22.

ALCOHOLS, PHENOLS AND

ETHERS

ALCOHOLS

1. INTRODUCTION
(a) These are the organic compounds in which –OH
group is directly attached with carbon.
(b) These are hydroxyl derivatives of alkanes, mono
alkyl derivatives of water.
(c) Their general formula is CnHn+1OH or CnH2n+2O.

1.1 Classification of Alcohols

Mono, Di, Tri or Polyhydric Compounds
Alcohols and phenols may be classified as mono-, di-,
tri- or polyhydric compounds depending on whether
they contain one, two, three or many hydroxyl groups
respectively in their structures as given below:

1.1.1 Compounds Containing Csp3 – OH Bond

In this class of alcohols, the –OH group is attached to an sp3 hybridised carbon atom of an alkyl group. They are
further classified
(a) Primary, secondary and tertiary alcohols:
In these types of alcohols, the –OH group is -CH₂-OH CH- OH - C- OH
attached primary secondary and tertiary carbon
atom, respectively as depicted below. o o o
Primary (1 ) Secondary (2 ) Tertiary (3 )

(b) Allylic alcohols: In these

- - - -

alcohols, the –OH group H -C-

- - -

is attached to an sp3 CH₂-

-CH-CH₂-OH CH₂-
-CH-C-OH CH₂-CH-C-OH
hybridised carbon next to
the carbon-carbon double -C- -C-
bond, i.e. to an allylic
carbon. For example
o
o
Primary (1 ) Secondary (2o) Tertiary (3 )
2 2 . 2 | Alcohols, Phenols and Ethers

(c) Benzylic alcohols: In these alcohols,

the –OH group is attached to an sp3 H C
–hybridized carbon atom next to an
CH2OH C OH C OH
aromatic ring.
For example Allylic and benzylic C C
alcohols may be primary, secondary
or tertiary
Primary Secondary Tertiary

1.1.2 Compounds Containing Csp2–OH Bond

OH
These alcohols contain –OH group bonded to a carbon- carbon double i.e., OH CH₃
to a vinylic carbon or to an aryl carbon. These alcohols are also known as
vinylic alcohols
Vinylic alcohol : CH2=CH-OH

2. PREPARATION OF ALCOHOLS

2.1 From Alkenes

H+
C=C +H₂O C-C
-
-

H OH
H-
CH₃CH=CH₂ + H₂O CH₃-CH-CH₃

2.1.1 By Acid Catalyzed Hydration

Alkenes react with water in the presence of acid as catalyst to form alcohol. In case of unsymmetrical alkenes, the
addition reaction takes place in accordance with Markonikov’s rule.
Mechanism: The mechanism of the reaction involves the following three steps:
+ +
Step 1 H2O + H H3O
H H
+ +
C=C +H -O -H C C + H2 O

Step 2 H
+
H H O H
+
C C + H2 O C C

Step 3 H H H OH
+ +
C C O H + H2 O C C + H3O

2.1.2 By Hydroboration-Oxidation
Diborane (BH3)2 reacts with alkenes to give trialkyl boranes as addition product. This is oxidized to alcohols in the
presence of aq. sodium hydroxide (NaOH) and peroxide.
 Chem i str y | 22.3

Note: This is the addition of water at double bond according to Anti-Markonikov Rule.

H3C-CH=CH2+ (H-BH2)3 CH3-CH-CH2

H BH2
CH3-CH=CH2
CH3-CH=CH2
(CH3-CH2-CH2)3B (CH3-CH2-CH2)2BH
H2O 2H2O2, OH

CH3-CH2-CH2-OH + B(OH)3
Proapn-1-ol

Mechanism of hydroboration – deboration

CH₃-CH- B₂H₆-THF/H₂O₂/OH- CH₃-CH₂-CH₂-OH

-CH₂

+ H- transfer
+ CH₃-CH-CH₂ CH-CH-CH₂ CH₃-CH₂-CH₂
-

-
:

+ - O. - BH₃ BH₂
.- BH₃
These steps are repeated thrice to form (CH3— CH2— CH2)3B and then

R .. .. R R
.. O
H O .. H -H
+ ..
R B R B O O H R B .. ..O
O H
-
R R R -OH

R B OR
R

OR
|
With H2O2, finally RO − B − OR is formed by above mentioned method.

OR
|
3NaOH
RO − B − OR  → Na3BO3 + 3ROH

2.1.3 Oxymercuration Demercuriation

Involves an electrophilic attack on the double bond by the positively charged mercury species. The product is a
mercurinium ion, an organometallic cation containing a three-membered ring.
With mercuric acetate, the product is 3-methyl-2-butanol (Markonikov’s addition with no rearrangement,
oxymercuration-demercuration reaction)

Hg(OCOCH3)2 NaBH4
(CH3)2 CHCH = CH2 (CH3)2 CHCH-CH2 (CH3)2CHCHCH3
3-Methylbut-1-ene
OH HgOCOCH3 OH
Not-isolated 3-Methyl-1-butanol
2 2 . 4 | Alcohols, Phenols and Ethers

OAc
Hg+
C C Hg(OAc) C C
mercurinium ion

Mercuration commonly takes place in a solution containing water and an organic solvent to dissolve the alkene.
Attack on the mercurinium ion by water gives (after deprotonation) an organomercurial alcohol.

Hg(OAc)
Hg(OAc) Hg(OAc)

- - -

- -

: - -

- -
-H+
-C C- -C C- -C C-
-

H-+O: :OH
:

H₂O:
:

H₂O: Organomercurial alcohol

H

Hg(OAc) H
- -
- -

- -
- -
- -
-C-C- + NaBH₄ + 4OH -C-C- +NaB(OH)₄ + 4Hg + 4OAc

OH OH
Organomercurial alcohol alcohol

The second step is demercuration, to form the alcohol. Sodium borohydride (NaBH4, a reducing agent replaces the
mercuric acetate with hydrogen.)

2.2 From Carbonyl Compounds

2.2.1 By Reduction of Carbonyl Compounds

LiAlH₄ / Na + C₂H₅OH
R-CHO + 2H R- CH-H
-
=

O OH
1o alcohol

LiAlH₄ / Na + C₂H₅OH
R-C-R + 2H R-CH-R
-
=

O OH
2o alcohol
2.3 From Acid Derivatives

2.3.1 By Reduction of Acid and its Derivatives

LiAlH₄
R - C - OH + 4H R-CH₂-OH
=

O
LiAlH₄
R - C - X + 4H R-CH₂-OH + HX
=

O
LiAlH₄
R - C - OR’ + 4H R-CH₂-OH + R’OH
=

O
LiAlH₄
RCOOCOR + 8H 2 RCH₂OH + H₂O
 Chem i str y | 22.5

2.4 From Grignard Reagents

2.4.1 Reaction with Oxirane

δ- +δ +

: :
R : MgX + H₂C -CH₂ : : R-CH₂-CH₂-O MgX

O
H₂O+

R-CH₂-CH₂-OH
Primary alcohol

2.4.2 Reaction with Carbonyl Compounds

- -

- i) ether
R : Mg - X +- C = O R-C-O-H + MgX₂
+
ii) H₃O , X-
- -

- - +
R : MgX +-C = O R-C-O MgX
- + + -
- -

- -

-
R - C - O MgX + H - O - H R- C - O-H + O-H + MgX₂
-

H H

2.4.3 Reaction with Acetaldehyde

CH₃ CH₃
CH₃ +
H₃O OH
CH₃-CH₂-MgBr + H O Ether H₃C H₃C
H OMgBr
butan-2-ol

2.4.4 Reaction with Ketone

CH₃ CH₃
CH₃ H₃C
H₃C H₃O OH
CH₃-CH₂-CH₂-MgBr + CH₃ O Ether
H₃C OMgBr
CH₃
2-methylpentan-2-ol

2.5 By Fermentation
Fermentation is a low decomposition of complex organic compounds into simpler compound in the presence of
suitable micro-organisms which are the source of biochemical catalyst known as yeast.

(C6H10 O5 )n → CH3CH2CH2CH2OH+ CH3COCH3

Starch n−Butylalcohol
2 2 . 6 | Alcohols, Phenols and Ethers

3. PHYSICAL PROPERTIES OF ALCOHOLS

(a) The lower alcohols are liquids while higher having more than 12 carbon atoms are solids. They are colourless,
neutral substance with characteristic sweet, alcoholic odour and burning taste.
(b) The lower alcohols are readily soluble in water and the solubility decreases with the increase in molecular
weight.
The solubility of alcohols in water can be explained due to the formation δ+ δ- δ+ δ- δ+ δ-
of hydrogen bond between the highly polarized –OH groups present H-O H-O H-O
both in alcohols and water.
H R H
However, in higher alcohols, the hydrocarbon character (alkyl chain)
increases, showing a steric hindrance. Hence, the solubility in water decreases.
When the ratio of C:OH is more than 4, alcohols have little solubility in water.
(c) Boiling points of alcohols are much higher than those of the corresponding δ+ δ- δ+ δ- δ+ δ-
alkanes. It is due to the intermolecular hydrogen bonding present H-O H-O H-O
between the hydroxyl groups of the two molecules of an alcohol with the
result several molecules are associated to form a large molecule. R R R

Among the isomeric alcohols, b.p. and m.p. show the following trend.
Primary > Secondary > Tertiary
This is because of the fact that in secondary and tertiary alcohols, the alkyl part (hydrogen character) outweighs
the –OH group due to branching.
(d) Lower alcohols form solid addition compounds with anhydrous metallic salts like CaCl2 and MgCl2, viz., CaCl2,
4C2H5OH and MgCl2.6C2H5OH
By analogy to water of crystallization, these alcohols molecules are referred to as alcohols of crystallization.
For this reason, alcohols cannot be dried over anhydrous calcium chloride.

MASTERJEE CONCEPTS

Preparation of alcohols:
•• Key takeaway - Hydration and oxymercuration-demercuration gives Markonikov’s product but
hydroboration-oxidation gives Anti-markonikov’s product.
•• Misconception - Hydroboration follows Markonikov’s rule but in this case, the electron deficient
species is Boron and not Hydrogen.
•• Note - On replacing water with carboxylic acid in hydroboration-oxidation, the product obtained is
alkane instead of alcohol.
•• Note - Tertiary alcohols cannot be obtained by reduction of carbonyl compounds.
•• Fact - If we use NaOH as a reductant in reduction of carbonyl compounds to alcohols, the process is
known as Darzen’s process.
•• Tips and tricks - In conversion of oxirane to alcohols using Grignard’s reagent, the alkyl part adds to
the carbon with less steric hindrance as it proceeds via SN2 mechanism.
Physical properties of alcohols:
Alcohols generally have high boiling point because of hydrogen bonding.

