1196 Alcohol, Phenol and Ethers

Chapter

26
Alcohol, Phenol and Ether

Hydroxy compounds CH 3 CH  CH 2  HOSO 2OH  

Markowniko ff'' s

Propene rule
Hydroxy compounds are those compounds in which
the hydroxy group, – OH is directly linked with the CH 3  CH  CH 3   CH 3  CH  CH 3
H 2O
| Boil |
aliphatic or aromatic carbon. OSO 2 OH OH
Propan - 2 - ol
Monohydric alcohols
CH 3 CH 3
These are compound containing one hydroxyl | |

group. Their general formula is Cn H 2n  2O  C  CH 2  H  H 2 SO 4
 C  CH 3  
H 2O

(1) Preparation : (i) From alkyl halide
CH 3
C 2 H 5 Br  KOH  C 2 H 5 OH  KBr |
(Aqueous)
Bromoethan e Ethanol
 C CH 3
C2 H 5 Br  AgOH  C2 H 5 OH  AgBr |
Bromoethan e Moist silver oxide Ethanol OH
Alcohol
 1° alkyl halide gives good yield of alcohols. (b) Oxymercuration-demercuration
 2° alkyl halide gives mixture of alcohol and
alkene. CC  H 2 O  Hg(OAc )2  
Oxy mercuration

Mercuric acetate
 3° alkyl halide gives alkenes due to
| |
dehydrohalogenation.  C  C    C  C 
NaBH 4
| | Demercuration | |
CH 3 CH 3
| | OH HgOAc OH H
CH 3  C  CH 3  KOH  CH 3  C  CH 2 Alcohol
| (Aqueous) 2-Methy lpropene
Br (Major product) This reaction is very fast and produces the alcohol
CH 3 in high yield. The alcohol obtained corresponds to

|
CH 3  C  CH 3  KBr  H 2 O
Markownikoff’s addition of water to alkene.
|
OH (c) Hydroboration oxidation (HBO) :
Tert. buty l alcohol(side product)
(Antimarkownikoff’s orientation)
(ii) From alkenes : (a) Hydration | | | |

C  C  H  BH 2   C  C  22   C  C 
| | H O , OH
Direct process : CC   C  C 
HOH
| | | |
Alkene dil H 2 SO 4 | | H BH 2 H OH
OH H Alcohol
Alcohol

Indirect process : Diborane is an electron defficient molecule. It acts

CH 2  CH 2  HOSO 2 OH  CH 3 CH 2 OSO 2 OH as an electrophile reacting with alkenes to form alkyl
Ethene Sulphuric acid Ethy l hy drogen sulphate boranes R 3 B .
 CH 3 CH 2 OH  H 2 SO 4
H 2O
Boil Ethanol

In case of unsymmetrical alkenes

 Alcohol, Phenol and Ethers 1197
RCH  CH
R  CH  CH 2  H  BH 2  R  CH  C H 2 
2
 CH 3 CH 2 NH 2  HONO 2

NaNO / HCl
| | Aminoethan e
H B H2
Alky l borane CH 3 CH 2OH  N 2  H 2O
Ethanol
RCH CH 2
(R CH 2 CH 2 )2 BH (RCH 2 CH 2 )3 B
Dialkyl borane Trialkyl borane  It is not a good method of preparation of
alcohols because number of by product are formed like
 Carbocation are not the intermediate in HBO
alkyl chloride alkenes and ethers.
hence no rearrangement take place.
(vii) From Grignard reagent
(iii) By reduction of carbonyl compounds
(a) With oxygen :
RCHO  H 2 
 RCH 2 OH
Pd
Aldehyde LiAlH 4 
Primary alcohol
2 R  Mg  X  O2  2 R  O  Mg  X .
Al 2 O 3
RCO R  H 2  R  CH  R 
NaBH 4
Ketone or Ni / Pt |
OH   2 ROH  2 Mg(X )OH
2 HOH
Secondary alcohol

H3O+ H2O CH3 CH3 (b) With ethylene oxide :

CH3   CH3
OH  
HO
CH2 CH2 R    Mg    X  CH 2  CH 2 
B 2 H6
HO – CH2OH O 
CH2
RCH 2CH 2  OMgX   RCH 2CH 2OH  Mg(X )OH
H 2O

LiAlH 4 also reduces epoxides into alcohol :

(c) With carbonyl compounds :
CH 2  CH 2  LiAlH 4  CH 3  CH 2 OH H H H
  | | |
O
R  Mg  X  R   C    R   C  R   R   C  R
H 2O
|| | |
Hydride selectively attacks the less alkylated O  OMgX OH
carbon of the epoxide.
 If R = H, product will be 1°alcohol.
CH 3
|
CH 3
|
 If R = R, product will be 2°alcohol.
CH 3  C  CH 2     CH 3  C  CH 3
LiAlH 4
 If carbonyl compound is a ketone, product will
H H |
O OH be 3° alcohol.
 It is the best method for preparation of alcohol
(iv) By reduction of carboxylic acids and their because we can prepare every type of alcohols.
derivatives (viii) The oxo process : It is also called
R  COOH    RCH 2 OH
(i) LiAlH 4
carbonylation or hydroformylation reaction. A mixture
Carboxylic acid (ii) H 2 O primary alcohol
of alkene carbon monoxides and hydrogen. Under
RCOOH  RCOO R  
 RCH 2 OH  R OH
H2 pressure and elevated temperature in the presence of
Carboxy lic acid Ester Cataly st
catalyst forms aldehyde.
Esters are also reduced to alcohols Catalyst is cobalt carbonyl hydride [CoH (CO)4 ]
(Bouveault Blanc reaction) product is a mixture of isomeric straight chain (major)
O and branched chain (minor) aldehydes. Aldehydes are
||
CH 3  C  OCH 3  4[H ] 25
 CH 3 CH 2 OH  CH 3 OH reduced catalytically to the corresponding alcohols.
Na / C H OH

Methy l acetate
(Ester)
Ethanol Methanol 2CH 3  CH  CH 2  2CO  2 H2 
H2
 Reduction with aluminium isopropoxide is CH3 – CH – CHO CH3 – CH – CH2OH
Zn – Cu
known as Meerwein-Ponndorff verley reduction (MPV) | |
reduction. CH3 CH3
(Minor) Isobutyl alcohol
Me 2 C  O  (CH 3 )2 CHOH 
 
2 Al(OCHMe )

Isopropy l alcohol H2
CH 3  CH 2  CH 2  CHO Zn – Cu
CH 3 (Major)
Me 2 CHOH  CO
CH 3 CH3 – CH2 – CH2 – CH2 –
OH
(v) By alkaline hydrolysis of ester (2) Physical properties of monohydric alcohols
n- Butyl alcohol
O O (i) Character : Alcohols are neutral substances.
|| ||
R  C  O R   HO Na (aq )  R  C  ONa  R OH . These have no effect on litmus paper. This is analytical
Sod. salt of acid Alcohol
test for alcohols.
(vi) From primary amines
 1198 Alcohol, Phenol and Ethers
(ii) Physical state : The lower alcohols (upto C12) > Tertiary and C – O – cleavage reactivity order :
are colourless alcohol with characteristic smell and Tertiary > Secondary > Primary alcohol
burning taste. The higher members with more than 12- (i) Reaction involving cleavage of with removal
carbon atoms are colourless and odourless solids. of ‘H’ as proton
(iii) Polar character : Oxygen atom of the – OH
Alcohols are stronger acids than terminal
group is more electronegative than both carbon and
acetylene but are not acidic enough to react with
hydrogen. Thus the electron density near oxygen atom
aqueous NaOH or KOH. Acidic nature is in the order
is slightly higher. Hydrogen bonding shown below
HOH  ROH  CH  CH  NH 3  RH .
H  O- - - - H  O- - - H  O- - - - H  O . This gives polar
| | | |
R R R R Acidic nature of alcohol decrease with increase of
character to OH bond. alkyl groups on – OH bonded carbon due to +I
(inductive) effect of alkyl group.
(iv) Solubility : The lower alcohols are miscible
in water.
H R R
1  
H  O :  - - - - -  H  O : Solubility 
|
| | Size of alkyl groups R   C O H  R  C O H  R  C O H
| | 
R H H H R
Increase in carbon-chain increases organic part (a) Reaction with Na : (Active metals)
hence solubility in water decreases.
2 RO  H  2 M  2 ROM  H 2 (M = Na, K, Mg, Al,
Isomeric 1°, 2°, 3° alcohols have solubility in order
etc.)
1°> 2°> 3°.
Evolution of H 2 shows the presence of –OH and
(v) Boiling points : Due to intermolecular
hydrogen bonding boiling points of alcohols are higher reaction show that alcohols are acidic in nature.
than hydrocarbon and ethers. Alcohols acts as Bronsted acids because they donate a
1 proton to a strong base (: B  ) .
B.P.  ; B.P. follows the trends :
No. of branche s Example :
1° alcohol > 2° alcohol > 3° alcohol .. ..
R  O  H  : B   R  O :  BH
(vi) Density : Alcohols are lighter than water. .. .. Conjugate acid
Base
Density  Molecular masses.
Alcohol Alkoxide
(acid) (conjugate base)

