Hoffmann product
⊕− 
(CH3–CH2)4 NOH
(E2)
 Elimination Reaction
E1 & E2
H H
𝛼
H3C–CH–CH–CH2
𝛽 𝛽
Y
H3C–CH=CH–CH3 H3C–CH2–CH=CH2

more substituted Less substituted

alkene is major product. alkene is major product.

Saytzeff Rule Hoffman Rule

NOTE

Al2O3
H2C CH2
350°
Intramolecular Dehydration

CH3—CH2—OH

Al2O3
CH3—CH2—O—CH2—CH3
250°
Intermolecular Dehydration
Physical Properties of Alkenes

Physical state: C1 – C3: gases ; C4 – C20: liquids ; > C20 : solids

Physical Homologus
Isomers
Properties Series

Increases with
Melting point trans > cis
molecular mass
cis > trans
Increases with
Boiling point # branching
molecular mass
decreases B.P.

Practically insoluble in cis > trans

water but fairly soluble in Polarity increases
Solubility nonpolar solvents like solubility in polar
benzene, ether, etc. solvents increases.
Example
Which one is correct about the boiling point of Cis-But-2-ene and
trans-But-2-ene?
CH3 CH3 H CH3
C=C C=C
H H CH3 H
(1) (2)
(A) (1) > (2) (B) (2) > (1) (C) (1) = (2) (D) Cannot compare

Solution

Ans. (A)
Example
Which one is the correct order of solubility in non-polar solvents?
(A) alkane > alkynes > alkene (B) alkane > alkene > alkynes
(C) alkenes > alkynes > alkane (D) alkynes > alkenes > alkane

Solution

Ans. (B)
CHEMICAL REACTION
OF
ALKENE
 Cold Conc. H2SO4
CH3–CH–CH2
(E.A.R, Carbocation)
HO3SO H (Markovnikov's rule)
X
H–X (HBr, HCl, Hl) (Markovnikov's rule)
H3C–CH–CH3
E.A.R

O–H Intermediate: carbocation

CH2—
—CH2 H+/H2O
H3C–CH–CH3 Thus, rearrangement
CH3—CH=CH2 E.A.R occurs.

O–H
Hg(OAc)2, NaBH4, E.A.R
(Non Classical carbocation) H3C–CH–CH3
NO rearrangement
H OH
B2H6/THF H 2 O2
(CH3–CH2–CH2)3B H3C–CH–CH2
E.A.R NaOH
(Anti-Markovnikov's)
(syn-addition)
 (NCC)
Br2 Br
H3C–CH–CH2
EAR Br– H3C–CH–CH2
Br  CCl4
Br
Anti addition of Br2
cis → d, l Threo H O–H
trans → Erythro O
H H3C–CH–CH2
Markovnikov's Rule (M.R.)
CH3—CH=CH2
Br
Cl
NaCl
H3C–CH–CH2
Br
l
Kl
H3C–CH–CH2

Br
 Br
+I—Br–
H3C–CH–CH2–I
EAR
– + Cl
Cl–N=O (Tilden Reagent)
H3C–CH–CH2–N=O NCC
EAR
– +
H–O–Cl
CH3—CH=CH2 H3C–CH–CH2–Cl
EAR
OH
HO OH
OsO4/NaHSO3
H3C–CH–CH2
or dil. Alk. KMnO4
(Syn-addition)
(Baeyer's reagent)
(Hydroxylation)
(Oxidation)
O OH
½O2/Ag/ H+/H 2 O18
H3C–CH–CH2 H3C–CH–CH2
or H3CCO3H 18 OH
(Oxidation)
(Anti-addition)
 O
O3
H3C–CH CH2
EAR (Ozonide)
O O
O O
H2O/Zn
H3C–C–H + H–C–H

CH3—CH=CH2 O
H 2 O2
H3C–C–OH+CO2

–
H+ or OH
CH3COOH + CO2
KMnO4,
 3n O2
2
nCO2 + nH2O
combustion
Cl
Cl2/500°C
CH2–CH=CH2
(FRSR) Allylic
Br halogenation
NBS
CH2—
—CH2 CH2–CH=CH2
(FRSR)
CH3—CH=CH2

High temp./Pressure
CH—CH2 n Polymerisation
Catalysts
CH3
HBr+R2O2 (FRAR)
CH3CH2CH2Br
(Anti-Markovnikov's rule)

(FRSR) → Free radical substitution reaction

(FRAR) → Free radical addition reaction
Hydroformylation or Oxo reaction

Alkenes react with Carbon monoxide and hydrogen at 100 – 150°C

temperature and high pressure (200 atm) in the presence of a Cobalt
catalyst to produce an aldehyde.

It does not follow Markovnikov’s rule.

The net reaction is the addition of a H–atom to one of the Olefinic

bonds and a formyl (–CHO) group to the other.
Example

R—CH2—CH2—CHO
Co/150C
R—CH== CH2+ CO + H2
high pressure
R—CH—CH3

CHO
Alkenylation (Addition of Alkene)

In the presence of H2SO4 or H3PO4 at 80°C, dimerisation of isobutylene

takes place and gives two isomers of octene.

CH3 CH3 CH3 CH3 CH3

H2SO4, 80C
2CH3—C=CH2 CH2 == C—CH2—C—CH3 + CH3—C == CH—C—CH3
CH3 CH3
Mechanism

CH3 CH3

CH3—C=CH2 + H CH3—C—CH3


CH3 CH3 CH3 CH3


CH3—C=CH2 + C—CH3 CH3—C—CH2—C—CH3

CH3  CH3
–H

CH3 CH3 CH3

CH2 == C— CH2—C—CH3 CH3—C == CH—C—CH3
CH3 CH3
Isomerisation

Alkene on heating to 500° to 700 °C or on heating in the presence of

catalyst [AlCl3 or Al2(SO4)3] undergoes isomerisation.

Example
Catalyst
CH3CH2—CH== CH2 CH3—CH== CH—CH3 + CH3—C== CH2


—
1–Butene 2–Butene CH3
Isobutylene
Polymerisation

Any process in which relatively small molecules, called monomers,

combine chemically to produce a very large chain-like or network-like
molecule, called a polymer.

The monomer molecules may be all alike, or they may represent two,
three, or more different compounds.

The molecular mass of a polymer is a simple multiple of monomers.

Polymerisation can be carried out by free radical or ionic mechanisms.

Polymerisation

Polythene is obtained by the polymerisation of ethene molecules at

high temperature and high pressure in the presence of a catalyst.

High temp. / Pressure

n(CH2=CH2) ( CH2—CH2 )n
Catalyst
Polythene

High temp. / Pressure

n(CH3—CH=CH2) ( CH—CH2 )n
Catalyst
CH3
Polypropene
Uses of Polymers

Polymers are used for the manufacture of plastic bags, squeeze bottles,
refrigerator dishes, toys, pipes, radio and T.V. cabinets etc.

Polypropene is used to manufacture milk crates, plastic buckets, and

other moulded articles.
Alkynes

Alkynes are unsaturated hydrocarbons.

General formula of alkynes is CnH2n-2.

The first stable member of the alkyne series is ethyne, which is

popularly known as acetylene.

Acetylene is used for arc welding purposes in the form of oxyacetylene

flame obtained by mixing acetylene with oxygen gas.
PREPARATION
OF
ALKYNE
 Br Br (i) Alc. KOH
CH2—CH2 (ii) NaNH2
E2

Br (i) Alc. KOH

H3C–CH (ii) NaNH2
Br E2
Preparation
Br Br
Zn dust
Br–C–C–Br H–CC–H
H H E2

H2C=CH–Cl Alc. KOH

NaNH2
E2

6Ag
2CHl3
Coupling reaction
 H2 O
CaC2
Acid Base reaction

CH–COOK Kolbe's
CH–COOK electrolysis Preparation
Free radical reaction
H–CC–H
R–CC–R
(i) NaNH2 or Na
H–CC–R
(ii) R–X
Acid Base reaction followed by SN2

– +
(i) CH3MgI
H–CC–R
(ii) R–X
Acid Base reaction followed by SN2.
Preparations of Alkyne (Ethyne or Acetylene)
from Calcium Carbide

Acetylene is prepared in the laboratory by the action of water on

calcium carbide.

CaC2 + 2H2O HCCH + Ca(OH)2

Preparations of alkyne from CHCl3/CHI3

Pure acetylene is obtained when iodoform (CHI3) or chloroform (CHCl3)

is heated with silver powder.

Cl Cl
HC Cl + 6Ag + Cl CH H—C  C—H + 6AgCl
Cl Cl
Preparation of Alkyne from Kolbe’s Electrolysis)

By the electrolysis of an aqueous solution of sodium or potassium,

fumarate acetylene is formed at the anode.

CH−COOK Electrolysis CH
+ CO2
CH−COOK CH
Preparation of Higher Alkynes by Grignard Reagent

By this method, lower alkyne is converted into higher alkyne.

CH3Mg−Br + R−C ≡ C−H ⎯→ R−C ≡ CMg−Br + CH4 R’−I

Br
R−C ≡ C−R’ + Mg
I
Preparation of Alkyne From
Dehalogenation of Tetra halo Alkane

X X
2Zn/dust
R−C−C−H R−C≡CH + 2ZnX2
X X
Physical Properties

First three members are gases, the next eight are liquids and the higher
ones are solids.

Ethyne has characteristic odour, other members are odourless.

Alkynes are weakly polar in nature, so they are insoluble in water but
soluble in organic solvents like ethers, carbon tetrachloride and
benzene.