Vaibhav Krishnan (JEE 2009, AIR 22)

 Chem i str y | 22.7

Illustration 1: Write the IUPAC names, as their names by Carbinol system, and classify them as 1º, 2º, 3º, allylic,
vinylic, benzylic, and propargylic of the following compound. (JEE MAIN)

Me Me
(A) Me (B) OH
Me Ph
OH Me

Me
(C)
(D) Et₃C OH
OH

Sol:

S.No. Structure IUPAC name Carbinol system name Type of alcohol

1
6 4 2 Me n-Butyl isopropyl
a. 7 3 2-Methyl heptan-3-ol 2º
Me 5 Me carbinol
OH
Me1 2
OH Dimethyl phenyl
b. 2-Phenyl propan-2-ol 3º
Ph carbinol
Me
3

3 1
2 Me Methyl vinyl
4
c. But-3-en-2-ol 2º allylic
carbinol
OH
5 4
3 OH
d. 3-Ethyl pentan-3-ol Triethyl carbinol 3º
2
Me
1

Illustration 2: (a) Write the structure of all isomeric alcohols of molecular formula C5H12O and give their IUPAC,
common and carbinol names. Indicate each as 1º, 2º and 3º and also their stereoisomers, if any-
(b) Write the structures and names of all the cyclic and stereoisomers of C4H7OH.  (JEE MAIN)

Sol: (a) (i)

4 5 24 2
OH OH
5 OH OH 4 5 4
OH 4 5 4
5 Me4 Me2 OH 5 2 2 5 3
2 1 2
3
1
Me 3 13 1 5 Me4 Me2 + Me + Me 5 Me4 3Me2 1 Me Me
3 1 Me 3
+ Me 13 1 Me Me
(I) (I) 3 1
OH OH
(I) [(II) + [(II)
(III)]+ (III)]
[(II) + (III)] OH
(O.A) (O.A) (IV) (IV)
(O.A) (IV)
IUPAC Pentan-1-ol (±)-Pentan-2-ol Pentan-3-ol
Common n-Amyl alcohol — —
Carbinol n-Butyl carbinol Methyl propyl carbinol Diethyl carbinol
Type 1º 2º 2º
 2 2 . 8 | Alcohols, Phenols and Ethers

(ii) Write the four atoms in a straight chain and put Me and (–OH) at different positions.
OH
OH 2 4 Me
3 1
Me
14
2 Me Me
 3
3
Me Me Me
1
4 2 2
OH
3
Me
1  3 Me
4Me Me 2 2 Me
Me OH 1
[(V)Me
+ VI] (O.A) Me OH Me3 Me
1
[(V) + VI] (O.A) OH (VII) Me (VIII)
(VII) (VIII)
IUPAC (±)-3-Methyl butan-2-ol 2-Methyl
butan-2-ol

Common –– t-Pentyl alcohol

Carbinol Isopropyl methyl carbinol Dimethylethyl carbinol

Type 2º 3º

(iii) Write the three C atoms in a straight chain and put two Me and (–OH) at different positions.

3 1
Me
Me 2 Me
4 2
Me 3 OH
Me Me Me 1
) OH Me
(VII) (VIII)
IUPAC 2,2-Dimethyl propan-1-ol
Common Neopentyl alcohol
Carbinol t-Butyl carbinol
Type 1º

Hence, total isomers including stereoisomers of C5H12O are 8.

Me
Me
MeMe2 22 Me
Me
MeMe2 22 2 1 11 1HH
HH
2 1 11 1OH
OH
OHOH
OH
OH
OHOH HHH H OH
OH
OHOH
OH
OH
OHOH HHH H HHH H
Me
Me
MeMe 3 33 3 3 33 3
(I)(I)
(I) (I) (III
(III+(III
(III ++IV)+
IV)IV)
IV)
Name (III
(III
(III+(III
++IV)
IV)
+
IV)IV)
(II)
(II)(II)
(II) O.A
O.A
O.A O.A O.A
O.A
O.A O.A
(±)
(±)
(±)
or
(±)
or
or
racemate
racemate
or
racemate
racemate (±)
(±)
(±)(±)
oror
or or racemate
racemate
racemate
racemate

Cyclopropyl 1-Methyl (±) or r-cis-2-Methyl (±) or r-trans-2-Methyl

methanol cyclopropan-1-ol cyclopropan-1-ol
cyclopropanol

OH
(cyclobutanol) Hence, the total isomers including stereoisomers of C4H7OH are 7.

(VII)
 Chem i str y | 22.9

Illustration 3: Cyclobutyl ethene

(A)

+
Dil. H2SO4
(B)
 Number of
isomeric products
including stereo-
isomers

 (JEE ADVANCED)

4 5
3
Sol: + Me
H Ring
expansion
2 1
4+
(A)
H OH H OH H₂O+ 5 Me
-H 2
 H  Me 1
2 C+
o

 
Me + H
+
(trans) (cis) Me
3 C+
o
Optically active Optically active
() or racemate () or racemate -H + H₂O
III and IV [ and I]
Me
OH
(V)
The total number of isomeric products including stereoisomers is 5.

Illustration 4: Synthesize the following:

(a) Butene to butanol and butan-2-ol
(b) 1-Chloro butane to pentanol and pentan-2-ol (JEE MAIN)

? 3 1
Sol: (a) Me
4
Me OH (Butan-1-ol) (I)
2
Butene
OH
4
Me (Butan-2-ol) (II)
3
2
1
Me

Hydroborato oxidation proceeds with Anti-Markovnikov addition, so it would give (I), while acid-catalysed hydration
and mercuration – demercuration reaction proceed with Markovnikov addition, so it would give (II).

Synthesis:
a. Anti-Mark
Dil H₂SO₄ Me
Me or Me
(i)B₂H₆ + THF
Me - Me OH Hg(OAc)₂/ -
OH
Mark H₂O+NaBH₄+OH
(ii)H₂O₂/OH (I) add HBr
Anti-Mark HBr + ROOR (II)
Me Me Aq. NaOH
Aq. KOH
Me Br
Br
3 1 4 2
4 5 OH
b. Me 2
Cl Me 3
1-Chlorobutane (Pentan-1-ol)
(I)
OH

Me Me
(Pentan-2-ol)
(II)
2 2 . 1 0 | Alcohols, Phenols and Ethers

The 4C-atom chain has to be increased to 5C-chain by a G.R. With CH2=O(HCHO)

3 1
4 Mg/ether
Me Cl Me MgCl
2 

R (i) CH₂ O
4 2
5 OH
Me (ii) H₃O +
3 1
(I)
4 2 1 4 2
Conc. H₂SO₄ 5 3 5 3
(I) Me Me + Me
1
-H₂O Pent-2-one Pent-1-one
(Major) (Major)

(i) B₂H₆/THF
-
(ii) H₂H₂/OH
OH
4
5
Me 3
2 Me
1
(II)

4. CHEMICAL PROPERTIES OF ALCOHOLS

4.1 Reaction with Active Metals-Acidic Character

Alcohols are weakly acidic in nature due to which when they react with group one alkali metals they liberate
hydrogen gas and form alkoxides.
2R – O – H + 2Na → 2R – O– Na+ + H2↑
The acidic order of alcohols is MeOH > 1º > 2º > 3º. This acidic nature of alcohol is due to the presence of polar
O-H bond.

4.2 Esterification/Reaction with Carboxylic Acid

Reaction of alcohol with carboxylic acid in presence of sulphuric acid gives an ester. In this reaction sulphuric acid
react as protonating agent as well as dehydrating agent.

2 4 conc.H SO
R – O – H + H – C – R → R – C – O – R + H2O
|| ||
O O

Mechanism:
+ -
H2SO4 H + HSO4

+ ROH
RCO H+H R C O H R C R O C R + RCOR
H2 O -H
O O H O H O O

Note : The above reduction is laboratory method of ester preparation.

 Chem i str y | 22.11

4.3 Reaction with Acid Derivatives

When alcohols are treated with acid derivatives , hydrogen of hydroxyl group is substituted by acyl group.

conc.H2SO4
R O H+X C R R O C R + HX

O O
conc.H2SO4
R O H +R C O C R R O C R

O O O

4.4 Reaction with Isocyanic Acid

ROH + H − N = C → H − N = C − OR → H2N − C − OR
|| | ||
O OH O
Amino ester

4.5 Reaction with Ethylene Oxide

- + ROH
R O H + CH₂ CH₂ CH₂ CH₂ CH₂ CH₂
-H₂O
O OR OH OR OR

1,2-dialkoxy ethane

4.6 Reaction with Diazomethane

R O H + CH2 N2 R O CH3
(ether)

4.7 Reaction with H2SO4

140oC
CH3 CH2 OH + H2SO4 (excess) CH3 CH2 O CH2 CH3

Mechanism:
+
H₂SO₄ H + HSO₄-
.. + ..
CH₃ CH₂ O + H CH₃ CH₂ O+ H
..

H H
-H₂O
.. CH₃ CH₂ OH
CH₃ CH₂ O CH₂ CH₃ CH₃ +CH₂
..

H
(protonated ether)
+
-H
..
CH₃ CH₂ ..
O CH₂ CH₃
o
160 C
(ii) CH3 CH2 OH + H2SO4 CH2 = CH2
(excess)
H + HSO-4
+
H2SO4
 2 2 . 1 2 | Alcohols, Phenols and Ethers

160oC
CH3 CH2 OH + H2SO4 CH2 = CH2
Mechanism:
(excess)
H + HSO-4
+
H2SO4

+ .. H
+

CH3 CH2 OH + H CH3 CH2 O H CH3 CH2 CH2 = CH2

-H2O
H

4.8 Action of Halogen Acids

Alcohol react with HX to give RX. Reactivity order of ROH is 1°>2°>3°. Hence primary alcohols react in presence of
catalyst (If X is Cl Luca’s reagent and if X is Br small amount of H2SO4), but secondary and tertiary alcohols can react
in absence of catalyst. However, when alcohol react with HI/Red P they reduced in hydrocarbon.