(vii) In toxicating effects : Methanol is poisonous On reaction of alkoxide with water, starting
and is not good for drinking purposes. It may cause alcohol is obtained.
blindness and even death. Ethanol is used for drinking ..
..
purposes. H  O H  R O  :  R  O  H  OH 
(3) Chemical properties : Characteristic reaction
.. .. Conjugate acid Conjugate base
Acid Base
of alcohol are the reaction of the – OH group. The This is the analytical test for alcohols.
reactions of the hydroxyl group consists of either
(b) Reaction with carboxylic acid [Esterification] :
cleavage of C – O bond or
| the cleavage

of O – H bond.
 C   O  H   RCO  OH  H  OR Conc. RCOO R H 2O
acid Alcohol H2SO4 Ester
|
When HCl gas is used as catalyst, the reaction is
Polar
bond
called fischer-speier esterification.
C – O bond is weaker in the case of tertiary Presence of bulky group in alcohol or in acid
alcohols due to +I effect of alkyl groups while – OH decreases the rate of esterification. This is due to steric
bond is weaker in primary alcohols as electron density hindrance of bulky group. Reactivity of alcohol in this
increase between O – H bond and hydrogen tends to reaction is 1o  2 o  3 o .
separates as a proton. (c) Reaction with acid derivatives : (Analytical test
H weaker R of alcohol)
| bond R
R  C O  H ; CH  OH ; R C OH O
| R ||
R weaker
H Secondary CH 3  C  Cl  H  O  CH 2 CH 3
Primary bond
Tertiary
Ethanoy l chloride Ethanol

Thus primary alcohols give the most of reaction O

||
by cleavage of O – H bond while tertiary alcohols are
 CH 3  C  OCH 2 CH 3  HCl
Py ridine
most reactive because of cleavage of C – O bond. Hence Ethy l ethanoate
(Ethy l acetate)
– O – H cleavage reactivity order : Primary > Secondary
 Alcohol, Phenol and Ethers 1199
O O In secondary and tertiary alcohols, the
|| ||
Acylation : CH 3  C  O  C  CH 3  H  OCH 2 CH 3 S N 1 mechanism operates
Acetic anhy dride Ethanol
H+ –H2O 
O R  OH R  OH 2 R  
X
 R  X
||
 CH 3  C  OCH 2 CH 3  CH 3 COOH (b) Reaction with PCl5 :
Ethy l ethanoate
ROH  PX 5  RX  POX 3  HX ; X = Cl (Analytical test
(d) Reaction with grignard reagents :
for alcohols)
CH 3 OH  C2 H 5 MgBr  C2 H 6  CH 3 OMgBr
Methy l Ethy l magnesium Ethane (c) Reaction with PCl3 :
alcohol br omide
3 ROH  PCl 3  3 RCl  H 3 PO 3
(e) Reaction with ketene : Alcohol Phosphorus Alky l Phosphorus
trichloride chloride acid
   
R  O  H  CH 2  C  O
(d) Reaction with thionyl chloride [SOCl2] :
 CH 2  C  O  R  CH 3  C  O  R
| || ROH  SOCl 2   RCl  SO 2  HCl
Py ridine

H O O
(enol form) (Keto form)
(e) Reaction with ammonia :
(f) Reaction with isocyanic acid :
ROH  NH 3   RNH 2
Al 2 O3
   360 o C Primary
R  O H H  N  C  H  N  C  O  R amine
|| |
O  OH
  R 2 NH 
ROH
 R 3 N
ROH
Al 2 O3 Al 2 O3
 H  NH  C  O  R Secondary
amine
Tertiary
amine
||
O
amino ester (f) Reaction with HNO3 :
(Urethane)
O
(g) Reaction with ethylene oxide : R  OH  conc. HNO 3  R  O  N  H 2O
O
R  O  H  CH 2  CH 2  CH 2  CH 2   CH 2  CH 2
ROH alky l nitrate
| |  H 2O | |
O OH OR OR OR (g) Reaction with H2SO4 [Dehydration of alcohol] :
1, 2 -dialkoxy et hane The elimination of water from a compound is known as
dehydration. The order of ease dehydration is Tertiary
(h) Reaction with diazomethane :
> Secondary > primary alcohol. The products of
R  OH  CH 2 N 2  R  O  CH 3  N 2 dehydration of alcohols are depend upon the nature of
(Ether)
dehydrating agents and temperature.
(ii) Alkylation : ROH  R2 SO 4  RO R  RHSO 4 Conc.
H2SO
17 4
CH2 = CH2
| | Ethylene
0
(iii) Reaction involving cleavage of  C  OH with
CH 3  CH 2  OH 
H 2 SO 4 110
| |
H°2SO4
C2H5HSO4
Ethyl hydrogen
removal or substitution of –OH group sulphate
140°C C2H5O – C2H5
(a) Reaction with hydrogen halides : Alcohols give
Diethyl ether
alkyl halide. The reactivity of HX is in the order of HI >
HBr > HCl and the reactivity of ROH is in the order of

benzyl > allyl > 3° > 2°> 1°. The reaction follows a –(H+)
nucleophilic substitution mechanism.
Grove’s process
CH 3 OH CH 3
| | | H+/H2SO
ROH  HX 
 R  X  H 2 O
ZnCl 2
anhy drous 
CH 3  C  C  C  CH 3 4
Shiftin +
| | | g
CH 3 CH 3 CH 3
If alcohols react with HI and red phosphorus,
alkane will be formed. 

C 2 H 5 OH  2 HI  C 2 H 6  I2  H 2 O
Red P
heat

Primary alcohols follow S N 2 mechanism . Alcohol leading to conjugated alkene are

dehydrated to a greater extent than those of alcohols
R  OH 2  X     X - - - R - - - OH 2   R  X  H 2 O leading to nonconjugated alkene. Thus dehydration is
Protonated
1o alcohol in order
 1200 Alcohol, Phenol and Ethers
CH 2  CH  C H  CH 3  CH 3  CH 2  CH  CH 3 CH 3 CH 3
| | | |
OH OH 3° CH 3  C  OH   CH 3  C  CH 2  H 2 O
Cu , 573 K
| 2-Methy lpropene
CH 3 CH 3 CH 3 (Alkene)
| | 2 -Methy lpropan - 2 -ol
CH 3  C  CH  CH 3   CH 3  C  CH  CH 3 
H 2 SO 4 (Tert. alcohol)
| |  H 2O | 
CH 3 OH CH 3 Important reagents used for oxidation of alcohols
 PCC [Pyridinium chloro chromate
CH 3 CH 3 CH 3 
| |
H  (C6 H 5 N H Cl CrO3 ) ] to oxidise 1° alcohols to aldehydes
CH 3  C  CH  CH 3  CH 3  C  C
 | and 2° alcohols to ketones.
CH 3 CH 3
2 - alkene  PDC [Pyridinium di chromate
(C 5 H 5 . NH )22  Cr2 O72  ] to oxidise 1° alcohols to aldehyde
 CH 2  CH  CH 2  CH 3
| and 2° alcohol to ketones.
H2SO4
OH H+
– H2O  H 2 CrO4 (chromic acid) to oxidise 1° alcohol to

CH 2  CH  CH 2  CH 3 carboxylic acid.

  CrO3  H 2 SO 4 / Acetone to oxidise 2° alcohol to
ketones.
 Jones reagents (chromic acid in aqueous acetone
CH 2  CH  CH  CH 3
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
CH  CH  CH 2  CH 3 and ketone respectively.
More amoun t
 N 2 O 4 in CHCl 3 oxidises primary and secondary
(iv) General reaction of alcohols benzyl alcohol.
 (d) Self condensation : Guerbet’s reaction
(a) Reduction : R  OH  2 HI  R  H  H 2 O  I2
R  CH 2  CH 2  OH  H  CH  CH 2  OH
(b) Oxidation : Difference between 1°, 2° and 3° |
R
alcohols.
R
1°  RCH 2 OH  R  C  O  R  C  O |
NaOC 2 H 5 , 

 R  CH 2  CH 2  CH  CH 2  OH
| |
H OH
Aldehy de Carboxy lic acid higher alcohol

2°  R  CH  R    R  C  R 
CrO 3
(e) Reaction with cerric ammonium nitrate :
Cerric ammonium nitrate  ROH  Red colour solution of
| ||
OH O Yellow colour
Secondary alcohol
complex. This is analytical test for alcohols.
 RCOOH  CO 2  H 2 O
O
Drastic conditions (f) Iodoform test : When a few drops of alcohol
CH 3 CH 3 are warmed with iodine and NaOH yellow precipitate of
| |
3°  CH 3  C  OH   CH 3  C  O
4 [O ]
iodoform with characteristic smell is obtained. Any
| (Under strong Acetone
CH 3 condition ) (Lesser number alcohol consists CH 3 CHOH group give iodoform test.
Tert. buty l alcohol of carbon atoms)
(Tertiary ) Since reaction takes place with alkali solution as
  CH 3 COOH  CO 2  H 2 O
4 [O ] one of the reagents hence alkyl halide like CH 3  CH 2 Cl
(Under strong Acetic acid
condition ) (Lesser number and CH 3  CH  R will also give this test.
of carbon atoms) |
Cl
 3° alcohols are resistant to oxidation, but on
taking stronger oxidising agent they form ketone. (4) Uses of monohydric alcohol :
(c) Catalytic oxidation/dehydrogenation (i) Uses of ethanol : It is used
H H
| | (a) In alcoholic beverages, (b) As a solvent
1° CH 3  C  O H    CH 3  C  O  H 2
Cu , 573 K
in paints, varnishes, oils, perfumes etc., (c) In the
| Ethanal
H (Acetaldehy de) preparation of chemical like chloroform, ether etc., (d)
Ethanol
(Pri. alcohol) As a fuel in spirit lamps, (e) As an antifreeze for
CH 3 CH 3 automobile radiators, (f) In the scientific apparatus
| |
2° CH 3  C  O H  CH 3  C  O  H 2 Cu , 573 K like spirit levels, (g) As power alcohol.
|
H
Propanone
(Acetone)
(ii) Uses of methanol :
2 -Propanol
(Sec. alcohol)
 Alcohol, Phenol and Ethers 1201
(a) Methanol is an important industrial starting OH O
| ||
material for preparing formaldehyde, acetic acid and CH 3  CH  CH 3 
 CH 3  C  CH 3 [O ]

other chemicals. Propan - 2- ol K 2 Cr2 O7 / H
(Iso- propy l alcohol)
(2 alcohol)
(b) As a fuel (a petrol substitute). A 20% mixture
of methyl alcohol and gasoline is a good motor fuel. OMgBr OH
| |
H  , H 2O
(c) As an antifreeze or automobile radiators.   
 CH 3  C  CH 3    CH 3  C  CH 3
CH 3 MgBr
| |
(d) To denature ethyl alcohol. The mixture is CH 3 CH 3
2 - Methy lpropan - 2 - ol
called methylated spirit. (3) (tert. buty l alcohol)

