Live Sahab20

Alcohols, Phenols &

Ethers
By Singh Sahab
Introduction
Alcohols Phenols Ethers
CH4
R–O–R
H
|
H–C–H CH3 – OR
|
H Replace H
CH3 – O – CH3
by – OH CH3 – O – C2H5
CH3 – OH
C2H5 – OH
Alcohols: Classification
i) Mono, Di, Tri or Polyhydric

Monohydric Dihydric Trihydric

ii) 1, 2, 3 Alcohols

1 C 2 C 3 C
iii) Allylic Alcohols

Allylic Group

C= C–C
|
OH
iv) Vinylic Alcohols

Vinylic Group
C= C
|
OH

Examples CH3
|
CH3 – CH = CH CH3 – CH2 – C = C – C2H5
| |
OH OH
v) Benzylic Alcohols

CH2 – OH

Benzyl Alcohol
Ethers
Ethers

Simple or Symmetrical Mixed or Unsymmetrical

Both alkyl groups are same Both alkyl groups are different

Examples- Examples-

CH3 – O – CH3 CH3 – O – C2H5

C2H5 – O – C2H5 C6H5 – O – C2H5

Preparation of Alcohols
1. From Alkenes
 H+
CH3 – CH = CH – CH3 + H2O CH3 – CH – CH – CH3
| |
H OH

H+
CH3 – CH = CH2 + H2O CH3 – CH – CH3
|
OH

Markovinikov’s Rule

Add H+ to the carbon having the greater no. of hydrogen.

2. From Aldehydes (Reduction)

H2
CH3 – CH2 – OH 1 Alcohol
Ni / Pd / Pt

NaBH4
CH3 – CHO CH3 – CH2 – OH

LiAlH4
CH3 – CH2 – OH
 3. From Ketones

H2
CH3 – CH – CH3 2 Alcohol
Ni / Pd / Pt
|
OH

NaBH4
CH3 – C – CH3 CH3 – CH – CH3
|| |
O OH

LiAlH4
CH3 – CH – CH3
|
OH
4. by Reduction of Carboxylic Acids

1. LiAlH4
CH3 – COOH CH3 – CH2 – OH
2. H2O
1 Alcohol
LiAlH4 is expensive so we first convert Acid into ester then we
reduce ester into alcohol by catalytic hydrogenation

C2H5OH H2
CH3 – COOH CH3 – COOC2H5 CH3 – CH2 – OH
H+ Catalyst
1 Alcohol

C2H5OH
5. From Grignard Reagent

Step 1 Step 2
 O OH
|| 1. C2H5MgBr |
CH3 – C – CH3 CH3 – C – CH3
2. H 2O |
C2H5

3 Alcohol
Preparation of Phenols
1. From Haloarenes
2. From Benzenesulphonic Acid

Benzenesulphonic Acid

Oleum → H2S2O7
3. From Diazonium Salts
4. From Cumene
Ethers
By dehydration of Alcohols
 By Williamson Synthesis

C2H5 – Cl + CH3O- Na+ C2H5 – O – CH3

This is SN2 reaction….favours 1o halide

E2
 Chemical Reactions
Acidity

Reaction with metals (Na, K, Al)

CH3 – OH + Al (CH3 – O)3 Al + H2

 Active Metal

Acidic H
Acidic Strength

CH3 CH3
| |
CH3 – CH2 – OH > CH3 – CH – OH > CH3 – C – OH
|
CH3
1 Alcohol 2 Alcohol 3 Alcohol

Reason - +I effect of R
Esterification

H+
+ H2O

O O
|| pyridine ||
C2H5OH + CH3 – C – Cl CH3 – C – O – C2H5 + HCl
 O O O O
|| || H+ || ||
CH3 – OH + R–C–O–C–R CH3 – O – C – R + HO – C – R
Lucas Test
Lucas Reagent: conc. HCl + ZnCl2

CH3 CH3
| |
CH3 – CH – OH + HCl CH3 – CH – Cl + H2O
2
Note:

3 Alcohol → Instant Turbidity

2 Alcohol → Turbidity after 5-10 minutes

1 Alcohol → Do not give Turbidity

Dehydration
Dehydrating Reagent: conc. H2SO4 + H3PO4
Relative Ease of dehydration- 3 > 2 > 1
Oxidation of alcohols
[O] [O]
CH3CH2OH CH3CHO CH3COOH

1 Alcohol Aldehyde Acid

Oxidation
CH3 – CH – OH CH3 – C – CH3
| ||
CH3 O

2 Alcohol Ketone
Alcohols PCC / CrO3 / Cu & heat KMnO4 / H+
POC K 2Cr2O7 / H+
mild O.A. Strong O.A.

1 Alcohol Aldehyde Carboxylic

Acid

2 Alcohol Ketone Ketone

3 Alcohol X X
Dehydrogenation
Chemical Reactions of Phenol
Reaction with Metals
Na

+ Na + H2

+ H2O
+ OH-
Esterification
Aspirin
Kolbe’s Reaction
Reimer-Tiemann reaction
Electrophilic Aromatic Substitution
Nitration
Halogenation
Oxidation
Reaction with Zinc Dust
Chemical Reactions of Ethers
Cleavage of C–O bond in ethers
Addition of Iodine : 3 > 1 > 2

H H

3– I OH
HI
Electrophilic Substitution
Halogenation
Friedel-Crafts reaction
Nitration