The reactivity of halogens is in the order: HI > HBr > HCl

SN1 reaction with the Lucas reagent (fast)

CH3 CH3 CH3 CH3
ZnCl2 ZnCl2
+ + Cl
H CH C 3O H H CHC 3O H H C CH H CH
C 3 Cl
ZnCl2 +
ZnCl2 3
+ CH3 Cl
H CHC 3O H H C CH3O H H C H CCH3Cl
HO ZnCl2 CH3
CH3 CH3 CH3
SN2 reaction with Lucas reagent is slow: HO ZnCl2
CH3CH2CH2 CH2CH2CH3
ZnCl2 -
- C O
+ +
ClCH3CH2HCH2 Cl CH2CHO
C
2CH3
ZnCl2
ZnCl
H 2 -
- C O
+
Cl C O +
ZnCl2
Cl HH H H H H
H TransitionHstate
H H
Transition state
CH2CH2CH3 ZnCl2
Cl C + O
CH2CH2CH3 ZnCl
H 2
Cl C + O
H H H
H H

4.9 Action of Thionyl Chloride

Alcohols react with thionyl chloride to form alkyl halide and reaction is called diarzon process.

C2H5OH + SOCl2 → C2H5Cl + HCl + SO2

Meachanism

Cl Cl O O
R O S =O R O S O R O S R O S + HCl
+ +
H Cl H Cl H Cl Cl

Thionyl chloride Cl-

Chlorosulfite ester

O O
(fast) O
R S=O R+ S=O R S=O
Cl Cl Cl
Chlorosulfite ester Ion pair
 Chem i str y | 22.13

This mechanism resembles the SN1, except that the nucleophile is delivered to the carbocation by the leaving
group, giving retension of configuration as shown in this following example. (Under different conditions, retension
of configuration may not be observed).
H H
OH SOCl₂ Cl
C C
CH₃(CH₂)₄CH₂ CH₃ CH₃(CH₂)₄CH₂ CH₃
(R)2-octanol dioxane (R)-2-chloroocatane
(solvent) (84%)

4.10 Action of Phosphorus Halides (PX5 and PX3)

Phosphorous halide react with alcohols to form corresponding haloalkanes.

For Example: C2H5OH + PCl5 → C2H5Cl + HCl + POCl3

Mechanism:
3 R- OH + PCl₅ P (OR)₃Cl₂+3HCl
P(OR)₂Cl₂ + ROH P (OR)₃Cl+HCl
Cl
(OR)₃P
(OR)₃P = O + RCl
: :

O
R
O

(RO₃)P = O + 3HCl P + 3ROH

Cl Cl Cl

4.11 Action of Ammonia

When vapours of ammonia with alcohol passed over heated alumina mixture of primary, secondary and tertiary
amines is formed.

Al2O3 ROH ROH

ROH + NH3 RNH2 R2NH R3N
Al2O3 Al2O3
0 0 0
1 amine 2 amine 3 amine

The ease of dehydration of alcohols is in the order Tertiary > Secondary > Primary

4.12 Dehydration
Alcohols undergo dehydration (removal of a molecule of water) to form alkenes on treating with acid e.g.,
concentrated H2SO4 or H3PO4 or catalysts such as anhydrous zinc chloride or alumina

+
H
C C C = C + H2 O
Heat
H OH
OH
85%H2PO4
CH3CH CH3 CH3 CH = CH2 + H2O
440 K

CH3 CH2
20%H2PO4
CH3 C OH CH3 C CH3 + H2O
358 K
CH3
2 2 . 1 4 | Alcohols, Phenols and Ethers

Mechanism of dehydration

H H H H H
Fast
Step 1 : H C C O H + H+ H C C O+ H
H H H H
Ethanol Protonated alcohol
(Ethyl oxonium ion)

H H H H H H
Fast
Step 2 : H C C O+ H H C C+ + O H
H H H H
Protonated alcohol Carbocation

H H H H
Step 3 : H C C+ C=C + H+
H H H H
Ethene

The acid used in step 1 is released in step 3. To drive the equilibrium to the right, ethane is removed as it is formed.
The relative ease of dehydration, i.e., 3º > 2º > 1º, of alcohols follows the order of stability of carbonium ions.

(a) With heated alumina (Al2O3): When vapours of an alcohol are passed over heated alumina, different products
are obtained at different temperatures as given below:
(i) At 513 – 523 K (240º – 250º C), intermolecular dehydration takes places to form ethers e.g.,
Al2O3
2CH3CH2OH CH3CH2 O CH2CH3 + H2O
513-523 K
Ethyl alcohol Diethyl ether

(ii) At 633 K (360ºC), intermolecular dehydration takes place to form alkenes, e.g.,
Al2O3
CH3CH2OH CH2 = CH2 + H2O
633K
Ethanol Ethene

4.13 Oxidation of Alcohols

(a) Oxidation: Oxidation of alcohols involves the formation of carbon-oxygen double bond with cleavage of O–H
and C–H bond.
H C O H C = O +H2

These are also called dehydrogenation reactions since it involves loss of hydrogen from the alcohol molecule. The oxidation
of alcohols can be carried out with a variety of reagents such as neutral, acidic or alkaline KMnO4, acidified K2Cr2O7 or dil.
HNO3. The ease of oxidations and nature of the products, however, depends upon the type of alcohol used.
(i) Primary Alcohols are easily oxidized first to aldehydes and then to acids, both containing the same
number of carbon atoms as the original alcohol.
H O
[O] [O]
RCH2OH R C=O R C OH
o
Oxidation Oxidation
1 Alcohol Aldehyde Carboxylic acid

CH3CH2OH+[O] K2Cr2O7 + DilH2SO4 CH CHO [O] CH3 COOH

3
-H2O
Ethyl alcohol Acetaldehyde Acetic acid
 H O
[O] [O]
RCH2OH R C=O R C OH
o
Oxidation Oxidation Chem i str y | 22.15
1 Alcohol Aldehyde Carboxylic acid

E.g., CH3CH2OH+[O] K2Cr2O7 + DilH2SO4 CH3CHO

[O] CH3 COOH
-H2O
Ethyl alcohol Acetaldehyde Acetic acid

The oxidation can, however, be stopped at the aldehyde stage if Cr(VI) reagent such as Collin’s reagent
(CrO3.2C5H5N, chromium trioxide-pyridine complex), Corey’s reagent or pyridinimum chlorochromate
(PCC, CrO3.C5H5N.HCl or C5H5NH + CrO3Cl–) pyridinimum dichromate [PDC, (C5H5NH)22+ Cr2O72–] in
anhydrous medium (i.e., CH2Cl2) are used as the oxidizing agents.

O
C5H5NH CrO3Cl- (PCC)
+
RCH2OH R C H
CH2Cl2
o
1 Alcohol Aldehyde

(ii) Secondary Alcohols are easily oxidized to ketones with the same number of carbon atoms. However,
ketones resist further oxidation but in some conditions, they are oxidized to carboxylic acids containing
lesser number of carbon atoms than the original alcohol.
CH₃ K₂Cr₂O₄/H₂SO₄ CH₃ K₂Cr₂O₄/H₂SO₄
CHOH C O CH₃COOH + CO₂ + H₂O
-H₂O
CH₃ CH₃
Acetic acid
Isopropyl alcohol Acetone

OH O
[O] [O]
CH₃ CH CH₂CH₂CH₃ CH₃ C CH₂CH₂CH₃ CH₂COOH HOOCCH₂CH₃
Pentane-2-ol Pentane-2-one Acetic acid Propionic acid

This oxidation be stopped at the ketone stage by using chromic anhydride (CrO3)
CrO₃/C₅H₅N
R CH R’ R CH R’
CH₂/Cl₂
OH O
Ketone
(iii) Tertiary Alcohols are resistance to oxidation in neutral or alkaline KMnO4 solution but are readily
oxidized in acidic solution (K2Cr2O7/H2SO4 or KMnO4/H2SO4) to a mixture of a ketone, and an acid each
containing lesser number of carbon atoms than the original alcohol. The oxidation presumably occurs
via alkenes formed through dehydration of alcohols under acidic conditions. For example
CH₃ CH₃
H+ [O] CH₃ [O]
CH₃ C OH -H₂O CH₃ C CH₂ CH₃ C O + [HCOOH] CO₂ + H₂O
CH₃
tert-Butyl alcohol 2-Methylprop-1-ene Acetone Formic acid

CH₃ CH₃
H + [O] CH₃
CH₃ C CH₂ CH₃-H₂O CH₃ C CH CH₃ C O + CH₃COOH
CH₃
OH
2-Methylbutan-2-ol 2-Methylbut-2-ene Acetone Acetic acid

4.14 Oppenauer Oxidation

The aluminium-catalyzed hydride shift from the α-carbon of an alcohol component to the carbonyl carbon of a
second component, which proceeds over a six-membered transition state, is named Meerwein-Ponndorf-Verley-
Reduction (MPV) or Oppenauer Oxidation (OPP) depending on the isolated product. If aldehydes or ketones are
the desired products, the reaction is viewed as the Oppenauer Oxidation.
2 2 . 1 6 | Alcohols, Phenols and Ethers

Non-enolizable ketones with a relatively low reduction potential, such as benzophenone, can serve as the carbonyl
component used as the hydride acceptor in this oxidation.

RO OR
OH O Al(OR)3 Al O OH
O O
1 2
+ 3 4 1 1 2
+ 3 4
R R R R R H 4
R R R R
2 3
R R R OPP MPV

Action of heated copper: Different classes of alcohols give different products when their vapors are passed over
heated copper at 573 K (300º C)
(a) Primary alcohols undergo dehydrogenation to give aldehydes.
Cu/573K
CH3CH2OH CH3 CHO +H2
Ethanol Ethanal
Ethyl alcohol Acetaldehyde

(b) Secondary alcohols also undergo dehydrogenation to give ketones.

H
CH3 Cu/573K
CH3
C C = O +H2
CH3 OH CH3
Propan-2-ol Propanone
(Isopropyl alcohol) (Acetone)

(c) Tertiary alcohols, however, undergo dehydration to form alkenes.

CH3 CH3
Cu/573K
CH3 C OH CH3 C = CH2 +H2O
CH3
2-Methylpropan-2-ol 2-Methylpropene
(tert-Butyl alcohol)

4.15 Pinacol-Pinacolone Rearrangement Reaction

When pinacols (mostly ditertiary alcohols) are treated with mineral acids, acid chlorides, ZnCl2 or other electrophilic
reagent, they rearrange to form ketones called pinacolones with the elimination of H2O.