(e) In the preparation of dyes, medicines and (iii) Primary alcohol into tertiary alcohol
perfumes. Methyl salicylate and methyl anthra anilate
are used in perfumery. CH 3 CH 3
| |
Table : 26.1 Difference between methanol and ethanol CH 3 CH CH 2 OH 
 CH 3  C  CH 2 HBr

H 2 SO 4 , Heat

2- Methy lpropan -1- ol (1) Dehy dration Markowniko ff's

Methanol Ethanol (Iso buty l alcohol) rule

(i) When CH3OH is heated on (i) It does not give

CH 3 CH 3
Cu coil it gives formalin like formalin like smell. | |
smell. CH 3  C  CH 3  CH 3  C  CH 3
aq. KOH
| |
(ii) When CH3OH is heated (ii) No such odour is Br OH
2- Methy lpropan - 2- ol (3)
with salicylic acid in H2SO4 given. (tert. buty l alcohol)
(conc.) then methyl salicylate
is formed which has odour (iv) Lower alcohol into higher alcohol (ascent of
like winter green oil. series)
(iii) It does not give haloform (iii) It gives CH 3 OH 
 CH 3 I 
HI
 CH 3 CN
KCN

Methanol
or iodoform test. haloform test (1 carbon atom)

Interconversion of monohydric alcohols   CH 3 CH 2 NH 2 

4 (H )
 CH 3 CH 2 OH
HONO
Reduction Ethanol
(i) Primary alcohol into secondary alcohols (2 carbon atoms)

C 3 H 7 OH   C 3 H 7 Cl 
SOCl 2
 CH 3 CH  CH 2
alc KOH
(v) Higher alcohol into lower alcohol [Descent
Propan -1-ol Propene
(1 alcohol) series]
 CH 3 CH CH 3 
HBr
 CH 3 CH CH 3
aq. KOH
C2 H 5 OH 2 2 
7

K Cr O , H 
 CH 3 COOH   CH 3 COONa
NaOH
| |
[O ]
Br OH Ethanol
(2 carbon atoms)
Propan - 2- ol
(2 alcohol)
NaOH  CaO
  CH 4  CH 3 Cl 
Cl 2
 CH 3 OH
aq. KOH
(ii) Secondary alcohol into tertiary alcohol Heat Methanol
(one carbon atom)

Distinguish between primary, secondary and tertiary monohydric alcohols

(i) Lucas test : A mixture of anhydrous ZnCl 2  conc. HCl is called as Lucas reagent.

Primary R  CH 2  OH 2  R  CH 2  Cl  ppt. appears after heating

conc. HCl / ZnCl anhy .
H 2O

Secondary R2 CH  OH   R 2  CH  Cl  ppt. appears with in 5 minutes

conc. HCl / ZnCl 2 anhy .
 H 2O

Tertiary R3 C  OH   R3C  Cl  ppt. appears immediately

ZnCl 2 / HCl

(ii) Victor mayer test : Also known as RBW test. RBW  Red, Blue, White test.
Primary P  I2
C2 H 5 OH   C2 H 5 I   C2 H 5 NO 2 
AgNO 2
 CH 3  C  NO 2 
HONO

NaOH
CH 3  C  NO 2
|| ||
NOH NONa
Nitrolic acid Sod. salt of nitrolic acid (Red colour)

P  I2
Secondary (CH 3 )2 CHOH (CH 3 )2 CHI (CH 3 )2  C NO 2 
AgNO 2
(CH 3 )2  C N O 2 
HONO
 No NaOH
reaction (Blue
| |
H NO
colour)
Tertiary P  I2
(CH 3 )3 COH  (CH 3 )3 Cl  (CH 3 )3 CNO 2 
AgNO 2
 No reaction (colourless)
HONO

Dihydric alcohols
 1202 Alcohol, Phenol and Ethers
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.  is 1, 2
Chlorohydrin
glycol,  is 1, 3 glycol.
(1) Preparation
(i) From ethylene : (a) Through cold dilute
alkaline solution of Bayer’s reagent
| |
(i) dil.
(ii) dil.
KMnO 4
–C= C–
OH– | |
| | OH OH
– C=C – (Syn-
hydroxylation)
OH
| | | |
RCO2OH H2O
–C–C– –C– C–
H+
| |
O OH
(Anti-
hydroxylation)
(b) With O2 in presence of Ag :
CH 2 1 CH 2 CH 2 OH
||  O2  
Cataly st
 | O  
H 2O
|
CH 2 2 Ag , 200  400 C CH dil. HCl
2 CH 2 OH
Ethy lene Ethy lene oxide Ethy lene gly col

(c) With HOCl followed by hydrolysis : (Industrial

method)
CH 2 CH 2 OH
||  HOCl  |
CH 2 CH 2 Cl
Ethy lene chlorohy drin

CH 2 OH
  
NaHCO 3
|  NaCl  CO 2
CH 2 OH
Gly col

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

CH 2 Br CH 2OH
|  Na 2 CO 3  H 2O  |  2 NaBr  CO 2
CH 2 Br CH 2OH
CH 2 Br CH 2 OOCCH 3
|  2CH 3 COOK   |
CH 3 COOH

CH 2 Br  2 KBr CH 2 OOCCH 3
Gly col diacetate

CH 2OH
  |
NaOH
 2CH 3 COONa
CH 2OH
(2) Physical properties
(i) It is a colourless, syrupy liquid and sweet in
taste. Its boiling point is 197°C.
(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.
(3) Chemical properties

Na CH2 ONa CH2 ONa

| N |
50° 160°
a
C CH2 OH C CH2 ONa
Dialkoxide
(Disodium
glycollate)
CH2Cl CH2 Cl
PCl PCl5
| |
5
CH2 OH CH2 Cl
1,2 Dichloroethane
 Alcohol, Phenol and Ethers 1203
Dioxalane formation provides a path of protecting CH 2 OH CH 2 OH
| |
a carbonyl group in reaction studied in basic medium in

 CH Cl
HOCl

 CH  OH
aq. NaOH
which acetals are not affected. The carbonyl compound | |
CH 2 OH CH 2 OH
may be regenerated by the addition of periodic acid to  - monochloro hy drin Gly cerol
aqueous solution of the dioxalane or by acidic
(iv) From propenal :
hydrolysis.
R R O  CH 2 CH 2  CHCHO 
 CH 2  CHCH 2 OH
H2
cataly st
C H 2 OH
C O |  C | 
CH 2 OH   HOCH 2CHOHCH 2OH
H 2O2 / O H
R R O  CH 2
Glycerol
  R  CO  R  2 HCHO
4 HIO
(2) Physical properties
Aldehyde is more reactive than ketone in dioxalane (i) It is a colourless, odourless, viscous and
formation. hygroscopic liquid.
O O (ii) It has high boiling point i.e., 290°C. The high
viscosity and high boiling point of glycerol are due to
+ CH2OH – CH2OH H association through hydrogen bonding.
CHO C (iii) It is soluble in water and ethyl alcohol but
insoluble in ether.
O O
This part does not react due to (iv) It is sweet in taste and non toxic in nature.
O steric hindrance O (3) Chemical properties
CH2 – OH
H3C CH3 | H3C CH3 (i) Reaction with sodium
CH2 – OH
CH 2 OH CH 2ONa CH 2ONa
| | |
O O CH  OH Na
 CH  OH Na
 CH  OH
O | Room | Room |

(4) Uses CH 2 OH temperatur e CH 2 OH temperatur e CH 2ONa

Monosodium gly cerol Disodium gly cerolate
(i) Used as an antifreeze in car radiators.
(ii) Reaction with PCl5, PBr3 and PI3
(ii) Used in the manufacture of dacron, dioxane CH 2OH CH 2Cl
etc. | |

(iii) As a solvent and as a preservatives. (a) CH OH  3 PCl 5  CH Cl  3 POCl 3  3 HCl

| |
(iv) As a cooling agent in aeroplanes. CH 2OH CH 2Cl
Gly cery l richloride
t
(v) As an explosives in the form of dinitrate. (1, 2, 3 - Trichloropropane)