Their melting point, boiling point and density increase with the increase
in molar mass.
CHEMICAL REACTION
OF
ALKYNE
 H X H
H–X HX
R–C=C–H R–C–C–H
(E.A.R)
X Markovnikov’s rule X H

Reaction Hg2+/dil.H2SO4
O
R–C=CH2 R–C–CH3
Kucherov
R–CC–H OH
O
B2H6/THF
R–CH2–C–H
H2O2/–OH
(E.A.R)

Br Br
2Br2/CCl4
R–C–CH
(Test of unsaturation)
(E.A.R) Br Br

OH O
HOCl HOCl
H3C–C=CH–Cl H3C–C–CH2Cl
(E.A.R)
 H2/Ni
Pd/Pt
R–CH2–CH3
(Reduction)

H2/Pd
CaCO3
(cis) R–CH=CH–R
(Partial Reduction)
H–C=C–H Lindlar
R–CC–H (coupling)
CuCl2 HCl
R–CC–R H–CC–H H2C=CH–CC–H
NH4Cl Cl
R’MgBr Chloroprene
Na/Liq. NH3
Birch reduction for terminal Alkyne)
(Partial Reduction)

R–CH=CH2 R–CCMgBr+R–H

Baeyer's reagent
R–C–C–R
(Test of unsaturation)
OO
 O3
R–C–OH
H2O (EAR)
O
KMnO4/H
R–C–OH

Reaction O
Combustion
H–CC–H CO2+H2O
3𝑛– 1
R–CC–H O2
2
Na/Liq. NH3
R–CCത Na
(for terminal Alkyne)
Acid Base
NaNH2
ത 
R–CCNa

Amm. AgNO3 R–CCAg

(tollens regent) (white ppt.)
Amm. CuCl
(for terminal Alkyne) R–CCCu
(Red ppt.)
Acidic Character of Alkyne

Reaction with Sodium (Na)

1
R—CC—H + Na R—CCNa + H2
2

R—CC—R + Na No reaction

Example

1
CH3—CC—H + Na CH3—CCNa + H
2 2
Sodium propynide
Reaction with Tollen’s Reagent

AgNO3 + NH4OH (ammoniacal silver nitrate solution)


AgNO3 +
R—CC—H NH4OH
R—CCAg + NH4NO3 + H2O
(White ppt.)

AgNO3 +
R—CC—R No reaction
NH4OH

AgNO3 +
Alkene No reaction
NH4OH

These are tests for distinguishing alkenes and 1-alkynes or 1-alkynes and
2-alkynes.
Reaction with Ammoniacal Cuprous Chloride Solution

(Cu2Cl2+ NH4OH)

Cu2Cl2 + 
R—CC—H NH4OH
R—CCCu + NH4Cl + H2O
(Red ppt.)

Cu2Cl2 +
R—CC—R NH4OH No reaction

Cu2Cl2 +
Alkene No reaction
NH4OH

These are tests for distinguishing alkenes and 1- alkynes or 1-alkynes

and 2-alkynes.
Polymerisation

Linear Polymerisation

Dimerisation: When two molecules of acetylene is passed through a solution

of Cu2Cl2 and NH4Cl a vinyl acetylene is obtained.

Cu2Cl2
2HC≡C—H NH4Cl CH2=CH—C≡C—H
(Mono vinyl acetylene)
When vinyl acetylene reacts with HCl, then chloroprene is obtained.

HCl Polymerisation
CH2=CH—C≡C—H CH2=CH—C=CH2 Neoprene
(Synthetic Rubber)
Cl
2–chloro–1,3–butadiene
[Chloroprene]

Trimerisation: When three molecules of acetylene is passed through a

solution of Cu2Cl2 and NH4Cl a divinyl acetylene is obtained.

Cu2Cl2
3CH≡CH NH4Cl CH2=CH—C≡C—CH=CH2
Divinylacetylene
Cyclic Polymerisation

When alkyne is passed through a red-hot metallic tube, cyclic

polymerisation takes place with the formation of an aromatic
compound.
Red hot
3CH≡CH
iron tube

Benzene

CH3

Red hot
3CH3—C≡CH
iron tube
H3C CH3
Mesitylene
 CH3
CH3 CH3

3CH3—C  C—CH3
Red hot
iron tube CH3 CH3
CH3
Hexa methyl benzene

CH CH
HC CH
Ni(CN)2
4CH  CH
HC CH
CH CH

1,3,4,7- cyclooctatetraene
Example
H2O Red hot Fe tube
CaC2 (A) (B), Product (B) of the reaction is
Calcium carbide

(A) Toluene (B) Ethyl-benzene

(C) Benzene (D) Butyne

Solution

Ans. (C)
Oxidation Reaction

(a) Combustion
3n−1
CnH2n–2 + O2 ⎯⎯→ nCO2 + (n–1) H2O + Heat
2

2HCCH + 5O2 ⎯⎯→ 4CO2 + 2H2O + 312 K.cal

The combustion of acetylene is used for welding and cutting of metals

in which oxy-acetylene flame having high temp (3000°C) is produced.
(b) Oxidation with Ozone (O3):

Example

(i) O3
CH3−C−OH + HCOOH
(ii) H2O
CH−C≡CH O
(i) O3
CH3−C − C−H
(ii) H2O/Zn
O O
Uses of Acetylene

Oxyacetylene flame used in welding and cutting

Acetylene is used as an illuminant.

Acetylene is used for the artificial ripening of fruits.

It is used for the manufacture of acetaldehyde, acetic acid, ethyl alcohol,

westron, westrosol, PVC, PVA, Chloroprene, butadiene, Lewisite etc.

It is used as a general anaesthetic.

 AROMATIC
HYDROCARBONS
Introduction

Aromatic Hydrocarbons are also known as arenes.

Most of them possess a pleasant odour.

Aromatic compounds containing a benzene ring are known as

benzenoids, and those not containing a benzene ring are known as non-
benzenoids. CH3

Benzene Toluene Naphthalene Biphenyl

Benzene

Methods of Preparation

Physical Properties

Chemical Properties
From Alkanes (by Aromatisation)

n-Alkanes having six or more carbon atoms on heating to 500°C at

10-20 atmospheric pressure in the presence of oxides of vanadium,
molybdenum or chromium supported over alumina (Al2O3) results in
the formation of aromatic hydrocarbons.
Cr2O3/Al2O3
CH3(CH2)4 CH3 500° C
+ 4H2

n-Hexane Benzene
CH3

Cr2O3/Al2O3
CH3(CH2)5 CH3 + 4H2
500° C
n-Heptane
Toluene

It provides an excellent method of passing from aliphatic to aromatic

series.
From Alkyne (by Cyclic Polymerisation)

Ethyne on passing through a red hot iron tube at 873K undergoes cyclic
polymerisation.

Red hot
3CH  CH
iron tube

Benzene
From Phenolic Compounds (by Reduction)

Phenol is reduced to benzene by passing its vapours over heated zinc

dust.
OH


+ Zn + ZnO

OH CH3
CH3 H

+ Zn + ZnO
From Carboxylic Acids (by Decarboxylation)

Sodium salt of benzoic acid on heating with sodalime gives benzene.

COONa

CaO
+ NaOH + Na2CO3


COONa
CH3 CH3
CaO
+ NaOH + Na2CO3

By Grignard Reagent

Grignard reagent is only stable in the aprotic solvents; it is unstable in

protic solvents.

MgCl H
H—OH

CH3 CH3
MgCl
H—OCH3
Physical Properties

Aromatic hydrocarbons are non-polar molecules and are usually

colourless liquids or solids with a characteristic aroma.

Naphthalene balls are used in toilets and for the preservation of clothes.

Aromatic hydrocarbons are immiscible with water but are readily miscible
with organic solvents.

It is highly inflammable and burns with sooty flame.

Carcinogenicity and Toxicity

Benzene and polynuclear hydrocarbons containing more than two

benzene rings fused together are toxic and said to possess cancer-
producing (carcinogenic) properties.

Such polynuclear hydrocarbons are formed by incomplete combustion

of organic materials like tobacco, coal, and petroleum.

They enter into human body and undergo various biochemical

reactions and finally damage DNA and cause cancer.
 Some of the carcinogenic hydrocarbons are:

H3C

3-Methylcholanthrene 1, 2-Benzpyrene

1, 2-Benzanthracene 1, 2, 5, 6-Dibenzanthracene
Addition Reaction

Addition of X2

Under ultra-violet light, three chlorine molecules add to benzene to

produce benzene hexachloride (C6H6Cl6).
Cl
Cl Cl
3Cl2 / hv Benzene hexachloride
∆ (BHC) or Gammaxane or
Cl Cl lindane
C6H6
Cl
(C6H6Cl6)
BHC is used as powerful insecticide
Addition of H2
(a) Complete hydrogenation

Under vigorous conditions, i.e., at high temperature and/or pressure in

the presence of a nickel catalyst, hydrogenation of benzene gives
cyclohexane.

Ni
+ 3H2

CH3 CH3
Ni
+ 3H2
Addition of H2
(b) Partial hydrogenation

Na/liquid NH3


COOH COOH

Na/liq. NH3


CH3 CH3
Na/liqNH3

Oxidation Reaction

Combustion

When heated in air, benzene burns with sooty flame producing CO2 and H2O.

15
C6H6 + O2 6CO2 + 3H2O
2
Catalytic Oxidation

OH

V2O5
300°C
Phenol

V2O5
O
450°C

O
Maleic anhydride
NOTE Cl

Cl2
AlCl3

Cl
Cl Cl
Cl2(excess)
Hexachloro benzene(C6Cl6)
AlCl3
Cl Cl
Cl
Cl
3Cl2 Cl Cl
Benzene hexachloride (C6H6Cl6)
UV/500K or Gammaxene
Cl Cl or Lindane
(used as an insecticides)
Cl
 COONa+
NaOH + CaO + 
decarboxylation
(– CO2)
OH
Zn/

SO3H
H+/H2O/
ipso substitution
MgBr
H2O

BENZENE
OH N2+Cl
CH3CH2OH: or H3PO2
H2 O

(SN1 type)
Cr2O3
Al2O3 (500)
 H E E
E
+
Reaction Arenium ion
Electrophilic NO2
HNO3+ H2SO4 Rate
Substitution C6H6=C6D6=C6T6
Reactions NO2
[Nitration]
SO3H
H2SO4 Rate
Electrophile SO3 C6H6>C6D6>C6T6
[Sulphonation]
CH3
CH3Cl+AlCl3
Benzene Friedel crafts
O O
Alkylation
CH3–C–O–C–CH3
+AlCl3
O C CH3
CH3C–Cl+AlCl3 Friedel crafts
Acylation
O +
(CH3–C=O)
 COOH
CO2
Carboxylation
AlCl3

