Detailed Revision

Alcohol phenol and ethers

Introduction of hydroxy compounds.

Hydroxy compounds are compounds in which the hydroxy group, OH is directly linked with the aliphatic
or aromatic carbon. Hydroxy compounds can be classified into following three categories.
(1) Aliphatic hydroxy compounds (alcohols) : Alcohols are regarded as hydroxy derivatives of
hydrocarbons.

Hydrocarbo n

OH

R OH (R = alkyl group)
Alcohol

They can be mono, di or tri-hydric alcohols depending upon whether they contain one, two or three
hydroxy groups.
Monohydric

Dihydric alcohol

Trihydric alcohol

Polyhydric alcohol

CH 2 OH

CH 2OH

CH 2 OH

CHOH

(CHOH )4

CH 2OH

CH 2 OH

alcohols
CH 3 OH
Methanol

CH 2 OH
C 2 H 5 OH

Glycol

Ethanol

Glycerol

sorbital or Mannitol

(2) Aromatic hydroxy compounds (Phenols) : Phenols are regarded as hydroxy derivatives of aromatic
hydrocarbons (arenes).
Ar

Arene

H
OH

Ar

OH

Phenol

They can be mono, di or tri-hydric phenols depending upon whether they contain one, two or three
hydroxy groups.

OH

OH

OH

OH

CH3
Monohydric phenols :
Phenol

o-cresol

m-cresol

CH3
CH3
p-cresol

OH

OH

OH
OH

Dihydric phenols :
Catechol

Resorcinol

OH
OH
Quinol

OH
OH

Pyrogallol

OH

OH

OH

OH
HO

Phloroglucinol

OH

Trihydric phenols :

(3) Aromatic alcohols : Compounds in which the hydroxy group is present in the side chain are termed
aromatic alcohols.

CH2CH2OH

CH2OH

Benzyl alcohol

2 phenyl ethanol

Monohydric alcohols.
Alcohols containing one hydroxyl group are known as monohydric alcohols. These alcohols may be
saturated or unsaturated depending on the nature of hydrocarbon groups. Saturated monohydric alcohols form
a homologous series of the general formula Cn H 2n 1 OH . They are also represented as R OH where R
represents an alkyl group. They may be regarded as derivatives of water, i.e., one hydrogen atom of the water
molecule is replaced by an alkyl group.
HOH

Water

OH

Alcohol

(1) Classification : Monohydric alcohols are subdivided into three classes

(i) Primary alcohols : In these alcohols, the hydroxyl group is attached with primary (1 o ) carbon atom.
They possess a characteristic group

CH 2 OH and their general formula is RCH 2 OH . R may be H in the first

member and alkyl group in the rest of the members.

Examples : HCH 2 OH ; CH 3 CH 2 OH ; CH 3 CH 2 CH 2 OH ;
Methyl alcohol

Ethyl alcohol

n - propyl alcohol

CH 3
CH 3

CH

CH 2 OH

isobutyl alcohol

(ii) Secondary alcohols : In these monohydric alcohols, the hydroxyl group is attached with secondary
(2) carbon atom. They possess a characteristic group

CHOH and the general formula

R
R

CHOH (R and

R may be same or different).

Example :

CH 3 OH
CH 3 OH

CHOH ;

Isopropyl alcohol

C2 H 5
CH 3

CHOH

sec. butyl alcohol

(iii) Tertiary alcohols : In these monohydric alcohols, the hydroxyl group is attached with tertiary (3)

R
carbon atom. They contain a characteristic group

and R may be same or different).

COH and have the general formula R

R

OH (R, R

CH 3

CH 3

C OH ; C 2 H 5

C OH

CH 3

CH 3

Examples : CH 3

tert. Butyl alcohol

tert. Amyl alcohol

(2) Nomenclature
(i) Common system : Named as alkyl alcohol.
Note : In higher members, it is always indicated whether the OH group is attached to primary,
secondary and tertiary carbon. By prefixing n for primary sec. for secondary and tert. for tertiary.
CH 3
|

Example : CH 3 CH 2 OH ; CH 3

CH 2

CH 3 ; CH 3

CH
|

Ethyl alcohol

OH

C OH
|

CH 3

sec. butyl alcohol

tert. butyl alcohol

(ii) Carbinol system : CH 3 OH is called carbinol. All other members are considered its alkyl derivatives.
Example : CH 3 OH ;
Carbinol

CH 3
CH 3

CHOH ;

CH 3
CH 3

Di methyl carbinol

CHCH 2 OH

Isopropyl carbinol

(iii) IUPAC system : Named as alkanol.

Example : CH 3 OH ; CH 3 CH 2 CH 2 OH ; CH 3 CH 2 CH 2 CH 2 OH
Propanol -1

Methanol

Butanol - 1

(3) Structure : Oxygen of OH group is bonded to sp 3 hybrid carbon by a sigma bond.

H

H
bond

sp

sp

..
:

108.5

H
H

C O

C O H = 108.5
C O bond length = 142 pm

HC
|

H
(4) Isomerism

CH 3
|

(i) Chain isomerism : CH 3 CH 2 CH 2 CH 2 OH

Butanol -1

(ii) Positional isomerism : CH 3 CH 2 CH 2 OH

Propanol -1

CH 3

CH CH 2 OH

2 Methyl propanol -1

CH 3 CH CH 3
|

OH

Propanol - 2

(iii) Functional isomerism : CH 3 CH 2 OH

Ethanol

CH 3 OCH 3
Methoxy methane

(5) General methods of preparation of monohydric alcohols

(i) From alkyl halide : C 2 H 5 Br

KOH

Bromoethan e

C 2 H 5 OH

(Aqueous)

KBr ; C 2 H 5 Br

Ethanol

Bromoethan e

AgOH

C 2 H 5 OH

Moist silver oxide

Ethanol

AgBr

Note : 1 alkyl halide gives good yield of alcohols.

2 alkyl halide gives mixture of alcohol and alkene.
3 alkyl halide gives alkenes due to dehydrohalogenation.
CH 3

CH 3

CH 3

C CH 3

KOH

(Aqueous)

CH 3

CH 2 KBr

H 2O

2 - Methylprop ene
(Major pro duct)

Br

Oxidation number of carbon in different organic compounds are given below in increasing order,
Alkane, alkene, alkyne, alkyl halide, alcohol, carbonyl compounds, acids and acid derivative s
Oxidation number of carbon in increasing order

Alkanes and alkenes can be converted into alcohols by oxidation method while carbonyl
compounds, acid and their derivatives can be converted into alcohol by reduction.
Oxidation no. of carbon in RX and ROH is same hence RX converts into ROH by displacement
reaction.
(ii) From alkenes
(a) Hydration
Direct process :

HOH

C C

Alkene

OH H
Alcohol

Indirect process : CH 2

CH 2 HOSO 2 OH

Ethene

CH 3 CH 2 OSO 2 OH

Sulphuric acid

Ethyl hydrogen sulphate

H 2O
Boil

CH 3 CH 2 OH H 2 SO 4
Ethanol

In case of unsymmetrical alkenes

CH 3 CH

CH 2

HOSO 2 OH

Markowniko ff' ' s

Propene

rule

CH 3

CH CH 3
|

H 2O
Boil

CH 3

OSO 2OH

CH 2

H 2 SO 4

C CH 3

OH

Propan - 2- ol

CH 3

CH 3

CH 3

CH CH 3

H 2O

C CH 3
|

OH
Alcohol

(b) Oxymercuration-demercuration

H 2O

Oxymercura tion

Hg (OAc )2

Mercuric acetate

NaBH 4

C C
|

OH HgOAc

C C

Demercurat ion

OH H
Alcohol

This reaction is very fast and produces the alcohol in high yield. The alcohol obtained corresponds to
Markownikoffs addition of water to alkene.

(c) Hydroboration oxidation (HBO) : (Antimarkownikoffs orientation)

|

H 2 O 2 , OH

C C
|

C C
|

H B

H OH
Alcohol

Diborane is an electron defficient molecule. It acts as an electrophile reacting with alkenes to form alkyl
boranes R 3 B .

CH

CH 2

BH 2

RCH CH 2

CH C H 2
|

B H2

(R CH 2 CH 2 ) 2 BH

RCH 2 CH 2

(RCH 2 CH 2 ) 3 B

Dialkyl borane

Trialkyl borane

Alkyl borane

Other examples :

(CH2 CH2)3B

(B2H6)

CH2 CH2OH

H 2O
Antimarkow nikoff' s rule

1-Alkanol

CH = CH2

CH CH2

Hg(OCOCH3)2

H3O

Markowniko ff' s rule

2-Alkanol

OCOCH3 HgOCOCH3
CH2 CH3

CH CH3

CH CH3

H 2O

OH CH2 CH3
OH

Less stable

Note : Carbocation are not the intermediate in HBO hence no rearrangement take place.
(iii) By reduction of carbonyl compounds : Bouveault Blanc
RCHO
Aldehyde

H2

Pd
LiAlH4

RCH 2 OH ;

RCO R
Ketone

Primary alcohol

H2

NaBH 4
or Ni / Pt

CH R
|

OH

Secondary alcohol

H3O

CH2

CH3

CH3

H 2O

CH2
B2H6

HO CH2

CH2OH

CH3
HO

CH3
OH

LiAlH 4 also reduces epoxides into alcohol : CH 2

CH 2 LiAlH 4

CH 3

CH 2 OH

O
Hydride selectively attacks the less alkylated carbon of the epoxide.

CH 3

CH 3

CH 3

C CH 2

LiAlH4

CH 3

C CH 3
|

OH

(iv) By reduction of carboxylic acids and their derivatives

R

COOH

Carboxylic acid

(i) LiAlH4

RCH 2 OH ; RCOOH

(ii) H 2 O

RCOO R

Carboxylic acid

primary alcohol

Ester

H2

RCH 2 OH

Catalyst

R OH

Esters are also reduced to alcohols

O
||

(Bouveault Blanc reaction) CH 3

C OCH 3

Na / C 2 H 5 OH

4[H ]

CH 3 CH 2OH CH 3 OH

Methyl acetate
(Ester)

Ethanol

Methanol

Note : Reduction with aluminium isopropoxide is known as Meerwein-Ponndorff verley reduction (MPV)
reduction.
Me 2 C

Al (OCHMe 2 )

O (CH 3 )2 CHOH

CH 3

Me 2 CHOH

||

(v) By hydrolysis of ester : R

CH 3

Isopropyl alcohol

||

C OR

HO / Na (aq )

(vi) From primary amines : CH 3 CH 2 NH 2 HONO

C ONa

Sod. salt of acid

NaNO 2 / HCl

R OH .
Alcohol

CH 3 CH 2 OH

Aminoethan e

N2

H 2O

Ethanol

Note : It is not a good method of preparation of alcohols because number of by product are formed like
alkyl chloride alkenes and ethers.

(vii) From Grignard reagent

(a) With oxygen : 2 R

Mg

O2

Al 2 O3

2 R O Mg

2 HOH

2 ROH

2 Mg( X )OH

(b) With ethylene oxide

Mg

CH 2 CH 2
O

Other examples
With cyclic ester

RCH 2 CH 2

OMgX

H 2O

RCH 2 CH 2 OH

Mg( X )OH

O
+ CH3Mg Br

Cl

Br +

OMgBr
O
CH3
M
g

O
CH3
Mg Br

CH3MgBr

CH 2 O

H
Mg X

H2O

CH2OMg Br

Cl

CH2OH

||

OH
C CH3
CH3

Hydrolysis

HO

Cl

(c) With carbonyl compounds : R

OH OMgBr
CH3
CH3

OH
H2O

C R

H 2O

C R
|

OMgX

OH

Note : If R = H, product will be 1alcohol.

If R = R, product will be 2alcohol.
If carbonyl compound is ketone, product will be 3 alcohol.
It is the best method for preparation of alcohol because we can prepare every type of alcohols.
(viii) The oxo process : It is also called carbonylation or hydroformylation reaction. A mixture of alkene
carbon monoxides and hydrogen. Under pressure and elevated temperature in the presence of catalyst forms
aldehyde.
Catalyst is cobalt carbonyl hydride [CoH (CO)4 ] product is a mixture of isomeric straight chain (major) and
branched chain (minor) aldehydes. Aldehydes are reduced catalytically to the corresponding alcohols.
CH3 CH CHO
|

2CH 3

CH

CH 2

2CO

2H 2

CH 3

CH 2

CH 2

CHO

CH3 CH CH2OH

CH3
H2
Zn Cu

CH3 CH
CH2 CH2 CH2 OH
3

(6) Physical properties of monohydric alcohols

(i) Character : Alcohols are neutral substances. These have no effect on litmus paper. This is analytical
test for alcohols.
(ii) Physical state : The lower alcohols (upto C12) are colourless alcohol with characteristic smell and
burning taste. The higher members with more than 12-carbon atoms are colourless and odourless solids.
(iii) Polar character : Oxygen atom of the OH group is more electronegative than both carbon and
hydrogen. Thus the electron density near oxygen atom is slightly higher. Hydrogen bonding shown below

O- - - - H

O- - - H

O- - - - H

O . This gives polar character to OH bond.

(iv) Solubility : The lower alcohols are miscible in water.

O:

-----

1
Size of alkyl groups

Solubility

O:
|

Increase in carbon-chain increases organic part hence solubility in water decreases.

Isomeric 1, 2, 3 alcohols have solubility in order 1 > 2 > 3.
(v) Boiling points : Due to intermolecular hydrogen bonding boiling points of alcohols are higher than
hydrocarbon and ethers.

1
; B.P. follows the trends : 1 alcohols > 2 > 3 alcohol
No. of branche s

B.P.

(vi) Density : Alcohols are lighter than water. Density

Molecular masses.