Trihydric alcohols. CH 2OH CH 2 Br

| |
The only important trihydric alcohol is glycerol (b) CH OH  PBr 3  CH Br  H 3 PO 3
(propane-1, 2, 3-triol). It occurs as glycosides in almost | |
CH 2OH CH 2 Br
all animal and vegetable oils and fats. 1, 2, 3 - Tribromopr opane
(1) Preparation CH 2OHCH 2 I  CH 2
(i) From oils and fats | |  ||
(c) CH OH  PI 3   CH I   CH  I 2
CH 2 OOCR CH 2 OH |
|  |
| | CH 2OH CH 2 I  CH 2 I
CH OOCR  3 H 2 O  CH OH  3 RCOOH Ally liodide (Unstable)
| steam | Fatty acids
CH 2 OOCR CH 2 OH (iii) Reaction with HCl or HBr
Oil or fat Gly cerol
CH 2 OH CH 2 Cl CH 2 OH
CH 2 OOCR CH 2 OH | | |
NaOH o
| | CH OH  
110 C
CH OH  CH Cl
 HCl
CH OOCR  NaOH 
 CH OH Hy droly sis
 3RCOONa | | |
| | Sodium salt of CH 2 OH CH 2 OH CH 2 OH
CH 2 OOCR NaOH CH 2 OH higher fatty acids  - Gly cerol  - Gly cerol
monochloro hy drin monochloro hy drin
Oil or fat (66%) (34%)
(ii) By fermentation of sugar CH 2 Cl CH 2 Cl
C6 H12 O6   C3 H 8 O3  CH 3 CHO  CO 2
Yeast | |
Glucose Na 2SO 3 Glycerol Acetaldehyde 
 Excess of HCl
CH Cl  CH OH
o | |
110 C
(iii) From propene [Modern method] CH 2 OH CH 2 Cl
Gly cerol Gly cerol
CH 3 CH 2 Cl CH 2 OH  ,  - dichlorohy drin  ,  - dichlorohy drin

| | | (56%) (44%)
CH  CH
Cl 2
   CH
NaOH (dil )
(iv) Reaction with HI
|| o || ||
600 C
CH 2 CH 2 CH 2
propene Ally lchloride Ally lalcohol
 1204 Alcohol, Phenol and Ethers
CH 2OH CH 2 I CH 2
| | ||
(a) CH OH  3 HI  
 CH I Warm
 CH  I2
| | |
CH 2OH CH 2 I CH 2 I
1,2,3 - Tri- iodopropan e Ally liodide
(Unstable)

CH 2 CH 3 CH 3 CH 3
|| | | |
 I2
(b) CH  HI  CH I 
 CH 

HI
CH I
| | || |
CH 2 I CH 2 I CH 2 CH 3
Ally liodide Unstable Propene Isopropy l iodide

(v) Reaction with oxalic acid

(a) At 110°C Glycerol is formed (viii) Reaction with nitric acid
CH 2 OH CH 2 OOC COOH CH 2OH CH 2ONO 2
| | | |
100 110 o C
CH OH  HOOC  COOH  CH OH CH OH  3 HNO 3 
 CH ONO 2  3 H 2 O
conc. H 2 SO 4
| Oxalic acid  H 2O | | |
CH 2 OH CH 2 OH CH 2OH CH 2ONO 2
Gly cerolmono - oxalate Gly cery l rinitrate
t (T.N.G.)

O
|| Dynamite is prepared from T.N.G.
CH 2 O  C  H CH 2 OH
| | Dynamite : A mixture of T.N.G. and glyceryl
 CO

  CH  OH 2 CH OH  H COOH
2 H O
| |
dinitrate absorbed in kieselguhr is called dynamite. It
Formic acid
CH 2 OH CH 2 OH was discovered by Alfred. Nobel in 1867. It releases
Gly cerolmono formate Gly cerol
large volume of gases and occupy 10,900 times the
(b) At 260°C, allyl alcohol is formed volume of nitroglycerine.
CH 2 OH CH 2 OOC
| HOOC 
| | C3 H5 (ONO)3  12CO2  10 H 2O  6 N 2  O2
CH OH  |  2 H 2
 CH OO C
O
| HOOC |
Blasting gelatin : A mixture of glyceryl trinitrate
CH 2 OH CH 2 OH
CH 2 and cellulose nitrate (gun cotton).
||
 2 CO 2
  CH  CH 2 OH Cordite : It is obtained by mixing glyceryl
Ally lalcohol trinitrate with gun cotton and vaseline it is smokeless
(vi) Dehydration explosive.
CH 2OH CH 2
| || (4) Uses
CH OH  
conc. H 2 SO 4 / P2 O5 / KHSO 4
CH  2H 2O
|  | (a) As antifreeze in automobile radiator.
CH 2OH CHO
Acrolene or
acraldehy de (b) In the preparation of good quality of soap-
(vii) Oxidation hand lotions shaving creams and tooth pastes.
CHO COOH COOH (c) As a lubricant in watches.
| | |
[O] CHOH [O CHOH [O] CHOH (d) As a preservatives.
dil. | ] | |
HNO3
CH2OH CH2OH COOH (e) As a sweetening agent in confectionary,
Glyceraldehy Glyceric Tartronic beverages and medicines being non toxic in nature.
de acid acid
(f) In manufacture of explosives such as
dynamite.
CHO CH2OH
| | (5) Analytical tests of glycerol
CH2OH Fenton’ CHOH C=O
sreage
+
| | | (i) Acrolein test : When glycerol is heated with
nt
CHOH CH2OH CH2OH KHSO 4 a very offensive smell is produced due to
| Glyceraldehy Dihydroxy
CH2OH de acetone formation of acrolein. Its aqueous solution restores the
Glyceros colour of schiff’s reagent and reduces Fehling solution
e
and Tollen’s reagent.
CH2OH CH2OH COOH
| | | (ii) Dunstan’s test : A drop of phenolphthalein is
[O [O] [O]
CO CO CO added approximately 5 ml of borax solution. The pink
KMnO
] 4
| | |
acidifi
CH2OH COOH COOH colour appears on adding 2-3 drops of glycerol, pink
ed
Dihydroxy Hydroxy Mesoxalic colour disappears. The pink colour appears on heating
acetone Pyruvic acid and disappears on cooling again.
acid

COOH
[O] | [O]
CO2 + H2O
COOH
Oxalic acid

2CH2O
2HIO
+
 Alcohol, Phenol and Ethers 1205
Unsaturated alcohols (Allyl alcohol) as carbolic acid. It is also present in traces in human
urine.
(1) Preparation
(1) Preparation
(i) From allyl halide
(i) From benzene sulphonic acid
CH 2  CH  CH 2 Br  H 2 O  CH 2  CH  CH 2 OH  HBr
Ally lalcohol C6 H 6   C6 H 5 SO 3 H
H 2 SO 4 (f uming )
 
NaOH

Benzene Benzene sulphonic acid

(ii) By heating glycerol with oxalic acid : 

C6 H 5 SO 3 Na   C6 H 5 ONa 
NaOH
  C6 H 5 OH
H / H 2O

Sodium benzene sulphonate Fuse Sodium phenoxide or CO 2 / H 2 O Phenol

CH 2 OH CH 2 OOC CH 2
| HOOC 2 H 2O
| | ||
This is one of the laboratory methods for the
CH OH  |   CH OO C   CH
Heat
| HOOC |  2 CO 2 | preparation of phenol. Similarly methyl phenols
CH 2 OH CH 2 OH CH 2 OH
Ally lalcohol (cresols) can be prepared.

(2) Physical properties SO3H OK OH

(a) It is colourless, pungent smelling liquid.

Solid H+/H2O

(b) It is soluble in water, alcohol and ether in all Fuse

KOH

proportion.
(3) Chemical properties CH3 CH3 CH3
H 2 p-Toluene p-
Pt
CH3CH2CH2OH
sulphonic Cresol
1-propanol
acid
Br2
CH2Br – CHBrCH2OH (ii) From benzene diazonium chloride
2, 3-dibromopropanol-1 HNO 3
C6 H 6   C6 H 5 NO 2   C6 H 5 NH 2
Sn / HCl
o
HBr Benzene H 2 SO 4 , 45 C Nitrobenze ne Aniline
CH2BrCH2 CH2OH
3-Bromopropanol-1
 NaNO 2
C6 H 5 N 2 Cl   C6 H 5 OH
H 2O

HOCl HCl , 0  5 o C Benzene diazonium chloride Warm Phenol

CH2OHCHClCH2OH
Glycerol  -monochlorohydrin NH2 N2Cl OH
Alk.
KMnO
(O + 4 CH2 OH – CHOH – CH2OH
Glycerol HNO H2 O
H2O)
2HCl

CH2 = CH – CH2OH – Na
CH2 = CH – CH2ONa CH3 CH3 CH3
(Allyl alcohol) m- m-Toluene m-
CH3COOH
CH2 = CH – CH2OOCCH3 Toluidine diazonium Cresol
Allyl acetate chloride
 Diazonium salts are obtained from aniline and
HCl
CH2 = CH – CH2Cl its derivatives by a process called diazotisation.
Allyl chloride
(iii) From Grignard reagent
COOH
Oxidati | + HCOOH C 6 H 5 Br  Mg  
Ether
C 6 H 5 MgBr
on Bromobenze ne Phenyl magnesium bromide
COOH Formic acid
Oxalic 
 C 6 H 5 OMgBr 
O2
 C 6 H 5 OH
H 2O
acid H Phenol
CH2 – CH – CH2
Br2 | | | (iv) From salicylic acid :
Br Br OH OH OH
HNO [O] COOH
3