Reaction O C H
CO + HCl Gattermann Koch
AlCl3 Aldehyde Synthesis

E.S.R
CHO
Benzene
HCN + HCl +ZnCl2 Gattermann Aldehyde
H 3 O+ Synthesis

Cl
6Cl2 + Anhyd.AlCl3 Cl Cl

Cl Cl
Cl
 O
O C H
Ph–C–Cl+AlCl3

Reaction

H2/Pt

Reduction
Benzene

Na/liq. NH3

Birch Reduction
 Baeyer's
No reaction
reagent

Reaction
CHO
O3 3
CHO
Zn/H2O Ozonolysis

Benzene

15
O (Combustion)
2 2
6CO2 + 3H2O
 Example
[JEE Main 2023]
In the following reaction ‘X’ is
Anhy. AlCl3
CH3(CH2)4CH3 HCl, 
X
major product

(A) CH3(CH2)4CH2Cl (B) Cl—CH2—(CH2)4—CH2—Cl

(C) CH3CH—(CH2)2CH3 (D)

CH3

Solution

Ans. (C)
 Example
[JEE Main 2021]
Identify A in the given chemical reaction:
CH3
CH2
Mo2O3
CH2 CH3 ‘A’
773K, 10-20 atm
CH major product
CH2 CH3
CH3 CH3
(A) (B) (C) (D)

Solution

Ans. (D)
 Example
Which of the following reagent is used for the following reaction?
?
CH3CH2CH3 ⎯⎯→ CH3CH2CHO [JEE Main 2021]
(A) Manganese acetate
(B) Copper at high temperature and pressure
(C) Molybdenum oxide
(D) Potassium permanganate

Solution

Ans. (C)
Hydrocarbons

Preparation
(1) Alkanes
Chemical properties

Preparation
(2) Alkenes
Chemical properties
 Example
Which one of the following alkenes when treated with HCl yields majorly an
anti Markovnikov product? [JEE Main 2019]
(A) F3C–CH=CH2 (B) Cl–CH=CH2
(C) CH3O–CH=CH2 (D) H2N–CH=CH2

Solution

Ans. (A)
 Example
The trans-alkenes are formed by the reduction of alkynes with
(A) NaBH4 (B) Na/liq. NH3
[JEE Main 2018]
(C) Sn - HCl (D) H2 - Pd/C, BaSO4

Solution

Ans. (B)
 Example
In the following sequence of reactions, the maximum number of atoms present
in molecule ‘C’ in one plane is __________.
[JEE Main 2020]
Red hot CH3 Cl 1.eq.
A B C
Cu tube Anhydrous AlCl3

(A is a lowest molecular weight alkyne)

Solution

Ans. (13)
 Example
For the given reaction: [JEE Main 2021]
1. NaNH2
CH=CHBr (A)
2. Red hot iron tube, 873K
CH3 (major product)

What is ‘A’?
H3C CH3
(A) CH3CH2CH2NH2 (B) CH=CH–NH2 (C) (D)
CH3 CH3
Solution
Solution CH=CHBr
1. NaNH2
(A)
2. Red hot iron tube, 873K
CH3 (major product)

Ans. (D)
 Example
Match List-I with List-II. [JEE Main 2021]
List-I List-II
(Chemicals) (Use/Preparation/Constituent)
(a) Alcoholic potassium hydroxide (i) Electrodes in batteries
(b) Pd/BaSO4 (ii) Obtained by addition reaction
(c) BHC (Benzene hexachloride) (iii) Used for -elimination reaction
(d) Polyacetylene (iv) Lindlar’s Catalyst
Choose the most appropriate match
(A) (a)-(ii), (b)-(i), (c)-(iv), (d)-(iii) (B) (a)-(iii), (b)-(iv), (c)-(ii), (d)-(i)
(C) (a)-(iii), (b)-(i), (c)-(iv), (d)-(ii) (D) (a)-(ii), (b)-(iv), (c)-(i), (d)-(iii)

Solution

Ans. (B)
 Example

+ CH3CH2CH2Cl
Anhydrous, AlCl3
‘A’ [JEE Main 2022]
Major Product
The stable carbocation formed in the above reaction is:
⊕ ⊕
(A) CH3CH2 C H2 (B) CH3 C H2
⊕ ⊕
(C) CH3–C H–CH3 (D) C HCH2CH3

Solution

Ans. (C)
 ALKYL AND
ARYL HALIDES
Alkyl and Aryl Halides

The replacement of hydrogen atom(s) in an aliphatic or aromatic

hydrocarbon by halogen atom(s) results in the formation of alkyl
halide(haloalkane) and aryl halide (haloarenes), respectively.

CH3—CH2—H X CH3—CH2—X

2(X)
CH3—CH—H CH3—CH—X

H X

H X
X

Where – X(–F, –Cl, – Br, – I)

IUPAC and Common Nomenclature

Structure Common Name IUPAC Name

CH3CH2CH(Cl)CH3 sec-Butyl chloride 2-Chlorobutane

(CH3)3CCH2Br neo-Pentyl bromide 1-Bromo-2,2-dimethylpropane

(CH3)3CBr tert-Butyl bromide 2-Bromo-2-methylpropane

CH2=CHCl Vinyl chloride Chloroethene

CH2=CHCH2Br Allyl bromide 3-Bromopropene

IUPAC and Common Nomenclature

Structure Common Name IUPAC Name

Cl 1-Chloro-2-methylbenzene
o-Chlorotoluene or
CH3
2-Chlorotoluene
CH2Cl
Benzyl chloride Chlorophenyl methane

CH2Cl2 Methylene chloride Dichloromethane

CHCl3 Chloroform Trichloromethane

IUPAC and Common Nomenclature

Structure Common Name IUPAC Name

CHBr3 Bromoform Tribromomethane

Carbon
CCl4 Tetrachloromethane
tetrachloride

CH3CH2CH2F n-Propyl fluoride 1-Fluoropropane

Classification of Alkyl and Aryl Halides

On the basis of On the basis of

On the basis of
compounds compounds
number of halogen
containing (Csp3 − X) containing (Csp2 − X)
atoms
bond bond

— C—X bond =C–X

sp3 sp2
1. On the basis of number of halogen atoms

(a) Monohaloalkane

Mono one

Halo F, –Cl, –Br , –I

Alkyl/Aryl —R

R—X
Monohaloalkane R—F/R—Cl/R — Br/R — I
Example
F

C2H5Cl C3H7Br

Chloroethane Bromopropane Fluorobenzene

Cl Br I

Chlorobenzene Bromobenzene Iodobenzene

(b) Dihaloalkane

Di two

Halo —F, —Cl, —Br, — I

Alkyl/Aryl —R
 Example

1 X
1 CH2—X R—CH
X
2 CH2—X
1,2–Dihaloalkane 1,1–Dihaloalkane
Vicinal dihalide Geminal dihalide

X
X X 1
1 1 2
X
2
2 3
3 X 4
X
1,2-Dihalobenzene 1,3-Dihalobenzene 1,4-Dihalobenzene
(c) Polyhaloalkanes/polyhaloarenes

No. of halogens > 2

X
1 CH2—X X 4
1 5 3
X
2 CH —X 2 6 2 X
1
3 CH2—X 3 X X

1,2,3-Trihalopropane 1,2,3-Trihalobenzene 1,2,4-Trihalobenzene

2. Compounds containing (sp3—X bond)

(a) Alkyl halides(containing all sigma bonds)

C sp
3
C R
sp3 R
R

4  bond + 0 p

Example
CH3
Et—C—X
sp3
H
(b) Allylic halides


CH2—
—X
Allylic carbon

Allylic carbon
X
 1 2 3
CH2 == CH—CH2—Cl
Allyl Chloride
X
3-Chloropropene
(c) Benzylic halide

R1
C—

R2
Benzylic carbon

 R1
CH2—X
C—X
Benzylic carbon R2
Benzylic carbon
3. Compounds containing (sp2 C—X bond)

(a) Vinylic Halides

C == C—X : CH2 == CH—Cl :

sp2
Vinyl chloride

(b) Aryl halides/phenyl halides

X: X:

H3C
PREPARATION OF ALKYL HALIDES
FROM HYDROCARBON
Preparation

PCl5
H3C–CH2–OH
(SN2)

PCl3
3H3C–CH2–OH
(SN2) CH3–CH2–X (R–X)
(General Product)
Red P + Br2
(X = F, Cl, Br, I)
3H3C–CH2–OH
(Radical Reaction)

SOCl2
H3C–CH2–OH
(SNi)
Preparation
SOCl2, Pyridine
H3C–CH2–OH
(SN2)

Br2, CCl4
H3C–COOAg
Hunsdiecker Reaction (Free Radical Reaction)

CH3–CH2–X (R–X)
HCl/ZnCl2 (General Product)
H3C–CH2–OH Lucas Reagent (X = F, Cl, Br, I)
(SN1 with 2°, 3° alcohol)
(SN2 with 1° alcohol)

NaBr + H2SO4
H3C–CH2–OH
(3°→Alkene)
(3°→Alkene)

(SN2 Reaction)

HI
H3C–CH2–OH Kl/H3PO4
(SN2 Reaction)
Preparation

H3C–CH=CH2 NBS
(Allylic substitution) CCl4
(Free Radical Reaction)

Cl2/hv
CH3–CH3
(Free Radical Reaction) X
|
H2C–CH=CH2
HBr CH3–CH2–X (R–X)
CH2=CH2 (General Product)
CCl4
(Electrophilic Addition (X = F, Cl, Br, I)
Reaction)
H3C–CH2–Cl Nal
(Finkelstein Reaction) Acetone
(SN2)

H3C–CH2–Cl AgF or Hg2F2

(Swart Reaction)
(SN2)
Preparation

HBr Br
Peroxide
(Free Radical Addition
H3C–CH2–CH2
Reaction)

Br2/800K Br
H3C–CH=CH2  CH2–CH=CH2
(Free Radical
Substitution Reaction)

NBS Br
CCl4 CH2–CH=CH2
(Free Radical
Substitution Reaction)
Preparation

HBr Br
CCl4 H3C–CH–CH3
(E.A.R.)

HCl Cl
H3C–CH=CH2 (E.A.R.) H3C–CH−CH3

Br2/CCl4 H3C–CH–CH2–Br
(E.A.R.)
Br
Physical Properties

Colour and Odour

Boiling Point & Melting Point

Solubility

Density

Dipole Moment
Colour & Odour

Pure alkyl halides are colourless.

Alkyl bromides and alkyl iodides develop colour when exposed to light.