(vii) Intoxicating effects : Methanal is poisonous and is not good for drinking purposes. It may cause
blindness and even death. Ethanal is used for drinking purposes.
(7) Chemical properties : Characteristic reaction of alcohol are the reaction of the OH group. The
reactions of the hydroxyl group consists of either cleavage of C O bond or the cleavage of O H bond.
|

Polar bond

C O bond is weaker in the case of tertiary alcohols due to +I effect of alkyl groups while OH bond is
weaker in primary alcohols as electron density increase between O H bond and hydrogen tends to separates
as a proton.
H

weaker bond

H ;

C O
|

R
R

CH

OH ;

R
R

Secondary

Primary

weaker bond
T ertiary

Thus primary alcohols give the most of reaction by cleavage of O H bond while tertiary alcohols are most
reactive because of cleavage of C O bond. Hence O H cleavage reactivity order : Primary > Secondary >
Tertiary and C O cleavage reactivity order : Tertiary > Secondary > Primary alcohol
(i) Reaction involving cleavage of with removal of H as proton
Alcohols are stronger acids than terminal acetylene but are not acidic enough to react with aqueous NaOH
or KOH. Acidic nature is in the order HOH

ROH

CH

CH

NH 3

RH .

Acidic nature of alcohol decrease with increase of alkyl groups on OH bonded carbon due to +I
(inductive) effect of alkyl group.

C O
|

C O
|

C O
R

(a) Reaction with Na : (Active metals)

2 RO

2M

2 ROM

H 2 (M = Na, K, Mg, Al, etc.)

Evolution of H 2 shows the presence of OH and reaction show that alcohols are acidic in nature. Alcohols
acts as Bronsted acids because they donate a proton to a strong base (: B ) .
..
O H :B
..

Example : R

Base

Alcohol
(acid)

..
O:
..

Conjugate acid

Alkoxide
(conjugate base)

On reaction of alkoxide with water, starting alcohol is obtained.

H

..
O H
..
Acid

..
RO :
..

R O

OH

Conjugate acid

Conjugate base

Base

This is the analytical test for alcohols.

(b) Reaction with carboxylic acid [Esterification] : RCO OH

acid

Conc. H2SO4

OR

RCOO R

Alcohol

H 2O

Ester

When HCl gas is used as catalyst, the reaction is called fischer-speier esterification.
Presence of bulky group in alcohol or in acid decreases the rate of esterification. This is due to steric
hinderence of bulky group. Reactivity of alcohol in this reaction is 1 o

2o

3o .

(c) Reaction with acid derivatives : (Analytical test of alcohol)

||

CH 3

C Cl

H O

Ethanoyl chloride

CH 2 CH 3

CH 3

Ethanol

C OCH 2 CH 3 HCl
Ethyl ethanoate
(Ethyl acetate)

C O

C CH 3

||

Acylation : CH 3

||

Pyridine

||

||

OCH 2 CH 3

CH 3

C OCH 2 CH 3 CH 3 COOH

Acetic anhydride

Ethyl ethanoate

(d) Reaction with grignard reagents : CH 3 OH C 2 H 5 MgBr

Methyl
alcohol

(e) Reaction with ketene : R

C 2 H 6 CH 3 OMgBr

Ethyl magnesium
bromide

O H CH 2

Ethane

CH 2

C O

CH 3

H O

||

CH 2

CH 2 CH 2
|

C O

NH

OH

CH 2

(g) Reaction with ethylene oxide : R

||

(Keto form)

(enol form)

(f) Reaction with isocyanic acid : R O H H

C O

OH

OH

C O
||

amino ester
(Urethane)

ROH
H 2O

CH 2 CH 2
|

OR

OR

1, 2-dialkoxyethane

(h) Reaction with diazomethane : R

OH

CH 2 N 2

R O CH 3

N2

(Ether)

(i) Alkylation : ROH

R 2 SO 4

RO R

(ii) Reaction involving cleavage of

R HSO 4
|

C OH with removal or substitution of OH group

(a) Reaction with hydrogen halides : Alcohols give alkyl halide. The reactivity of HX is in the order of
HI > HBr > HCl and the reactivity of ROH is in the order of allyl, benzyl > 3 > 2> 1. The reaction follows a
nucleophilic substitution mechanism.
Groves process : ROH

HX

ZnCl2

anhydrous

H 2O

If alcohols react with HI and red phosphorus, alkane will be formed.

C 2 H 5 OH

2 HI

Red P

C2 H 6

heat

Primary alcohols follow SN

I2

H 2O

mechanism . R OH 2

X - - - R - - - OH 2

H 2O

Protonated
1o alcohol

In secondary and tertiary alcohols, the SN1 mechanism operates

+

R OH

R OH 2

H2O

(b) Reaction with PCl5 : ROH

PX5

(c) Reaction with PCl3 : 3 ROH

RX

POX 3

PCl 3
Phosphorus
trichloride

Alcohol

3 RCl

Alkyl
chloride

HX ; X = Cl
H 3 PO 3
Phosphorus
acid
Pyridine

(d) Reaction with thionyl chloride [SOCl2] : ROH

SOCl 2

Al 2 O3

RNH 2

(e) Reaction with ammonia : ROH

(f) Reaction with HNO3 : R OH

NH 3

360 C

conc. HNO 3

(Analytical test for alcohols)

ROH
Al 2 O3

Primary
amine

R O

RCl

R 2 NH
Secondary
amine

SO 2
ROH
Al 2 O3

HCl

R3 N
T ertiary
amine

O
H 2O
O

alkyl nitrite

Mechanism : HNO 3

R O

O H
|

NO 3

H 2O

R ; R

NO 3

O
O

alkyl nitrite

(g) Reaction with H2SO4 [Dehydration of alcohol] : The elimination of water from a compound is known as
dehydration. The order of case dehydration is Tertiary > Secondary > primary alcohol. The products of
dehydration of alcohols are depend upon the nature of dehydrating agents and temperature.

(H )
Conc. H2SO4

CH2 = CH2

170

CH 3

CH 2

CH 3 OH CH 3

Ethylene

H 2 SO 4

OH

110
H2SO4

C2H5HSO4

CH 3

C CH 3H+/H2SO4

Shifting

CH 3 CH 3 CH 3

Ethyl hydrogen sulphate

140C

C2H5O C2H5
Diethyl ether

Alcohol leading to conjugated alkene are dehydrated to a greater extent than those of alcohols leading to
nonconjugated alkene. Thus dehydration is in order CH 2

CH

CH

CH 3

CH 3

CH 2

CH

OH
CH 3

CH 3

CH 3

CH CH 3

CH 3

H 2O

CH 3 OH

OH

CH 3 CH 3

H 2 SO 4

CH 3

C CH CH 3
|

CH 3

CH CH 3

CH 3

C
|

CH 3

CH 3

/
C
\

CH 3
CH 3

2- alkene

CH 2
CH 2

CH

CH 2

CH 3

OH

CH 2

CH CH 2

CH

CH

CH 3

CH 2

CH 3

CH 3

H 2 SO 4
H 2O

CH

CH

More amoun t

(iii) General reaction of alcohols

(a) Reduction : R OH

2 HI

(b) Oxidation : Difference between 1, 2 and 3 alcohols.

1

RCH 2 OH

CH

CrO3

OH

Carboxylic acid

CH 3

C OH
|

CH 3
Tert. butyl alcohol
(Tertiary)

C R
||

CH 3

RCOOH

Drastic conditions

CO 2

H 2O

Secondary alcohol

OH

Aldehyde

CH 3
4 [O ]
(Under strong
condition )

CH 3

Acetone
(Lesser number
of carbon atoms)

4 [O ]
(Under strong
condition )

CH 3 COOH

CO 2

H 2O

Acetic acid
(Lesser number
of carbon atoms)

Note : 3 alcohols are resistant to oxidation, but on taking stronger oxidising agent they form ketone.

(c) Catalytic oxidation/dehydrogentaion

H

Cu , 573 K

1 CH 3 C O H

CH 3

O H2

Ethanal
(Acetaldeh yde)

Ethanol
(Pri. alcohol)

CH 3

CH 3

2 CH 3

Cu , 573 K

C OH
|

CH 3

Propanone
(Acetone)

CH 3

CH 3

H2

2- Propanol
(Sec. alcohol)

3 CH 3

Cu , 573 K

C OH
|

CH 3

CH 2 H 2 O

2- Methylprop ene
(Alkene)

CH 3
2- Methylprop an - 2- ol
(Tert. alcohol)

This is dehydration process and difference between 1, 2 and 3alcohols.

(d) Oxidation through Fentons reagent : [FeSO 4

H 2 O2 ]

Mechanism
CH 3
Fe

H 2O2

Fe

CH 3

OH

OH;

CH 3

C CH 2 H

OH

OH
CH 3
|

CH 3

CH 3

C C H 2 CH 2

C C H3

OH

OH

CH 3

|
|

CH 3

C C H2
|

H 2O

OH
CH 3
|

C CH 2 CH 2

C CH 3

OH

OH

CH 3

2, 5 - dimethyl hexandiol - 2, 5

Important reagents used for oxidation of alcohols

PCC [Pyridinium chloro chromate (C 6 H 5 N H Cl CrO 3 ) ] to oxidise 1 alcohols to aldehydes and 2
alcohols to ketones.
PDC [Pyridinium di chromate (C 5 H 5 . NH ) 22 Cr 2 O 72 ] to oxidise 1 alcohols to aldehyde and 2 alcohol
to ketones.

H 2 CrO4 (chromic acid) to oxidise 1 alcohol to carboxylic acid.

CrO3 H 2 SO 4 / Acetone to oxidise 2alcohol to ketones.

Jones reagents (chromic acid in aqueous acetone solution) oxidise 1 alcohol to aldehyde and 2
alcohol to ketone without affecting (C = C) double bond.

MnO 2 selectively oxidises the OH group of allylic and benzylic 1 and 2 alcohols to give aldehyde
and ketone respectively.

N 2 O 4 in CHCl 3 (fields) oxidises primary and secondary benzyl alcohol.

(e) Self condensation : Guerbets reaction

R
R

CH 2

CH 2

OH

CH CH 2
|

NaOC 2 H 5 ,

OH

CH 2

CH 2

CH CH 2

OH

higher alcohol

(f) Reaction with cerric ammonium nitrate : Cerric ammonium nitrate

Red colour solution of

ROH

Yellow colour

complex. This is analytical test for alcohols.

(g) Iodoform test : When a few drops of alcohol are warmed with iodine and KOH yellow precipitate of
iodoform with characteristic smell is obtained. Any alcohol consists CH 3 CHOH group give iodoform test.
Example : CH 3 CH 2 OH , CH 3

CHOH

CH 3 , C6 H 5

CHOH

CH 3

Since reaction takes place with alkali solution as one of the reagents hence alkyl halide like

CH 3

CH 2 Cl and CH 3

CH R will also give this test.

|

Cl

2 NaOH

I2

CH 3 CHO
CI3

NaI
3 NaOH

CHO

HCl

NaOI

H 2 O ; CH 3 CH 2 OH

CI3 CHO
CHI 3

3 NaOH ; CI 3

2 NaOI
CHO

CH 3 CHO

NaOH

2 NaOH

CHI 3
Iodofiorm

2 HI

HCOONa

HCOOH

Other example
CHOH CH3
(O)

COCH3

COONa

KOH/I2

CHI3 +

CHOHCH3

I2/NaOH

O
COCH3

COCI3

I2

(8) Individual members of monohydric alcohols

Methanol
(i) Preparation
(a) By destructive distillation

HCl
H2O

COOH
+ CHI3

WOOD
Destructive distillation
Volatilepro
ducts
Passed into condenser

Non-volatile residue
(Charcoal)

Uncondensed gases

Distillate

(Wood gas)

allowed to settle
Lower coloured layer
(Wood tar)

Upper layer
(Pyroligneous acid)
Acetic acid 10%, methanol 2.5%
Passed through milk of lime
and distilled
and acetone 0.5%

Residue

Distillate

(Calcium acetate)

(Methanol and acetone)

Fractionally distilled

Distilled with H2SO4

Acetone (impure)

Methanol (impure)

CH3COOH

(b.pt. 56 C)

(b.pt. 64.5 C)

Acetic acid

Purified by

Purified by anhydrous

sodium bisulphite

Calcium chloride

(b) From water gas : C

H 2O

1300 o C

CO

H 2 ; CO

water gas

(c) From natural gas : 2CH 4

O2
(9 :1) by volume

2H 2
Compressed gases

ZnO Cr2 O3
300 o C

CH 3 OH
Methyl alcohol

2CH 3 OH

(ii) Physical properties

(a) It is a colourless liquid and boils at 64.5 C.
(b) It is miscible in water, good solvent for fats and oils.
(c) It is inflammable and burns with a faint luminous flame.
(d) It has pleasant smell and burning taste.
(iii) Uses
(a) For the manufacture of formaldehyde and formaline. CH 3 OH

K 2 Cr2 O7

(b) A 20% mixture of methyl alcohol and gasoline is a good motor fuel.
(c) Use as an antifreeze for automobile radiators.
(d) To denaturate ethyl alcohol, mixture is called methylated spirit.
(e) In the preparation of dyes, medicines and perfumes.

CH 2 O

H 2O

Ethanol
(i) Preparation
(a) From Ethylene : C 2 H 4

H 2O

H 3 PO 4

CH

(b) From acetylene :

|||

CH

C 2 H 5 OH Yield of ethyl alcohol is 95%.

300 o C , 70 atm

H 2O

H 2 SO 4 (40 %)
1 % HgSO 4 , 60 o C

Acetylene

CH 3 CHO

H2

CH 2
||

CHOH

CH 3 CHO
Acetaldehy de

Vinyl alcohol
(Unstable)

Ni
C 2 H 5 OH
110 140 o C Ethyl alcohol

(c) Fermentation : This word is given by Lebeig. Fermentation process is exothermic. Ethanol is prepared
by molasses and invert sugar molasses is the waste product in sugar industry. It is a mixture of sugar (30%)
and invert sugar (32-40%) combine form of glucose and fructose called invert sugar. Temperature should be
25-30C. low concentration (8-10%) is favourable.
C12 H 22 O11

H 2O

yeast cell
invertase enzyme

C 6 H 12 O 5 C 6 H 12 O 6 ; C6 H 12 O6
glucose

fructose

yeast cell
zymase enzyme

C 2 H 5 OH

CO 2

H 2O

Certain amounts of inorganic compound such as ammonium sulphate, phosphate should be added.
Oxygen is necessary for the growth of ferments. Boric acid, mercury salts etc. should not be present in the
solution as these retards the fermentation.
(d) From starch : 2(C 6 H 10 O 5 )n nH 2 O

diastase

starch

2C 6 H 12 O 6

zymase

C 2 H 6 OH

nC12 H 22 O11 ; C12 H 22 O11

maltose (wort)

CO 2

H 2O

H 2O

maltose

maltose

2C 6 H 12 O 6
glucose

energy

By this method ethanol prepared is 10-12% called wash. Raw spirit

Fractional
distillation

C 2 H 5 OH

H 2O
95 .5 %
4 .5 %
rectified spirit

Manufacturing of ethyl alcohol (absolute) from rectified spirit called Azeotrophic distillation.