CH2 – CH – COOH + 2NaOH CaO + Na2CO3 + H2O

| |
Br Br
Salicylic Phenol
Zn (CH3OH
acid
dust ) (v) Middle oil of coal tar distillation : Middle oil
CH2 = CH – COOH
Acrylic acid of coal-tar distillation has naphthalene and phenolic
compounds. Phenolic compounds are isolated in
Phenol (Carbolic acid), C6H5OH or Hydroxy benzene following steps.
It was discovered by Runge in the middle oil Step I : Middle oil is washed with H 2 SO 4 . It
fraction of coal-tar distillation and named it ‘carbolic dissolves basic impurities like pyridine (base).
acid’ (carbo = coal, oleum = oil) or phenol containing Step II : Ecessive cooling separates naphthalene
5% water is liquid at room temperature and is termed (a low melting solid)
 1206 Alcohol, Phenol and Ethers
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.
C6 H5 OH  NaOH  C6 H5 ONa  H 2O

   C6 H5 OH  Na2CO3
CO 2 , H 2 O

Step IV : Crude phenol (of step III) is subjected to H H

+ – + | + + |
fractional distillation. H – O-------H –– –
O-------H – O-------H –
180°C  –

o, m, p-cresols O-------

Crude fraction
distillati
al
phenols on 211°- xylols (hydroxy
235°C (crossed intermolecular H-bonding between
(vi) Raschig’s process xylenes)
water and phenol molecules)
1
C 6 H 6  HCl  O 2    C 6 H 5 Cl  H 2 O
CuCl 2 / FeCl 3
Due to intermolecular H- bonding and high dipole
Benzene 2 250 o C Chlorobenz ene
moment, melting points and boiling points of phenol
o
C 6 H 5 Cl  H 2 O   C 6 H 5 OH  HCl
425 C are much higher than that of hydrocarbon of
Chlorobenz ene steam Phenol comparable molecular weights.
(vii) Dow process (iii) It has a peculiar characteristic smell and a
C 6 H 5 Cl  2 NaOH  
o
 C 6 H 5 ONa  NaCl  H 2 O
300 C strong corrosive action on skin.
Chlorobenz ene High pressure (iv) It is sparingly soluble in water but readily
sodium phenoxide on treatment with mineral acid soluble in organic solvents such as alcohol, benzene and
yields phenol. ether.
2C6 H 5 ONa  H 2 SO 4  2C6 H 5 OH  Na 2 SO 4 (v) It is poisonous in nature but acts as antiseptic
and disinfectant.
(viii) Oxidation of benzene
(3) Chemical properties
2C 6 H 6  O 2  
V2 O5
o
 2C 6 H 5 OH (i) Acidic nature : Phenol is a weak acid. The
315 C
acidic nature of phenol is due to the formation of stable
(ix) Oxidation of isopropyl benzene [Cumene]
phenoxide ion in solution.
H3C CH3
C6 H 5 OH  H 2 O ⇌ C 6 H 5 O   H 3 O 
AlCl3 Phenoxide ion
+ CH3CH2CH2Cl CH
The phenoxide ion is stable due to resonance.

O– O O O
AlCl3
+ CH3CH = CH2 Cumene –
.. –
..
O – OH
| ..
–
C(CH3)2 OH
The negative charge is spread throughout the
benzene ring. This charge delocalisation is a stabilising
O2 H2O/H
Cataly + + (CH3)2CO factor in the phenoxide ion and increase acidity of
st Acetone phenol. [No resonance is possible in alkoxide ions (RO–)
Cumene Phenol derived from alcohols. The negative charge is localised
hydroperoxi
de on oxygen atom. Thus alcohols are not acidic].
(2) Physical properties
 Phenols are much more acidic than alcohols but
(i) Phenol is a colourless crystalline, deliquescent less so than carboxylic acids or even carbonic acid. This
solid. It attains pink colour on exposure to air and is indicated by the values of ionisation constants. The
light. relative acidity follows the following order
(ii) They are capable of forming intermolecular H-
K a (approx. ) (10 5 )  (10 7 )  (10 10 )  (10 14 )  (10 18 )
bonding among themselves and with water. Thus, they RCOOH H 2 CO 3 C6 H 5 OH HOH ROH
Carboxy lic acid Water Alcohols
have high boiling points and they are soluble in water. Carbonic acid Phenol

Effects of substituents on the acidity of phenols

: Presence of electron attracting group, (e.g.,  NO 2 , –

+ – + –
H – O-------H – O-------H – O-------H –
O-------   + –
+ –

(intermolecular H-bonding among phenol

 Alcohol, Phenol and Ethers 1207
X,  NR 3 , –CN, –CHO, –COOH) on the benzene ring This is the test of phenol.
increases the acidity of phenol as it enables the ring to (b) Ether formation : Phenol reacts with alkyl
draw more electrons from the phenoxy oxygen and thus halides in alkali solution to form phenyl ethers
releasing easily the proton. Further, the particular (Williamson’s synthesis). The phenoxide ion is a
effect is more when the substituent is present on o- or nucleophile and will replace halogenation of alkyl
p-position than in m-position to the phenolic group. halide.
The relative strengths of some phenols (as acids) C 6 H 5 OH  NaOH  C 6 H 5 ONa  H 2 O
Sod. phenoxide
are as follows :
C 6 H 5 ONa  ClCH 3  C 6 H 5 OCH 3  NaCl
p-Nitrophenol > o-Nitrophenol > m- Nitrophenol Methy l phe ny l ether (Anisole)
> Phenol C 6 H 5 OK  IC2 H 5  C 6 H 5  O  C 2 H 5  KI
Presence of electron releasing group, (e.g., CH 3 , Ethoxy benzene (Phenetol)

C 2 H 5 ,  OCH 3 ,  NR 2 ) on the benzene ring decreases C 6 H 5 ONa  Cl  HC(CH 3 )2  C 6 H 5  O  HC(CH 3 )2

Isopropy l chloride Isopropy l pheny l ether
the acidity of phenol as it strengthens the negative Ethers are also formed when vapours of phenol
charge on phenoxy oxygen and thus proton release and an alcohol are heated over thoria (ThO 2 ) or Al 2 O3 .
becomes difficult. Thus, cresols are less acidic than
, ThO 2
phenol. C6 H 5 OH  HOCH 3   C6 H 5  O  CH 3
Methoxy benzene
However, m-methoxy and m-aminophenols are
stronger acids than phenol because of –I effect and (c) Ester formation : Phenol reacts with acid
absence of +R effect. chlorides (or acid anhydrides) in alkali solution to form
phenylesters (Acylation). This reaction (Benzoylation)
m-methoxy phenol > m-amino phenol > phenol >
is called Schotten-Baumann reaction.
o-methoxy phenol > p-methoxy phenol
Chloro phenols : o- > m- > p- C6 H 5 OH  NaOH  C6 H 5 ONa  H 2 O

Cresols : m- > p- > o- O

||
Dihydric phenol : m- > p- > o- C 6 H 5 ONa  Cl C CH 3  C 6 H 5 OOCCH 3  NaCl
Sodium phenoxide Acety lchloride Pheny l acetate
The acidic nature of phenol is observed in the
C 6 H 5 OH  (CH 3 CO ) 2 O 
 NaOH
following : Acetic anhydride
(a) Phenol changes blue litmus to red. C 6 H 5 OOCCH 3  CH 3 COOH
Pheny l acetate (ester)
(b) Highly electropositive metals react with
phenol. 2C6 H 5 OH  2 Na  2C6 H 5 ONa  H 2 O
||
(c) Phenol reacts with strong alkalies to form C 6 H 5 OH  Cl C  C 6 H 5  
NaOH

Benzoy l chloride
phenoxides. C6 H 5 OH  NaOH  C6 H 5 ONa  H 2 O
O
||
However, phenol does not decompose sodium
C 6 H 5  O  C  C 6 H 5  NaCl  H 2 O
carbonate or sodium bicarbonate, i.e., CO 2 is not Pheny l benzoate

