Class-12 Chemistry

Chapter-11: Alcohols, Phenols and Ethers

• Structure of alcohols:

• Preparation of alcohols:
a) From alkene
Acid catalysed hydration
(H 2 O , H + )
Mark, Addition
Or
Hydroboration - oxidation
B2 H 6 , H 2O2 / OH −
Mark, addition
Alkene → Alcohol
Product is anti mark

b) From esters
Esters 
H 2 catalyst
→ Alcohol
c) From aldehydes and ketones
H 2 / Pd
or
NaBH 4
Or
LiAlH 4
Or
Alcoho l ←
 Aldehyde and ketone
Grignard ' s reagent

d) From carboxylic acids

Alcoho l ←
LiAlH 4 H 2 O
Carboxylic acids
• Structure of phenols:

• Preparation of phenols:
a) From benzene

+

Oleum
→ 
NaOH / H
→
 b) From chlorobenzene


NaOH at 623K,320 atm.pres
→ →
HCl

c) From cumene

+
→
H 2 O,H

O2
→
d) From aniline

→
NaNO 2 ,HCl

H 2 O,warm
→

• Physical properties of alcohols and phenols:

a) Boiling points
Boiling points of alcohols and phenols are higher in comparison to other classes of
compounds. This is because the –OH group in alcohols and phenols is involved in
intermolecular hydrogen bonding.

The boiling points of alcohols and phenols increase with increase in the number of
carbon atoms. This is because of increase in van der Waals forces with increase in
surface area.
In alcohols, the boiling points decrease with increase of branching in carbon chain.
This is because of decrease in van der Waals forces with decrease in surface area.
b) Solubility
 Solubility of alcohols and phenols are soluble in water due to their ability to form
hydrogen bonds with water molecules. The solubility of alcohols decreases with
increase in size of alkyl/aryl (hydrophobic) groups.
• Chemical properties of alcohols:
I. Reactions involving cleavage of O–H bond: Alcohols react as nucleophiles:
a) Reaction with metals

2 R − O − H + 2 Na → 2 R − O − Na + H 2
Sodium alkoxide

b) Esterification reaction
H+
RO − H + R '− COOH ⇔ ROCOR '+ H 2O
Alcohol

H+
RO − H + ( R ' CO2 )O ⇔ ROCOR '+ R ' COOH
Alcohol

RO − H + R ' COCl →

Pyridine
R − OCOR '+ HCl
Alcohol

II. Reactions of alcohols involving cleavage of carbon – oxygen (C–O) bond:

a) Reaction with hydrogen halides
conc . HCl + ZnCl2 / Lucas reagent
ROH + HX  → RX + H 2O
b) Reaction with phosphorus trihalides
3ROH + PX 3 → 3R − X + H 3 PO3 ( X = Cl , Br )
c) Dehydration reaction
Pr otic acids(conc.H 2 SO4 orH 3 PO4 )
Or
Alcohol → C = C + H 2O
Catalysts ( anhyd . ZnCl2 or alumina)

d) Oxidation reaction
Alcohol 
Acidified potassium permanganat
→ Carboxylic acid
CU ,573 k
Or
CrO3
Or
i) Primary Alcohol 
→ Aldehyde
PCC

CU ,573 k
Or
ii) Secondary Alcohol 
→ Ketone CrO3

CU ,573 k
Or
iii) Tertiary Alcohol 
→ AlkeneKMnO4

• Chemical properties of phenols:

I. Reactions involving cleavage of O–H bond: Alcohols react as nucleophiles:
a) Reaction with metals
b) Esterification reaction
H+
Ar − OH + R '− COOH ⇔ Ar − OCOR '+ H 2O
Phenol

