ALCOHOLS AND PHENOLS

Reaction of Aliphatic and Aromatic Alcohols

1. Removal of the hydrogen from the OH bond
2. Replacement of the hydroxyl group in the form of the protonated hydroxyl
group
Oxidation of Alcohols
Primary alcohols yield aldehydes
Secondary alcohols yield ketones
Dehydrogenation oxidation of primary and secondary alcohols to aldehydes
and ketones
Phenols more acidic than alcohols because of the tendency of a lone pair of
electrons of oxygen to interact with the pi electrons of the benzene
ring
Experimental Results
1. Ceric Nitrate Test test for the presence of the OH group
positive result is indicated by a change in color of the
reagent from yellow to red
positive for alcohols and phenols containing no more
than 10 carbon atoms
2. Reaction with HCl (Lucas Test) to differentiate primary, secondary, and
tertiary alcohols
a. ethyl alcohol
CH3CH2OH + HCl

CH3CH2Cl (no oily chloride layer)

b. isopropyl alcohol
CH3CHOH
|
CH3

+ HCl

CH3CHCl
|
(oily chloride layer)
CH3

c. tert-butyl alcohol
CH3
|
CH3 C OH + HCl
|
CH3

CH3
|
CH3 C Cl
|
CH3

(oily chloride layer)

Ease of reaction: 3o > 2o > 1o

Basis: basic characteristic of ROH
+
accepts H+ to form protonated ROH, ROH
|
H
The reaction of alcohol with HCl is a replacement reaction of the OH
by the halide.
Steps:
a. protonation of alcohol
b. removal of water molecule
c. formation of carbocation
d. combination of carbocation with the halide ion
3. Oxidation of alcohols by means of chromic acid, H 2CrO4
chromic acid = K2Cr2O7 + H2SO4
primary alcohols oxidized to aldehydes; blue green solution is formed
secondary alcohols oxidized to ketones; blue green solution is observed
tertiary alcohols no reaction; orange color is retained
a. ethyl alcohol 1o alcohol, oxidized to acetaldehyde; further oxidation yields
acetic acid
b. isopropyl alcohol 2o alcohol, oxidized to acetone
Ease of reaction: 1o > 2o > 3o
Basis: removal of H

The tertiary alcohols cannot be oxidized because no H is attached to carbinol

carbon.
3. Esterification reaction between a monocarboxylic acid (RCOOH) and
alcohol (ROH) or phenol (ArOH) to produce ester (RCOOR) and H 2O
RCOOH + ROH

RCOOR + H2O

O
O
||
||
OH + CH3COCCH3

a.

O
||
O C CH3

KOH
faster

Phenyl
acetate
KOH basic catalyst

+
CH3COOH

Esterification is faster with phenol because there is no steric effect.

O
//
C
OH
b.

O
O
||
||
+ CH3COCCH3

KOH
slower

O
//
C
OCH3
OH

OH
Salicylic acid

slower due to intramolecular H-bonding

4. Reaction with bromine water

phenol + 3 Br2

2,4,6-tribromophenol + 3 HBr
white crystalline solid

5. Reaction with phthalic anhydride

H2SO4

phenol + phthalic anhydride

phenolphthalein
faster

6. Reaction with FeCl3

phenol + FeCl3

violet color