evolved because phenol is weaker than carbonic acid. The phenyl esters on treatment with anhydrous
(ii) Reactions of –OH group AlCl 3 undergoes Fries rearrangement to give o- and p-
(a) Reaction with FeCl3 : Phenol gives violet hydroxy ketones.
colouration with ferric chloride solution (neutral) due OH OH
OOCCH3
to the formation of a coloured iron complex, which is a
COCH3
characteristic to the existence of keto-enol AlCl3
tautomerism in phenols (predominantly enolic form). (anhydrous)
+
hea
t
OH O
Phenyl
acetate COCH3
o p-
-
hydroxy
acetophenone
Enol Keto
(d) Reaction with PCl5 : Phenol reacts with PCl 5 to
OH
form chlorobenzene. The yield of chlorobenzene is poor
3–
and mainly triphenyl phosphate is formed.
6 + FeCl3  3H + FeO
+ + 3HCl
C6 H 5 OH  PCl 5  C6 H 5 Cl  POCl 3  HCl
6
 1208 Alcohol, Phenol and Ethers
3C6 H 5 OH  POCl 3  (C 6 H 5 )3 PO 4  3 HCl (c) Nitration : Phenol reacts with dilute nitric acid
at 5-10°C to form ortho and para nitro phenols, but the
(e) Reaction with zinc dust : When phenol is
yield is poor due to oxidation of phenolic group. The –
distilled with zinc dust, benzene is obtained.
OH group is activating group, hence nitration is
C6 H 5 OH  Zn  C6 H 6  ZnO possible with dilute nitric acid.
(f) Reaction with ammonia : Phenol reacts with OH OH OH
ammonia in presence of anhydrous zinc chloride at NO2
300°C or (NH 4 )2 SO 3 / NH 3 at 150°C to form aniline. HNO3(dil.
+
)(5-
This conversion of phenol into aniline is called
10°C)
Bucherer reaction. o-
Nitrophenol NO2
C 6 H 5 OH  NH 3 
 C 6 H 5 NH 2  H 2 O
ZnCl 2
p-
300 o C Aniline
Nitrophenol
It is believed that the mechanism of the above
(g) Action of P2S5 : By heating phenol with
reaction involves the formation of o- and p- nitroso
phosphorus penta sulphide, thiophenols are formed.
phenol with nitrous acid, HNO 2 (NaNO 2  HCl) at 0-5°C,
5 C 6 H 5 OH  P2 S 5  5 C 6 H 5 SH  P2 O 5
Thiophenol
which gets oxidised to o- and p- nitrophenol with dilute
nitric acid.
(iii) Reactions of benzene nucleus : The –OH
OH OH OH
group is ortho and para directing. It activates the
benzene nucleus. NO
HONO
+
(a) Halogenation : Phenol reacts with bromine in (0-
5°C)
carbon disulphide (or CHCl 3 ) at low temperature to o-
form mixture of ortho and para bromophenol. Nitrosophenol NO
p-
OH OH OH Nitrosopheno
Br OH OH l
(CS2
+ Br2 ) + NO2
[O] +
o- HNO3
Bromophenol (Dil.)
Br
p-
OH OH Bromophenol NO2
o- p-
Br Br Nitrophenol
+ 3Br2 + 3HBr
However, when phenol is treated with
concentrated HNO3 in presence of concentrated
Br H 2 SO 4 , 2,4,6-trinitrophenol (Picric acid) is formed.
2, 4, 6-
OH OH
Phenol forms a Tribromophenol
white precipitate
with excess of
bromine water yielding 2, 4, 6-tribromophenol. O2N NO2
HNO3
(b) Sulphonation : Phenol reacts with conc. (conc.)
H2SO4-
H 2 SO 4 readily to form mixture of ortho and para (conc.)

hydroxy benzene sulphonic acids. NO2

OH OH OH To get better yield of2, 4, picric
6- acid, first
Trinitrophenol
sulphonation of phenol is made (picric
and then
acid) nitrated.
SO3H
Presence of SO 3 H group prevents oxidation of phenol.
(H2SO4
) +
(d) Friedel-Craft’s reaction : Phenol when treated
o- with methyl chloride in presence of anhydrous
Hydroxybenzene SO3H aluminium chloride, p-cresol is the main product. A very
sulphonic acid
p- smallOH
amount of o-cresol is alsoOH
formed. OH
Hydroxybenzene
sulphonic acid CH3
At low temperature (25°C), the ortho-isomer is AlCl
+ CH3Cl +
the major product, whereas at 100°C, it gives mainly 3

the para-isomer. o-cresol

(minor)
CH3
p-Cresol
(major
product)
 Alcohol, Phenol and Ethers 1209

RX and AlCl 3 give poor yields because AlCl 3

coordinates with O. So Ring alkylation takes place as
follows,
C6 H 5 OH  AlCl 3  C6 H 5 OAlCl 2  HCl
Thus to carry out successful Friedel-Craft’s
reaction with phenol it is necessary to use a large
amount of AlCl 3 . The Ring alkylation takes place as
follows :
 OH
 CH 3 CH  CH 2 /
C6 H 5 OH   2   o - and p - C6 H 4
H SO 4

(CH 3 )2 CH  OH or HF \
 CH (CH 3 )2
OH OH OH
COCH3
anhydrous (g) Gattermann’s reaction : Phenol, when treated
+ CH3COCl +
AlCl3
Acetyl chloride with liquid hydrogen cyanide and hydrochloric acid gas
in presence of anhydrous aluminium chloride yields
COCH3 mainly p-hydroxy benzaldehyde (Formylation).
orth Para
o HCl  HC  N   ClCH  NH
AlCl 3
hydroxy
acetophenone
(e) Kolbe-Schmidt reaction (Carbonation) : OH OH OH
ONa OCOONa OH
AlCl H2 O
COONa + ClCH = NH
3HCl –NH3
+ CO2 130- Rearrangem
6
140°C ent
atm
Sodium Sodium CH = NH CHO
salicylate p-Hydroxy
phenyl
benzaldehyd
carbonate OH (h) Mercuration e
COOC6H5 OH OH OH

HgOCOCH3

Salol + +
OH
OCOCH3 (CH3COO)2Hg
COOH o-Hydroxy phenyl
COOH mercuric acetate HgOCOCH3
H+
H2 O CH3COCl
p-Hydroxy
phenyl
Salicylic acid
Aspiri mercuric acetate
(i) Hydrogenation
n
OH
OH OH
COOCH3
CH3OH

+ 3H2 Ni
150-
Oil of winter 200°C
(f) Reimer-Tiemann reaction : green
Phenol, on refluxing Phenol Cyclohexanol
(C6H5OH (C6H11,OH)
with chloroform and sodium hydroxide (aq.) followed ) (used as a good
by acid hydrolysis yields salicylaldehyde (o-hydroxy (iv) Miscellaneous reactions solvent)

benzaldehyde) and a very small amount of p-hydroxy (a) Coupling reactions : Phenol couples with
benzaldehyde. However, when carbon tetrachloride is benzene diazonium chloride in presence of an alkaline
used, salicylic acid (predominating product) is formed. solution to form a red dye (p-hydroxy azobenzene).
OH ONa
H N = NCl + OH NaO
H+2 –HCl
H
CHO O CHO Benzene diazonium Phenol
Salicylaldehy
NaOH chloride
de
OH N=N OH
CHCl3
OH
NaOH(aq. p-
) CHCl2 Hydroxyazobenzene
 1210 Alcohol, Phenol and Ethers

(c) Liebermann’s nitroso reaction : When phenol is

Phenol couples with phthalic anhydride in reacted with NaNO 2 and concentrated H 2SO 4 , it gives a
presence of concentrated H 2 SO 4 to form a dye, deep green or blue colour which changes to red on
(phenolphthalein) used as an indicator. dilution with water. When made alkaline with NaOH
O O original green or blue colour is restored. This reaction
|| ||
is known as Liebermann’s nitroso reaction and is used
C – OH C
as a test of phenol.
 O
OH HONO NO OH
C – OH C O NO
|| || Phthalic H
p- Quinoxi
O O anhydride
Nitrosophenol m
Phthalic
H H H2SO
acid O N OH + H OH
4H2O

O N OH NaO Sod. Salt of

–H2O
H
indophenol
OH OH Indo phenol (Red) (blue)
Phenol (2
molecules) (d) Oxidation : Phenol turns pink or red or brown
O on exposure to air and light due to slow oxidation. The
||
C colour is probably due to the formation of quinone and
phenoquinone.
Conc. O
H2SO
(–4 O2 by C6H5OH
H2O) C C6H5OH OH O O
air
or
or CrO3
p-
benzoquinone

OH - - - O O - - - HO
Phenoquinone
(pink)
OH OH OH O
Phenolphthale
in
[O
(b) Condensation with formaldehyde : Phenol CrO]2Cl + H2O
condenses with formaldehyde (excess) in presence of 2
Phenol
sodium hydroxide or acid (H  ) for about a week to O
form a polymer known as bakelite (a resin). p-
benzoquinone
OH OH OH But on oxidation with potassium persulphate in
alkaline solution, phenol forms 1, 4-dihydroxy benzene
CH2OH
(Quinol). This is known as Elbs persulphate oxidation.
NaO
+ CH2O +
H OH OH
o-hydroxy
benzyl alcohol CH2OH K2S2O8
p-hydroxy in
alkaline
benzyl alcohol solution
Pheno
l
OH
OH OH Quinol

Condensation (4) Uses : Phenol is extensively used in industry.

CH2 CH2 CH2
with HCHO
continues give The important applications of phenol are

CH2 CH2

Polymer Bakelite (a
resin)
 Alcohol, Phenol and Ethers 1211
(i) As an antiseptic in soaps, lotions and (i) Aqueous solution of phenol gives a violet
ointments. A powerful antiseptic is “Dettol” which is a colouration with a drop of ferric chloride.
phenol derivative (2, 4-dichloro-3, 5-dimethyl phenol).
(ii) Aqueous solution of phenol gives a white
(ii) In the manufacture of azo dyes,
precipitate of 2, 4, 6-tribromophenol with bromine
phenolphthalein, etc.
water.
(iii) In the preparation of picric acid used as an
explosive and for dyeing silk and wool. (iii) Phenol gives Liebermann’s nitroso reaction.
(iv) In the manufacture of cyclohexanol required
for the production of nylon and used as a solvent for
Phenol in conc. sulphuric acid   Red
NaNO 2
Excess of water
rubber and lacquers.
(v) As a preservative for ink.
colour 
 Blue colour
NaOH
(Excess)
(vi) In the manufacture of phenol-formaldehyde
plastics such as bakelite. (iv) Phenol combines with phthalic anhydride in
(vii) In the manufacture of drugs like aspirin, presence of conc. H 2 SO 4 to form phenolphthalein which
salol, phenacetin, etc. gives pink colour with alkali, and used as an indicator.
(viii) For causterising wounds caused by the bite
(v) With ammonia and sodium hypochlorite,
of mad dogs.
phenol gives blue colour.
(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

Table : 26.2 Difference between phenol and alcohol

Property Phenol (C6H5OH) Alcohol (C2H5OH)
Odour Typical phenolic odour Pleasant alcoholic odour
Nature, reaction with alkali Acidic, dissolves in sodium Neutral, no reaction with alkalies.
hydroxide forming sodium
phenoxide.
Reaction with neutral FeCl3 Gives violet colouration due to No reaction.
formation of complex compound.
Reaction with halogen acids No reaction with halogen acids. Forms ethyl halides.
Oxidation Pink or brown colour due to Undergoes oxidation to give
formation of quinone and acetaldehyde and acetic acid.
phenoquinone.
Reaction with HCHO Forms polymer (bakelite). No reaction.
Liebermann’s nitroso reaction Positive. Does not show.
Coupling with benzene diazonium Forms azo dye. Does not form any dye.
chloride
Reaction with PCl5 Mainly forms triphenyl phosphate. Forms ethyl chloride
Iodoform test Does not show. Positive.