Absolute alcohol is prepared by distillating rectified spirit with benzene.

The first fraction consists of constant boiling mixture of ethyl alcohol, water and benzene [18.5% +
7.4% + 74.1%] and distills over at 64.8C.
The second fraction consists of a boiling mixture of ethyl alcohol and benzene [32.4% + 67.6%] and
distills at 68 .2 o C .
Pure alcohol distills at 78 .3 o C and known as absolute alcohol (100%).

(ii) Properties : Same as monohydric alcohols.

(iii) Uses
(a) In the manufacture of alcoholic beverages.

(b) As a preservative for biological specimens.

(c) As a low freezing and mobile liquid in scientific apparatus such as thermometers and spirit levels.
(d) In hospitals as an antiseptic.
(e) As a petrol substitute (power alcohol).
(9) Interconversion of monohydric alcohols
(i) Primary alcohol into secondary alcohols
SOCl 2

C 3 H 7 OH

C 3 H 7 Cl

alc KOH

CH 3 CH

HBr

CH 2

CH 3 CH CH 3

Propene

Propan -1 - ol
(1 alcohol)

aq. KOH

CH 3 CH CH 3

Br

OH

Propan - 2 - ol
(2 alcohol)

(ii) Secondary alcohol into tertiary alcohol

OH
CH 3

CH

OMgBr

CH 3

Propan - 2- ol
(Iso - propyl alcohol)
(2 alcohol)

[O ]
K 2 Cr2 O7 / H

||

CH 3

CH 3 MgBr

C CH 3

CH 3

C CH 3

OH
H , H 2O

CH 3

CH 3

C CH 3
|

CH 3
2- Methtylpro pan - 2- ol
(3 ) (tert. butyl alcohol)

(iii) Primary alcohol into tertiary alcohol

CH 3

CH 3

CH 3 CH CH 2 OH
2 -Methylprop an -1-ol (1 )
(Iso butyl alcohol)

H 2 SO 4 , Heat
Dehydratio n

CH 3

CH 3

CH 2

CH 3

HBr
Markowniko ff' s
rule

CH 3

aq. KOH

C CH 3
|

CH 3

Br

C CH 3
|

OH
2 -Methylprop an - 2 -ol (3 )
(tert. butyl alcohol)

(iv) Lower alcohol into higher alcohol (ascent of series)

CH 3 OH

HI

CH 3 I

KCN

CH 3 CN

Methanol
(1 carbon atom)

4 (H )
Reduction

CH 3 CH 2 NH 2

HONO

CH 3 CH 2 OH
Ethanol
(2 carbon atoms)

(v) Higher alcohol into lower alcohol [Descent series]

C 2 H 5 OH
Ethanol
(2 carbon atoms)

K 2Cr2O7 , H
[O ]

CH 3 COOH

NaOH

CH 3 COONa

NaOH CaO
Heat

CH 4

Cl2

CH 3 Cl

aq. KOH

CH 3 OH
Methanol
(one carbon atom)

(10) Alcoholic beverages : Liquors used for drinking purposes containing ethyl alcohol as the principal
constituent are called alcoholic beverages. Besides alcohol, these contain large amounts of water, colouring
and flavouring materials. Alcoholic beverages are of two types :
(i)

Undistilled beverages : These are prepared from fruit juices and grains. Those prepared from
grapes and other fruit juices are known as wines. Wines contain 18-20% of ethyl alcohol and are
used as such after fermentation, i.e., with distillation. The natural wines when made stronger by
the addition of rectified alcohol are known as fortified wines.

Name

Undistilled Percentage of
alcohol

Source

Beer

3-6

Barley

Cider

2-6

Apples

Wine (Champagne)

8-10

Grapes

Claret

7-13

Grape juice

Port and Sherry (Fortified)

14-24

Grape juice

(ii) Distilled beverages : These are prepared by the fermentation of molasses, barley, maize, etc. The
fermented liquor is then distilled. These contain a higher percentage of ethyl alcohol which may be as high as
50%.
Name

Distilled Percentage of alcohol

Source

Whisky

35-40

Malt

Rum

45-55

Molasses

Gin

40-45

Maize

Brandy

40-45

Grape juice

Cognac

40-50

Grape juice

(11) Alcoholometry : The process of determining the percentage of alcohol in a given sample is known
as alcoholometry. An alcohol water mixture having specific gravity 0.91976 at 15C and containing 57.1% of
ethyl alcohol by volume or 49.3% by mass is called proof-spirit. A sample having higher percentage of ethyl
alcohol in comparison to proof-spirit is referred to as over-proof (O.P.) and the one having lower alcohol content
than proof-spirit is known as under-proof (U.P.). Thus 15 U.P. means that 100 ml of the sample contains as
much alcohol as 85 ml of proof spirit. Similarly, 15 O.P. means that 100 ml of the sample contains as much of
alcohol as 115 ml of proof spirit.
(12) Power alcohol : Alcohol used for the generation of power is called power alcohol. Generally it is a
mixture of 80% petrol and 20% absolute alcohol with cosolvent benzene. It is cheaply obtained from waste
petrol.
(13) Methylated spirit : Ethyl alcohol containing 5 to 10% of methyl alcohol is known as methylated spirit
or denatured spirit. Denaturing can also be done by adding 0.5% pyridine, petroleum naptha, rubber distillate
(caoutchoucine) or CuSO 4 .
(14) Toxicity of alcohols : The toxicity of alcohols is mainly due to their biological to oxidation takes
place in living organism. Methyl alcohol is highly toxic and its consumption causes, blindness and death. Ethyl
alcohol is non toxic but produces physiological effect disturbing brain activity on drinking. The commercial
alcohol is made unfit for drinking by mixing in it copper sulphate (which gives its colour) and pyridine (which
makes it foul smelling liquid). It is known as denaturation of alcohol.
(15) Distinguish between primary, secondary and tertiary monohydric alcohols

(i) Lucas test : A mixture of anhydrous ZnCl 2

Primary
Secondar

R CH 2

R2 CH

conc. HC / ZnCl 2 anhy.

OH

R CH 2

H 2O

conc. HCl / ZnCl 2 anhy.

OH

H 2O

conc. HCl is called as Lucas reagent.

R2

CH

ppt. appears after heating

Cl

Cl

ppt. appears with in 5 minutes

y
Tertiary

ZnCl 2 / HCl

R3 C OH

ppt. appears immediately

R3 C Cl

(ii) Victor mayer test : Also known as RBW test. RBW

Primary

P I2

C2 H 5 OH

C2 H 5 I

AgNO2

C2 H 5 NO2

Red, Blue, White test.

HONO

CH 3

NaOH

C NO2

CH 3

||

NOH

(CH 3 )2 CHOH

P I2

(CH 3 )2 CHI

HONO

(CH 3 )2

C NO2
|

NaOH

||

NONa

Nitrolicacid

Secondar

C NO2

Sod. salt of nitrolicacid (Red colour)

No reaction (Blue colour)

NO

y
Tertiary

(CH 3 )3 COH

P I2

(CH 3 )3 Cl

AgNO 2

(CH 3 )3 CNO2

HONO

No reaction (colourless)

Difference between methanol and ethanol

Methanol

Ethanol

(i) When CH3OH is heated on Cu coil it gives (i) It does not give formalin like smell.
formalin like smell.
(ii) When CH3OH is heated with salicylic acid in H- (ii) No such odour is given.
2SO4

(conc.) then methyl salicylate is formed which

has odour like winter green oil.

(iii) It does not give haloform or iodoform test.

(iii) It gives haloform test

Dihydric alcohols.
These are compound containing two hydroxyl groups. These are dihydroxy derivatives of alkanes. Their
general formula is Cn H 2n 2 O 2 . The simplest and most important dihydric alcohol is ethylene glycol. They are
classified as , , .. glycols, according to the relative position of two hydroxyl groups.
3 glycol.

is 1, 2 glycol,

is 1,

(1) Preparation
(i) From ethylene : (a) Through cold dilute alkaline solution of Bayers reagent
|
(i) dil. KMnO4

(ii) dil. OH
|

H2CO2OH

C=C

|
|

C=C

OH

OH
OH
|
|

H2O
+
(Syn-hydroxylation) H

RCO2OH

OH

OH

cis

Conc. H2SO4

OH

(Anti-hydroxylation)

HCO3H/H

OH

trans

CH 2
||

CH 2

1
O2
2

OH

Syn-addition (cis)

Alkaline
KmnO4

OH

(b) With O2 in presence of Ag :

OH

C C
OH

OH

KMnO4/OH

CC

OH

Anti addition(Trans)

CH 2

Cataly st

Ag , 200 400 C

Ethy lene

CH 2 OH

H 2O

dil. HCl

CH 2
Ethy lene oxide

CH 2 OH
Ethy lene gly col

(c) With HOCl followed by hydrolysis : (Industrial method)

CH 2
||

HOCl

CH 2

CH 2 OH

NaHCO 3

CH 2 Cl

CH 2 OH
|

CH 2 OH

Ethylene chlorohydr in

NaCl CO2

Glycol

(ii) From 1, 2 dibromo ethane [Lab method]:

CH 2 Br
|

CH 2 Br

CH 2 Br
|

CH 2 Br

2CH 3 COOK

CH 3 COOH
2 KBr

CH 2 OOCCH 3
|

NaOH

CH 2 OOCCH 3

CH 2 OH
|

CH 2 OH

Na2 CO3

H 2O

CH 2 OH
|

CH 2 OH

2 NaBr CO 2

2CH 3 COONa

Glycol diacetate

Note : Vinyl bromide is formed as by product.

Best yield of glycol can be obtained by heating 1, 2-dibromo ethane with CH 3 COOK in glacial acetic
acid.
(2) Physical properties
(i) It is a colourless, syrupy liquid and sweet in taste. Its boiling point is 197C.
(ii) It is miscible in water and ethanol in all proportions but is insoluble in ether.
(iii) It is toxic as methanol when taken orally.
(iv) It is widely used as a solvent and as an antifreeze agent.

CH 3 CH 3
|

Pinacol; 2-3-dimethyl-2, 3 butanediol : H 3 C C

C CH 3

2, 3 - Dimethyl - 2 - butene

CH 3 CH 3
(O H 2 O )
dil alk. KMnO 4

H 3C

C C CH 3
|

OH OH
Pinacol

When pinacol react with mineral acid then pinacolone is formed.

CH 3 CH 3
|

CH 3

H 3 C C C CH 3
|

H 3 C C C CH 3
||

OH OH

. This arrangement is called as Pinacol-pinacolon rearrangement

O CH 3
3, 3 - Dimethyl - 2 - butanone
(Pinacolon e)

2,3 - dimethyl - 2, 3 - butanediol

(Pinacol)

Per iodic oxidation of polyhdroxy alcohol gives

following information,
(1) There is cleavage of (C C) bond. When two OH
CHon
3 adjacent carbon positions.
groups or oxo groups are
Oxidised to ketone

CH3 C
Here cleavage takes place

OH
Oxidised to aldehyde

(2) Both CHO are present in one molecule indicating

cyclic compound.
CH2
CH2OH
OH
CH
CHO
2

HIO4

CHO

CH2

OH

CH2
(3) On one side presence of COOH group indicates
keto group adjacent to (C OH) group in (C).
CH2
OH
CH
CHO
2

HIO4

COOH

CH2

CH2
(4) Formation of two molecule of glyoxalic acid indicate
that D is cyclic compound of four C atom with C = O
and C OH groups on both sides.
OC CHOH
|

OC CHOH
Dehydration
18

OH

OH

H5PO4
H2O

18

Due to formation of stable carbocation

(3) Chemical properties

CH2 ONa

Na
50C

CH2 OH

CH2 ONa
Dialkoxide
(Disodium
glycollate)

CH2Cl

PCl5

CH2 ONa

Na
160C

CH2 Cl

PCl5

CH2 OH

CH2 Cl
1,2 Dichloroethane

CH2Br

PBr3

CH2Br

PBr3

CH2 OH

CH2Br
1, 2-dibromoethane

CH2I

PI3

CH2

I2

||

CH2I

CH2

Ethylene iodide
(Unstable)

Ethylene

CH2Cl

HCl
160C

HCl
200C

CH2OH

CH2OOCCH3

CH3COOH

CH2Cl
|

CH2Cl
CH3COOH

CH2OH

CH2OOCCH3
|

CH2OOCCH3
Glycoldiacetate

CH2OH

Conc. HNO3
Conc. H2SO4

CH2ONO2
|

CH2ONO2
Ethylene
dinitrate

heat
600C

CH2OH

CH2 CH2

Glycol

Conc. HNO3
[O]

KMnO4/H

COOH
O
|

COOHoxide
Ethylene
Oxalic acid
HCOOH
Formic acid

HIO4 or
(CH3COO)4Pb

Conc. H2SO4

HCHO
Formaldehyd
e

CH2 CH2 OH

CH2 CH2 OH
Diethylene glycol

Dehydration
ZnCl2

CH2

Isomerisation

||

CH3CHO

Acetaldehyde

CH2OH
Unstable

CH3CHO
(HCl)

CH2O
|

CH2O

Cyclic acetal

CH3

CH2O
O=C

(HCl)

CH2O
CH3

CHCH3

Cyclic
ketal

CH3
CH3
(1,3 Dioxalane)

CH2 CH2
CH2 CH2
Dioxane

Dioxalane formation provides a path of protecting a carbonyl group in reaction studied in basic medium in
which acetals are not affected. The carbonyl compound may be regenerated by the addition of periodic acid to
aqueous solution of the dioxalane or by acidic hydrolysis.