Generally, volatile halogen compounds have a sweet smell.

Boiling Point

Boiling point of
Haloalkanes depends on

Polarity & molar mass of the compound

Branching of parent chain

Boiling Point

Boiling point of Haloalkanes is directly proportional to the van der Waals

force of attraction.

Higher the molecular mass, more will be its boiling point.

Example
Compare boiling point of given below compounds:
CH3F , CH3Cl , CH3Br , CH3I

Solution
 For isomeric haloalkane, boiling point decreases as branching increases.

1
Boiling Point of isomeric haloalkanes 
Branching

Example
CH3
Br
CH3—C—Br

—
CH3—CH2—CH2—CH2—Br CH3—CH—CH2—CH2
CH3

1-bromobutane 2-bromobutane 2- bromo-2- methyl

propane

375 K 364 K 346 K

Melting Point

Para isomers have high melting points as compared to their ortho and
meta isomers due to the symmetry of para-isomers that fits in the crystal
lattice better as compared to ortho- and meta-isomers.

Boiling point of isomeric di halobenzene is nearly the same.

Cl Cl
Cl
Cl

Cl
Cl
M.P 256 K 249 K 323 K

B.P 453 K 446 K 448 K

Solubility

Haloalkanes are very slightly soluble in water.

It is due to the energy released when new attractions formed in

between haloalkane & H2O molecules is not sufficient to overcome the
attraction between haloalkane molecules and to break H-bonds
between H2O molecules.

Haloalkanes are easily soluble in organic solvents, because the new

intermolecular attractions have the same strength as the one being
broken in the separate haloalkane and solvent molecules.
Density

Bromo, iodo and polychloro derivatives of hydrocarbons are heavier than

water.

Density  Number of carbon atoms

Density  Number of halogen atoms
Density  Atomic mass of halogen atoms

Example

CH3I < CH3CH2I < CH3CH2CH2I

CH3I > CH3Br > CH3Cl > CH3F

CH2Cl2 < CHCl3 < CCl4

Example
Which of the following statements is/are correct?
(A) Solubility of haloalkanes in water is low.
(B) Haloalkanes are soluble in organic solvent.
(C) Molecules with better packing have higher melting points.
(D) As branching increases, the boiling point decreases in isomeric
haloalkanes.

Solution

Ans. (A, B, C, D)
Dipole Moment

It is a vector quantity which measures the bond polarity.

μ=qxd

Where, μ is dipole moment.

q is charge on electron.

d is distance between opposite charges.

Dipole moment depends upon both magnitude of charge and distance

between them.
Chemical Properties of
Alkyl Halide
REACTIONS Nucleophilic substitution: Rate for alkyl halide
a. SN1 : 3 > 2 > 1
b. SN2 : 1 > 2 > 3

Nal/Acetone
H3C–CH2–I
(SN2)

(C2H5)2CuLi
H3C–CH2–CH2–CH3
CH3–CH2–X (R–X) (SN2) Corey house synthesis
(General Reactant)
(X = F, Cl, Br, I) NH3
excess H3C–CH2–NH2
(SN2)

H–CC
ഥNa+
H3C–CH2–CC–H
(SN2)
REACTIONS Nucleophilic substitution: Rate for alkyl halide
a. SN1 : 3 > 2 > 1
b. SN2 : 1 > 2 > 3

LiAlH4/Et2O H3C–CH2–H
(SN2) (1°,2° not 3°R–X)

CH3–CH2–X (R–X)
NaNO2/DMF O
(General Reactant) H3C–CH2–N
(X = F, Cl, Br, I) (SN2) O

CH3–CH2Oഥ Na+
C2H5–O–C2H5
(SN2)
(Williamson ether synthesis)

NaBH4/EtOH
R–X(2° & 3° not 1°) R–H
SN1
REACTIONS

Na/Et2O
H3C–CH2–CH2–CH3 Wurtz reaction
(Free Radical Reaction)

CH3–CH2–X (R–X) Br /Na/Et2O

(General Reactant) H3C–CH2 Wurtz-Fittig
(X = F, Cl, Br, I) (Free Radical Reaction) Reaction

Mg/Et2O
(Formation of organic
C2H2MgBr
(Insertion Reaction) metallic compound)
REACTIONS

Alc. KOH
H2C=CH2
(E2)

CH3–CH2–X (R–X)
NaSH/Alc.
(General Reactant) H3C–CH2–SH
(X = F, Cl, Br, I) (SN2)

CH3SNa
H3C–CH2–S–CH3
(SN2)
 (Reactivity order)
REACTIONS
(R–I > R–Br > R–Cl > R–F)
⊖ ⊖
Ambident Nucleophile:- CN, O–N=O

Aq. KOH or Moist Ag2O

H3C–CH2–OH
(SN2)

KCN/EtOH
(SN2) H3C–CH2–CN
CH3–CH2–X (R–X)
(General Reactant)
(X = F, Cl, Br, I) AgCN + −
(SN2) H3C–CH2–N C

K+O–N=O
H3C–CH2–O–N=O
(SN2)
 (Reactivity order)
REACTIONS
(R–I > R–Br > R–Cl > R–F)
⊖ ⊖
Ambident Nucleophile:- CN, O–N=O

Ag–O–N=O O
H3C–CH2–N
(SN2) O

AlCl3/
CH2–CH3
(E.A.S.) F.C. Alkylation
CH3–CH2–X (R–X)
(General Reactant)
(X = F, Cl, Br, I) RMgX
R–R
(SN2)

RCOO–
(SN2) RCOOCH3
Physical Properties

(1) Dipole moment: CH3–Cl > CH3–F > CH3–Br > CH3–I

(2) Bond enthalpies: CH3–F > CH3–Cl > CH3–Br > CH3–I

(3) Boiling point: R–I > R–Br > R–Cl > R–F

> >
Br
Br Br

(4) Density: n–C3H7Cl < n–C3H7Br < n–C3H7I

(5) Solubility → Haloalkanes are very slightly soluble in water.

Tri-halo alkane

O OH
Cl2 + NaOH
CH3–C–R or H3C–CH–H
(Haloform test) or NaOCl
(Addition-Elimination)
O
CaOCl2
H3C–C–CH3
Bleaching powder
(Addition-Elimination) CHCl3
O Chloroform
NaOH
CCl3–C–H
(Addition-Elimination)

Fe/HCl
CCl4
(Redox Reaction)
Tri-halo alkane

3Cl2/H CH4

O2/Light Cl
O=C +HCl
Cl
HNO3 Cl3C–NO2
(Chloropicrin) (tear gas)
CHCl3 Ag/
Chloroform HCC–H

OH O
NaOH / OH C
H

Reimer Tiemann
CH3NH2 (In presence of base) + −
CH3–NC (Test of primary amine)
Tri-halo alkane

Boiling point Melting point

F Cl Br I Cl Cl Cl
Cl
< < <
< <
(i)
Cl
Cl
Cl Cl Cl
Cl
< <
(ii)
Cl
Cl
Properties of dicholoro
methane, choloroform,
Iodoform, CCl4, Freons
Dichloromethane

Dichloromethane is a geminal organic compound and is also called

methylene chloride or methylene dichloride.

Uses of Dichloromethane

It is used as a solvent, a paint remover, a propellant in aerosols and as

a process solvent in the manufacture of drugs.

It is also used as a metal cleaning and finishing solvent.

Adverse Effect of Dichloromethane

Methylene chloride harms the human central nervous system.

Exposure to lower levels of methylene chloride in air can lead to slightly

impaired hearing and vision.

Higher levels of methylene chloride in the air cause dizziness, nausea,

tingling and numbness in the fingers and toes.

In humans, direct skin contact with methylene chloride causes intense

burning and mild redness of the skin.

Direct contact with the eyes can burn the cornea.

 Trichloromethane

Chloroform, also referred to as trichloromethane is an organic compound.

It was first prepared in 1831.

Uses of Chloroform (CHCl3)

It was once used as a general anaesthetic in surgery but has been

replaced by less toxic, safer anaesthetics, such as ether.

Chloroform is used as a solvent for fats, alkaloids and iodine.

The major use of chloroform is in the production of the freon refrigerant

R-22 (CHClF2).
Why chloroform stored in dark bottles?

Chloroform is slowly oxidised by air in the presence of sunlight to an

extremely poisonous gas, ‘phosgene’.

light C
2CHCl3 + O2 2 Cl Cl + 2HCl
Phosgene

To prevent this, chloroform is stored in dark bottles that

are completely filled to keep out the air.
Adverse Effect of Trichloromethane

Inhaling chloroform vapours depresses the central nervous system and

it causes dizziness, fatigue, and headache.
Iodoform

Iodoform, which is also called triiodomethane (CHI3), is a yellow

crystalline solid.

It is insoluble in water but soluble in solvents like ethanol, chloroform,

and ether.

Iodoform was used earlier as an antiseptic, but its antiseptic properties

are due to the liberation of free iodine, not to the iodoform itself.

skin
CHI3 I2 (has antiseptic properties)
contact
Tetrachloromethane (Carbon Tetrachloride)

It is a colourless liquid with a “sweet” smell. The molecular formula

of carbon tetrachloride is CCl4.

Uses of Tetrachloromethane (Carbon Tetrachloride)

It is produced in large quantities for use in the manufacture of refrigerants

and propellants for aerosol cans.

It is also used as feedstock in the synthesis of chlorofluorocarbons,

pharmaceutical manufacturing, and general solvent use.
Uses of Tetrachloromethane (Carbon Tetrachloride)

CCl4 is stable to heat and its vapours do not catch fire thus it is used as a
fire extinguisher.

It was also widely used as a cleaning fluid, both in industry, as a

degreasing agent, and in the home as a spot remover.
Adverse Effect of Tetrachloromethane

The chemical may irritate the eyes on contact.

Due to exposure of carbon tetrachloride, the most common effects are

dizziness, light headedness, nausea and vomiting, which can cause
permanent damage to nerve cells and also cause liver cancer.
Adverse Effect of Tetrachloromethane

When carbon tetrachloride is released into the air, it rises in the

atmosphere and depletes the ozone layer.

Depletion of the ozone layer is believed to increase human exposure to

ultraviolet rays, leading to increased skin cancer, eye diseases and
disorders, and possible disruption of the immune system.
Freons (CFCS)

The chlorofluorocarbon compounds of methane and ethane are collectively

known as freons and it contains C, F and Cl.