Derivatives of phenol
NITROPHENOLS
Cl OH
(1) Preparation
(ii) C6 H 4   C 6 H 4
NaOH

OH OH OH 120 C
NO 2 NO 2
o - and p - chloro nitrobenze ne o - and p - nitropheno l
NO2
Dil. OH
HNO3
+
(iii) C6 H 5 NO 2 
 C6 H 4Solid KOH

Nitrobenze ne heat
o-isomer
NO 2
(steam NO2 o - and p - nitropheno l
volatile) p-isomer
(non-volatile)
 1212 Alcohol, Phenol and Ethers
(iv) NO2 NH2

NH4HS NaNO2/HCl
or 0-5°C
NO2 Na2S NO2
m- m-Nitroaniline
Dinitrobenzen
e (ii) From phenol through disulphonic acid
N2Cl OH
OH OH OH
H2 O
SO3H O2N NO2
H2SO4 HNO3
NO2 NO2
m-Nitrobenzene m-Nitrophenol
diazonium
chloride Phenol
(2) Properties : o-Nitrophenol is a yellow SO3H NO2
Phenol disulphonic Picric acid
coloured crystalline compound, while m- and p-isomers acid
are colourless crystalline compounds.
Isomer ortho meta para (iii) OH
m.pt. (C) 45 97 114 O2N NO2 O2N NO2
Ke3Fe(CN)
The lowest melting point of o-isomer is due to + [O] 6

intramolecular hydrogen bonding whereas meta and

para isomers possess intermolecular hydrogen
NO2 NO2
bonding and thus, they have higher melting points.
TNB Picric
They are stronger acids than phenol. The order is acid

: (2) Properties : It is a yellow crystalline solid,

melting points 122°C. it is insoluble in cold water but
p-isomer > o-isomer > m-isomer > phenol
soluble in hot water and in ether. It is bitter in taste.
When reduced, they form corresponding Due to the presence of three electronegative nitro
aminophenols. o- and p-Nitrophenols react with groups, it is a stronger acid than phenol and its
bromine water to form 2, 4, 6-tribromophenol by properties are comparable to the carboxylic acid. It
replacement of nitro group. OH neutralises alkalies and decomposes carbonates with
OH Br Br evolution of carbon dioxide.
/
C6 H 4 
Br2 Dry picric acid as well as its potassium or
\ ammonium salts explode violently when detonated. It
NO 2
o - or p - isomer reacts with PCl 5 to form picryl chloride which on
Br
shakingOH
with NH 3 yields Cl
picramide. NH2
2,4,6 Tribromophenol
O2N NO2 O2N NO2 O2N NO2
PCl5 NH3
Picric acid (2, 4, 6-trinitrophenol) H2O

(1) Preparation : It is obtained when phenol is

treated with conc. HNO 3 . However, the yield is very NO2 NO2 NO2
Picryl Picramide
poor. It is prepared on an industrial scale : chloride
(i) From chlorobenzene
When distilled with a paste of bleaching powder,
Cl Cl it gets decomposed and yields chloropicrin, CCl 3 NO 2 ,
NO2 as one of the products and is thus employed for the
HNO3 Aq. manufacture of tear gas.
H2SO4 Na2CO3
It forms yellow, orange or red coloured molecular
Chlorobenze compounds called picrates with aromatic hydrocarbons,
ne NO2
2, 4-
amines and phenols which are used for characterisation
Dinitrochlorobenzene of these compounds.
OH OH  Picrates are explosive in nature and explode
NO2 O2N NO2 violently when heated. These are prepared carefully.
HNO3
H2SO4

NO2 NO2
Picric acid
(2, 4, 6-
Trinitrophenol)
 O O
||
OH ||
OH
C OH C OH
Con H2SO4
O+ (–
C H2O) C
|| ||
O Alcohol, Phenol and Ethers 1213
O
Phthalic Alizar
anhydride in
(3) Uses : It is used as a yellow dye for silk and (3) Uses : It finds use as photographic developer,
wool, as an explosive and as an antiseptic in treatment in the manufacture of alizarin and adrenaline hormone
of burns. and as an antioxidant (inhibitor in auto oxidation) for
Catechol (1, 2-Dihydroxy benzene) preserving gasoline.
(1) Preparation Resorcinol (1, 3-Dihydroxy benzene)
(i)OH OH (1) Preparation : It is prepared by alkali fusion of
1,3, benzene disulphonic acid (Industrial method).
Cl OH
NaOH + CO2 + NaCl SO3H ONa OH
;
NaOH HCl
Catecho
COOH l Fuse
SO3H ONa OH
Cl ONa OH
Cl ONa OH
(2) Properties : It is a colourless crystalline solid,
NaOH H+/H2
200°C, O melting points 110°C. it is affected on exposure by air
Cu2+ and light. It is soluble in water, alcohol and ether. It
(ii) shows tautomerism. Its aqueous solution gives violet
OH OK OH colour with FeCl 3 . It reduces Fehling’s solution and
SO3K OK OH Tollen’s reagent on warming.
2HCl With bromine water, it gives a crystalline
+ 3KOH
precipitate, 2, 4, 6-tribromoresorcinol.
o-phenol Catechol OH OH
sulphonic
(iii) Br Br
acid CHO OH
+ 3Br2 + 3HBr
+ H2O2 + + HCOONa + H2O
NaOH OH OH
OH OH Br
Salicylaldehy Catechol
de
(2) Properties : It is a colourless crystalline solid, On nitration, it forms 2, 4, 6-trinitro-1, 3-
melting points 105°C. it is soluble in water. It is dihydroxybenzene.
affected on exposure to air and light. It acts as a OH OH
reducing agent as it reduces Tollen’s reagent in cold O2N NO2
and Fehling’s solution on heating. With silver oxide it is HNO3
oxidised to o-benzoquinone. H2SO4

OH O OH OH
Resorcinol
OH NO2
O Styphnic acid
+ Ag2O + 2Ag + H2O It condenses with phthalic anhydride and forms
fluorescein. OH OH
o-
Benzoquinone
It forms insoluble lead salt (white ppt.) when
treated with lead acetate solution and gives green O H OH O
colour with FeCl 3 which changes to red on adding Conc. H2SO4
O=C C= O+ – O=C C O
Na 2 CO 3 solution. It forms alizarin dye stuff when H OH 2H2O
condensed with phthalic anhydride in the presence of
sulphuric acid.
OH OH
O O Phthalic Fluorescei
||
OH ||
OH Resorcinol
n
anhydride (2 moles)
C OH C OH
Con H2SO4
O+ (–H2O) With nitrous acid, it forms 2, 4-
C C
|| ||
dinitrosoresorcinol
O O OH OH O
Phthalic Alizarin
anhydride NO NOH
HNO2

OH OH O
NO NOH
 1214 Alcohol, Phenol and Ethers
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 220°C.
Resorcinol behaves as a tautomeric compound.
OH OH
This is shown by the fact that it forms a dioxime and a
bisulphite derivative. OH OH
OH O hea
220°
t + CO2
HOOC C
OH OH
Gallic Pyrogallol
acid
OH O
Dienol Diketo Phloroglucinol is obtained from trinitrotoluene
form form (TNT) by following sequence of reactions.
(3) Uses
(i) It is used as antiseptic and for making dyes. CH3 COOH
(ii) It is also used in the treatment of eczema. 2, O2N NO2 O2N NO2
4, 6-trinitroresorcinol is used as an explosive. KMnO4 Fe/HCl
[O] [H]
Hydroquinone or quinol (1, 4-Dihydroxy
benzene)
(1) Preparation : It is formed by reduction of p- NO2 NO2
2, 4, 6-trinitro
benzoquinone with sulphurous acid toluene
(H 2 SO 3  H 2 O  SO 2 ) . COOH
O O+SO2+2H2O HO OH+H2SO4
H2N NH2 HO OH
H2SO3+H2O H2O/H+
Quinol
100°C +CO2+3NH4Cl

(p-Benzoquinone is obtained by oxidation of NH2 OH

aniline) Phlorogluci
nol
Hydroxyquinol is prepared by the alkaline fusion
NH2 O OH of hydroquinone in air.
OH OH
[O Fe/H2
MnO2]/H2SO [H
O OH
4 ] NaOH
+ ½ O2 Fus
Aniline
O OH e
Quino
(2) Properties : It is a colourless crystalline solid, l OH OH
Quinol Hydroxy
melting points 170°C. it is soluble in water. It also Quinol
shows tautomerism. It gives blue colour with FeCl 3 The three isomers are colourless crystalline
compounds. All are soluble in water and their aqueous
solution.
solutions give characteristic colour with FeCl 3 (Red,
It acts as a powerful reducing agent as it is easily
oxidised to p-benzoquinone. It reduces Tollen’s reagent brown or bluish violet). Alkaline solutions absorb
and Fehling’s solution. oxygen rapidly from air.