Mechanism:

Me Me Me Me
H
Me Me Me Me
Step 1
OH OH OH2 OH
Slow R.D.S
Step 2

Me Me shift Me Me
Me Me Step 3
Me Me
Me O H OH
3oC
-H Step 4

Me Me
Me
Me O
 Chem i str y | 22.17

4.16 Dihydric Alcohols

Ethylene glycol or ethane-1, 2-diol
(a) Preparation:
(i) 3CH2 = CH2 + (alkaline) KMnO4 + 4H2O
3HOH2C-CH2OH+2MnO2+2KOH

O2/Ag
(ii) CH2 = CH2 O (Epoxy ethane) or
575 K
H2O/473K
(Ethylene epoxide) HOH2C-CH2OH
Hydrolysis

Ethylene glycol undergoes extensive intermolecular H-bonding . As a result, dihydric alcohols are highly
associated and have high b.p., high viscosity, and are highly soluble in H2O.
(b) Reactions:
PCl5 or HCl, 433K
(i) HOCH2 CH2 OH CH2Cl CH2Cl
or SOCl2

2Hl
(ii) HOCH2 CH2 OH -H O [l-CH2-CH2-l]
2

CH2=CH2+l2
H2SO4
(iii) HOCH2 CH2OH+HNO3 CH2ONO2+2H2O

CH2ONO2
Ethylene dinitrate

CH3COOH/H2SO4
(iv) HOCH2 CH2OH CH2O COCH3

CH2OCOCH3
Glycol diacetate

(c) Oxidation: Ethylene glycol on oxidation with conc. HNO3 mainly gives glycolic acid and oxalic acid. The other
oxidation products such as glyoxal and glyoxalic acid are also formed in small quantities because they are
more readily oxidized than glycol itself.

HOCH2 CH2OH
[O]
OCH CH2OH HOOC CH2OH
Glycoaldehyde Glycollic acid
[O] [O]
[O] [O]
OHC CHO HOOC CHO (COOH)2
Glyoxal Glyoxalic acid Oxalic acid

(d) Dehydration:
(i) HOCH2 CH2 OH
773K
O + H2 O

(ii) HOCH2 CH2 OH Anhd.ZnCl2 [CH2 = CHOH]

-H2O
Vinyl alcohol
Tautomerise
CH3 CHO
Conc.H3SO4
(iii) With conc. H2SO4: HO CH2 CH2 O H
distill
+ 2H2O
H O CH2 CH2 OH
Dioxane
2 2 . 1 8 | Alcohols, Phenols and Ethers

(iv) Conc.H3PO4
HO CH2 CH2OH distill

H O CH2 CH2 OH
CH2 CH2OH
O
CH2 CH2OH
Diethylene glycol

Trihydric Alcohols; Glyerol or Glycerine 1, 2, 3-Propanetriaol

(a) Preparation:
(i) CH3CH = CH2
Cl2773K
Cl CH2 CH = CH2
-HCl

aq. KOH or aq. Na2CO3

HO CH2 CH = CH2
423 K, 1-2 atm
Allyl alcohol
HOCl
HO CH2 CHCl CH2OH
+ -
Cl OH

aq. NaOH
-NaCl HOCH2 CHOH CH2OH

(b) Properties: Due in the presence of three (–OH) groups, it undergoes extensive intermolecular H-bonding and
thus it has high boiling point viscosity and is highly soluble in H2O.
(c) Reaction: When glycerol is treated with a small amount of HI or Pl3 allyl iodide is formed.
l2
3Hl (-3H2O) [lCH2 CHl CH2l] CH2 = CH CH2l
HOCH2 CHOH CH2OH 1,2,3-Triiodopropane (glycerol tri-iodide) Allyliodide
(Unstable)
When large moment of HI is used, the main product is isopropyl iodide.
+Hl
CH2 = CH CH2l [lCH3 CHl CH2l]
Allyliodide
-l2

+Hl
CH3 CHl CH3 CH3 CH = CH2

(d) Nitration:
Conc.HNO3
+Conc. H2SO4
HOCH2 CHOH CH2OH O2NOCH2 CHONO2 CH2ONO2
(283-298 K)
(Glyceryl trinitrate) (Nitroglycerine)

A mixture of glycerol trinitrate and glyceryl dinitrate absorbed on Kieselguhr is called dynamite discovered by
Alfred Noble.

(e) Dehydration with KHSO4 or conc. H2SO4:

KHSO4, 473-508K
HOCH2 CHOH CH2OH
-2H2O

Unstable
CH2 = CH CHO [CH2 = C = CHOH]
Tautomerisation
 Chem i str y | 22.19

(f) Oxidation:
[O] [O] [O]
HOCH2 CHOH CH2OH OHC CHOH CH2OH HOOC CH2OH
[O] Glyceraldehyde Glyceric acid
[O]
OH CH2 CO CH2OH HOOC CO COOH HOOC CHOH COOH
Dihydroxy acetone Mesoxalicacid Tartonic acid

(i) With dil. HNO3, a mixture of glyceric and tartaric acid is obtained.
(ii) With conc. HNO3 mainly glyceric acid is obtained.
(iii) With bismuth nitrate, only mesoxalic acid is obtained.
(iv) Mild oxidizing agent, such as Br2 water, sodium hypobromite (Br2/NaOH) and fenton’s regagent (H2O2 +
FeSO4) give a mixture of glyceraldehyde and dihydroxy acetone. This mixture is called glycerose.

(g) Reaction with HIO4: HOCH2 CHOH CH2OH + 2HlO4

HOCH2 CHOH CH2OH + 2HlO4

2HCHO + HCOOH + 2HlO + H O

2HCHO + HCOOH + 2HlO3 +3H2O 2
HOCH2 CHOH CH2OH + 6[O]
(h) With acidic KMnO4: HOCH2 CHOH CH2OH + 6[O]
HOOC COOH (oxalic acid) + CO2 +3H2O
HOOC COOH (oxalic acid) + CO2 +3H 2O

(i) Reaction with oxalic acid: When oxalic acid is heated with glycerol at 383 K, it forms glycerol mono-
oxalate which loses a molecule of CO2 to give glycerol mono- formate which in turn on hydrolysis gives
formic acid.
HOCH2 CHOH CH2 OH + HO OCH COOH
 383 K
CH2 OOC COO H
-CO2 -H2O
COOH
CH2OH
HOH
HOH2C CHOH CH2 OOCH
OH H
HCOOH + HOH2C CHOH CH2OH
(ii) At 230º C (503 K), oxalic acid reacts with glycerol to form glycerol dioxalate which loses two molecules
of CO2 to give allyl alcohol.

5. D
 ISTINCTION BETWEEN PRIMARY, SECONDARY AND TERTIARY
ALCOHOLS
(a) Lucas test: This test is based on the difference in the three types of alcohols (having δ or less carbon towards
Lucas reagent (a mixture of conc. Hydrochloric acid and anhydrous zinc chloride)

ROH + HCl
ZnCl2
RCl + H2O

Since alkyl halides are insoluble, their formation is indicated by the appearance of a turbidity in the reaction
mixture. The order of reactivity is tertiary >secondary >primary, the tertiary alcohols produce turbidity
immediately, the secondary alcohols give turbidity within 5 – 10 minutes, and the primary alcohols do not
give turbidity at all, at room temperature.
2 2 . 2 0 | Alcohols, Phenols and Ethers

(b) Catalytic dehydrogenation (action of reduced copper at 300°). Discussed earlier,

(i) Primary alcohols form aldehydes
(ii) Secondary alcohols form ketones.
(iii) Tertiary alcohols form olefins.

(c) Victor Meyer test: This test is based on the different behaviour of primary, secondary and tertiary nitroalkanes
towards nitrous acid. The test involves the following steps.
(i) Alcohols is treated with concentrated hydroiodic acid or red phosphorus and iodine to form the
corresponding alkyliodide.
(ii) Alkyl iodide is reacted with silver nitrite to form the corresponding nitroalkane.
(iii) The nitroalkane is treated with nitrous acid (NaNO2 + HCl) followed by treatment with alkali (NaOH or
KOH). Upon such treatment different alcohols give different colours.
•• Primary alcohols produce a blood red colour
•• Secondary alcohols produce a blue colour
•• Tertiary alcohols produce no colour.

Primary Secondary Tertiary
CH₃CH₂OH (CH₃)₂CHOH (CH₃)₂COH
P + l₂ P + l₂ P + l₂

CH₃CH₂l (CH₃)₂CHl (CH₃)₃Cl

AgNO₂ AgNO₂ AgNO₂

CH₃CH₂NO₂ (CH₃)₂CHNO₂ (CH₃)₃CNO₂

HONO HONO HONO

CH₃CNO₂ (CH₃)₂CNO₂ No reaction

(Colour less)
NOH NO
Nitrolic acid (Pseudonitril)
NaOH NaOH

CH₃CNO₂ NO reaction
(Blue colour)
NONa
Sod. salt of nitrolic acid
(Red colour)

Illustration 5: Give the structure of the major organic product when 3-ethylpent-2-ene is treated with Hg(OAc)2 ,
H2O, NaBH4. (JEE MAIN)

Sol:
CH2CH3 CH2CH3 CH2CH3
Hg(OAc)2/H2O NaBH
CH3CH2 C = CH CH3 CH3CH2 C CH 4
CH3 Reduction CH3CH2 C CH2CH3
(Mark addition)
3-Ethylpent-2-ene
OH HgOAc OH
3-Ethylpentan-3-ol
 Chem i str y | 22.21

Absolute alcohol:

Wash-Absolute alcohol

Wash [10-15% EtOH]

Distillation

Raw sprit [90% EtOH]

Fractional distillation

o
o
20-21 C 78 C

Mainly CH3CHO Rectified spirit [95.5% EtOH] Fuel oil

Excess benzene Azeotropic distillation [Glycerol + CH3COCH3

65oC + Higher alcohol]

C6H6+C2H2OH + H2O
(74.1%)(18.5%) (7.4) (Ternary mixture)

68oC

C6H6+EtOH
(Binary mixture)
(80%) (20%)

78.3oC

Absolute alcohol
[100% EtOH]

Flowchart 22.1 Preparation of absolute alcohol

2 2 . 2 2 | Alcohols, Phenols and Ethers

MASTERJEE CONCEPTS

Chemical properties of alcohols:

(a) Rate of reaction of alcohols with carbonyl compounds depends on two factors:
(i) Leaving group ability of the substituent: Better the leaving group, faster the reaction.
(ii) Bulkiness of the alkyl part of alcohol: Bulkier the alkyl part, slower is the reaction because of steric
hinderance.
(b) Only alkyl methyl ether can be prepared by reaction of alcohol with Diazomethane.
(c) In reaction of alcohols with excess of sulphuric acid at lower temperatures, we obtain ethers. But, as
the temperature increases, alkenes become the favourable product. Also, in case of secondary and
tertiary alcohols, alkene is the predominant product due to ease of elimination.
(d) In reaction of alcohols with SOCl2 it proceeds via SNi mechanism. Thus, the configuration in case of
chiral carbon is retained. But, if pyridine is used as a solvent, the reaction proceeds via SN2 mechanism
with inversion of configuration.
(e) In reaction of alcohols with PCl5 and PCl3 proceeds via SN2 mechanism.
(f) Weak oxidizing agents like PCC, PDC etc oxidize 1⁰ alcohols to aldehydes while strong reagent
oxidizes 1⁰ alcohols to carboxylic acids. All these oxidizing agents oxidize 2⁰ alcohols to ketones but
3⁰ alcohols are not affected.
(g) In pinacol-pinacolone rearrangement, With unsymmetrical glycols, the product obtained is
determined mainly by the OH that is lost as H2O to give more stable carbocation and, thereafter, by
the better migrating group.
(i) The order of migratory aptitudes is Ar > > H > R.
(ii) The migratory order in aryl: Ar containing more e--donating (or more e- rich) migrates. For
example,