R
C

C H 2 OH

O
C

CH 2 OH

CH 2
HIO 4

|
O CH 2

CO

2 HCHO

Aldehyde is more reactive than ketone in dioxalane formation.

This part does not react due to steric hindrance

O
H 3C

+ CH2OH CH2OH
CHO

H
C

CH3

H3C

CH3

;
CH2 OH

O
CH2 OH

(4) Uses
(i) Used as an antifreeze in car radiators.

(ii) Used in the manufacture of dacron, dioxan etc.

(iii) As a solvent and as a preservatives.

(iv) As a cooling agent in aeroplanes.

(v) As an explosives in the form of dinitrate.

Trihydric alcohols.
The only important trihydric alcohol is glycerol (propane-1, 2, 3-triol). It occurs as glycosides in almost all
animal and vegetable oils and fats.
(1) Preparation
(i) From oils and fats
CH 2OOCR
CH OOCR
|

CH 2OOCR

CH 2OOCR

CH 2OH

3H 2O
steam

Oil or fat

CH OH

3 RCOOH ; CH OOCR

NaOH

CH 2OH

CH 2OOCR

NaOH

Glycerol

Oil or fat

Fatty acids

(ii) By fermentation of sugar : C 6 H 12 C 6

Glucose

Yeast
Na 2 SO 3

CH 2OH

NaOH

CH OH
|

CH 2OH

C 3 H 8 O 3 CH 3 CHO
Glycerol

Hydrolysis

CO 2

Acetaldehy de

(iii) From propene [Modern method]

CH 3
|

CH
||

CH 2
propene

CH 2Cl
Cl2
600 o C

CH
||

CH 2
Allylchloride

CH 2OH
NaOH (dil)

CH
||

CH 2
Allylalcohol

CH 2OH
HOCl

CH Cl
|

CH 2 OH
- monochloro hydrin

CH 2 OH
aq. NaOH

CH OH
|

CH 2 OH
Glycerol

3RCOONa

Sodium salt of higher fatty acids

(iv) From propenal : CH 2

H2

CHCHO

CH 2

catalyst

H 2O2 / O H

CHCH 2 OH

HOCH 2 CHOHCH 2 OH
Glycerol

(2) Physical properties

(i) It is a colourless, odourless, viscous and hygroscopic liquid.
(ii) It has high boiling point i.e., 290C. The high viscosity and high boiling point of glycerol are due to
association through hydrogen bonding.
(iii) It is soluble in water and ethyl alcohol but insoluble in ether.
(iv) It is sweet in taste and non toxic in nature.
(3) Chemical properties
CH 2 OH

CH 2ONa

(i) Reaction with sodium : CH OH

|

CH 2 OH

CH 2ONa

Na

Na

CH OH
|

Room
temperatur e

Room
temperatur e

CH 2 OH
Monosodium glycerol

CH OH
|

CH 2ONa
Disodium glycerolate

(ii) Reaction with PCl5, PBr3 and PI3

CH 2OH

CH 2Cl

(a) CH OH

3 PCl5

CH Cl

3 POCl 3

CH 2OH

CH 2Cl
Glyceryl trichloride
(1, 2, 3 - Trichloropropane)

CH 2OH

CH 2 Br

3 HCl

(b) CH OH

PBr 3

CH Br

H 3 PO 3

CH 2OH

CH 2 Br
1, 2, 3 - Tribromopr opane

CH 2OH
|

CH 2 I

CH 2

CH I

CH

(c) CH OH

PI3

||

CH 2OH

CH 2 I
(Unstable)

I2

CH 2 I
Allyliodide

(iii) Reaction with HCl or HBr

CH 2OH
|

CH OH
|

CH 2OH

110 C
HCl

CH 2Cl

CH 2OH

CH OH

CH Cl

CH 2OH

CH 2OH

- Glycerol
monochloro hydrin
(66%)

- Glycerol
monochloro hydrin
(34%)

(iv) Reaction with HI

Excess of HCl
110 o C

CH 2Cl

CH 2Cl

CH Cl

CH OH

CH 2OH

CH 2Cl

Glycerol
, - dichlorohy drin
(56%)

Glycerol
- dichlorohy drin
(44%)

CH 2OH
|

(a) CH OH
|

CH 2

CH I

CH

Warm

3 HI

CH 2 I
|

CH 2OH

CH 3

||
|

CH 2 I
Allyliodide

CH 3

HI

I2

CH 2 I
1,2,3 - Tri- iodopropan e
(Unstable)

CH 2

(b) CH

||

I2

CH I

CH 3

HI

CH

CH I

||

CH 2 I

CH 2 I

CH 2

CH 3

Allyliodide

Unstable

Propene

Isopropyl iodide

(v) Reaction with oxalic acid

(a) At 110C Glycerol is formed
O
||

CH 2OH

CH 2OOC COOH

CH OH

HOOC

COOH

100 110 C

Oxalic acid

CO 2

CH OH

CH 2OH

CH OH
|

CH 2 OH

Glycerol mono -oxalate

CH 2OH
H 2O

CH OH

H 2O

CH 2OH

CH 2O C H

CH 2OH

Glycerol mono formate

Glycerol

(b) At 260C, allyl alcohol is formed

CH 2OH

CH 2OOC

HOOC

CH OH

2 H 2O

HOOC

CH 2OH

CH OO C

CH 2
2 CO 2

||

CH CH 2 OH
Allylalcohol

CH 2OH
CH 2OH

CH 2

||

conc. H 2 SO 4 / P2 O5 / KHSO 4

(vi) Dehydration : CH OH

CH

CH 2OH

(vii) Oxidation

CHO

Acrolene or
allyl aldehyde

CHO
[O]
dil. HNO3

COOH

CH2OH
|

CHOH
|

CH2OH

[O]
KMnO4

COOH
[O]

CHOH

CHOH

|
CHO
Fentons
reagen
t

2H 2O

|CH2OH

CHOH

CH| 2OH
+

| CH2OH

Glyceraldehyde
CHOH
C Glyceric
= O acid
Glyceros
e
|
|
CH2OH
CH2OH
[O]
CH
OH
CH|2OH
| 2

COOH
Tartronic
acid

COOH
[O]

[O]

COOH

|
|

acidifie
d

Glyceraldehyd
e CO
|

2HIO4

2CH2O

Dihydroxy
CO
acetone
|

Oxalic acid

COOH

Hydroxy

Mesoxalic

Pyruvic acid

acid

COOH
acetone

COOH

+ 2HIO3 + H2O
CH2OH
COOH
+
Dihydroxy

CO

[O]

CO2 + H2O

H COOH
Formic acid

CH 2OH

CH 2ONO 2

(viii) Reaction with nitric acid : CH OH

3 HNO 3

CH 2OH

conc. H 2 SO 4

CH ONO 2
|

3H 2O

CH 2ONO 2
Glyceryl trinitrate (T .N.G.)

Dynamite is prepared from T.N.G.

Dynamite : A mixture of T.N.G. and glyceryl dinitrate absorbed in kieselguhr is called dynamite. It was
discovered by Alfred. Nobel in 1867. It releases large volume of gases and occupy 10,900 times the
volume of nitroglycerine.

C3 H5 (ONO )3

12CO2 10 H 2O 6 N 2

O2

Blasting gelatin : A mixture of glyceryl trinitrate and cellulose nitrate (gun cotton).

Cordite : It is obtained by mixing glyceryl trinitrate with gun cotton and vaseline it is smokeless explosive.
(4) Uses
(a) As antifreeze in automobile radiator.
(b) In the preparation of good quality of soap-hand lotions shaving creams and tooth pastes.
(c) As a lubricant in watches.
(d) As a preservatives.
(e) As a sweetening agent in confectionary, beverages and medicines being non toxic in nature.
(f) In manufacture of explosives such as dynamite.
(5) Analytical tests of glycerol
(i) Acrolein test : When glycerol is heated with KHSO 4 a very offensive smell is produced due to formation of
acrolein. Its aqueous solution restores the colour of schiffs reagent and reduces Fehling solution and Tollens reagent.
(ii) Dunstans test : A drop of phenophthalein is added approximately 5 ml of borax solution. The pink colour
appears on adding 2-3 drops of glycerol, pink colour disappears. The pink colour appears on heating and disappears on
cooling again.

Unsaturated alcohols.
(Allyl alcohol)

(1) Preparation
(i) From allyl halide : CH 2

CH

CH 2 Br

H 2O

CH 2

CH 2OH

CH

CH 2 OH
Allylalcohol

CH 2OOC

HOOC

(ii) By heating glycerol with oxalic acid : CH OH

2 H 2O

CH OO C

HOOC

CH 2OH

HBr

CH 2OH

CH 2
Heat
2 CO 2

||

CH
|

CH 2OH
Allylalcohol

(2) Physical properties

(a) It is colourless, pungent smelling liquid.
(b) It is soluble in water, alcohol and ether in all proportion.
H2
(3) Chemical properties
Pt

Br2

CH3CH2CH2OH
1-propanol

CH2Br CHBrCH2OH
2, 3-dibromopropanol-1

HBr

CH2BrCH2 CH2OH
3-Bromopropanol-1

HOCl

CH2OHCHClCH2OH
Glycerol -monochlorohydrin

Alk. KMnO4
(O + H2O)

CH2 = CH CH2OH

Na

(Allyl alcohol)

CH3COOH

CH2 OH CHOH CH2OH

Glycerol

CH2 = CH CH2ONa
CH2 = CH CH2OOCCH3
Allyl acetate

HCl

CH2 = CH CH2Cl
Allyl chloride

COOH
Oxidation

COOH + HCOOH
Formic acid

Oxalic
acid

Br2

CH2 CH
CH2
|

Br

Br

OH

CH2 CH COOH
[O]
HNO3

Br

Br

Zn dust
(CH3OH)

CH2 CH COOH
Acrylic acid

Phenol (Carbolic acid), C6H5OH or Hydroxy benzene.

It was discovered by Runge in the middle oil fraction of coal-tar distillation and named it carbolic acid
(carbo = coal, oleum = oil) or phenol containing 5% water is liquid at room temperature and is termed as
carbolic acid. It is also present in traces in human urine.
(1) Preparation

(i) From benzene sulphonic acid : Sodium salt of benzene sulphonic acid is fused with sodium
hydroxide (NaOH) when sodium phenoxide is formed. Sodium phenoxide on treatment with dilute acid or
carbon dioxide yields phenol. The start can be made with benzene.
H 2 SO 4 (f uming )

C6 H 6

NaOH

C 6 H 5 SO 3 H

Benzene

NaOH

C 6 H 5 SO 3 Na

Benzene sulphonic acid

Fuse

Sodium benzene sulphonate

H / H 2O

C 6 H 5 ONa
Sodium phenoxide

or CO 2 / H 2 O

C 6 H 5 OH
Phenol

This is one of the laboratory methods for the preparation of phenol. Similarly methyl phenols (cresols)
can be prepared.SO H
OK
OH
3
H+/H2O

Solid KOH
Fuse

CH3
p-Toluene

CH3

CH3
p-Cresol

(ii) From benzene diazonium chloride : When benzene diazonium chloride solution is warmed,
sulphonic acid
phenol is formed with evolution of nitrogen. The phenol from solution is recovered by steam distillation. In this
case also, benzene can be taken as the starting material. This is also a laboratory method.
C6 H 6

HNO 3

C 6 H 5 NO 2
o
Benzene H 2 SO 4 , 45 C Nitrobenze ne

Sn / HCl

C 6 H 5 NH 2
Aniline

NH2

NaNO 2

N2Cl

CH3

H 2O
Warm

C 6 H 5 OH
Phenol

OH

HNO2

m-Toluidine

C 6 H 5 N 2 Cl
Benzene diazonium chloride

HCl , 0 5 o C

HO2

m-Toluene

CH3

m-Cresol

CH3

Note : Diazonium salts are obtained from

aniline and its derivatives by a process called diazotisation.
diazonium chloride
(iii) From Grignard reagent : Chlorobenzene or bromobenzene is first converted into phenyl magnesium halide in
presence of dry ether. The Grignard reagent on reaction with oxygen and subsequent hydrolysis by a mineral acid, yields
phenol.
C6 H 5 Br

Mg

Ether

C6 H 5 MgBr

Bromobenze ne

O2

C6 H 5 OMgBr

Phenyl magnesium bromide

H 2O
H

C6 H 5 OH
Phenol

(iv) From salicylic acid : When salicylic acid or its sodium salt is distilled with soda lime, decarboxylation occurs and
phenol is formed.
OH
OH
COOH
CaO
+ 2NaOH
+ Na2CO3 + H2O
Salicylic acid

Phenol

(v) Middle oil of coal tar distillation : Middle oil of coal-tar distillation has naphthalene and phenolic compounds.
Phenolic compounds are isolated in following steps.
Step I : Middle oil is washed with H 2 SO 4 . It dissolves basic impurities like pyridine (base).
Step II : Excessive cooling separates naphthalene (a low melting solid)
Step III : Filtrate of step II is treated with aqueous NaOH when phenols dissolve as phenoxides. Carbon dioxide is
then blown through the solution to liberate phenols.

C 6 H 5 OH

NaOH

C 6 H 5 ONa

H 2O

CO 2 , H 2 O

C 6 H 5 OH

Na 2 CO 3

Step IV : Crude phenol (of step III) is subjected to fractional distillation.

180C

Crude phenols

fractional
distillation

190-203C
211-235C

o, m, p-cresols

xylols (hydroxy xylenes)

(vi) Raschigs process : Chlorobenzene is formed by the interaction of benzene, hydrogen chloride and air at 250C
in presence of catalyst cupric chloride and Ferric chloride it is hydrolysed by superheated steam at 425C to form phenol

and HCl. This is one of the latest methods for the synthesis of phenol. HCl may be again used to convert more of benzene
into chlorobenzene.
C6 H 6

1
O2
2

HCl

Benzene

CuCl 2 / FeCl 3

H 2 O ; C 6 H 5 Cl

C 6 H 5 Cl

250 C

Chlorobenz ene

H 2O

Chlorobenz ene

425 o C

C 6 H 5 OH

steam

HCl

Phenol

(vii) Dow process : This process involves alkaline hydrolysis of chlorobenzene. Large quantities of phenol are formed
by heating chlorobenzene with a 10% solution of caustic soda or sodium carbonate at 300C under a very high pressure
(200 atm).
C 6 H 5 Cl

2 NaOH

Chlorobenz ene

300 o C
High pressure

C 6 H 5 ONa

NaCl

H 2O

sodium phenoxide on treatment with mineral acid yields phenol.