H+
Ar − OH + ( R ' CO) 2 O ⇔ Ar − OCOR '+ R ' COOH
Phenol

Ar − OH + R ' COCl →

Pyridine
ArOCOR '+ HCl
Phenol

II. Other chemical reactions of phenols:

III. Acidic nature of phenol and alcohol:

a) Phenol > H2O > Primary alcohol > Secondary alcohol > Tertiary alcohol
The acidic character of alcohols is due to the polar nature of O–H bond. Alkyl group is
an electron-releasing group (–CH3, –C2H5) or it has electron releasing inductive effect
(+I effect). Due to +I effect of alkyl groups, the electron density on oxygen increases.
This decreases the polarity of O-H bond. And hence the acid strength decreases.
b) Phenol is more acidic than alcohol:
In phenol, the hydroxyl group is directly attached to the sp2 hybridised carbon of
benzene ring which acts as an electron withdrawing group whereas in alcohols, the
hydroxyl group is attached to the alkyl group which have electron releasing inductive
effect. In phenol, the hydroxyl group is directly attached to the sp2 hybridised carbon
of benzene ring whereas in alcohols, the hydroxyl group is attached to the sp3
hybridised carbon of the alkyl group. The sp2 hybridised carbon has higher
electronegativity than sp3 hybridised carbon. Thus, the polarity of O–H bond of
phenols is higher than those of alcohols. Hence, the ionisation of phenols is higher
than that of alcohols.
The ionisation of an alcohol and a phenol takes place as follows:

In alkoxide ion, the negative charge is localised on oxygen while in phenoxide ion, the
charge is delocalised.

The delocalisation of negative charge makes phenoxide ion more stable and favours the
ionisation of phenol. Although there is also charge delocalisation in phenol, its resonance
structures have charge separation due to which the phenol molecule is less stable than
phenoxide ion.
 c) In substituted phenols, the presence of electron withdrawing groups such as nitro
group enhances the acidic strength of phenol. On the other hand, electron releasing
groups, such as alkyl groups, in general, decreases the acid strength. It is because
electron withdrawing groups lead to effective delocalisation of negative charge in
phenoxide ion.
• Differentiate between organic compounds:
a) Alcohols and phenols
Phenol on reaction with neutral FeCl3 gives purple colour whereas alcohols do not
give purple colour.
6C6 H 5OH + Fe3+ → [ Fe(OC6 H 5 )6 ]3− + 6 H +
Purple colour

b) Primary, secondary and tertiary alcohols

Lucas reagent test:
conc . HCl + ZnCl2 / Lucas reagent
ROH + HCl  → RCl + H 2O
If it is a primary alcohol, no turbidity appears at room temperature. Turbidity
appears only on heating. If it is a secondary alcohol, turbidity appears in 5 minutes. If
it is a tertiary alcohol, turbidity appears immediately.
c) Methanol and ethanol
Iodoform test: Ethanol when reacted with (I2 and NaOH) or NaOI gives yellow ppt of
iodoform since it has the presence of CH3-CH (OH)- group.
C2 H 5OH + 4 I 2 + 6 NaOH → CHI 3 + 5 NaI + 5 H 2O + HCOONa
Yellow ppt

CH 3OH + I 2 + NaOH → No yellow ppt

• Structure of ethers:

• Preparation of ethers:
a) From alcohols
Alcohol →
H 2 SO4 or H3 PO4 at413K
Ethers
 b) From alkyl halide and sodium alkoxide
Ethers ←  Alkyl halide and sodium alkoxide
Williamson ' s synthesis

Here, the alkyl halide should be primary and alkoxide should be tertiary. In case of
aromatic ether, the aromatic part should be with phenoxide ion.
• Physical properties of ethers:
a) Miscibility:
Miscibility of ethers with water resembles those of alcohols of the same molecular mass.
This is due to the fact that just like alcohols, oxygen of ether can also form hydrogen
bonds with water molecule.

b) Boiling points:
Ethers have much lower boiling points than alcohols. This is due to the presence of
hydrogen bonding in alcohols. Hydrogen bonding is absent in ethers.
R R
| |
R − O− H − O− H − O− H − O−
| |
H R

• Chemical properties of ethers:

a) Cleavage of C–O bond in ethers:
R-O-R’ + HX → R-X + R’OH
Excess
The order of reactivity of hydrogen halides is as follows: HI > HBr > HCl
Alkyl halide formed is always the lower alkyl group. But if a tertiary alkyl group is
present, the alkyl halide is always tertiary. In case of phenolic ethers, the cleavage occurs
with the formation of phenol and alkyl halide.
b) Electrophilic substitution reaction in aromatic ethers:

The electrophilic substitution reaction of aromatic ether involves the following reaction:
• Other conversion reactions:
a) Phenol to salicyldehyde

b) Phenol to benzene diazonium chloride