MeO Me Ph- Cl

p-Anisyl p-Tolyl p-Chlorophenyl

(iii) The phenyl group is more e- rich than (Me) group, therefore, (Ph) group migrates in preference
of (Me) group
(iv) The migrating group should be trans (anti) to the leaving (–H) group.
(v) The (–OH) group will be lost from the C atom which would leave the most stable carbocation.
(vi) The rate determining step (R.D.S. and slow) is the formation of stable carbocation, i.e., conversion
in step 2 to step 3.
T P Varun (JEE 2012, AIR 64)

Illustration 6: Arrange the following compounds in the decreasing order of their b.p s’ and solubility in H2O.
 (JEE MAIN)
(a) (I) Methanol (II) Ethanol (III) Propan-1-ol
(IV) Butan-1-ol (V) Butan-2-ol (VI) Pentan-1-ol
(b) (I) Pentanol (II) n-Butane (III) Pentanal
(IV) Ethoxy ethane
 Chem i str y | 22.23

(c) (I) Pentane (II) Pentane – 1, 2, 3-triol

(III) Butanol

Sol: (c) B.P. order: VI > IV > V > III > II > I
Solubility order: I > II > III > V > IV > VI
Explanation: All of the mare alcohol so all have H-bonding. As the molecular mass and surface area increases, the
B.P. increases and solubility decreases.
Out of (IV) and (V), there is branching in (V) and has less surface are than (IV), So the boiling point of (IV) > (V), but
solubility of (V) > (IV)
(b) B.P.order : I > III > IV > II
Solubility order: I > III > IV > II
In (I), there is H-bonding, in (II) (aldehyde), dipole-dipole interaction, in (III) (ether), slightly polar due to EN of O
and in (IV) (alkane), Van der Waals interaction (non-polar)
(c) B.P. Order: II > III > I
Solubility Order: II > III > I
In (II), there (–OH) groups, more H-Bonding; in (II), one (–OH) group, less H-bonding; in (I) (alkane), Van der Waals
interaction

Illustration 7: Explain the following: (JEE MAIN)

(a) Which has higher B.P.?
(i) Phenol (ii) Benzenethiol
(b) Which has higher melting point?
(i) Hydroquinone (ii) Catechol
(c) Explain the less solubility and lower b.p. of :
(i) o-Nitrophenol (ii) o-Hydroxy benzaldehyde
(iii) o-hydroxybenzoic acid (salicylic acid) compared with their p-and m-isomers.

Sol: (a) Although the molecular mass of benzenethiol (Ph – SH) is higher, phenol has high boiling point. It is
because there is no H-bonding in PhSH.

OH (II) because of the

(b) Hydroquinone HO OH (I) has high M.P. than catechol
OH
Symmetrical packing of p- is its crystal
lattice which requires more energy for its
O H OH
melting. O
N C C
O O
(c) In ortho-isomers of (I), (II) and (III), H
intramolecular H-bonding (chelation) O O H O H
occurs which inhibits the intermolecular
o-Nitophenol o-Hydroxybenzaldehyde o-Hydroxybenzoic acid
attraction between these molecules and
(Salicylaldehyde) (Salicylic acid)
thus, lowers the b.p. and also reduces
H-bonding of these molecules with H2O thereby, decreases water solubility. Intermolecular chelation does not
occur in p –and m-isomers.
2 2 . 2 4 | Alcohols, Phenols and Ethers

Illustration 8: Synthesize the following: (JEE MAIN)

(a) Benzene to (4-chorophenyl)propan-1-ol)
(b) Ethyne to butanol
(c) Propane to allyl alcohol
(d) Propane to propanol and propan-2-ol

Synthesis:
(a) 3 2 1 2
OH
CH₂CH₂CH₂OH 3
1

or (I)

Cl Me Cl Me

CH₃Cl + AlCl₃ Cl₂ + Fe

F.C. alkylation

(o-,p-directing)
Cl
CH₂ MgCl CH₂ Cl (Major)
(i)
O Mg NBS
+ Reacts at
(ii) H₃O Allylic
benzylic
halide
Cl R Cl
CH₂CH₂CH₂OH

(I)

Cl

3 1
(b)
4
HC CH Me 2
OH 1-Butanol (I)
Ethyne(A)
NaNH₂ - CH₃CH₂Br
(A) HC C
1 mol
H₂ + Pd + BaSO₄
(Lindlar’s catalyst)
(C C)  (C C)
HC C CH₂CH₃
(i)BH₃/THF
H₂C CH CH₂CH₃ -
(ii)H₂O₂/OH
Anti-Mark

HOCH₂CH₂CH₂CH₃
(I)
 Chem i str y | 22.25

(c) MeCH₂Me H₂C CH CH₂ OH

Propane (A) Allyl alcohol (I)
Cl
Cl₂/hv alc. KOH
(A) Me Me Me CH CH₂
-HCl
Allylic NBS
aq. NaOH
(I) BrCH₂ CH CH₂

OH (Propan-1-ol) (I)
(d) MeCH₂Me Me
OH
(Propane)
Me Me (Propane-2-ol) (II)
as in 1. B₂H₆/THF
(A) Me CH CH₂ - (I)
(f)
2. H₂O₂/OH
dil. H₂SO₄ Anti-Mark

Mark. add
(II)

Illustration 9: Complete the following: (JEE MAIN)

H
3 1
4
(A) Me O
2
But-2-cn-l-al
(a) (b) (c) (d) (e) (f)
LiAlD₄/ LiAlD₄/ NaBD₄/ NaBD₄/ D₂/Pt in D₂/Pt in
H₃O D₂O H₂O D₂O aprotic H₂O
solvent

I II III IV V VI
Me

(B) with reagents (a) to (f)

O
Mechanism:
D form LiAlD 4 and NaBD 4 isadded to C of (C = O)group 
 
and solvent gives H or D to O atom to form OH or OD,e.g.,

(i) (ii)

H AlH₃Li - H OH D AlD₃Li - H OH
R₂C O or R₂C O - R₂C O or R₂C O -
H BH₃Na -OH D BD₃Na -OH
H R₂C OH D R₂CD OH
R₂C OD
D OH
D
(iii) LAH and NaBH4 do not reduce (C = C) bond whereas catalytic hydrogenation reduces (C = C) bond to (C – C)
bond
2 2 . 2 6 | Alcohols, Phenols and Ethers

(iv) LAH and catalytic hydrogenation reduce epoxide but NaBH4 does not

H D D
Reagent H
Reagent in (b) and (d) in (c) OD H₂O
Me OH Me
in (a) and (c) Syn add. of
D
D₂ at (C C ) (V) D
(I) or (III)
H D
DH
Reagent
Me OD in (f)
Me OH
D (VI) D
(II) or (IV)

The D of ROD rapidly exchanges for the H of H2O Mechanism in (B).

Me -
H from LiAlH₄ or NaBH₄ H
-
Me H₂O Me
O D from LiAlH₄ or NaBH₄ CH₂ CH₂ H
- -
Nu attack at less hindered site by O D₂O OH
Sn² mechanism
Me
H₂/catalyst CH₂ H
(Or)
OD
D₂/catalyst Me D H₂O Me
Me H CH₂ CH₂D
Me -
CH₂ CH₂ D O OH
D₂O
OH OD Me
CH₂ D
OD

Reaction:
Reagent in Me
(B) CH₂D (VII)
(a)
OH
in (b) Me
CH₂D (VIII)
OD
in (c) and (d)
(B) No reaction

in (c) Me
(B) CH₂ D
OD H₂O
in (f) Me
CH₂ D
OH
The D of ROD rapidly exchanges for H of H₂O
 Chem i str y | 22.27

POINTS TO REMEMBER

+
H /H₂O
( i) Hydroboration

( ( I) Oxirane
ii) Carbonyl
( R Mg X



ii) Oxymercuration Compds
C=C Grignard
Demercuration
Reagent
Alkenes

Preparation
R-OH
H₂
Reduction
Reduction
Fermentation i) R-C-OH


C=O
O Acid &
Organic
ii) R-C-X its
Carbonyl Compounds
Derivatives
Compounds O
iii) R-C-OR’

O
Reactions of Alcohols

o o NH₃ anhy.ZnCl₂
1 / 2 / 3o Amine R-Cl
Al₂O₃
H
+ CH₂N₂
C=C R-O-CH₃
[O ] SOCl₂
Aldehyde/Carboxylic acid R-OH
R-OH RCl
Pinacol Pinacolone PCl₅
RCl
Rearrangement
H₂SO₄(ex.)
Aldehyde/Ketone R-O-R



CH₂ CH₂
 
CH₂ CH₂



OR OR R O Na
O Na

R-OH  
R C H


  
NH₂ C O R
 
H N C
 
R C X R  C O R






O
O O O
R   R
C O


O
2 2 . 2 8 | Alcohols, Phenols and Ethers

Alcohol
GMP GR
HX or PX3 or PX5
HO (1) RX
(1) Alkene or Kl + H3PO4 or SOCl2 or SO2Cl2
aq. NaOH or aq. KOH RedP/Hl
(2) RX (2) RH
or aq. K2CO3 or moist Ag2O
dil. H2SO4 NH3 o o o
1 ,2 ,3 amines
(3) R-O-X (3)
dil. H2SO4 H2S
(4) ROOOR (4) R - SH Thiol
RCOOH Tho2
o HNO2 Na
(5) 1 amine (5) RONa
H2S
Exception-Methyl amine gives
CH3MgX
CH3-O-CH3 or ether (6) CH4
NaH R’ OR
(6) Aldehyde or ketone Darzon reduction ald. R’-CHO
(1o alc.) (2o alc.) (7) C Acetal
dry HCl
(7) Acid or Na/EtOH H OR
Acid derivative Bouveault Blanc reduction
o
(1 alc.)
o
(2 alc.) R-OH R’ OR
Ket one R’COR’
(8) C Ketal
dry HCl
(8) HCHO or Ald. or ketone RMgX R OR
(1o alc.) (2o alc.) (3o alc.) H2O R’COZ
(9) R’COOR ester (Z=OH, Cl, OCOCH3)
H2SO4
(10) ROSO2OH(Alkyl hydrogen sulphate)
O2
(9) RMgX
H2O (11) HNO3 RONO2(Alkyl nitrate)