2C6 H 5 ONa

H 2 SO 4

2C6 H 5 OH

Na2 SO 4

(viii) Oxidation of benzene : This is the latest method for the manufacture of phenol. The mixture of benzene and
air is passed over vanadium pentaoxide at 315C. Benzene is directly oxidised to phenol.
2C 6 H 6

O2

V2 O5
315 o C

2 C 6 H 5 OH

(ix) Oxidation of isopropyl benzene [Cumene] : Cumene is oxidised with oxygen or air into cumene hydroperoxide
in presence of a catalyst. This is decomposed by dilute sulphuric acid into phenol and acetone.
H3C
AlCl3

+ CH3CH2CH2Cl

CH3

O OH

CH
O2
Catalyst

AlCl3

+ CH3CH = CH2

Cumene

OH

C(CH3)2

H2O/H

+ (CH3)2CO

Cumene

Phenol

Acetone

hydroperoxide

(2) Physical properties

(i) Phenol is a colourless crystalline, deliquescent solid. It attains pink colour on exposure to air and light.
(ii) They are capable of forming intermolecular H-bonding among themselves and with water. Thus, they have high
b.p. and they are soluble in water.
H
+
+

H O-------H + O-------H
O-------H O------
+

H O-------H O-------H O-------H O------(crossed intermolecular H-bonding between water

(intermolecular H-bonding among phenol molecules)
Due to intermolecular H- bonding and high dipole moment, m.p.
b.p. molecules)
of phenol are much higher than that of
andand
phenol
hydrocarbon of comparable molecular weights.

Compounds

Molecular weight

Phenol

94 g mol

Toluene

92 g mol

Boiling point

Melting point

182C

41C

111C

95C

(iii) It has a peculiar characteristic smell and a strong corrosive action on skin.
(iv) It is sparingly soluble in water but readily soluble in organic solvents such as alcohol, benzene and
ether.
(v) It is poisonous in nature but acts as antiseptic and disinfectant.
(3) Chemical properties
(i) Acidic nature : Phenol is a weak acid. The acidic nature of phenol is due to the formation of stable phenoxide ion
in solution.

C 6 H 5 OH

H2O C6 H 5 O

H3O

Phenoxide ion

The phenoxide ion is stable due to resonance.

O

..

..
..

The negative charge is spread throughout the benzene ring. This charge delocalisation is a stabilising factor in the
phenoxide ion and increase acidity of phenol. [No resonance is possible in alkoxide ions (RO) derived from alcohols. The
negative charge is localised on oxygen atom. Thus alcohols are not acidic].

Note :

Phenols are much more acidic than alcohols but less so than carboxylic acids or even carbonic acid. This is
indicated by the values of ionisation constants. The relative acidity follows the following order

K a (approx. )

(10 5 )
RCOOH

Carboxylic acid

(10 7 )
H 2CO3

(10 10 )
C6 H 5 OH

Carbonic acid

Phenol

(10 14 ) (10 18 )
HOH
ROH
Water

Alcohols

Effects of substituents on the acidity of phenols : Presence of electron attracting group, (e.g.,

NO 2 , X, NR 3 ,
CN, CHO, COOH) on the benzene ring increases the acidity of phenol as it enables the ring to draw more electrons
from the phenoxy oxygen and thus releasing easily the proton. Further, the particular effect is more when the
substituent is present on o- or p-position than in m-position to the phenolic group.
The relative strengths of some phenols (as acids) are as follows :
p-Nitrophenol > o-Nitrophenol > m- Nitrophenol > Phenol
Presence of electron releasing group, (e.g., CH 3 , C2 H 5 , OCH 3 , NR 2 ) on the benzene ring decreases the
acidity of phenol as it strengthens the negative charge on phenoxy oxygen and thus proton release becomes difficult.
Thus, cresols are less acidic than phenol.
However, m-methoxy and m-aminophenols are stronger acids than phenol because of I effect and absence of +R
effect.
m-methoxy phenol > m-amino phenol > phenol > o-methoxy phenol > p-methoxy phenol
Greater the value of K a or lower the value of pK a , stronger will be the acid. Some other examples of acidic nature
of phenols are,
Chloro phenols : o- > m- > pCresols : m- > p- > oDihydric phenol : m- > p- > oThe acidic nature of phenol is observed in the following :

(a) Phenol changes blue litmus to red.

(b) Highly electropositive metals react with phenol. 2C6 H 5 OH

2 Na

(c) Phenol reacts with strong alkalies to form phenoxides. C6 H 5 OH

2C6 H 5 ONa
NaOH

H2

C6 H 5 ONa

H 2O

However, phenol does not decompose sodium carbonate or sodium bicarbonate, i.e., CO 2 is not evolved because
phenol is weaker than carbonic acid.
(ii) Reactions of OH group
(a) Reaction with FeCl3 : Phenol gives violet colouration with ferric chloride solution (neutral) due to the formation
of a coloured iron complex, which is a characteristic to the existence of keto-enol tautomerism in phenols (predominantly
enolic form).
OH
O
OH
3

;
Enol

+ FeCl3

3H + Fe

+ 3HCl

O
6

Keto

This is the test of phenol.

(b) Ether formation : Phenol reacts with alkyl halides in alkali solution to form phenyl ethers (Williamsons
synthesis). The phenoxide ion is a nucleophile and will replace halogenation of alkyl halide.
C 6 H 5 OH

NaOH

C 6 H 5 ONa H 2 O ; C 6 H 5 ONa

ClCH 3

C 6 H 5 OCH 3
Methyl phe nyl ether (Anisole)

Sod. phenoxide

C 6 H 5 OK

IC2 H 5

KI ; C 6 H 5 ONa

C6 H 5

O C2 H 5
Ethoxy benzene (Phenetol)

Cl

HC (CH 3 )2
Isopropyl chloride

C6 H 5

NaCl
O

HC (CH 3 )2

Isopropyl phenyl ether

Ethers are also formed when vapours of phenol and an alcohol are heated over thoria (ThO 2 ) or Al2 O3 .
C 6 H 5 OH

, ThO 2

HOCH 3

C6 H 5

O CH 3

Methoxy benzene

(c) Ester formation : Phenol reacts with acid chlorides (or acid anhydrides) in alkali solution to form phenylesters
(Acylation). This reaction (Benzoylation) is called Schotten-Baumann reaction.
O
||

C6 H 5 OH

NaOH

C6 H 5 ONa

H 2 O ; C 6 H 5 ONa
Sodium phenoxide

C 6 H 5 OH

(CH 3 CO ) 2 O

NaOH

Acetic anhydride

C 6 H 5 OOCCH

C 6 H 5 OOCCH

Acetyl chloride

NaCl

Phenyl acetate

CH 3 COOH ;

Phenyl acetate (ester)

||

C6 H 5 OH

Cl C CH 3

Cl C C6 H 5

NaOH

||

C6 H 5

Benzoyl chloride

O C C6 H 5 NaCl

H 2O

Phenyl ben zoate

The phenyl esters on treatment with anhydrous AlCl3 undergoes Fries rearrangement to give o- and p- hydroxy
ketones.

OH

OOCCH3

OH
COCH3

AlCl3 (anhydrous)
heat

Phenyl acetate

COCH3
p

ohydroxy acetophenone

(d) Reaction with PCl5 : Phenol reacts with PCl5 to form chlorobenzene. The yield of chlorobenzene is poor and
mainly triphenyl phosphate is formed.
C6 H 5 OH PCl5
C6 H 5 Cl POCl 3

HCl ; 3C6 H 5 OH

POCl 3

(C6 H 5 )3 PO4

3 HCl

(e) Reaction with zinc dust : When phenol is distilled with zinc dust, benzene is obtained.

C6 H 5 OH

Zn

C6 H 6

ZnO

(f) Reaction with ammonia : Phenol reacts with ammonia in presence of anhydrous zinc chloride at 300C or
(NH 4 )2 SO 3 / NH 3 at 150C to form aniline. This conversion of phenol into aniline is called Bucherer reaction.
C 6 H 5 OH

ZnCl2

NH 3

300 o C

C 6 H 5 NH 2

H 2O

Aniline

(g) Action of P2S5 : By heating phenol with phosphorus penta sulphide, thiophenols are formed.
5 C 6 H 5 OH P2 S 5
5 C 6 H 5 SH P2 O 5
Thiophenol

(iii) Reactions of benzene nucleus : The OH group is ortho and para directing. It activates the benzene nucleus.
(a) Halogenation : Phenol reacts with bromine in carbon disulphide (or CHCl 3 ) at low temperature to form
mixture of ortho and para bromophenol.
OH

OH
+ Br2

OH

OH

OH
Br

Br

(CS2)

Br

+ 3Br2

+ 3HBr

o-Bromophenol

Br

Br

2, 4, 6-Tribromophenol

p-Bromophenol

Phenol forms a white precipitate with excess of bromine water yielding 2, 4, 6-tribromophenol.
(b) Sulphonation : Phenol reacts with conc. H 2 SO 4 readily to form mixture of ortho and para hydroxy benzene
sulphonic acids.
OH

OH

OH
SO3H
(H2SO4)

+
o-Hydroxybenzene
sulphonic acid

SO3H
p-Hydroxybenzene

sulphonic acidat 100C, it gives mainly the paraAt low temperature (25C), the ortho-isomer is the major product, whereas
isomer.
(c) Nitration : Phenol reacts with dilute nitric acid at 5-10C to form ortho and para nitro phenols, but the yield is
poor due to oxidation of phenolic group. The OH group is activating group, hence nitration is possible with dilute nitric
acid.
OH
OH
OH
NO2
HNO3(dil.)
+
(5-10C)
o-Nitrophenol

NO2
p-Nitrophenol
It is believed that the mechanism of the above reaction involves the formation of o- and p- nitroso phenol with
nitrous acid, HNO 2 (NaNO2 HCl) at 0-5C, which gets oxidised to o- and p- nitrophenol with dilute nitric acid.
OH
OH
OH
OH
OH
NO
2
NO
[O]
HONO
+
+
HNO3 (Dil.)
(0-5C)
o-Nitrosophenol

NO

NO
p- 2

o-

p-Nitrosophenol
Nitrophenol

However, when phenol is treated with concentrated HNO 3 in presence of concentrated H 2 SO 4 , 2,4,6trinitrophenol (Picric acid) is formed.

OH

OH
O2N

NO2

HNO3 (conc.)
H2SO4(conc.)

NO2
2, 4, 6-Trinitrophenol
(picric acid)

To get better yield of picric acid, first sulphonation of phenol is made and then nitrated. Presence of

SO 3 H

group prevents oxidation of phenol.

(d) Friedel-Crafts reaction : Phenol when treated with methyl chloride in presence of anhydrous aluminium
chloride, p-cresol is the main product. A very small amount of o-cresol is also formed.
OH

OH

OH

CH3
AlCl3

+ CH3Cl

+
o-cresol

CH3
p-Cresol
(major product)

RX and AlCl3 give poor yields because AlCl3 coordinates with O. So Ring alkylation takes place as follows,

C6 H 5 OH

AlCl3

C6 H 5 OAlCl 2

HCl

Thus to carry out successful Friedel-Crafts reaction with phenol it is necessary to use a large amount of AlCl3 . The
Ring alkylation takes place as follows :

C 6 H 5 OH

CH 3 CH CH 2
(CH 3 ) 2 CH OH

OH

H 2 SO 4
or HF

/
o - and p - C 6 H 4
\

OH
CH (CH 3 )2

OH

OH
COCH3

+ CH3COCl

anhydrous AlCl3

Acetyl chloride

COCH3
ortho
hydroxy acetophenone

(e) Kolbe-Schmidt reaction (Carbonation) : This involves the interaction of sodium phenoxide with carbon dioxide at
130-140C under pressure of 6 atmospheres followed by acid hydrolysis, Salicylic acid (o-Hydroxy benzoic acid) is formed.

OH
COOC6H5

ONa

OH

OCOONa

Salol

OH

OCOCH3

COONa
130-140C

+ CO2

COOH

COOH

Rearrangement

6 atm

CH3COCl

H2 O
Sodium salicylate

Sodium phenyl

Salicylic acid
Aspirin

carbonate

OH
COOCH3
CH3OH

Winter green

The probable mechanism is : C 6 H 5 OH

C6 H 5 O

H
OH

O
H

CO

+C=O
||

OH
CO

H
+
+H

COOH

H
||

||

O
At higher temperature (250-300C), p-isomer is obtained.
O
O
(f) Reimer-Tiemann reaction : Phenol, on refluxing with chloroform and sodium hydroxide (aq.) followed by acid
hydrolysis yields salicylaldehyde (o-hydroxy benzaldehyde) and a very small amount of p-hydroxy benzaldehyde.
However, when carbon tetrachloride is used, salicylic acid (predominating product) is formed.
OH
OH

CHCl3
NaOH(aq.)

ONa

CHCl2

OH
+

NaOH

H
H2O

CHO

Salicylaldehyde

60C

OH
CCl4
NaOH(aq.)

ONa

CHO

OH
+

NaOH

H
H2O

CCl3
COONa
COOH
Salicylic acid
The electrophile is dichloromethylene : CCl 2 generated from chloroform by the action of a base.
60C

OH

CHCl 3 HOH

: C Cl 3

Cl

: CCl 2
Dichloro carbene

Reimer-Tiemann reaction involves electrophilic substitution on the highly reactive phenoxide ring.
C 6 H 5 OH

C6 H 5 O

Phenoxide

Attack of electrophile (: CCl 2 )

O
CHCl2
+ : CCl2

O
CH(OH)2

CHCl2
+ 2NaOH

CHO

OH
CHO
+ H+

Hydrolysis
H2O

CHO
Salicylaldehyde

(g) Gattermanns reaction : Phenol, when treated with liquid hydrogen cyanide and hydrochloric acid gas in
presence of anhydrous aluminium chloride yields mainly p-hydroxy benzaldehyde (Formylation).