Example

CCl2F2 , C2F4Cl2 etc.

They are extremely stable, unreactive, non-toxic, non-corrosive and easily
liquefiable gases.

Freon 12 or R-12 (CCl2F2) is one of the most common. It is manufactured

from tetrachloromethane by Swarts reaction.

These are usually produced for aerosol propellants, refrigeration and air
conditioning purposes.
p, p’-Dichlorodiphenyltrichloroethane (DDT)

It was the first chlorinated organic insecticide prepared in 1873.

Prepared by heating chloral and chlorobenzene in the presence of conc.

H2SO4.

Cl Cl
Cl Cl Cl Cl

CH
O H+
H H
-H2O
Cl Cl
Cl Cl (DDT)
Example
Match List - I with List - II. [JEE Main 2024]
List - I List - II
Compound Use
(A) Carbon tetrachloride (I) Paint remover
(B) Methylene chloride (II) Refrigerators and air conditioners
(C) DDT (III) Fire extinguisher
(D) Freons (IV) Non Biodegradable insecticide
Choose the correct answer from the options given below:
(1) (A)-(I), (B), (II), (C)-(III), (D)-(IV)
(2) (A)-(III), (B)-(I), (C)-(IV), (D)-( II)
(3) (A)-(IV), (B)-(III), (C)-(II), (D)-(I)
(4) (A)-( II), (B)-(III), (C)-(I), (D)-(IV)

Solution

Ans. (2)
Example
Match List I with List II: [JEE Main 2024]
Choose the correct answer from the options given below:
List-I List-II
(Compound) (Uses)
(A) Iodoform (I) Fire extinguisher
(B) Carbon tetrachloride (II) Insecticide
(C) CFC (III) Antiseptic
(D) DDT (IV) Refrigerants
(1) A-I, B-II, C-III, D-IV (2) A-III, B-II, C-IV, D-I
(3) A-III, B-I, C-IV, D-II (4) A-II, B-IV, C-I, D-III

Solution

Ans. (3)
Example
The increasing order of the boiling points of the major products A, B and C of
the following reactions will be
O

(C6H5CO)2
(A) + HBr A (B) + HBr B

(C) + HBr C

(1) C < A < B (2) B < C < A

(3) A < B < C (4) A < C < B

Solution [JEE Main 2020]

Ans. (2)
Example
The correct decreasing order of densities of the following compounds is:
Cl Br
Cl

Cl Cl
(A) (B) (C) (D)

(1) (D) > (C) > (B) > (A) (2) (C) > (D) > (A) > (B)
(3) (C) > (B) > (A) > (D) (4) (A) > (B) > (C) > (D)

Solution [JEE Main 2021]

Ans. (1)
Example
Identify the correct order for the given property for the following compounds:
Cl <
(A) Boiling point: Cl < Cl
Cl <
(B) Density: Br < l
Br Br
Br
(C) Boiling point: Br < Br < Br

l < Br < Cl
(D) Density:
Br Br
Cl > Cl
(E) Boiling point: Cl >
Choose the correct answer from the option given below:
(1) (B), (C) and (D) only (2) (A), (C) and (E) only
(3) (A), (C) and (D) only (4) (A), (B) and (E) only
[JEE Main 2023]
Solution

Ans. (2)
Example
The correct order of melting point of dichlorobenzenes is [JEE Main 2023]
Cl Cl Cl Cl Cl Cl
Cl Cl
(1) > > (2) > >
Cl Cl
Cl Cl
Cl Cl Cl Cl Cl Cl
Cl Cl
(3) > > (4) > >
Cl Cl
Cl Cl
Solution
Cl Cl
Cl
Cl

Cl
Cl
M.P 256 K 249 K 323 K

B.P 453 K 446 K 448 K

Ans. (4)
Example
The pair from the following pairs having both compounds with net
non-zero dipole moment is
(1) Benzene, anisidine (2) 1,4-Dichlorobenzene, 1,3-Dichlorobenzene
(3) CH2Cl2, CHCl3 (4) cis-butene, trans-butene

Solution [JEE Main 2023]

Ans. (3)
Example
Consider the following bromides:
Me Me
Me Br Me
Br Br
A B C
The correct order of SN1 reactivity is
(1) A > B > C (2) B > C > A (3) B > A > C (4) C > B > A

Solution [AIEEE 2010]

Ans. (2)
Example
The product of the reaction given below is:
1. NBS/hv
2. H2O/K2CO3 X

CO2H OH O
(1) (2) (3) (4)

Solution [JEE Main 2016]

Ans. (3)
Example
The major product of the following reaction is:
CH3
OH
(i) aq. NaOH
(ii) CH3I

CH3 CH3 CH3

CH3
OH OH
OH OCH3
(1) (2) (3) (4)
CH3 CH3 CH3

Solution [JEE Main 2019]

Ans. (4)
Example
Which of the following potential energy (PE) diagrams represents the SN1
reaction?

(1) PE (2) PE
Progress of reaction Progress of reaction

(3) PE PE
(4)
Progress of reaction Progress of reaction

Solution [JEE Main 2019]

Ans. (4)
Alcohol

Alcohols are compounds that contain one or more hydroxyl groups

(–OH) bonded to saturated or unsaturated carbon atoms.

Aliphatic hydroxy
derivatives

HYDROXY
DERIVATIVES
Aromatic hydroxy
derivatives
(a) Classification according to number of —OH groups

(i) Monohydric [one –OH group] CH3CH2—OH Ethyl alcohol

(ii) Dihydric [two –OH groups] CH2 CH2 Ethylene

|
| | glycol
OH OH

CH2 CH CH2 Glycerol

|
(iii) Trihydric [Three –OH groups] | | |
OH OH OH

CH2–OH
(iv) Polyhydric [n –OH groups] |
(CHOH)4 Sorbitol
|
CH2–OH
Open-chain saturated monohydric alcohols are called alkanols.

In general, alcohols containing two or more –OH groups are referred to as

polyhydric alcohols.
(b) Classification according to nature of Carbon

In these three types of alcohols, the –OH group is attached to

primary, secondary and tertiary carbon atom, respectively.

OH
CH3–CH2–OH H3C — CH — CH3
Primary (1°) Secondary (2°)
alcohol alcohol

OH CH3
H3C — C — OH

Secondary (2°) CH3

alcohol Tertiary (3°)
alcohol
 OH
H2C = CH—OH
Vinylic alcohols

R'
OH
CH2–OH C—OH
H2C = CH—CH2—OH
R
Allylic alcohols
Benzylic alcohols
 Structure of Methyl Alcohol

Bond Lengths
H 110°
C—H 110 pm 109°
C — O∶

∶
O—H 96 pm H 108.5°
H H Slightly less than the tetrahedral
C—O 143 pm
angle. This is due to repulsion
between the lone pairs of electrons,
 Fig.–Methanol which is stronger than that
C—H between the bond pair and the lone
by the linear overlap sp3 orbital of pair of electrons.

carbon with 1s orbital of hydrogen


O— H
by the linear overlap sp3 orbital of oxygen with 1s orbital of hydrogen

C— O
by the linear overlap sp3 orbital of carbon with sp3 orbital of oxygen
Ethers

Ethers are compounds in which an oxygen atom is bonded to two hydrocarbon

groups.

R—O—R

R = alkyl, alkenyl, vinyl, alkynyl, aryl or cycloalkyl.

Symmetrical ether (R—O—R)

Or
Simple ether
Classified as

Unsymmetrical ether (R—O—R)

Or
Mixed ether
 CH3—O—CH3 CH3CH2—O—CH2CH3 CH3CH2—O—CH3

Dimethyl ether Diethyl ether Ethyl methyl ether

(a symmetrical ether) (a symmetrical ether) (an unsymmetrical ether)

(CH3)2CH—O—CH2CH3 O—CH3 O

Ethyl isopropyl ether Methyl phenyl ether (Anisole) Diphenyl ether

(a saturated aliphatic ether) (an aliphatic aromatic ether) (an aromatic ether)
The ethers in which the oxygen is part of a ring are called cyclic ethers.
Three-membered cyclic ethers are called epoxides or oxiranes.

O O O O
Oxirane Oxetane Furan Oxolane
(Ethylene oxide) (Trimethylene oxide) (Tetrahydrofuran)
(an epoxide)

O O O
Oxane 1,4–Dioxane
–Pyran
(Tetrahydropyran)
Open-chain saturated monoethers (R—O—R, R = alkyl) have the general
formula CnH2n + 2O.

IUPAC Name :- alkoxyalkanes

O O CH3 O CH3
CH3 CH2 CH
CH3
Methoxybenzene Ethoxybenzene (1-Methylethoxy) benzene, or
(Methyl phenyl ether) (Ethyl phenyl ether) Isopropoxybenzene
(Isopropyl phenyl ether)

O CH3 O
C
CH3 CH3
(1,1 Dimethylethoxy)benzene, or Phenoxybenzene
t–Butoxybenzene (Diphenyl ether)
(t–Butyl phenyl ether)
 Structure of Ethers Bond Bond
(pm) (degree)
lengths angles
C—H 110 C—O—C 111.7

∶
C—O 141 O—C—H ~109.5

O Or H—C—H ~109.5
CH3

CH3 Close to tetrahedral (109.5°)

∶
H H
Fig. – Structure of O
H C C H
dimethyl ether 111.7° Slightly greater than the tetrahedral
angle (109.5°) due to repulsive
H H interaction between the two bulky
alkyl groups bonded to oxygen
 Close to tetrahedral (109.5°)
C— O
by the linear overlap sp3 orbital of carbon with sp3 orbital of oxygen

C—H
by the linear overlap sp3 orbital of carbon with 1s orbital of hydrogen
 H H H H H H

C H C C
H O H O H
H C C H H C C
H
H H H H

Ethyl methyl ether Diethyl ether

Fig. – Structure of ethyl methyl ether and diethyl ether


C— C
Formed by sp3 —sp3 orbital linear overlap.
Phenols

Aromatic compounds that contain one or more hydroxy groups (—OH)

bonded directly to benzene or benzenoid ring such as naphthalene are
called phenols.