H2O CH2 PhSO2Cl

(12) RSO2Ph(Alkyl benzene sulphonate)
CHCH
(10) CH3MgBr O (13) H2C-CH(OR)2 Acetal
H3O+ CH2N2
(14) R-O-CH3 Ether
O

Fermentation H2C CH2

(10) Sugar (15) RO-CH2-CH2-OH

CH2=C=O
(16) ROCOOH3 Ether

Formation of EtOH by fermention Dehydrofon

(17) Alkene
Crystallization
(1) Cane sugar Molasses Catalytic dehydrogenation
Sucrose (18) Aldehyde or ketone
Invertase Zymase 1 or2o alcohol, Cu or ZnO, 300oC
o

Invert sugar EtOH

Hydrolysis Fermentation
Exception -3o alc  Alkene
o [O] [O]
(2) Grain Starch
Diastase (19)1 alc. Aldehyde Acid (same no. of C-atom)
Maltose
HOH
o [O] [O]
Maltase Zymase (20)2 alc. Ketone
Glucose EtOH o [O] [O]
Hydrolysis Fermentation (21)2 alc. Ketone
o [O]
(22)3 alc.
-
(23)3o alc. OH,CrO4 No reaction (No. green colour)
(orange)
 Chem i str y | 22.29

PHENOLS

1. INTRODUCTION
When OH group is attached at benzene ring,the compound is known as phenol
OH

Nomenclature of Phenols

OH OH OH OH
CH₃ H₃C CH₃

CH₃
2-Methyl phenol 3-Methyl phenol 2-6 Dimethyl phenol
CH₃
(o-Cresol) (o-Cresol)
2-Methyl phenol
(o-Cresol)
Some dihydric and trihydric phenols are given below:

OH OH OH
OH

OH
1,2-Benzenediol 1,3-Benzenediol
OH
(Catechol) (Resorcinol)
1,4-Benzediol
(Quinol)

OH OH OH
OH

OH OH HO OH
1,2,3-Benzenediol OH
(Pyragallol)
1,3,4-Benzenetriol 1,3,5-Benzenetriol

2. METHODS OF PREPRATION OF PHENOLS

2.1 From Haloarenes

- +
Cl ONa OH

123K HCl
+ NaOH 300 atm
2 2 . 3 0 | Alcohols, Phenols and Ethers

2.2 From Benzenesulphonic Acid

SO3H OH

Oleum (i) NaOH

(ii) H+

2.3 From Diazonium Salts

+ -
NH2 N2Cl NH2

(I) NaNO2 H2 O
+ N2 + HCl
(ii) +HCl Warm

Aniline Benzene diazonium

chloride

When diazonium salts react with water vapour it gives phenol.

2.4 From Cumene

When cumene (isopropylbenzene) is oxidized in the presence of air and acid, it gives phenol and acetone.
CH3 CH3

CH3 CH CH3 C O O H OH

Oleum +
H
+ CH3COCH3
H2O
Cumene Cumene
hydroperoxide

3. PHYSICAL PROPERTIES OF PHENOLS

(a) Pure phenols are generally colorless solids or liquids. The light colour usually associated with phenols is due
to its oxidations by air in presence of light.
(b) Phenols, generally are insoluble in water; but phenol itself, and polyhydric phenols are fairly soluble in water
which is believed to be due to the formation of hydrogen bond with water.
(c) Due to intermolecular hydrogen bonding, phenols usually have relatively high boiling points than the
corresponding hydrocarbons aryl halides and alcohols. For example, phenol (mol. Wt. 94) boils at 182ºC while
toluene (mol. Wt. 92) boils at 110ºC.
Higher b.p. than alcohols is due to higher polarity of the O-H bond and consequently stronger intermolecular
hydrogen bonding in phenols than in alcohols. Appreciable solubilities of the phenol and polyhydric phenols
in water is also due to strong hydrogen bonding between phenols and water molecules.
 Chem i str y | 22.31

O
Ar Ar H
O O
O H Ar O H O
H H H N
Intermolecular hydrogen Hydrogen bonding between o-Nitro phenol (Intermolecular
bonding phenols phenols and water molecules H-bonding possible due to
close mass of NO2 and -OH
groups)

Phenols containing groups like-NO2 or –COOH in the ortho position to the –OH group can also form
intermolecular hydrogen bonds (e.g. o-nitro phenol) which is responsible for their lower boiling points and less
solubility in water than the corresponding meta or para isomer. Due to possibility of intermolecular hydrogen
bonding (also known as chelatom) in the ortho isomer, intermolecular hydrogen bonding is not possible and
hence the ortho isomer can neither get associated nor can from hydrogen bonding with water with the results
it has a low b p. and less solubility in water than the meta and para isomers which can associate (union of two
or more molecules of the same speoins) as well as can form hydrogen bonding with water.

O H O O H
OH O
H
N

N
N
O O O H
O O H H
O
p-Nitro phenol (1 molecules) Hydrogen bonding
(intermolecular H-bonding) is not between p-nitro and
possible due large distance between-NO2 water
and -OH occups hence intermolecular
H-bonding is possible.

(d) They possess characteristic colour. They are highly toxic in nature and possess antiseptic properties. They may
produce wounds on skin.
(i) Phenol exists as resonance hybrid of the following structures.
+ + +
OH OH OH OH
- -
Mirror Image of I

-
I II III IV
Due to resonance oxygen atom of the –OH group acquires & positive charge (see structures III to V) and
hence attract electron pair of the O–H bond leading to the release of hydrogen atom as proton.

O H O

+ H+

Phenol Phenoxide ion

2 2 . 3 2 | Alcohols, Phenols and Ethers

Since resonance is not possible in alcohols (due to absence of conjugation of the lone pair of electron of
oxygen with a double bound), the hydrogen atom is more firmly linked to the oxygen atom and hence
alcohols are neutral in nature.
(ii) Once the phenoxide ion is formed, is stabilizes itself by resonance, actually phenol acid ion is more stable
than the parent phenol.
O O O O
- -
Mirror Image of V

-
V VI VII VIII

Comparison of acidity of phenols and carbonic acid

Relative acidity of the various common compounds.
RCOOH > H2CO3 > C6H5OH > HOH > ROH
Carboxylic acid Carbonic acid Phenol Water Alcohols.

4. CHEMICAL PROPERTIES OF PHENOLS

4.1 Nitration
(a) When phenol react with dilute nitric acid at low temperature (290 K), give a mixture of ortho and para nitro
phenols. OH OH OH
NO₂
Dilute HNO₃
+

o-Nitrophenol NO₂
p-Nitrophenol

(b) When phenols react with concentrated nitric acid, it gives 2, 4, 6-trinitrophenol.

OH
OH
O₂N NO₂
Conc.HNO₃

NO₂
2,4,6-Trinitrophenol
(Picric acid)

4.2 Halogenation
(a) When the reactions carried out in solvents of low polarity such as CHCl3 or CS2 and at low temperature,
monobromophenols are formed.
OH OH OH
Br
Br₂ in CS₂
273 K +
Minor Br
Major
 Chem i str y | 22.33

(b) When phenol is treated with bromine water 2, 4, 6-tribromophenol is formed as white precipitate.
OH
OH
Br Br

+ 3Br₂

Br
2,4,6-Trinitrophenol

4.3 Kolbe’s Reaction

OH ONa OH
(i) CO2 COOH
NaOH
+
(ii) H

2-Hydroxybenzoic acid
(Salicylic acid)

Mechanism of Reaction

O H
H O OH
+- O H - O OH
Na O C O
tautomerisation + O
O O Na+ H3O
Na+
O Salicyclic acid
Sodium salicylate

4.4 Reimer-Tiemann Reaction

On treating phenol with chloroform in the presence of sodium hydroxide, a–CHO group is introduced at ortho
position of benzene ring. This reaction is known as Reimer – Tiemann reaction. The intermediate substituted benzal
chloride is hydrolyzed in the presence of alkali to produce salicyladehyde.

- +
- +
OH O Na O Na OH
CHO + CHO
CHCl3 + aq. NaOH NaOH H

Intermediate Salicylaldehyde

The mechanism of the Reimer – Tiemann reaction is believed to involve the formation of dichloromethylene.
NaOH + CHCl3 → :CCl2 + NaCl+ H2O

O Cl O Cl O
O O
Cl H Cl
CCl2 H H2O +H
+ Cl OH- O
-
OH ;H O Cl H2O
2
2 2 . 3 4 | Alcohols, Phenols and Ethers

Phenols with blocked p-positions give cyclohexadienones containing the dichloromethyl group.
OH OH O

NaOH O
CHCl3

CH3 CH3 H3C CH3

In the Reimer-Tiemann reaction, the o-isomer predominates, but if one of the o-position is occupied the aldehyde
group tend to go to the p-positions; e.g. guaiacol forms vanillin
OH OH
O O
CH3 NaOH CH3
CHCl3

O
4.5 Libermann’s Reaction
When phenol is treated with sodium dissolved in conc. Sulphuric acid a red colouration appears which changes to
blue on adding aqueous NaOH. This reaction is called Libermann’s reaction.

2NaNO2 + H2SO4 Na2SO4 + 2HNO2

Nitrous acid

HO H + H - O - N=O HO N=O O= = N - OH
-H2O
p-nitrosophenol

H- -OH
NaOH - +
O= =N HO O= =N ONa
-H2O -H2O
Blue
Indophenol (Red)

4.6 Reaction of Phenol with Zinc Dust

When phenol is heated with zinc dust, it gives benzene.  OH

+ Zn + ZnO

4.7 Oxidation
Oxidation of phenol with chromic acid produces a conjugate diketone known OH O
as benzoquinone. In the presence of an oxidizing agent, phenols are slowly
Na2Cr2O7
oxidized to dark coloured moisture containing benzoquinone.
H2SO4

O
Benzoquinone
 Chem i str y | 22.35

5. DISTINCTION BETWEEN ALCOHOL AND PHENOLS

(a) Phenols turns blue litmus red but alcohols do not.
(b) Phenols neutralize base, while alcohols do not.
OH ONa

+ NaOH + H2O

R-OH + NaOH No reaction

(c) Phenols give violet colour with FeCl3. while alcohols do not.

