11.

Alcohols, Phenols and Ethers


Classification of alcohols and phenols:
Mono, di, tri or polyhydric –



On the basis of hybridisation –

3
C
sp
– OH
 Primary, secondary and tertiary
 Allylic alcohols


 Benzylic alcohols




2
C
sp
– OH
 Vinylic alcohol


 Phenol





Classification of ethers:
Simple or symmetrical –
C
2
H
5
OC
2
H
5
, C
6
H
5
OC
6
H
5

Mixed or unsymmetrical –
C
2
H
5
OCH
3,
CH
3
OC
6
H
5


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
2 2
RCHO H RCH OH


 By reduction of carboxylic acids and esters
4
2
i LiAlH
2 ii H O
catalyst
2 2 catalytic hydrogenation
RCOOH RCH OH
RCOOR H RCH OH 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
2
2ROH 2Na 2R O Na H
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
2
ROH HX RX H O
 Lucas test – Used for distinguishing between 1°, 2° and 3° alcohols.
(Lucas reagent – Concentrated HCl and anhydrous ZnCl
2
)
 Reaction with phosphorus trihalide
3 3 3
3R OH PX 3R X H PO X Cl,Br


 Dehydration
Treated with concentrated H
2
SO
4
or H
3
PO
4
or Anhyd. ZnCl
2
, or Al
2
O
3




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 KMnO
4

directly
Alcohol Carboxylic acid
 Oxidising agent Anhyd. CrO
3

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