Classified as

Monohydric Dihydric Trihydric

Etc.
Monohydric

OH OH
OH
CH3

Benzenol 2-Methylphenol 2-Naphthol

(Phenol) (o-Cresol) (-Naphthol)

Many of these phenols have special names. For example, methylphenols

have the special name cresols.
Dihydric

OH
OH OH
OH

OH
OH
Benzene-1,2-diol Benzene-1,3-diol Benzene-1,4-diol
(Catechol) (Resorcinol) (Hydroquinone or quinol)
Trihydric

OH OH OH
OH OH

OH HO OH
OH
Benzene-1,2,3-triol Benzene-1,2,4-triol Benzene-1,3,5-triol
(Pyrogallol) (Hydroxyquinol) (Phloroglucinol)
Preparation
OF
Alcohol
 Pd + H2 or LiAlH4/NaBH4
CH3—CHO H 3 O+

Pd + H2 or LiAlH4/NaBH4
CH3—C—CH3 H2 O
O

LiAlH4/NaBH4 CH3—CH2—OH
CH3—C—Cl
H2O (S AE, NAR)
N CH3—CH—CH3
O
LiAlH4 OH
CH3—C—OH
H2 O (SNAE, NAR)
O

LiAlH4
CH3—C—OCH3
H2O (SNAE, NAR)
O
 (EAR) Dil. H2SO4
CH2=CH2

Hg(OAc)2/H2O
CH2=CH2
NaBH4

B2H6/THF
CH2=CH2
(EAR) H2O2/NaBH4
CH3—CH2—OH
CH3—CH—R
RMgX OH
CH3–CHO (NAR) H2 O

C12H22O11+H2O (i) Invertase

(ii) Zymase
sucrose
 B2H6/THF
(CH3)3C—CH—CH2
H2O2/NaOH
H OH

CH3
CH3 dil.H2SO4
CH3—C—CH—CH3
CH3—C—CH=CH2 OH CH3
CH3

CH3
Hg(OAc)2/H2O
NaBH4 CH3—C—CH—CH3
CH3 OH
 O
CH2—CH2
H3O+ CH3—CH2—CH3—OH

CH2—CH—CH3 OH
O
CH3—CH2—CH—CH3
H3O+

Grignard
Reagent O2/60°C
H 3 O+
2CH3OH
CH3—MgBr

O O OH
CH3—C—O—Et CH3MgBr
CH3—C—CH3 CH3—C—CH3
(SNAE) H3O+
(NAR) CH3

O
O
H—C—OEt CH3MgBr
H3C—C—H H3C—CH—CH3
(SNAE) H3O+
(NAR) OH
 O O OH
CH3—C—Cl CH3MgBr
CH3—C—CH3 3° CH3—C—CH3
(SNAR) H3O+
(NAR) CH3

O
OH
(NAR) CH3—C—CH3
Grignard 3° CH3—C—CH3
Reagent
CH3
CH3—MgBr
O OH
(NAR)
CH3—C—H
2° H3C—C—CH3
H3O+
H


O O— MgBr
(NAR) H—C—H H3O+
H3C—C—H 1° CH3—CH2—OH
H3O+
H
Physical Properties

(i) C1 to C11 are colourless liquids and higher alcohols are solids.
(ii) Density of monohydric alcohol is less than H2O.
(iii) Density  mol. mass (for monohydric alcohol).
(iv) Solubility: C1 to C3 and t-butyl alcohol are completely soluble in H2O
due to H–bonding.

1 1
Solubility  
No. of Carbon Molecular weight
atoms

Order of solubility:

C4H9OH > C5H11OH > C6H13OH

Boiling Points

B.P.  Molecular weight or No. of carbon Atoms

C4H9OH < C5H11OH < C6H13OH

1
If no. of carbon atoms is same, then B.P. 
branching

CH3
CH3CH2CH2CH2OH > CH3CH2CH OH > CH3 C OH

CH3 CH3

Number of —OH increases, H-bonding increases

CH3CH2CH2 < CH3 CH CH2 < CH2 CH CH2

OH OH OH OH OH OH
Example

Boiling point of alcohol is more than corresponding ether. Why ?

Solution

Reason: H-bonding in alcohol

O H ------- O H ------- O H ------- O H -------

R R R R
Example

Boiling point of alcohol is less than corresponding carboxylic acid. Why ?

Solution

Reason: Dimer formation in carboxylic acid.

O H— O
R—C C—R
OH O
 Key Point

1. Diols and triols have higher b.p's and are more water soluble.

2. In Thiols, Hydrogen bonding is much weaker than that in alcohols.

3. Thiols have Lower boiling points than similar alcohols.

4. Thiols are much more acidic than similar alcohols.

CHEMICAL REACTION
OF Alcohol
 PCl5
POCl3 + CH3 – CH2Cl
PCl3
H3PO3 + 3CH3 – CH2–Cl
PBr3
H3PO3 + 3CH3 – CH2–Br
SOCl2
CH3—CH2—OH H3PO3 + 3CH3 – CH2–Br
(NSR)
SOCl2/
N
SO2 + CH3 – CH2 – Cl +
NH+Cl–

H2SO4//140°C
CH3 – CH2 – O – CH2 – CH3

Conc. H2SO4
CH2 = CH2
170°C

H2SO4
CH3–CH2HSO4
110°C
 Na
ഥ a+
CH3CH2 – ON
Acid base reaction
CH3MgBr –+
CH4 + CH3–CH2OMgBr
O O
||
CH3–C–OH ||
CH3–C–O–CH2–CH3 (SNAE)
Conc. H2SO4
O
(CH3–CO)2O ||
(SNAE)
CH3–C–O–CH2–CH3
CH3—CH2—OH
HCl/ZnCl2
Lucas Reagent CH3 – CH2Cl

HBr or CH3–CH2–Br
Substitution
NaBr + H2SO4 [3° R–O–H → Alkene]

NH3
CH3 – CH2 – NH2
Al2O3
Al2O3
CH2 = CH2
620 K
(Elimination)
Na
CH3CH2–O–CH2–CH3
CH3–CH2–I (1°)
Williamson ether Substitution
 DEHYDROGENATION
OH CH3
OH | |
Reagent | H3C–CH2–CH–CH3 H3C–C–OH
H3C–CH2–CH2–CH2 |
2° Alcohol
CH3

PCC/PDC/Anhy. O O
|| || No reaction
CrO3 H3C–CH2–CH2–C–H H3C–CH2–C–CH3

K2Cr2O7/ H O O O
ഥ || || ||
KMnO4/H+/OH/ H3C–CH2–CH2–C–OH H3C–C–OH+CH–C–OH No reaction
Jones Regent

O O CH3
|| || |
cu/5000 °C H3C–CH2–CH2–C–H CH3–CH2–C–CH3 H3C–C=CH2

Cloudiness appear
Lucas Reagent
upon heating after 30 Within five min. Immediately
HCI/ZnCI2
mins.
ETHER
Preparation of Ethers from Hydrocarbons

(i) Addition of alcohols to alkenes

H
C=C + ROH H—C—C—OR

Example

H
H2C=CH2 + EtOH Et—O—Et
(ii) Alkoxy mercuration demercuration

The reaction of an alkene with an alcohol in the presence of mercuric salts

such as mercuric acetate or trifluoro acetate leads to an alkoxy mercuric
intermediate, which upon reaction with sodium borohydride yields an ether.

Example

NaBH4
C=C + R—OH + Hg(OOCCF3)2 —C—C— —C—C—

RO HgOOCCF3 RO H
Ether
(iii) From alkyl halide by Dry Ag2O

RX + dry Ag2O ROR + 2AgX

 By Dehydration of Alcohols

(1) Reagent - protic acids (H2SO4, H3PO4).

Ethanol is dehydrated to ethene in the presence of sulphuric acid at 443 K
and at 413 K, ethoxyethane is the main product.

Conc. H2SO4
H2C = CH2
170C, 
Intramolecular Dehydration

CH3—CH2—OH

Conc. H2SO4
CH3—CH2—O—CH2—CH3
140C, 
Intermolecular Dehydration
2. The catalytic dehydration of ethanol with Al2O3 at 250 – 260°C also gives
diethyl ether.

Al2O3
H2C = CH2
350°
Intramolecular Dehydration

CH3—CH2—OH

Al2O3
CH3—CH2—O—CH2—CH3
250°
Intermolecular Dehydration
Preparation of Ether by Substitution Reaction

(i) Williamson’s Ether Synthesis

Formation of ether by reaction between alkoxide (R–OX) with substrate.

SN 2 mechanism
RONa + RX R−O−R

The alkoxide ion (RO-) for a Williamson ether synthesis can be prepared by
using sodium hydride (NaH) to remove a proton from an alcohol.

ROH + NaH → RO– + Na+ + H2

 Mechanism

[SN2 Reaction]


C2H5ONa C2H5O + Na

H H H H
 Slow Fast
C2H5O C— I C2H5O ------ C -----I C2H5—O—CH3 + I

H H
Key Points

This method is particularly useful for preparing mixed ethers. It is best to

use the alkoxide of the secondary or tertiary alcohol and primary alkyl
halide because secondary and tertiary alkyl halides readily decompose
into olefins.

The reaction is not successful for tertiary R (because of elimination) and

low yields are often obtained with secondary R.

Consequently, a Williamson ether synthesis should be designed so that

the less hindered alkyl group is provided by the alkyl halide and the more
hindered alkyl group comes from the alkoxide ion.
Example

CH3 CH2

CH3—C—Cl + CH3ONa C — CH3

CH3 CH3
 CH3
|
2. To prepare CH3—C—OC2H5 (t-butyl ethyl ether), the suitable
|
CH3
reagent used will be Me3CO– and EtCl. If we use Me3CCl and ethoxide
ion, we will get 2-methylprop-1-ene as the major product.

Example

CH3 CH3 CH3

CH3—C—ONa + CH3—CH2—Cl CH3—C—O—CH2—CH3 + CH3—C—OH

CH3 CH3 CH3

CH2=CH2 + Br-
Example

OH O
OH–
Cl

NaOH
OH Cl
O

SH
OH– S

Cl
Example
Allyl phenyl ether can be prepared by heating: (JEE Main 2014)

(1) CH2=CH–CH2–Br + C6H5ONa

(2) C6H5–CH=CH–Br + CH3–ONa
(3) C6H5Br + CH2=CH–CH2–ONa
(4) CH2=CH–Br + C6H5–CH2–ONa

Solution

Ans. (1)
2. Cleavage of Ether

H2O
NH3
R—O—R +
ROH ⎯→ NO reaction

Na
NaOH

Ether are stable in basic medium.

Reaction involving cleavage of C–O bond in Ethers

The cleavage of (C—O) bond in ethers takes place under drastic conditions
with excess of HX, i.e., with conc. HI or HBr at high temperature (373K).

HX
R—O—R + HX RX + ROH R — X + H2O
Reaction with conc. HI/HBr

Ethers are readily attacked by concentrated hydriodic or hydrobromic acid,

the final products depending on the temperature of the reaction.

(i) In the cold:

R2O + cold HI ⎯→ RI + ROH

(ii) In the Hot:

R2O + Hot HI ⎯→ 2RI + H2O

 NOTE

In the case of a mixed ether, the iodine atom attaches itself to the smaller
alkyl radical:

CH3OC2H5 + HI ⎯→ CH3I + C2H5OH

 Mechanism (When both alkyl groups are 1°, The Halide formed is with the
Smaller Alkyl group).

The cleavage of ethers takes place with conc. HI or HBr because these
reagents are sufficiently acidic.

Me Me  ⊝ Step 2
O+H—I O—H+I MeI + EtOH
Step 1 I⊝ attacks at less
Et Et Substituted C atom
of oxonium ion H—I
(Strong nucleophile) by SN2 mechanism
Step 3 (If HI is in excess
and temperature is
high)


I
CH3 —CH2—I + H2O CH3—CH2 —O—H

—
H
When one of the (R—) group is 3°, allylic or benzylic group, then the
reaction will follow SN1 mechanism, and the halide formed is 3° RI, allylic
halide and benzylic halide.

Me Me
Me ——O—Me + cold HI Me —— I + MeOH
Me Me
 Mechanism

The halide formed is 3° RI because, in step 2 of the reaction, the departure of

leaving group (CH3—OH) produces a more stable 3° C and the reaction
follows SN1 mechanism, for example,

Me  Me
Step 1 Me SN1

—
—O — Me + H — I — O — Me + I⊝ + MeOH

—


—
Me Slow
Me Me Me

—
Me Me H Stable 3°Carbocation

I⊝ Fast

Me

—
—I
Me Me
Example

NaOH
R—O—R No reaction.
Hence, ethers are stable in basic medium.

conc. HI
R—O—R R—OH + RI
or Cold HI

conc. HI (excess)
R—O—R 2RI + H2O
or Hot HI

conc. HI (excess)
R—O—R’ RI + R'I + H2O
or Hot HI
 NOTE

Cold HI or conc. HI
Ar—O—R Ar–OH + RI
Hot HI or conc. HI (excess)
Ar–OH + RI

Ar–X can't be formed by SN1 and SN2 on aryl groups.

Ph–O–Ph ; O ; Ph—O

does not undergo cleavage by HI.

Example

HI
Et–O–Me EtOH + MeI

HI
Ph—O—Me PhOH + MeI

O HI OH + MeI

HI
O OH + EtI

CH3 CH3
| |
HI
CH3–CH2–CH–CH2–O–CH2–CH3 CH3–CH2–CH–CH2–OH + CH3–CH2I
Example

HI
Ph–O–CH2Ph PhOH + PhCH2I

HI
Me3C–O–Et Me3C–I + EtOH

HI
Et3C–O–CH2–CH2–CH3 Et3C–I + CH3–CH2–CH2–OH

HI
CH2=CH–CH2–O–Et CH2=CH–CH2I + EtOH
Example
18OH I

HI
O +
18

cold HI
Ph—O—CH3 Ph — OH + CH3I

I
Hot HI
Excess
O
I
HI
No reaction

O
Example

heat
ROR + PCl5 2RCl + POCl3

OC2H5 OH
+ HBr (excess) + C2H5Br
Example

The major product of the following reactions: [JEE (Main) Online 2019]
OCH3
Conc. HBr(excess)
heat
CH=CH2

OH Br Br OH
(1) (2) (3) (4)

CH2CH2Br CH2CH2Br Br–CHCH3 Br–CHCH3

Solution

Ans. (4)
Example
HBr
In the reaction OCH3 the products are
[JEE 2010]

(A) Br OCH3 and H2 (B) Br and CH3Br

(C) Br and CH3OH (D) OH and CH3Br

Solution

Ans. (D)
Reaction of Ether by Aqueous HI and Anhydrous HI

t-Buty methyl ether with aqueous or conc. HI undergoes cleavage by SN1

mechanism and with anhydrous HI/ether, cleavage takes place by SN2
mechanism, e.g.,

Me Me  Me Me
SN2
—O—Me anhydrous HI —O + I⊝ —OH + MeI

—
Me Me Me Me

—
Me Ether Me H

aq HI

Me  Me Me
SN1 I⊝
—O—Me  + MeOH —I
—

—
Me Me Me
—

Me H Me Me
Example

anhy.HI
CH3CH2—O—CH3 CH3I + CH3CH2OH
Hydrolysis of ether

H/H2O
R — O— R' Or dil. H2SO4 or H3O
R — OH + R' —OH

Case (I) Case (II)

R R’ R R’
3° 3° 3° 3°
3° 2° 2° 3°
3° 1° 1° 3°

(A) In all the above cases, cleavage of open chain ether follows SN1
pathway.
(B) If R = 1° and R’ = 1°,
then in such case cleavage of open chain ether follow SN2 pathway.
Example

O
H3C H3C
18 H H/H 
H3C O―CH3 H3C O―CH3
| 18
H3C H3C
H

SN1

O
OH
H H CH3 18

+ CH3―OH
H3C CH3
CH3 CH3
CH3
Example

H
H/H2O | SN2
CH3―O―CH3 CH3―O―CH3 2CH3OH
H2O

··

Example

NaOH/H2O
1. R—O—R No reaction

H+/H2O
2. R—O—R 2 ROH
(or) dil.H2SO4

H+/H2O
3. R—O—R’ (or) dil.H2SO4
R — OH + R’OH

18 18
H+/H2O
4. O — CH3 + CH3OH
OH
 Example
18
O OH
18 H+/H2O
5. + CH3OH

18
H+/H2O
6. O OH + OH
18

H2O
7. O No reaction

H2O
8. O No reaction
Cyclic Ether (Epoxidation)

Preparation of Epoxides

(i) Epoxidation of alkenes by reaction with peroxy acids

(ii) Base-promoted ring closure of vicinal halohydrins

(iii) In the presence of Ag catalyst

Epoxidation of alkenes by reaction with peroxy acids

O O
C=C + R–C–OOH C—C + R–C–OH

Peroxy acid O
Epoxide

Mechanism

O R
C O O
C O C
|| | || O C—R C—C + R—C—OH
C O C ||
H O
Epoxide O
 Example

O O
CH2 = CH–(CH2)9CH3 + CH3–C–OOH CH2–CH—(CH2)9CH3 + CH3–C–OH
O
Example

O O
+ CH3–C–OOH O + CH3–C–OH

NOTE

Epoxidation is a stereospecific syn addition.

Example
O
C6H5 H
C=C + CH3–C–OOH
H C6H5

(E) -1,2-diphenyl ethene

Solution

Ans. C6H5 O
H
+ CH3–C–OH
H O C6H5
Trans-2,3-diphenyl oxirane
(ii) Base-catalysed ring closure of vicinal halohydrins

H
H
OH
NaOH
O
H
Br H
trans-2-bromocyclohexanol 1,2-epoxycyclohexane
(iii) In the presence of Ag catalyst

Alkenes reacts with oxygen in the presence of Ag catalyst at 250°–400°C

to form epoxides.

O OH
1 Ag H2O
CH2== CH2 + O2 
CH2— CH2 CH2— CH2
2
OH
(anti addition)
Reaction of Epoxides

The highly strained three-membered ring molecules of epoxides make them

much more reactive towards nucleophilic substitution than other ethers.

(i) Acid catalysed ring opening of Epoxide

Acid catalysis assists epoxide ring opening by providing a better-leaving

group at the carbon atom undergoing nucleophilic attack.

In strong acidic medium (H3O+, HBr, ROH/H2SO4) attacking nucleophiles

attack the carbon of cyclic ether on which  +ve charge is more stable.
Reaction of Epoxides

H H

—C—C— + H —C—C—
:O Fast :O 
H
Protonated epoxide
Me Me
H  H O
H O—H
Slow Fast
—C—C— + O—Me —C—C— —C—C—
−H+

O H O O
H H H
 Example

HBr
(i) H2C—CH2 BrCH2CH2OH
10°C
O

(ii) H2C—CH2 HBr

BrCH2CH2Br
Excess
O

H3C CH3 OCH3

CH3OH
(iii) C C CH3—CH — C—CH3
H2SO4
H O CH3 HO CH3
2,2,3-trimethyl oxirane 3-methoxy-3-methyl-2-butanol
(ii) Base catalysed ring opening of Epoxide

Epoxides can also undergo base(or neutral) catalysed ring opening such
reactions do not occur with other ethers provided that the attacking
nucleophile is also a strong base such as an alkoxide ion or hydroxide ion.

Base ⊝
R—OH fast
R—O

⊝ ⊝ H—O—R ⊝
R—O + —C—C— RO—C—C—O RO—C—C—OH + RO
O
If the epoxide is unsymmetrical, in base catalysed ring opening attack by the
alkoxide ion occurs primarily at the less substituted carbon atom.