 
OH OH

3 + FeCl3 Fe + 3HCl

Violet
R-OH + FeCl3 No reaction

Illustration 1: Identify the major products in the following reactions:

NO2 OH
CH3
HNO3 Bromine
(I) A (II) B
H2SO4 Water
O

CH3
Sol: (I) The nitrating mixture gives the attachment of the nitro group on the ortho position. The presence of
methoxy group is an electron-donating groupwhich makes the ortho position more electron-rich enabling the
attachment of the electron-withdrawing NO2 group.
(II) Bromine is an electrophile and the presence of electron donating groups i.e. –OH and CH3 make the ortho and
the para positions available for the attachment.

CH3 Br
O OH
A= O2N B=
Br CH3
NO2
2 2 . 3 6 | Alcohols, Phenols and Ethers

MASTERJEE CONCEPTS

•• Phenols although colourless turn reddish due to atmospheric oxidation.

•• Phenols and alcohol have high boiling point due to intermoelcular hydrogen bonding
•• Out of three isomeric nitrophenols, only ortho isomer is steam volatile and has lesser solubility and
lower boiling point than meta and para. Ortho cannot form H-bond with water and in ortho there
exist intramolecualr H- Bonding.
•• Phenols are stronger acids than alcohols but weaker than carboxylic acid and carbonic acid.
•• Phenols are stronger acids than alcohols because the phenoxide ion formed after the release of
proton is stabilised by resonance where as alkoxide ion does not.
•• TEST OF PHENOL– Phenols give violet colour with neutral FeCl3. Depending upon the nature of Phenol,
colour varies from violet to blue green or even red.
•• Preparation of phenol from cumene proceeds via peroxide radical mechanism.

Saurabh Chaterjee JEE Advanced 2013, AIR

POINTS TO REMEMBER

MgBr SO3Na
O2 NaOH;Fusion
H2O OH H+/H2O
+
OH N2Cl-
COOH Phenol
NaOH + CaO Preparation Warm H2O

H3O+ 2NaOH
300oC
Cl
HCl
H3C - CH- CH3 1/2 O2
O2
O
O Raschig’s
H process
H3C - CH- CH3
Cumene
 Riemer Tiemann Reaction
ONa
343 K
OH Kolbe
CHCl3 H3CO NaOH
NaOOC Schmidt NaOH CH4Cl Na ONa
CO2; NaOH CO CHO -H2
473 K Miscellanous O Cleavage
O
CO CH3COCl of O-H
4-100 atm Phenolphthalein H3C-C
OH OH OH Conc NaOH OH
HOH2C indicator NaOH
H2SO4 ONa
HCHO OH -H2O
HCl +HCN O
H2SO4
AlCl3 Et-C C2H5COCl
CH2OH Schotten
NaCl
Bakelite Baumann
CHO
Reaction
Gatteramann
Reaction
Reaction
OH OH of
H3COCO OH
+ OH OH NH3
CH3COCl Br2 +
Br ZnCl2 Zn
OCOCH3 Br 573K Cleavage
OH OH OH
NO2 NO2 HOS3 Br OH Br of C-O
HNO3 Substitution Br2 Cl
+ OH
H2SO4 OH PCl2
NO2 SO3H Br P2S5
F.C. H2SO4
OH OH OH OH HS -P2O5
H3 C +
+ SO3H
SO3H
CH3
Chem i str y | 22.37
2 2 . 3 8 | Alcohols, Phenols and Ethers

ETHERS

1. INTRODUCTION
The ethers are those compounds that have a C–O–C in their structure where, importantly, each C can only be part
of an alkyl or an aryl group – i.e. R–O–R’. The electronegative oxygen, flanked as it is by two electron pushing alkyl
groups, has very little tendency to participate in any reaction. This lack of reactivity is also attributed to the two alkyl
groups enveloping the oxygen, shielding it from reagents. The ether molecule appears to have an outer unreactive
alkyl shield or sphere with the “reactive” oxygen sitting in the centre.
 
Without any hydrogens directly attached to the oxygen, the molecules are H H
not capable of forming H-bonds. The consequence of this is that the melting
and boiling points are lower than the corresponding alcohols. Compatibility /   
solubility with water is also affected; though the smallest ether is miscible with R C O C R
water, any increase in the size of the alkyl chain drastically lowers the ether’s
solubility in water and soon forms immiscible mixtures.
H H
 

2. METHODS OF PREPARATION OF ETHERS

(a) Williamson’ Synthesis: Heating of alkyl halide with sodium or potassium alkoxide gives ether. This is a good
method for preparation of simple as well as mixed either.
R
R − X + Na − O − R ' → R − O − R '+ NaX

This method is not applicable to tert alkyl halides because the alkoxide ions being both powerful nucleophiles
and bases could bring dehydrogenation of the tertiary alkyl halides to form alkenes.
R - ONa R - O- + Na+

R O Na + R’ X R O R + Nax

R’ O Na R O R
R X+
Ar O Na R O Ar
Aryl Ether

aq. NaOH
- OH + CH3 - CH2 - Br - O - CH2 - CH3

The reactivity of primary (1º) alkyl halide is in the order CH3- > CH3 – CH2- > CH3 – CH2 – CH2- and the
tendency of the alkyl halide to undergo elimination is 3º > 2º > 1º. Hence for better yield the alkyl halide
should be primary of the alkoxide should be secondary or tertiary.

C2H5Br + NaO - C - C2H5 - O - C + NaBr

(b) By Heating excess of alcohols with conc. H2SO4 e.g.,

conc. H2SO4
C2H5 - OH + HO - C2H5 C2H5 - O - C2H5 + H2O
o
Ethanol (2 molecules) 140 C Diethyl ether

Recall that 2° and 3° alcohols under the above conditions give alkenes as the main product. Moreover, this
method is limited only for the preparation of simple ethers.
 Chem i str y | 22.39

(c) By heating alkyl halide with dry silver oxide (only for simple ethers)

C2H5l + Ag2O + lC2H5 C2H5OC2H5 + 2Agl

Remember that reaction of alkyl halides with moist silver oxides (Ag2O + H2O = AgOH) gives alcohols.
(d) By the use of diazomethane to form methyl ethers.
BF3
n-C7H15OH + CH2N2 n-C7H15OCH3 + N2
Methyl n-heptyl ether
BF3
n-C7H15OH + CH2N2 C6H5OCH3
Anisole

3. PHYSICAL PROPERTIES OF ETHERS

(d) Due to absence of intermolecular H-bonding, B.P of ether is much lower than isomeric alcohols.
(e) Ethers are slightly polar with some net dipole. (e.g. 1.18 D for diethyl ether.)This is due to a bend structure with
bond angle of 1100 which causes because of repulsion between bulky alkyl groups.

4. CHEMICAL PROPERTIES OF ETHERS

Ethers are less reactive than compounds containing other functional group. They do not react with active metals
like Na, strong base like NaOH, reducing or oxidizing agents.

4.1. Formation of Peroxides

On standing in contact with air, ethers are overrated into unstable peroxides (R2O → O) which are highly explosive
even in low concentrations. Hence ether is always purified before distillation. Purification (removal of peroxide) can
be done by washing ether with a solution of ferrous salt (which reduces peroxide to alcohols) or by distillation with
conc. H2SO4 (which oxidizes peroxides).
The presence of peroxides in ether is indicated by formation of red colour when ether is shaken with an aqueous
solution of ferrous ammonium sulphate and potassium thiocyanate. The peroxide oxidizes Fe2+ to Fe3 which reacts
with thiocyanate ion to given red colour of ferric thiocyanate
CNS −
Peroxide + Fe2+ → Fe3+  → Fe (CNS)3

Red

However, the formation of peroxide is prevented by adding a little Cu2O to it.

4.2 Basic Nature

Owing to the presence of unshared electron pairs on oxygen, ethers are basic, Hence they dissolve in strong acids
(e.g., HCl, conc. H2SO4 ) at low temperature to form oxonium salts.

(C2H5 )2 O + H2SO 4 → [(C2H5 )2 OH]− HSO −4

Diethyl ether Diethyloxonium
hydrogen sulphate

On account of this property ether is removed from ethyl bromide by shaking with conc. H2SO4. The oxonium salts
are stable only at low temperature and in a strongly acidic medium. On dilution, they decompose to give back the
original ether and acid.
2 2 . 4 0 | Alcohols, Phenols and Ethers

Ether also form coordination complexes with Lewis acids like BF3, AlCl3 RMgX, etc.
R2O R
R2O + BF3 R2O BF3 (b) R2O + RMgX Mg
R2O X
It is for this reason that ethers are used as solvent for Grignard reactions.

4.3 Action of Dilute H2SO4 (Hydrolysis)

dil. H2SO4 heat
C2H5-O-C2H5 2C2H5-OH
Pressure

4.4 Action of Concentration H2SO4

Heat
C2H5-O-C2H5+H2SO4(conc.) C2H5OH + C2H5HSO4

4.5 Action of Conc. HI or HBr.

(i) C2H5-O-C2H5+HI(cold) C2H5-OH + C2H5+I
(ii) C6H5-O-C2H5+HI C6H5OH + C2H5I

Mechanism of reaction: SN2 and SN1 mechanisms for the cleavage of ethers. SN2 cleavage occurs at a faster rate
with HI than with HCl.

Step 1 : R O R’ + Hl + -
O +I
R R’
base1 acid2 acid1 base2

H
+
- O
Step 2 for SN2 I + R R’ slow o
Rl + HOR’ (R is 1 )

Step 3 for SN2 R+ + I-

o
Rl (R is 3 )

(a) The transfer of H+ to ROR’ in step 1 is greater with HI, which is a stronger acid, than with HCl Furthermore, in
step 2, I, being a better nucleophile than Cl+, reacts at a faster rate.
 Chem i str y | 22.41

MASTERJEE CONCEPTS

•• Boiling point of ethers is lower than alcohol due to absence of hydrogen bonding.

+
HCl (conc) R-O-R
-
H Cl oxonium salts

BF3 R
O BF3
R
R
RMgX R R
O Mg O
R R
X
HI (excess)
2RI +H2O

HI
ROR R-OH +R - I

dil. H2SO4
2ROH

PCl5
2RCl+ POCl3

R’COCl
R’ -COOR

Cl. light
First - hydrogen gets halogenated

•• In reaction with HI, if cold and dilute HI solution is treated with ether, alcohols are formed while in hot
and concentrated HI, alkyl halides are formed.
•• The reaction mechanism in case of HI depends on the substrate. If the substrates attached to oxygen
are 10 or 20 ,then the mechanism is SN2 but if the substrate is 30 or the carbocation is very stable then
the mechanism is SN1.
Nikhil Khandelwal (JEE 2009, AIR 94)

Illustration 1: How are the ethers distinguished from alcohols? (JEE MAIN)

Sol: (i) All alcohols give CH4 (methane gas) when reacted with MeMgBr.