HCl

HC

AlCl3

ClCH

NH

OH

OH

+ ClCH = NH

OH

AlCl3

H2O

HCl

NH3

CH = NH

CHO
p-Hydroxy
benzaldehyde

(h) Mercuration : Phenol when heated with mercuric acetate undergoes mercuration to form o- and pisomers.
OH

OH

OH
HgOCOCH3
+ (CH3COO)2Hg

+
o-Hydroxy phenyl

HgOCOCH3

mercuric acetate

p-Hydroxy phenyl
mercuric acetate

(i) Hydrogenation : Phenol, when hydrogenated in presence of a nickel catalyst at about 150-200C,
forms cyclohexanol.
OH
OH

+ 3H2

Ni
150-200C

Phenol

Cyclohexanol (C6H11,OH)

(C6H5OH)

(used as a good solvent)

(iv) Miscellaneous reactions

(a) Coupling reactions : Phenol couples with benzene diazonium chloride in presence of an alkaline
solution to form a red dye (p-hydroxy azobenzene).

N = NCl +

NaOH
HCl

OH

Benzene diazonium chloride

N=N

Phenol

OH

p-Hydroxyazobenzene

Phenol couples with phthalic anhydride in presence of concentrated H 2 SO 4 to form a dye,

(phenolphthalein) used as an indicator.
O

||

||

C OH
C OH

C
C

||
Phthalic acid

O
||

Conc. H2SO4
(H2O)

C
C

Phthalic anhydride

||

(b) Condensation with formaldehyde : Phenol condenses with formaldehyde (excess) in presence of
OH
OH
OH
OH
Phenolphthalein
(2 molecules)
sodium hydroxide or acid (H ) for about aPhenol
week
to form a polymer known
as bakelite (a resin).
OH

OH

OH

OH

CH2OH
+ CH2O

NaOH

CH2

Condensation with
HCHO

+
o-hydroxy benzyl
alcohol

CH2OH

continues give

OH
CH2

CH2

p-hydroxy benzyl
alcohol

CH2

CH2

Polymer Bakelite (a resin)

(c) Liebermanns nitroso reaction : When phenol is reacted with NaNO 2 and concentrated H 2 SO 4 , it
gives a deep green or blue colour which changes to red on dilution with water. When made alkaline with NaOH
original green or blue colour is restored. This reaction is known as Liebermanns nitroso reaction and is used as
a test of phenol.
OH

HONO

NO

OH

Quinoxim

p-Nitrosophenol

N OH + H

OH

NOH

H2SO4
H2O

OH

NaOH
H2O

Sod. Salt of indophenol

(blue)

Indo phenol (Red)

(d) Oxidation : Phenol turns pink or red or brown on exposure to air and light due to slow oxidation. The
colour is probably due to the formation of quinone and phenoquinone.
C6H5OH or

OH

O2 by air
or CrO3

C6H5OH

OH - - - O

Phenoquinone (pink)

p-benzoquinone

OH

O - - - HO

O
[O]
CrO2Cl2

+ H2O

Phenol

O
But on oxidation with potassium persulphatep-benzoquinone
in alkaline solution, phenol forms 1, 4-dihydroxy benzene
(Quinol). This is known as Elbs persulphate oxidation.
OH

OH
K2S2O8 in
alkaline solution

Phenol

OH

Quinol

(4) Uses : Phenol is extensively used in industry. The important applications of phenol are :
(i) As an antiseptic in soaps, lotions and ointments. A powerful antiseptic is Dettol which is a phenol
derivative (2, 4-dichloro-3, 5-dimethyl phenol).
(ii) In the manufacture of azo dyes, phenolphthalein, etc.
(iii) In the preparation of picric acid used as an explosive and for dyeing silk and wool.
(iv) In the manufacture of cyclohexanol required for the production of nylon and used as a solvent for
rubber and lacquers.
(v) As a preservative for ink.
(vi) In the manufacture of phenol-formaldehyde plastics such as bakelite.
(vii) In the manufacture of drugs like aspirin, salol, phenacetin, etc.
(viii) For causterising wounds caused by the bite of mad dogs.
(ix) As a starting material for the manufacture of nylon and artificial tannins.
(x) In the preparation of disinfectants, fungicides and bactericides.
(5) Tests of phenol : (i) Aqueous solution of phenol gives a violet colouration with a drop of ferric
chloride.
(ii) Aqueous solution of phenol gives a white precipitate of 2, 4, 6-tribromophenol with bromine water.
(iii) Phenol gives Liebermanns nitroso reaction.
Phenol in conc. sulphuric acid

Red colour

NaNO 2

Blue colour

NaOH
(Excess)

Excess of water

(iv) Phenol combines with phthalic anhydride in presence of conc. H 2 SO 4 to form phenolphthalein which
gives pink colour with alkali, and used as an indicator.
(v) With ammonia and sodium hypochlorite, phenol gives blue colour.
Difference between phenol and alcohol
Property
Odour
Nature, reaction with alkali
Reaction with neutral FeCl3
Reaction with halogen acids
Oxidation
Reaction with HCHO
Liebermanns nitroso reaction
Coupling with benzene diazonium
chloride
Reaction with PCl5
Iodoform test

Phenol (C6H5OH)
Typical phenolic odour

Alcohol (C2H5OH)
Pleasant alcoholic odour

Acidic, dissolves in sodium hydroxide

forming sodium phenoxide.
Gives violet colouration due to
formation of complex compound.
No reaction with halogen acids.
Pink or brown colour due to formation
of quinone and phenoquinone.
Forms polymer (bakelite).
Positive.

Neutral, no reaction with alkalies.

Forms azo dye.

Does not form any dye.

Mainly forms triphenyl phosphate.

Does not show.

Forms ethyl chloride

Positive.

No reaction.
Forms ethyl halides.
Undergoes
oxidation
to
acetaldehyde and acetic acid.
No reaction.
Does not show.

give

Derivatives of phenol.
NITROPHENOLS

(1) Preparation
(i) Phenol easily undergoes nitration. Ortho and para nitrophenols are obtained by nitration of phenol with
dilute HNO 3 in cold. Ortho isomer is separated by steam distillation as it is steam volatile.
OH

OH

OH
NO2

Dil. HNO3

+
o-isomer
(steam volatile)

NO2
p-isomer
(non-volatile)

(ii) o- and p-forms are also obtained by treating chloro or bromo nitrobenzene with caustic alkali at 120C.
Cl
OH
NaOH
C6 H 4
C6 H 4
NO 2
NO 2
o - and p -chloro nitrobenze ne

o - and p - nitropheno l

(iii) When heated with solid potassium hydroxide, nitrobenzene produces a mixture of o- and pnitrophenols.
OH
Solid KOH
C 6 H 5 NO 2
C6 H 4
heat
Nitrobenze ne
NO 2
o - and p - nitropheno l

(iv) m-Nitrophenol is obtained from m-dinitrobenzene. One of the nitrogroup is converted into
group which is diazotised. The diazonium compound on boiling yields m-nitrophenol.
NO2

NH2

N2Cl

NH4HS

NaNO2/HCl

or Na2S

0-5C

NO2

OH

H2O

NO2

m-Dinitrobenzene

NO2

m-Nitroaniline

NH 2

m-Nitrobenzene

NO2
m-Nitrophenol

diazonium chloride

(2) Properties : o-Nitrophenol is a yellow coloured crystalline compound, while m- and p-isomers are
colourless crystalline compounds.
Isomer
ortho meta para
m.pt. ( C)
45
97
114
the lowest melting point of o-isomer is due to intramolecular hydrogen bonding whereas meta and
para isomers possess intermolecular hydrogen bonding and thus, they have higher melting points.
They are stronger acids than phenol. The order is :
p-isomer > o-isomer > m-isomer > phenol
When reduced, they form corresponding aminophenols. o- and p-Nitrophenols react with bromine water
to form 2, 4, 6-tribromophenol by replacement of nitro group.
OH
Br
Br
OH
/
Br2
C6 H 4
\
NO 2
o - or p -isomer
Br
2,4,6 Tribromophenol

Picric acid (2, 4, 6-trinitrophenol)

(1) Preparation : It is obtained when phenol is treated with conc. HNO 3 . However, the yield is very poor.
It is prepared on an industrial scale :
(i) From chlorobenzene
Cl
Cl
OH
OH
NO2
NO2
O2N
NO2
HNO3
H2SO4

Aq. Na2CO3

HNO3
H2SO4

Chlorobenzene

NO2
2, 4-Dinitrochlorobenzene

NO2

NO2
Picric acid
(2, 4, 6-Trinitrophenol)

(ii) From phenol through disulphonic acid

OH

OH

OH
SO3H
HNO3

H2SO4

O2N

NO2

Phenol

SO3H
Phenol disulphonic acid

NO2
Picric acid

(iii) It may be prepared in the laboratory by oxidation of s-trinitrobenzene (TNB) with potassium
ferricyanide.
OH
O2N

NO2
+ [O]

O2N

Ke3Fe(CN)6

NO2

NO2

NO2
Picric acid

(2) Properties : It is a yellow crystalline solid, m.pt. 122C. it is insoluble in cold water but soluble in hot
water and in ether. It is bitter in taste. Due to the presence of three electronegative nitro groups, it is a stronger
acid than phenol and its properties are comparable to the carboxylic acid. It neutralises alkalies and
decomposes carbonates with evolution of carbon dioxide.
Dry picric acid as well as its potassium or ammonium salts explode violently when detonated. It reacts
with PCl5 to form picryl chloride which on shaking with NH 3 yields picramide.
OH
O2N

Cl
NO2
PCl5

NH2

O2N

NO2

NH3

O2N

NO2

H2O

NO2

NO2
Picryl chloride

NO2
Picramide

When distilled with a paste of bleaching powder, it gets decomposed and yields chloropicrin, CCl3 NO2 , as
one of the products and is thus employed for the manufacture of tear gas.
It forms yellow, orange or red coloured molecular compounds called picrates with aromatic hydrocarbons,
amines and phenols which are used for characterisation of these compounds.

Note : Picrates are explosive in nature and explode violently when heated. These are prepared carefully.
(3) Uses : It is used as a yellow dye for silk and wool, as an explosive and as an antiseptic in treatment of burns.

Catechol (1, 2-Dihydroxy benzene)

(1) Preparation
(i) By fusion of chlorosubstituted phenolic acid with caustic soda. or by hydrolysis of o-dichlorobenzene or
o-chlorophenol with dilute NaOH solution at 200C and in the presence of copper sulphate catalyst.
OH

OH
Cl

OH
NaOH

;
+ CO2 + NaCl

Catechol

COOH

Cl

ONa
Cl

OH
ONa

NaOH
2+
200C, Cu

OH
+

H /H2O

(ii) By fusing alkali salt of o-phenol sulphonic acid with caustic alkali and then hydrolysing the product
with mineral acid.
OH
OK
OH
SO3K
OK
OH
2HCl
+ 3KOH

(iii) It may be conveniently prepared in the laboratory by treating salicylaldehyde with alkaline H 2 O 2 .
CHO
OH
+ H2O2 + NaOH
+ HCOONa + H2O
OH
OH
Salicylaldehyde
Catechol

(2) Properties : It is a colourless crystalline solid, m.pt. 105C. it is soluble in water. It is affected on
exposure to air and light. It acts as a reducing agent as it reduces Tollens reagent in cold and Fehlings solution
on heating. With silver oxide it is oxidised to o-benzoquinone.
OH

O
OH
O
+ Ag2O

+ 2Ag + H2O

o-Benzoquinone

It forms insoluble lead salt (white ppt.) when treated with lead acetate solution and gives green colour with
FeCl3 which changes to red on adding Na 2 CO 3 solution. It forms alizarin dye stuff when condensed with
phthalic anhydride in the presence of sulphuric acid.
O
O
OH
OH
||

||

OH

Con H2SO4

O+

OH

(H2O)

||

||

Phthalic anhydride

Alizarin

O
O
(iii) Uses : It finds use as photographic developer, in the manufacture of alizarin and adrenaline hormone
and as an antioxidant (inhibitor in auto oxidation) for preserving gasoline.

Resorcinol (1, 3-Dihydroxy benzene)

(1) Preparation : It is prepared by alkali fusion of 1,3, benzene disulphonic acid (Industrial method).
SO3H

ONa
NaOH

OH
HCl

Fuse

SO3H

ONa

OH

(2) Properties : It is a colourless crystalline solid, m.pt. 110C. it is affected on exposure by air and light. It
is soluble in water, alcohol and ether. It shows tautomerism. Its aqueous solution gives violet colour with FeCl3
. It reduces Fehlings solution and Tollens reagent on warming.
With bromine water, it gives a crystalline precipitate, 2, 4, 6-tribromoresorcinol.
OH

OH
Br

Br

+ 3Br2

+ 3HBr

OH

OH
Br

On nitration, it forms 2, 4, 6-trinitro-1, 3-dihydroxybenzene.

OH

OH
O2N

NO2

HNO3
H2SO4

OH

OH
NO2
Styphnic acid

It condenses with phthalic anhydride and forms fluorescein.

OH

O
O=C

OH

OH
Conc. H 2SO4

C=O+

O=C

2H2O

OH
OH

Phthalic anhydride

Fluorescein

Resorcinol
(2 moles)

With nitrous acid, it forms 2, 4-dinitrosoresorcinol

OH

OH

O
NO

NOH

OH

HNO2

OH
NO

NOH

OH

Resorcinol behaves as a tautomeric compound. This is shown by the fact that it forms a dioxime and a
bisulphite derivative.
OH
O

OH

Dienol form

Diketo form

(3) Uses
(i) It is used as antiseptic and for making dyes.
(ii) It is also used in the treatment of eczema. 2, 4, 6-trinitroresorcinol is used as an explosive.

