Alcohols, Phenols & Ethers

Chapter-11
 Classification

Alcohols— Mono, Di, Tri or Polyhydric alcohols

 Alcohols & Phenols
✓ Preparation of Alcohols

✓ From Alkenes
 By Hydroboration–Oxidation
Diborane (BH3)2 reacts with alkenes to give trialkyl boranes
as addition product. This is oxidised to alcohol by hydrogen
peroxide in the presence of aqueous sodium hydroxide.
 From Carbonyl Compounds
𝐏𝐝
✓ 𝐑𝐂𝐇𝐎 + 𝐇𝟐 ⟶ 𝐑𝐂𝐇𝟐 𝐎𝐇

𝐍𝐚𝐁𝐇𝟒
𝐑𝐂𝐎𝐑′ ⟶ 𝐑 − 𝐂𝐇 − 𝐑 ′
𝐈
𝐎𝐇

(i) 𝐋𝐢𝐀𝐥𝐇𝟒
✓ 𝐑𝐂𝐎𝐎𝐇 ⟶ 𝐑𝐂𝐇𝟐 𝐎𝐇
(ii) 𝐇𝟐𝐎
Give the structural formula and IUPAC name of the
product formed by the reaction of propanone with
CH3 MgBr in dry ether, followed by hydrolysis.
Identify the product:
Preparation of Phenols From Haloarenes
From Benzenesulphonic Acid
From Diazonium Salts
From Cumene
What is cumene? Explain the preparation of phenol from
cumene.
 Physical Properties
Boiling Points
Alcohols and phenols have higher boiling points. Why ?
Chemical Reactions
 Reactions Involving Cleavage of O–H
Bond
✓ Acidity of Alcohols & Phenols
Phenol is more acidic than ethanol. Why?
 Esterification
✓ Alcohols and phenols react with carboxylic acids, acid
chlorides and acid anhydrides to form esters.
Reactions Involving Cleavage of Carbon – Oxygen (C–
O)

✓ Bond In Alcohols

✓ Reaction with hydrogen halides:

✓ 𝐑𝐎𝐇 + 𝐇𝐗 → 𝐑 − 𝐗 + 𝐇𝟐 𝐎
Explain Lucas test to distinguish primary, secondary and
tertiary alcohols.
A mixture of anhydrous 𝐙𝐧𝐂𝐥𝟐 and conc. 𝐇𝐂𝐥 is an
important reagent used to distinguish primary, secondary
and tertiary alcohols. How the above reagent is used to
distinguish the three types of alcohols?
Reaction with Phosphorus Trihalides
 Dehydration
H2 SO4
✓ C2 H5 OH ⟶ CH2 = CH2 + H2 O
443 K
Oxidation
 Reactions of Phenols
✓ Electrophilic Aromatic Substitution

✓ Nitration:
Halogenation:
Kolbe’s Reaction
Reimer-Tiemann Reaction
Write the chemical equation representing Reimer-
Tiemann reaction.
Reaction of Phenol With Zinc Dust
Oxidation
Identify X and name the reaction.

(b) How can the following conversions be effected:

(i) Phenol ⟶ Benzene
(ii)Phenol ⟶ 2,4, 6-Trinitrophenol
i. How are the following conversions carried out?
A. Propene to Propan-2-ol.
B. Ethanal to Ethanol.

ii. Name the enzyme which converts glucose to ethanol.

 Some Commercially Important Alcohols
✓ Methanol

𝐙𝐧𝐎−𝐂𝐫𝟐 𝐎𝟑
✓ 𝐂𝐎 + 𝟐𝐇𝟐 ⟶ 𝐂𝐇𝟑 𝐎𝐇
𝟐𝟎𝟎−𝟑𝟎𝟎 𝐚𝐭𝐦
𝟓𝟕𝟑−𝟔𝟕𝟑 𝐊
 Ethanol
Invertase
✓ 𝐂𝟏𝟐 𝐇𝟐𝟐 𝐎𝟏𝟏 + 𝐇𝟐 𝐎 ⟶ 𝐂𝟔 𝐇𝟏𝟐 𝐎𝟔 + 𝐂𝟔 𝐇𝟏𝟐 𝐎𝟔

Glucose Fructose

Zymase
✓ 𝐂𝟔 𝐇𝟏𝟐 𝐎𝟔 ⟶ 𝟐𝐂𝟐 𝐇𝟓 𝐎𝐇 + 𝟐𝐂𝐎𝟐
a) Phenol when treated with Conc. HNO gives,
(i) o-Nitrophenol
(ii) P-Nitrophenol
(iii) 2,4,6 − Trinitrophenol
(iv) Mixture of o-nitrophenl and p-nitrophenol

b) Methanol and ethanol are two commercially important

alcohols. Write one method each for the preparation of
methanol and ethanol.
 Ethers
✓ Preparation of Ethers

✓ By Dehydration of Alcohols
 Williamson Synthesis
✓ An alkyl halide is allowed to react with sodium alkoxide to
give Ether.
What is Williamson's synthesis ? How is it used to prepare
• [3]
methoxy benzene ?
 Chemical Reactions
1. Cleavage of C–O bond in ethers

✓ R − O − R + HX ⟶ RX + R − OH
R − OH + HX ⟶ R − X + H2 O
(i) Identify A and B in the following reaction
2. Electrophilic substitution
Halogenation:
Friedel Craft Alkylation:
Friedel Craft Acylation:
Nitration: