11.

Alcohols, Phenols and Ethers

Classification of alcohols and phenols:

Mono, di, tri or polyhydric –

On the basis of hybridisation –

 Csp – OH
3

 Primary, secondary and tertiary

 Allylic alcohols

 Benzylic alcohols

 Csp – OH
2

 Vinylic alcohol

 Phenol
Classification of ethers:
Simple or symmetrical –
C2H5OC2H5, C6H5OC6H5
Mixed or unsymmetrical –
C2H5OCH3, CH3OC6H5

Common names of some phenols:

Alcohols and phenols:

Preparation of alcohols –
 From alkenes
 Acid catalysed hydration

[According to Markovnikov’s rule]

 Hydroboration – oxidation
  From carbonyl compounds
 By reduction of aldehydes and ketones.
Aldehydes give 1 and ketones give 2 alcohols.
Pd
RCHO H2 RCH2OH

 By reduction of carboxylic acids and esters

i LiAlH 4
RCOOH ii H 2 O
RCH 2OH
catalyst
RCOOR H2 catalystic hydrogenation
RCH 2OH R OH
 From Grignard reagents

Methanol gives 1 , other aldehydes give 2 , and ketones give 3 alcohols.

Preparation of phenols –
 From haloarenes

 From benzenesulphonic acid

  From diazonium salts

 From cumene

Physical properties of alcohols and phenols –

 Boiling points:
 The boiling points of alcohols and phenols increase with increase in number
of carbon atoms as it involves increase in van der Waals forces.
 The boiling points of alcohols decrease with increase of branching. This is
because van der Waals forces decrease with decrease in surface area.
 Solubility:
 Alcohols and phenols form H-bonds, so they are soluble in water.
 Their solubility decreases with increase in size of alkyl/aryl groups.

Chemical reactions: Alcohols react both as nucleophiles and electrophiles

Reactions that involve cleavage of O – H bond
 Acidity of alcohols and phenols
 Reaction with metals
2ROH 2Na 2R O Na H 2
Sodium
alkoxide
  Acidity of alcohols
The increasing order of acidity of alcohols is

 Acidity of phenols
Phenols are more acidic than alcohols and water.
Electron-withdrawing groups increase the acidity of phenols while
electron-releasing groups decrease the acidity of phenols.

 Esterification
Pyridine
R/ArOH R COCl R/ArOCOR HCl
 Acetylation of salicylic acid

Reactions that involve cleavage of C – O bond in alcohols

 Reaction with hydrogen halide
ROH HX RX H2O
 Lucas test – Used for distinguishing between 1°, 2° and 3° alcohols.
(Lucas reagent – Concentrated HCl and ZnCl2)
 Reaction with phosphorus trihalide
3R OH PX3 3R X H3PO3 X Cl,Br
  Dehydration
Treated with concentrated H2SO4 or H3PO4 or Anhyd. ZnCl2, or Al2O3

The order of increasing reactivity towards dehydration is

1 alcohol < 2 alcohol < 3 alcohol
 Oxidation (also known as dehydrogenation)
It involves formation of a carbon–oxygen double bond.
 Oxidising agent – Acidified KMnO4
directly
Alcohol Carboxylic acid
 Oxidising agent Anhyd. CrO3
1 alcohol Aldehyde
alcohol Ketone
 Pyridinium chlorochromate (PCC)
1 alcohol Aldehyde
 Oxidising agent Heated Cu at 573 K
1 alcohol Aldehyde
alcohol Ketone
 3 alcohols do not undergo oxidation

Reactions of phenols:
 Electrophilic aromatic substitution reaction
 Nitration

The o-isomer is steam volatile due to intramolecular H-bonding

while the p-isomer is less volatile due to intermolecular H-bonding.
So, they can be separated by steam distillation.
 Halogenation

 Kolbe’s reaction

 Reimer–Tiemann reaction

 Reaction of phenol with zinc dust

  Oxidation

Ethers:
Preparation of ethers –
 By dehydration of alcohols

 Williamson synthesis

 But in case of 2 and 3 halides, instead of substitution, elimination takes

place, resulting in alkenes.
 Phenols are converted into ethers.

Physical properties of ethers –

 Boiling points:
 The boiling points of ethers are lower than those of alcohols of comparable
molecular masses due to the presence of H-bonding in alcohols.

Chemical reactions of ethers:

 Cleavage of C – O bond
 Least reactive; under drastic conditions with excess of hydrogen halides, the
C – O bond is cleaved

 The order of increasing reactivity of hydrogen halides is

HCl < HBr < HI
 Electrophilic substitution
 Halogenation

 Friedel Craft’s alkylation

 Friedel Craft’s acylation

  Nitration

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