Example

⊝
CH3—CH2—O + H2C—CH—CH3 CH3—CH2—O—CH2—CH—CH3
⊝
O O

CH3–CH2OH

⊝
CH3—CH2—O + CH3—CH2—O—CH2—CH—CH3
OH
1–ethoxy–2–propanol
Example

(i) diethylether
RMgX + H2C — CH2
(ii) H3O+
O

Solution

Ans. RCH2CH2OH (primary alcohol)

Example

CH3
(i) diethylether
CH2MgCl + H2C—C
CH3 (ii) H3O+
O
Benzyl magnesium 1, 1-dimethyl
chloride Ethylene oxide

Solution

Ans. CH3
|
CH2CH2COH
|
CH3
Example

H3C CH3
NaOCH3
C C
CH3OH
H O CH3

Solution

Ans. OCH3 CH3

CH3—CH — C—CH3
OH
Example
The organic compound that gives following qualitative analysis is:
Test Inference
(a) Dil. HCl Insoluble
(b) NaOH Solution soluble
(c) Br2/water Decolourization
OH NH2 NH2 OH
(1) (2) (3) (4)

Solution [JEE Main 2019]

Ans. (1)
Example
(i) NaI, H3PO4
(ii) Mg, Dry ether
H3C—CH2—CH—CH3 (iii) D2O [X]
|
OH Product

Product [X] formed in the above reaction is:

H
(1) H3C—CH2—CH—CH3 (2) |
| H3C—CH2—C—CH3
D |
OH
(3) H3C—CH2—CH=CH2 (4) H3C—CH=CH—CH3

Solution [JEE Main 2023]

Ans. (1)
Example
When neopentyl alcohol is heated with an acid, it slowly converted into an
85 : 15 mixture of alkenes A and B, respectively. What are these alkenes?
H3C CH3 H3C CH3 CH3
CH3 CH3 CH2
(1) and (2)
and
H3C H3C CH3
CH2
H3C CH2 H3C CH3 H3C CH3
CH3 H3C
(3) and (4) and
H3C CH2 H3C CH2
Example
When neopentyl alcohol is heated with an acid, it slowly converted into an
85 : 15 mixture of alkenes A and B, respectively. What are these alkenes?
Solution [JEE Main 2020]

Ans. (4)
Example
Which of the following derivatives of alcohols is unstable in an aqueous base
?
O
RO
(1) RO – CMe3 (2) (3) (4)
RO Me RO O

Solution [JEE Main 2020]

Ans. (2)
Example
Identify products A and B:
CH3 dil.KMnO4 CrO3
273 K A B

CH3 CH3 CH3 CH3

(1) A : OH B : (2) A : OH B : OH
OH O OH O
O
||
A : OHC—CH2CH2CH2—C—CH3 CH3 CH3
(3) O (4) A : B:
||
B : HOOC—CH2CH2CH2—C—CH3 OH O

Solution [JEE Main 2021]

Ans. (2)
Example
The major product of the following reaction, if it occurs by SN2 mechanism is:
OH
K2CO3
+ Br acetone
O
O O
(1) (2)

O
(3) O (4)

Solution [JEE Main 2021]

Ans. (4)
Example
In the given reaction,
(i) K2Cr2O7
(ii) C6H5MgBr
HO 'X'
(iii) H2O
(iv) H+, heat Major Product
the number of sp2 hybridised carbon (s) in compound 'X' is_____.
Solution [JEE Main 2022]

Ans. (8)
Example
Find out the major product from the following reaction.
H2SO4 (Concentrated)
⎯⎯⎯⎯⎯⎯⎯ Δ
→
OH

(1) (2) (3) (4)

Solution [JEE Main 2023]

Ans. (1)
Example
Two compounds, A and B, with the same molecular formula (C3H6O)
undergo Grignard's reaction with methyl magnesium bromide to give
products C and D. Products C and D show the following chemical tests.
Test C D
Ceric ammonium nitrate Test Positive Positive
Lucas Test Turbidity obtained after five minutes Turbidity obtained immediately
Iodoform Test Positive Negative
C and D respectively are:
CH3
|
(1) C=H3C—C—OH ; D=H3C—CH2—CH—CH3
| |
CH3 OH
(2) C=H3C—CH2—CH2—CH2—OH
OH CH3
| |
(3) C=H3C—CH2—CH—CH3 ; D=H3C—C—OH
|
CH3
(4) C=H3C—CH2—CH2—CH2—OH ; D=H3C—CH2—CH—CH3
|
OH
Example
Test C D
Ceric ammonium nitrate Test Positive Positive
Lucas Test Turbidity obtained after five minutes Turbidity obtained immediately
Iodoform Test Positive Negative

C and D respectively are: [JEE Main 2020]

CH3
|
(1) C=H3C—C—OH ; D=H3C—CH2—CH—CH3
| |
CH3 OH
(2) C=H3C—CH2—CH2—CH2—OH
OH CH3
| |
(3) ;
C=H3C—CH2—CH—CH3 D=H3C—C—OH
|
CH3
(4) C=H3C—CH2—CH2—CH2—OH ; D=H3C—CH2—CH—CH3
|
OH
Solution
Ans. (3)
Example
An organic compound 'A' (C9H10O) when treated with conc. HI undergoes
cleavage to yield compounds 'B' and 'C'. 'B' gives the yellow precipitate with
AgNO3 whereas 'C' tautomerizes to 'D'. 'D' gives a positive iodoform test. 'A'
could be :

(1) O—CH=CH—CH3 (2) CH2—O—CH=CH2

(3) O—CH2—CH=CH2 (3) H3C O—CH =CH2

Solution [JEE Main 2020]

Ans. (2)
Example
Which is the most suitable reagent for the following transformation?
OH
|
CH3–CH = CH – CH2 – CH – CH3 ⎯→ CH3–CH = CH–CH2CO2H
(1) alkaline KMnO4 (2) I2/NaOH
(3) Tollen's reagent (4) CrO2/CS2
Solution [JEE Main 2019]

Ans. (2)
Example
From amongst the following alcohols the one that would react fastest with
conc. HCl and anhydrous ZnCl2, is:
(1) 1–Butanol (2) 2–Butanol
(3) 2–Methylpropan–2–ol (4) 2–Methylpropanol
Solution [AIEEE 2010]

Ans. (3)
Example
An unknown alcohol is treated with the "Lucas reagent' to determine
whether the alcohol is primary, secondary or tertiary. Which alcohol reacts
fastest and by what mechanism?
(1) secondary alcohol by SN1 (2) tertiary alcohol by SN1
(3) secondary alcohol by SN2 (4) tertiary alcohol by SN2

Solution [JEE Main 2013]

Ans. (2)
Example
Consider the following reactions:
Ag2O
ppt
A
Hg2+/H+ NaBH4 ZnCl2
Turbidity
B C conc. HCl within 5 minutes
'A' is:
(1) CHCH (2) CH3–CCH (3) CH2=CH2 (4) CH3–CC–CH3
Solution [JEE Main 2019]

Ans. (2)
Example
Consider the following reaction:
OHc
d HO CH3 Chromic
'P'
anhydride
OHb
OHa
The product 'P' gives positive ceric ammonium nitrate test. This is because
of the presence of which of these –OH group(s)?
(1) (c) and (d) (2) (b) only (3) (d) only (4) (b) and (d)
Solution [JEE Main 2020]

Ans. (2)
Example
Suitable reaction conditions for the preparation of Methyl phenyl ether is:
(1) Ph − Br, MeO− Na+ (2) PhO− Na+ , MeOH
(3) PhO− Na+ , MeBr (4) Benzene, MeBr

Solution [JEE Main 2023]

Ans. (3)
Example
The major product obtained in the following conversion is:
O
O
Br2 (1 eqv.)
MeOH

O O
CH3 CH3 O CH3 O
O CH3
Br O OMe O Br O
O
(1) (2) (3) (4)
Br OMe Br
O O O
O
Solution [JEE Main 2019]

Ans. (2)
Example
Consider the following reaction:
C2H5OH + H2SO4 → Produce
Among the following, which one cannot be formed as a product under any
conditions?
(1) Ethyl-hydrogen sulphate (2) Ethylene
(3) Acetylene (4) Diethyl ether

Solution [AIEEE 2011]

Ans. (3)
Example
The major product of the following reaction is:
O
HI (excess)


NC O
OH I OH I
(1) (2) (3) (4)

NC I NC OH NC OH NC I

Solution [JEE Main 2019]

Ans. (1)
Example
In the following reaction squence, structures of A and B, respectively will be:

O
HBr Na
 A Ether
(Intramolecular Product) B
CH2Br
OH OH Br CH2Br
(1) Br OH
& (2)
&
CH2Br CH2Br O
Br Br
OH OH
(3) OH
& O (4) Br &
CH2Br
CH2Br
Solution [JEE Main 2020]

Ans. (4)
Example
The major aromatic product C in the following reaction sequence will be:
O HBr
(excess) (i) KOH(Alc.) O3
(A) B Zn/H3O+
C

OH OH Br Br
(1) CO2H (2) (3) (4)
CHO CHO CO2H

Solution [JEE Main 2020]

Ans. (2)
Example
The major product [B] in the following reactions is:
CH3
| HI H2SO4
CH3—CH2—CH—CH2—OCH2—CH3 Heat [A] alcohol 
[B]
CH3
|
(1) CH3—CH2—C=CH2 (2) CH3–CH2–CH=CH–CH3
CH3
|
(3) CH2=CH2 (4) CH3—CH=C—CH3

Solution [JEE Main 2020]

Ans. (4)
Example
Identify A and B in the chemical reaction. [JEE Main 2021]
OCH3
HCl NaI
[A] dry acetone [B]
(major) (major)
NO2
OCH3 OCH3 OCH3 I
Cl
(1) A = B= (2) A= B=
Cl Cl Cl
NO2 NO2 NO2 NO2
OCH3 I OCH3 OCH3
Cl Cl Cl I
(3) A = B= (4) A = B=

NO2 NO2 NO2 NO2

Solution
Ans. (4)
Example
Compound I is heated with Conc. HI to give a hydroxy compound A which is
further heated with Zn dust to give compound B. Identify A and B.
O
Conc.HI Zn,

A B
OH O
OH
(1) A = , B= (2) A =
, B=

OH O
OH
(3) A = , B= (4) A =
,B=

Solution [JEE Main 2022]

Ans. (4)
Example
'A' and 'B' formed in the following set of reactions are:
OH HBr OH
A HBr B
 

CH2OH OCH3
Br Br OH Br
(1) A = , B= (2) A = , B=

CH2OH Br CH2Br OCH3

OH OH OH OH
(3) A = , B= (4) A = , B=

CH2Br Br CH2Br OH

Solution [JEE Main 2023]

Ans. (4)
Example
The major product formed in the following reaction is:

O HI
Heat
O

(1) I (2) OH (3) I (4) OH

I I OH OH

Solution [JEE Main 2018]

Ans. (3)