Hydroquinone or quinol (1, 4-Dihydroxy benzene)

(1)
(H 2 SO 3

Preparation
H 2 O SO 2 ) .

It

is

formed

by

reduction

O + SO2 + 2H2O

of

p-benzoquinone

HO

with

sulphurous

acid

OH + H2SO4

H2SO3 + H2O
Quinol

(p-Benzoquinone is obtained by oxidation of aniline)

NH2

OH

[O]

Fe/H2O

MnO2/H2SO4

[H]

OH
Quinol

(2) Properties : It is a colourless crystalline solid, m.pt. 170C. it is soluble in water. It also shows
tautomerism. It gives blue colour with FeCl3 solution.

It acts as a powerful reducing agent as it is easily oxidised to p-benzoquinone. It reduces Tollens reagent
and Fehlings solution.
[O]

OH

HO

FeCl3

p-Benzoquinone

Due to this property, it is used as photographic developer.

(3) Uses : It is used as an antiseptic, developer in photography, in the preparation of quinhydrone
electrode and as an antioxidant.
Trihydric Phenols : Three trihydroxy isomeric derivatives of benzene are Pyrogallol (1, 2, 3), hydroxy
quinol (1, 2, 4) and phloroglucinol (1, 3, 5).
Pyrogallol is obtained by heating aqueous solution of gallic acid at 220C.

OH

OH
OH

OH
heat

+ CO2

220C

OH

HOOC

OH

Gallic acid

Pyrogallol

Phloroglucinol is obtained from trinitrotoluene (TNT) by following sequence of reactions.

CH3
COOH
COOH
O2N

NO2

NO2

O2N

NO2

H2N

NH2

HO

KMnO4

Fe/HCl

H2O/H

[O]

[H]

100C

NO2

OH

+ CO2 + 3NH4Cl

NH2

OH

2, 4, 6-trinitro toluene

Phloroglucinol

Hydroxyquinol is prepared by the alkaline fusion of hydroquinone in air.

OH

OH
OH
+ O2

OH
Quinol

NaOH
Fuse

OH
Hydroxy Quinol

The three isomers are colourless crystalline compounds. All are soluble in water and their aqueous
solutions give characteristic colour with FeCl3 . For example, Pyrogallol-red; Hydroxy quinol-greenish brown;
Phloroglucinol-bluish violet. Alkaline solutions absorb oxygen rapidly from air.
Uses of pyrogallol
(i) As a developer in photography.
(ii) As a hair dye.
(iii) In treatment of skin diseases like eczema.
(iv) For absorbing unreacted oxygen in gas analysis.

Introduction of ether.
Ethers are anhydride of alcohols, they may be obtained by elimination of a water molecule from two
alcohol molecules.
R OH HO R
R O R H 2O
Ether

General formula is Cn H 2n 2 O
(1) Classification : It may be divided in two category.
(i) Aliphatic ethers : Both R of ether are alkyl group.
H
Example : CH 3

CH 3 , CH 3

C O CH 2

CH 2

Dimethyl ether

CH 3 .

CH 3
Isopropyl propyl ether

(ii) Aromatic ethers : In which either one or both R of ether are aryl groups.
Example : C 6 H 5 O CH 3 or C 6 H 5 O C 6 H 5
Methyl phe nyl ether

Diphenyl ether

Aromatic ethers are divided in two category.

(a) Phenolic ethers : Ethers in which one of the group is aryl and other one is alkyl.
Example : C 6 H 5 O CH 3 .
methyl phe nyl ether

(b) Diaryl ether : In which both the groups are aryl group.
Example : C 6 H 5 O C 6 H 5
Diphenyl ether

(iii) Symmetrical and unsymmetrical ethers,

(a) An ether in which both the R are same known as symmetrical ethers.
Example : CH 3 O CH 3 , C 6 H 5 O C 6 H 5 .
Dimethyl ether

Diphenyl ether

(b) An ether in which the both R are different called unsymmetrical ethers or mixed ethers.
Example: CH 3 O C 2 H 5 and CH 3 O C 6 H 5 .
Ethyl methyl ether

Methyl phe nyl ether

(2) Structure : The oxygen atom in ether is sp 3 hybridised. Two of the hybrid orbitals overlap with hybrid
orbital (one each) of two carbon atoms to form sigma bonds.

C O C

. The bond angle is 110 o .

Besides the open chain saturated homologous series, there are numerous organic compounds in which O
functional group is present. These compounds are also termed ethers.
O
LONE PAIRS
CH ; H C CH ;
; C H OCH
CH
OCH CH ; CH
3
Methyl vinyl ether
{unsaturat ed}

O
Ethylene oxide
{cyclic}

H 2 C CH 2
O

H2C
|

CH2

6
5
3
Anisole
(Methyl ph enyl ether)

110

Tetra hydro furan

H2C O CH2
(3) Nomenclature : There are two systems for namingDioxan
ethers.

(i) Common names : When both the alkyl group are same, the prefix di- is used. In case of
unsymmetrical ethers two alkyl groups are named in alphabetical order.
Example : CH 3 OCH 3 , C 2 H 5 OC 3 H 7 .
Di methyl ether

Ethyl prop yl ether

(ii) IUPAC system : Ethers are named as alkoxy alkanes.

(a) The ethernal oxygen is taken with smaller alkyl group.
Example : CH 3 O ; C 2 H 5 O .
Methoxy

Ethoxy group

(b) The R group having the longest carbon chain is chosen as the parent alkane.
Example : CH 3 O C 2 H 5 ,
OCH3
Methoxy ethane
Methoxy benzene

Note : In case of simple ethers common names are also accepted in IUPAC system.
(4) Isomerism : Ether show the following types of isomerism :
(i) Chain isomerism
CH 3
|

Example : CH 3

CH 2 CH 2 CH 2 CH 3 , CH 3

CH 2

CH 3 .

CH

1- methoxy - 2 - methyl pro pane

1- methoxy butane

(ii) Functional isomerism

Example : CH 3

CH 3

CH 3

Dimethyl ether

OCH3

OH ,

CH 2
Ethanol

Benzyl alcohol

Anisole

(iii) Metamerism
Example : CH 3 CH 2

CH2OH

O CH 2 CH 3

CH 3

O CH 2

Ethoxy ethane

CH 2

CH 3

Methoxy propane

General methods of preparation of ethers.

(1) From alkyl halides
(i) Williamsons synthesis : It is the laboratory method for the preparation of ethers.
It is a nucleophilic substitution reaction and proceed through SN

RONa

RX

RO R

NaX

C 2 H 5 ONa
Sodium ethoxide

CH 3

C 2 H 5 ONa

C 2 H 5 Br

C 2 H 5 OC 2 H 5

Sodium ethoxide

Ethyl brom ide

Ethoxyetha ne

CH 3 OC 2 H 5

mechanism.

NaI

Ethyl methyl ether

(a) Order of reactivity of primary halide is CH 3 X

NaBr

CH 3 CH 2 X

(b) Tendency of alkyl halide to undergo elimination is 3 o

2o

CH 3 CH 2 CH 2 X .
1o .

(c) For better yield alkyl halide should be primary and alkoxide should be secondary or tertiary.

CH 3

CH 3

C 2 H 5 Br
Ethyl brom ide

NaO

C CH 3
|

CH 3
Sodium salt of
tert. butyl alcohol

C2 H 5

C CH 3
|

CH 3
Ethyl tert. butyl ether

(d) Secondary and tertiary alkyl halides readily undergo E 2 elimination in the presence of a strong base to form
alkenes.
C 2 H 5 ONa

C Cl

CH 3

CH 3
2

SN

Cl , CH 3

slow

C2 H 5 I

C2 H 5O

CH 3

C C 2 H 5 OH
||

CH 2 H

CH 3

mechanism : C 2 H 5 ONa C 2 H 5 O

C2 H 5O

CH 3

CH 3

CH 3

CH 3

CH 3

CH 2

Na ,
Fast

C 2 H 5 O - - - -C 2 H 5 - - - - I

I , Na

C 2 H 5 OC 2 H 5

NaI

Trnsition state

Note :

Aryl halide and sodium alkoxide cannot be used for preparing phenolic ethers because aryl halide are less

reactive toward nucleophilic substitution reaction than alkyl halides.

(ii) By heating alkyl halide with dry silver oxide

2 RX

heat

Ag 2 O

heat

2 AgX , 2C 2 H 5 Br Ag 2 O

C 2 H 5 OC 2 H 5

Ethyl brom ide

2 AgBr

Diethyl ether

(2) From alcohols

(i) By dehydration of alcohols
(a) With conc. H2SO4 at 140 C : ROH

H 2 SO 4 (conc. )

HOR

140 o C

2 molecules of alcohol

ROR
Ether

H 2O .

Note : In this reaction alcohol must be present in excess.

This reaction is mainly applicable for the dehydration of primary alcohols. Secondary and tertiary alcohols
form alkenes mainly.
When this reaction is carried out between different alcohols then there is a mixture of different ethers is
obtained.
Example : CH 3 OH C 2 H 5 OH
Methanol

H 2 SO 4 (conc. )

CH 3

140 o C

Ethanol

Al 2 O 3

(b) With Al2O3 at 250 C : 2 ROH

R O

250 o C

C2 H 5

CH 3

CH 3

C2 H 5

C2 H 5

H 2O

(ii) By the action of diazomethane on alcohols : This reaction is in presence of catalyst, boron trifluoride or HBF4 .

ROH

BF3

CH 2 N 2

CH 3

N2

(iii) Addition of alcohols to alkenes : CH 2

CH 2

HOR

H 2 SO 4

Alcohol

CH 3

OR .

CH 2
Ether

The intermediate is carbonium ion.

CH 2

H CH 3 C H 2 , CH 3 C H 2

CH 2

HOR

CH 3 CH 2

O R,
|

H
CH 3 CH 2

O R
|

CH 3 CH 2

R.

Ether

H
(a) This method is very useful for preparing mixed ethers.
(b) In higher cases, there can be 1, 2-hydride or 1, 2-methyl shift to form more stable carbonium ion.
(3) Alkoxy mercuration-demercuration
C

alkene

OH

Hg [OOCCF 3 ] 2
Mercuric t rifluoro acetate

OR HgOOCCF 3

Note : This is the best method for the preparation of t-ethers.

NaBH 4

C C
|

OR H
Ether

(4) Reaction of lower halogenated ether with grignard reagent

ROCH 2 X XMg R
Halogenate d
ether

ROCH 2 R

Grignard
reagant

MgX 2

Higher
ether

(i) Higher members can be prepared by the action of grignard reagent on lower halogenated ethers.
(ii) Ether form soluble coordinated complexes with grignard reagent.

General properties of ethers.

Physical properties
(1) Physical state : Methoxy methane and methoxy ethane are gases while other members are volatile liquid
with pleasant smell.
(2) Dipole moment (D.M.) : Bond angle of ether is due to sp 3 hybridisation of oxygen atom. Since C O bond is
a polar bond, hence ether possess a net dipole moment, even if they are symmetrical.
D.M. of dimethyl ether is 1.3 D
D.M. of di ethyl ether is 1.18 D

Note : The larger bond angle may be because of greater repulsive interaction between bulkier alkyl groups as
compared to smaller H-atoms in water.
(3) Boiling points : Boiling points of ethers are much lower than those of isomeric alcohols, but closer to alkanes
having comparable mass. This is due to the absence of hydrogen bonding in ethers.
(4) Solubility : Solubilities of ethers in water are comparable with those of alcohols.
Example : Di ethyl ether and n-butyl alcohol have approximately the same solubility in water. This is because, ether
form hydrogen bond with water much in the same way as alcohol do with water.
R
O .......... H
O
R
R
Ether
H .......... . O
Water
R
Ether

Note : Solubility of ether in water decreases with the size of alkyl groups.
(5) Hydrogen bonding : There is no hydrogen directly attach (bonded) to oxygen in ethers, so ethers do not
show any intermolecular hydrogen bonding.

O- - - H

O- - - H

O- - -

hydrogenbo nding in alcohols

No hydrogen bond in ether

(6) Density : Ethers are lighter than water.

Chemical properties : Ethers are quite stable compounds. These are not easily attacked by alkalies, dilute mineral
acids, active metals, reducing agents or oxidising agents under ordinary conditions.
(1) Reaction due to alkyl group
(i) Halogenation : CH 3 CH 2 OCH 2 CH 3

Cl2

Diethyl ether

dark

CH 3 CH 2OCH 2 CH 3

Cl 2

Diethyl ether

dark

CH 3 CHClOCH 2 CH 3
( -Monochloro diethyl ether )

CH 3 CHClOCHClC H 3
( ,

- Dichlorodi ethyl ether )

C 2 H 5 OC 2 H 5

Cl 2

10 Cl 2

light

C 2 Cl 5 OC 2 Cl 5
(Perchlorod iethyl ether )

10 HCl

(ii) Burning : Ethers are highly inflammable. They burn like alkanes.
C 2 H 5 O C 2 H 5 6O2
4 CO 2 5 H 2 O
(2) Reaction due to ethernal oxygen
..
..
(i) Peroxide formation : C 2 H 5 O C 2 H 5 O :
..
..

..
C 2 H 5 O C 2 H 5 or (C2 H5 )2 O

O.

..
:O :
..
(a) The boiling point of peroxide is higher than that of ether. It is left as residue in the distillation of ether
and may cause explosion. Therefore ether may never be evaporated to dryness.
(b) Absolute ether can be prepared by distillation of ordinary ether from conc. H 2 SO 4 and subsequent storing over
metallic sodium.

Note :

Formation of peroxide can be prevented by adding small amount of Cu 2 O to ether.

With strong oxidising agent like acid, dichromate ethers are oxidised to aldehydes.
2[ O ]

CH 3 CH 2 OCH 2 CH 3

2CH 3 CHO H 2 O
Acetaldehy de

The presence of peroxide can be indicated by the formation of blood red colour complex in the following
reaction.