CH₃O H + Me MgBr CH₄ + CH₃OMgBr

o
1 alcohol
Me Me
O H + Me MgBr CH₄ + OMgBr
Me Me
o
2 alcohol

Me Me
O H + Me MgBr CH₄ + OMgBr
Me Me
Me Me
3o alcohol
2 2 . 4 2 | Alcohols, Phenols and Ethers

(ii) K2Cr2O7 in acid has bright orange colour. When it oxidizes 1º or 2º alcohol, it is reduced to blue green due to
the formation of Cr3+.

2-
MeCH2OH + Cr2O7 + H
o
1 alcohol Orange
colour
( (
3+
Me COOH + Cr + H2O
Acetic acid (blue-green)
Me - + Me
OH + Cr₂O₇² + H +
O + Cr³ + H₂O
Me o
Me
2 alcohol

(iii) All alcohols evolve H2 gas on addition of sodium (Na).

(iv) Dry ethers give negative test with all the reagents (a, b and c).

Illustration 2: Complete the following reaction:  (JEE MAIN)

Ph
H+
Ph O Ph
Ph
Sol:

Ph
H+ Ph
Ph O Ph HO +
Ph
Ph Ph
SE reaction (More stable3oC+ )
o

at p-position (Acts as electrophile)

of phenol
Ph
HO Ph
Ph
Mainly para isomer, no ortho isomer due to
steric hindrance of bulkyl Ph₃C gp.

Illustration 3: There are two paths for the preparation of phenyl-2, 4-dinitro phenyl either (C). Which path is
feasible and why? (JEE ADVANCED)

Sol:
Br Br
NO₂ PhONa
Dinitration
Path I: Ac₂O+N₂O₅

(A)
NO₂
(B) NO₂
Br
O NO₂

Path II: +PhONa (C)

(D)
(A)
O Dinitration
(E) Ac₂O+N₂O₅
 Chem i str y | 22.43

a. Path I is feasible. ArSN reaction (Williamson’s synthesis) of nucleophile PhOΘ with (B) is feasible. Also, Br of (B)
is activated by the two EWG (–NO2) groups.
b. Path II is not feasible. ArSN reaction of the nucleophile PhOΘ with (A) is not feasible because no activating
group is present in (A).
c. Dinitration of (E) does not give (C) but it gives because the first nitro
group is deactivating so that second nitro group enters the other ring
at p-position.
( O₂N O NO₂ (
Illustration 4: Complete the following: (JEE ADVANCED)

C₂H₅OH O
a. A B
H+ H+
O

+
H₂O/H O
b. C D
O H+

CH₃NH₂ O
c. E F
O H+ H+

Sol:
a.

b.

c.

Illustration 5: Complete the following reaction: (JEE MAIN)

OH
(i)NaOH
D D (i)NaOH
(Major) (B) (ii)CO₂
(ii)CO₂
(iii)D + (iii)H +

(A) (Major)

OH O-
 (i)NaOH
D D (i)NaOH
(Major) (B) (ii)CO₂
(ii)CO₂
(iii)D + (iii)H +
2 2 . 4 4 | Alcohols, Phenols and Ethers
(A) (Major)
Sol:
OH O-
O
D D D D
NaOH D D

OD O
- O
D COO D
-
C O C O

H+ D+ O
OD
OD
D COOD
D COOH

(B)
(A)
Last image is (A) not (D)

Illustration 6: Complete the following reactions:  (JEE MAIN)

OH OH
D D D D
CHClBrI CBr₂l₂
(B) (Major) (ii) - (D) (Major)
(i) EtO
-
OH

D D
(A) (C)

OH
D CCl₂BrI + OH
-
CHClBrI (iv) (E) (G)
(iii) - (F) H₃O
+
t-BuO

(E) NH₂

Sol: Cl
(a) EtO
-
-
H C Br EtOH + CClBrl
(Base) I breaks
Acidic
CClBrl
Chloro bromo
carbene

O O
D D D D
-
CClBr CClBr
-
e-deficient
acts as electrophile
D D
(SE reaction)
-
OH O
D CD O D CDClBr
(i)+H +
(ii)+H₃O +

D D
(o-isomer, major)
 Chem i str y | 22.45

(b)
a. CBr₂l₂
4NaOH -2H₂O C O
a. CBr₂l₂ 2NaBr + 2Nal + C(OH)₄
4NaOH -2H₂O C O
2NaBr + 2Nal + C(OH)₄ O
O
This produces CO2 ,the reaction is Kolbe reaction.
O O
O
b. O O
b. D DO D D
D D D
SE reaction D -
++
CC O O COO COO
- SE reaction -
-

DD
(C) OD
(C) OD OD OD
-
DD COOH D D COO COO-
COOH H₃O +
H₃O +

(D)
(D) D D
(o-Isomer D
is major) D
(o-Isomer is major)
Cl
- -
Me₃CO H C BrCl Me₃COH+ CClBrI
c. (Base) - I -
Me₃CO H C Br Me₃COH+ -ICClBrI
-
c. (Base) Acidic CBrCl
I
-
+ − -I
Acidic CBrCl
( − N ≡ C −)
(c) Carbene also converts (– NH2) group to (Carbylamine reaction) and also adds to (C = C) bond of
cyclopentane ring and undergoes Reimer-Tiemann reaction at o-position w.r.t. (–OH) group in benzene ring.

OH OH Bond breaks
4
D O C 5
CBrCl 3

D 6
Br
1 2
+ -
NH₂ N C Cl
(E)
OH
4
O CD 5
3 Ring ecpansion
Weak C-Br
6
1
2 Cl bond breaks
+ - -HBr

( (
N C
Numbering in accordance
with problem
understanding
(F)

(d) CCl₂BrI 4NaOH

2NaCl + NaBr + Nal
-2H₂O
+C(OH)₄ CO₂

OH OH
O
D HOOC
+ C O

NH₂ NH₂
(E) (G)
 Ph Me
2 2 . 4 6 | Alcohols, Phenols and Ethers Ph H
HNO₂
(B)
-H+
(C)
(A)
OH NH₂
Illustration 7: Complete the following reactions: (JEE ADVANCED)
O
Ph Me
HNO₂ -H+ CH₃NO₂ LAH HNO₂
Ph H (B) (C) (B) (B) (C) (D)
(A) EtO - -H
+
OH NH₂ (Aldol type)
(A)
O
Sol: CH₃NO₂ LAH HNO₂
(B) (B) (C) (D)
(A) EtO - +
-H
Ph(AldolMe
type) Ph Me
(A) HNO₂
Ph H Ph H
Ph Me Ph Me
HNO₂ -N₂
Ph OH NH₂H Ph OH NH N
-N₂
OH(A)NH₂ OH N (B)
N
(A) (B)
Ph Ph Me
+ Ph migrates
Ph Ph Me PhPh Me+ H
+ Ph migrates
HPh O H Me Ph OH + H
H O H OH
+
-H
+
-H
Ph Ph
Ph Ph
O Me
H Me
O H
(C)
(C)
-  -
EtO- H CH₂ NO₂ EtOH + CH₂NO₂
-
(B) EtO H

CH₂
-H NO₂
atoms are EtOH + CH₂NO₂
-H atoms
acidic due to are
-lacidic
effectdue
of NO₂
to
-l effect of NO₂

O
HO CH₂NO₂ HO CH₂NH₂
-
CH₂NO₂ [H]
LAH
(A) (B) (C) HNO₂

+ 1 +
HO CH₂ HO CH₂ N N
Ring 7
-N₂
6 2
expansion
5 3
4

O
H O
+
7 1 + 7 1
2 -H 2
6 3 6 3
5 4 5 4
(D)
(cycloheptanone)
 Chem i str y | 22.47

POINTS TO REMEMBER
R’ONa moist
R-X
Preparation Ag₂O

conc. R-O-R’ BF₃

2R-OH
H₂SO₄ CH₂N₂

dil. air
2R-OH Peroxide
H₂SO₄ Reactions
+
conc. R-O-R’ H
R-OH+RHSO₄ Oxonium salts
H₂SO₄ Low
HI/ temp.
conc.
HBr
R-OH + R’-I/R’-Br
2-
Ag CO3
(A) Me3C Br AgBr + Me3C 2-
Ag CO3
(A) Me3C Br AgBr + Me3C O
Me3C -CO2C O
Me3C O Me3C O C O
Solved Examples
Me C 3
Me3C O
-CO2C
Me3C O C O
Me3C O CMe3
Me3C (A)
O CMe3
(A)
JEE Main/Boards H
(B)b. Me OH Me + Me CH = O
-H
H 2O
(B) Me OH Me + Me CH = O
Example 1: Complete the following reactions: -H2O
Cl
Me CH OMe Me CH OMe
Ag CO
2 3 → (A)
a. 2Me3C− Br 
∆ Me CH OMe
Cl
Me CH OMe
Cl
b. 2MeOH + MeCH =
O + HCl (g) → (B) ( Chloroether
Cl )
 Chloroethyl
( Chloroether) ether
methyl
c. MeOH + H2C =O + HCl (g) → (C)
 Chloroethyl methyl ether
(C) CH =O MeOH CH OMe ( Chlorether dimethyl ether)
Sol: A = Me3 C – O – Me3 (Di-t-butyl ether)
2 2
+ HCl
(C)c. CH =O MeOH CH OMe ( Chlorether dimethyl ether)
2 2
+ HCl Cl
Ag+ reacts with Br− leaving Me3CΘ ,which reacts with
Cl
CO32– to give Me3C – OCO2Θ . The latter loses CO2 leaving
Me3COO which reacts with Me3C⊕ to give the product.
Due to steric hindrance, the yield is less.
Example 2: Complete the following reactions:
Mechanism:
a. C6H6 + MeCOCl
AlCl3 HNO3 NaBH
4 H SO
B C D 2 4 E
2- AlCl3 H2SO
HNO 4 NaBH4 H SO
(A)a. Me3C
Ag CO3 Benzene
C6H (A)
6 + MeCOCl B 3
C D 2 4 E
Br AgBr + Me3C H2SO4 
Benzene (A)
O NaBH4 H2SO4 HNO 3
(B) F G H
4 H2SO
b. (B) NaBH4
Me3C -CO2C H2SO HNO 3
4

Me3C O Me3C O C O F G H
 H2SO4

Me3C O CMe3
(A)

H
(B) Me OH Me + Me CH = O
-H2O

Cl
Me CH OMe Me CH OMe

Cl
( Chloroether)
 Chloroethyl methyl ether