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 Markovnikovs 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 carbonoxygen 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


Kolbes reaction


ReimerTiemann 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 Crafts alkylation



Friedel Crafts acylation





Nitration