Peroxide

Fe

Fe

SCN

[Fe(SCN )n ]3

Blood red colour

(n 1 to 6 )

(ii) Oxidation with K2Cr2O7 / H : R CH 2 O CH

(a) Oxidation of ether can only be possible if any one of the alkyl groups of ether has hydrogen on -carbon.
(b) -carbon having two hydrogens converts in carboxylic group and -carbon having only one hydrogen converts
into keto group.
K 2 Cr2 O7

CH 3 CH 2 O CH 2 CH 2 CH 3

CH 3 COOH

H /

CH 3 CH 2 COOH
O

CH 3

CH 2

CH 3
CH 3

CH

||

K 2 Cr2 O7
H

CH 3

COOH

CH 3

C CH 3

(iii) Salt formation : Due to lone pair of electrons on oxygen atom. Ether behaves as Lewis base and form stable
oxonium salt with strong inorganic acids at low temperature.
H
|

C 2 H 5 OC 2 H 5

HCl

(C 2 H 5 )2 O Cl
..

or [(C 2 H 5 )2 O H ] Cl

Diethyl oxonium chloride

..
C 2 H 5 OC 2 H 5

H 2 SO 4

(C 2 H 5 )2 O HSO 4
|

Diethyl oxonium hydrogen sulphate

or [(C 2 H 5 ) 2 O H ] HSO 4

The oxonium salts are soluble in acid solution and ethers can be recovered from the oxonium salts by treatment
H 2O

with water. (C 2 H 5 ) 2 O Cl
|

(C 2 H 5 ) 2 O HCl
Diethyl ether

Oxonium salt

Note :

The formation of oxonium salt is similar to the formation of ammonium salts from ammonia and

acids.
Ether is removed from alkyl halides by shaking with conc. H 2 SO 4 .
Ethers can be distinguished from alkanes with the help of this reaction.
(iv) Reaction with Lewis acids : Being Lewis bases, ethers form complexes with Lewis acids such as BF3 , AlCl 3 ,

..
O : BF3

CH 3 CH 2
FeCl 3 , etc. These complexes are called etherates.
CH 3 CH 2

CH 3 CH 2
CH 3 CH 2

..
O

BF3

Boron trifluoride etherate (complex)

Similarly, diethyl ether reacts with Grignard reagent forming Grignard reagent etherate.

2(CH 3 CH 2 )2 O

RMgX

R
(CH 3 CH 2 )2 O

O(CH 2 CH 3 )2
X

Mg

Grignard reagent etherate

Due to the formation of the etherate, Grignard reagents dissolve in ether. That is why Grignard reagents are usually
prepared in ethers. However, they cannot be prepared in benzene, because benzene has no lone pair of electrons and
therefore, cannot form complexes with them.
(3) Reaction involving cleavage of carbon-oxygen bond
(i) Hydrolysis
(a) With dil. H 2 SO 4 :

ROR

C 2 H 5 OC 2 H 5

H 2 SO 4

H 2O
H 2O

H 2 SO 4

Diethyl ether

(b) With conc. H 2 SO 4 :

2 ROH

2C 2 H 5 OH
Ethanol

C 2 H 5 OC 2 H 5 H 2 SO 4
C 2 H 5 OH C 2 H 5 HSO 4
C2 H 5 OH H 2 SO 4 C2 H 5 HSO 4 H 2O
C 2 H 5 OC 2 H 5 2 H 2 SO 4
2C 2 H 5 HSO 4 H 2O
Diethyl ether

Ethyl hydrogen sulphate

(ii) Action of hydroiodic acid

Cold

(a) With cold HI :

C 2 H 5 OC 2 H 5 HI

Note :

Same reaction are observed with HBr and HCl. The order of reactivity of halogen acid HI>HBr>HCl.

Diethyl ether

OC2H5

C2 H 5 I
Ethyl iodide

OH

+ C2H5Br

+ HBr

Phenyl ethyl ether

Mechanism of the reaction

Phenol

Ethyl bromide

C 2 H 5 OH
Ethyl alcohol

R O

Ether

R H

..
O R

Nucleophil e

, X

O
..

Alkyl halide

OH

Alcohol

Protonated ether

This can be explained on the basis of steric hinderence.

The above reaction is a S N reaction.
The ether molecule gets protonated by the hydrogen of the acid to form protonated ether and the protonated
ether undergoes nucleophilic attack by halide ion [X ] and form alkyl alcohol and alkyl halide.
(b) With hot HI : R

(iii) Zeisel method : RI

Note :

heat

2 HI

RI

AgNO 3 (alc.)

RI

AgI

H 2O

RNO 3

The silver iodide thus form can be detected and estimated. This formed the basis of Zeisel method for the
detection and estimation of alkoxy group in a compound.

(iv) Action of PCl5 : R

heat

PCl 5

POCl 3 . There is no reaction in cold.

2 RCl

(v) Reaction with acetyl chloride : CH 3 COCl

Acetyl chloride

Al 2 O 3

2 CH 2

CH 2

CH 2

CH 2

2CH 3 COOC 2 H 5

heat

Ethyl acetate

H 2O
BF3 / 150 o C

CO

CH 2

C 2 H 5 COOC 2 H 5

500 atm.

Diethyl ether

ZnCl2

Diethyl ether

(viii) Reaction with carbon mono oxide : C 2 H 5 OC 2 H 5

(ix) Action of bases : L i C H 3

Ethyl acetate

C2 H 5 O C2 H 5

Acetic anhydride

300 o C

CH 3 COOC 2 H 5

heat

Diethyl ether

(vi) Reaction with acid anhydride : CH 3 CO O OCCH

(vii) Dehydration : C 2 H 5 OC 2 H 5

ZnCl2

C2 H 5 O C2 H 5

CH 3

Ethyl propionate

CH 4

CH 2

CH 2

L iO C2 H 5

(4) Ring substitution in aromatic ethers : Alkoxy group is ortho and para directing and it directs the incoming
groups to ortho and para position. It activates the aromatic ring towards electrophilic substitution reaction.
..

..

:OR

:O R

..

..

..

OR

OR

OR

..

:
..

II

III

IV

III, Iv and V show high electron density at ortho and para position.
(i) Halogenation : Phenyl alkyl ethers undergo usual halogenation in benzene ring.
For example, Bromination of anisole gives ortho and para bromo derivative even in the absence of iron
(III) bromide catalyst.
OCH
OCH
OCH
3

Br
Br2

CS 2

Anisole

o-Bromoanisole

Br
p-Bromoanisole

Para isomer is obtained in 90% yield.

(ii) Friedel craft reaction

OCH3

OCH3
AlCl3

AlCl3

+ CH 3 COCl

Ortho

Anisole

CH3

OCH3

OCH3

Para

OCH3
COCH3

Methyl chloride
Anisole

OCH3

CH3

+ CH 3 Cl

OCH3

OCH3

OCH3

+
o-Methoxy
acetophenone

p Methoxy
acetophenone

NO3

(iii) Nitration :

HNO 3 / H 2 SO 4

COCH3

Methyl phenyl

Methyl-2

NO3
ether

nitrophenyl ether

(Anisole)

(o-Nitroanisole)

Methyl-4
nitrophenyl ether
(p-Nitroanisole)

Note : Ethers are relatively less reactive than phenol towards electrophilic substitution reaction.
Some commercially important compounds of ethers.
(1) Di methyl ether : It is the simplest ether.
(i) Preparation
(a) It can be prepared by using any of the general method of preparation.
(b) 2CH 3 OH

, Alumina
350 o 400 o C , 15 atm

CH 3

O CH 3

H 2O

(c) It can be manufactured by dehydration of methyl alcohol with conc. H 2 SO 4 at 140 o C .

(ii) Properties
(a) It is colourless highly inflammable gas having B.P. of 24 .8 o C .
(b) It is soluble in water, alcohols and other organic solvents and gives all the characteristic reactions of
ethers.
(iii) Uses
(a) It is used in the form of compressed liquid as a refrigerant, low temperature solvent and propellant for
sprays.
(b) It is used for storing food stuffs by freezing on direct contact because it doe not leave any undesirable
taste or smell.
(2) Diethyl ether (Sulphuric ether) : It is the most important member of the ether series and is known as
ether. It may also be regarded as an anhydride of C 2 H 5 OH (ethanol).
(i) Preparation : Laboratory method :

C 2 H 5 OH

C 2 H 5 HSO 4

H 2 SO 4

heat

C 2 H 5 HSO 4

C 2 H 5 OH

C 2 H 5 OC 2 H 5

[Excess]

Diethyl ether

H 2O

H 2 SO 4

It is also known as Williamsons etheral continuous process.

(ii) Properties
(a) It is a colourless, highly volatile and inflammable liquid having boiling point 34 .5 o C .
(b) It has a pleasant smell and burning taste.
(c) It is only slightly soluble in water but readily soluble in organic solvents.
(d) Di ethyl ether is itself a very good solvent even for fats and oils.
(e) It produces unconsciousness when inhaled.
(iii) Uses
(a) It is used as a refrigerant.
(b) It is used as a reaction medium in LiAlH 4 reduction and grignard synthesis.
(c) It is used as an extracting solvent in laboratory.
(d) Mixture of alcohol and ether is used as petrol substitute under the trade name Natalite.
(e) It is used in perfumary and in the manufacture of smokeless powder.
(3) Di-isopropyl ether
(i) Preparation : 2 CH 3 CH

CH 2

H 2O

H
3 7 atm
75 125 o C

(CH 3 )2 CHOCH (CH 3 )2

(ii) Properties : It is a colourless liquid with a pear like odour having B.P. 68 .5 o C .
(iii) Uses : It is used for reducing knocking of petrol.
(4) Divinyl ether

CH 2 CH O CH CH 2 2 KCl H 2 O
(i) Preparation : CH 2 ClCH 2 OCH 2 ClCH 2 2 KOH
(ii) Properties
(a) It is highly inflammable liquid.
(b) It is colourless and boils at 28 .3 o C .
(iii) Uses : It is better anaesthetic than di ethyl ether because of its rapid action and rapidrecovery from
anaesthesia.
|

(5) Epoxides [oxirane] or cyclic ether

C C
O

(i) Preparation
(a) By oxidation of ethylene with oxygen : 2CH 2

CH 2

Ag

O2

250 o C

2CH 2

CH 2

O
(b) By oxidation of ethylene with peroxy acids : RCH

C6 H 5 CO3 H

CHR

or CF3 CO3 H

R CH

CH

R.

(c) By treatment of ethylene chlorohydrin with NaOH

CH 2

CH 2

HOCl

ClCH 2

CH 2 OH

NaOH

CH 2

CH 2

Ethylene chlorohydr in

O
(ii) Properties
(a) It is a poisonous, flammable gas.
(b) Its B.P. is 14 o C .
(c) It is very reactive compound because of its strained configuration.
(d) An epoxide is converted into protonated epoxide by acid which can undergo attack by any nucleophilic
reagent.

HOH

C C

C C

OH OH

Glycol

H
(Protonated epoxide )

Some of the chemical reactions

(a) Case I : Base catalysed ring opening : In this case nucleophile attack on less hindered carbon of the
oxirane ring and reaction is SN
R
R

mechanism.
OCH 3

CH R

R
R

CH 3 O Na / CH 3 OH

C
|

CH R .

OH

(b) Case II : Acid catalysed ring opening : Nucleophile attacks on carbon of oxirane ring which is highly
substituted. SN 2 reaction is there.
R
R

CH R
O

CH 3 OH / H

OCH 3
|

R
R

C CH R
|

OH

Some reactions of oxirane are given below

CH3OH/H

CH2 CH2OH
|

OCH3
HX

2-Methoxy ethanol

CH2OH CH2X
Ethylene halohydrin

NH3

CH2OH CH2NH2

CH2 CH2

2-Amino ethanol

OCH3
O
(Ethylene oxide)

CH3ONa
CH3OH

CH2 CH2OH
2-Methoxy ethanol

(i) RMgX
(ii) HOH

R CH2 CH2 OH
Alcohol

(i) R2CuLi
(ii) HOH

R CH2 CH2 OH

(i) LiAlH4

Uses
(a) It is used in the manufacture of ethylene glycol.

(ii) HOH/H

CH3 CH2 OH
Ethanol

(b) It is used in the manufacture of dacron.

(c) It is used in the manufacture of solvent ethoxy ethanol used in varnishes and enamels for quick drying.
(6) Crown ethers : The crown ethers are heterocyclic poly-ethers usually with at least four oxygen atoms.
These are called crown ethers because they have crown like shape.
18-crown-6 means compound is eighteen member ring compound out of which [18 6 = 12] 12 atoms are
carbon [i.e. six ethylene group CH 2 CH 2 ] and six atoms of oxygen.
Crown ethers have remarkable affinity for metal ions.
Example : 12-crown-4 has affinity with Li

Example : K C N
C6 H 5

CH 2

Cl

CH 2

K F

and 18-crown-6 has affinity with K .

18 - crown - 6

benzene

18 -crown -6
acetonitri le

CH 2

CN

KX

100 % yield

C6 H 5

CH 2

F K Cl

100% yield

O
O

O
12-crown-6

18-crown-6

A crown ether binds certain metal ions depending on the size of the cavity.
O

..
O
..

Na+

+ Na+

O
O
..
Inclusion compound

Host

In this reaction, the crown ether is the host and the species it binds is the guest. The crown-guest complex is
called an inclusion compound.
(7) Anisole (Methyl phenyl ether) C6H5OCH3 or (methoxy benzene)
(i) Preparation
(a) By the action of methyl iodide on sodium phenoxide.

C6 H 5 ONa

ICH 3

C6 H 5 OCH 3

NaI

(b) By passing vapours of phenol and methyl alcohol over heated thoria.

C 6 H 5 OH

CH 3 OH

ThO 2

C 6 H 5 OCH 3

H 2O

(c) By methylation of phenol with diazomethane.

C6 H 5 OH
(ii)

CH 2 N 2

C6 H 5 OCH 3

N2

Properties : It is a pleasant smelling liquid. It is used as a solvent in some organic reactions. Anisole
undergoes electrophilic substitution reactions.

OCH 3 group is o- and p- directing.

OCH3

OCH3

OCH3

+ E+

+ H+

+
E

Anisole is decomposed by conc. hydroiodic acid again into phenol.

OCH3

OH

+ HI

heat

+ CH3I