[O]
HO OH FeCl3
O O Uses of pyrogallol
Quinol p- (i) As a developer in photography.
Benzoquinone (ii) As a hair dye.
Due to this property, it is used as photographic
developer. (iii) In treatment of skin diseases like eczema.
(3) Uses : It is used as an antiseptic, developer in (iv) For absorbing unreacted oxygen in gas
photography, in the preparation of quinhydrone analysis.
electrode and as an antioxidant.
Ether
 Alcohol, Phenol and Ethers 1215
Ethers are anhydride of alcohols, they may be ROH  HOR 24 ROR  H 2 O .
H SO (conc.)

obtained by elimination of a water molecule from two 2 molecules of alcohol 140 o C Ether

alcohol molecules.  In this reaction alcohol must be present in

R  OH  HO  R  R  O  R  H 2 O excess.
Ether
 This reaction is mainly applicable for the
General formula is Cn H 2n  2O dehydration of primary alcohols. Secondary and tertiary
General methods of preparation of ethers alcohols form alkenes mainly.
(1) From alkyl halides  When this reaction is carried out between
different alcohols then there is a mixture of different
(i) Williamson’s synthesis
ethers is obtained.
It is a nucleophilic substitution reaction and
(b) With Al2O3 at 250° C :
proceed through S N 2 mechanism.
2 ROH 2
  R  O  R  H 2O
3 Al O

RONa  RX  RO R  NaX 250 o C

C 2 H 5 ONa  CH 3  I  CH 3 OC 2 H 5  NaI (ii) By the action of diazomethane on alcohols :

Sodium ethoxide Ethy l methy l ether This reaction is in presence of catalyst, boron
C 2 H 5 ONa  C 2 H 5 Br  C 2 H 5 OC 2 H 5  NaBr trifluoride or HBF4 .
Sodium ethoxide Ethy l brom ide Ethoxy etha ne
ROH  CH 2 N 2   R  O  CH 3  N 2
3 BF

(a) Order of reactivity of primary halide is

(a) This method is very useful for preparing
CH 3 X  CH 3 CH 2 X  CH 3 CH 2CH 2 X .
mixed ethers.
(b) Tendency of alkyl halide to undergo (b) In higher cases, there can be 1, 2-hydride or 1,
elimination is 3 o  2 o  1o . 2-methyl shift to form more stable carbonium ion.
(c) For better yield alkyl halide should be primary (3) Alkoxy mercuration-demercuration
and alkoxide should be secondary or tertiary.  C  C   R  OH  Hg[OOCCF3 ]2
alkene Mercuric trifluoro acetate
CH 3 CH 3
| | | | | |
C 2 H 5 Br  NaO  C  CH 3  C 2 H 5  O  C  CH 3  C  C    C  C
NaBH 4
| | | | | |
Ethy l brom ide
CH 3 CH 3 OR HgOOCCF3 OR H
Sodium salt of Ethy l tert. buty l ether Ether
tert. buty l alcohol
 This is the best method for the preparation of t-
(d) Secondary and tertiary alkyl halides readily ethers.
undergo E2 elimination in the presence of a strong base (4) Reaction of lower halogenated ether with
to form alkenes. grignard reagent
CH 3 CH 3 ROCH 2 X  XMg R  ROCH 2 R MgX 2
| | Halogenate d Grignard Higher
 CH 3  C   Cl  ,
ether reagant ether
CH 3  C  Cl 2 5 
C H ONa
| |
CH 3 CH 3 (i) Higher members can be prepared by the action
of grignard reagent on lower halogenated ethers.
CH 3 CH 3 (ii) Ether form soluble coordinated complexes
| |
 
CH 3  C  C 2 H 5 O  CH 3  C  C 2 H 5 OH with grignard reagent.
| ||
CH 2  H CH 2 Physical properties
(1) Physical state : Methoxy methane and
 Aryl halide and sodium alkoxide cannot be used
methoxy ethane are gases while other members are
for preparing phenolic ethers because aryl halide are less
volatile liquid with pleasant smell.
reactive toward nucleophilic substitution reaction than
alkyl halides. (2) Dipole moment (D.M.) : Bond angle of ether
is due to sp 3 hybridisation of oxygen atom. Since C – O
(ii) By heating alkyl halide with dry silver oxide
bond is a polar bond, hence ether possess a net dipole
2 RX  Ag 2 O   R  O  R  2 AgX ,
heat
moment, even if they are symmetrical. dipole moment
of dimethyl ether is 1.3 D and dipole moment of di
2C2 H 5 Br  Ag 2 O   C2 H 5 OC 2 H 5  2 AgBr
heat

Ethyl bromide Diethyl ether ethyl ether is 1.18 D.

(2) From alcohols  The larger bond angle may be because of greater
(i) By dehydration of alcohols repulsive interaction between bulkier alkyl groups as
compared to smaller H-atoms in water.
(a) With conc. H2SO4 at 140° C
 1216 Alcohol, Phenol and Ethers
(3) Boiling points : Boiling points of ethers are  Formation of peroxide can be prevented by
much lower than those of isomeric alcohols, but closer adding small amount of Cu 2 O to ether.
to alkanes having comparable mass. This is due to the
 With strong oxidising agent like acid,
absence of hydrogen bonding in ethers.
dichromate ethers are oxidised to aldehydes.
(4) Solubility : Solubilities of ethers in water are
CH 3 CH 2 OCH 2 CH 3   2CH 3 CHO  H 2 O
2[O ]
comparable with those of alcohols. Acetaldehyde

Example : Di ethyl ether and n-butyl alcohol have  The presence of peroxide can be indicated by the
approximately the same solubility in water. This is formation of blood red colour complex in the following
because, ether form hydrogen bond with water much in reaction.
the same way as alcohol do with water. 
Peroxide  Fe 2  Fe 3  
SCN
 [Fe (SCN )n ]3 n
R Blood red colour
(n 1 to 6 )
O .......... H O
R R
Ether H .......... . O (ii) Oxidation with K2Cr2O7 / H
Water
R   R
Ether R  CH 2  O  CH
R
 Solubility of ether in water decreases with the
size of alkyl groups. (a) Oxidation of ether can only be possible if any
one of the alkyl groups of ether has hydrogen on -
(5) Hydrogen bonding : There is no hydrogen
carbon.
directly attach (bonded) to oxygen in ethers, so ethers
do not show any intermolecular hydrogen bonding. (b) -carbon having two hydrogens converts in
carboxylic group and -carbon having only one
R R R
| | | hydrogen converts into keto group.
H  O- - - H  O- - - H  O- - - R O R  
hy drogenbo nding in alcohols No hy drogen bond in ether
CH 3  CH 2  O  CH 2  CH 2  CH 3
(6) Density : Ethers are lighter than water.
   CH 3  COOH  CH 3  CH 2  COOH
K 2 Cr2 O7

Chemical properties : Ethers are quite stable H /

compounds. These are not easily attacked by alkalies, CH 3

CH 3  CH 2  O  CH
dilute mineral acids, active metals, reducing agents or CH 3
oxidising agents under ordinary conditions.
O
(1) Reaction due to alkyl group ||
 

 CH 3  COOH  CH 3  C  CH 3
K 2 Cr2 O7

(i) Halogenation : H /

(iii) Salt formation : Due to lone pair of electrons

CH 3 CH 2 OCH 2 CH 3  CH 3 CHClOCH 2 CH 3
Cl 2

Diethyl ether dark ( -Monochloro diethyl ether ) on oxygen atom. Ether behaves as Lewis base and form
stable oxonium salt with strong inorganic acids at low
CH 3 CH 2 OCH 2 CH 3 
 CH 3 CHClOCHClC H 3
Cl 2

Diethyl ether dark ( ,  -Dichlorodiethyl ether )

temperature.
H
C 2 H 5 OC 2 H 5  10 Cl 2 
 C 2 Cl 5 OC 2 Cl 5  10 HCl
Cl 2 |
light (Perchlorodiethyl ether ) C 2 H 5 OC 2 H 5  HCl  (C 2 H 5 )2 O  Cl  or
..
(ii) Burning : Ethers are highly inflammable. Diethy l oxonium chloride

They burn like alkanes. [(C 2 H 5 )2 O  H ] Cl 

C 2 H 5  O  C 2 H 5  6O2  4 CO 2  5 H 2 O ..

(2) Reaction due to ethernal oxygen C 2 H 5 OC 2 H 5  H 2 SO 4  (C 2 H 5 )2 O  HSO 4 or
|
(i) Peroxide formation : H
Diethy l oxonium hy drogen sulphate
.. ..
C 2 H 5 O C 2 H 5  O :  (C 2 H 5 )2 O  O . [(C 2 H 5 )2 O  H ] HSO 4
.. ..
The oxonium salts are soluble in acid solution and
(a) The boiling point of peroxide is higher than
ethers can be recovered from the oxonium salts by
that of ether. It is left as residue in the distillation of
treatment with water.
ether and may cause explosion. Therefore ether may
(C2 H 5 )2 O Cl 2 (C2 H 5 )2 O  HCl
H O
never be evaporated to dryness. | Diethy l ether
(b) Absolute ether can be prepared by distillation H
Oxonium salt
of ordinary ether from conc. H 2 SO 4 and subsequent  The formation of oxonium salt is similar to the
storing over metallic sodium. formation of ammonium salts from ammonia and acids.
 Alcohol, Phenol and Ethers 1217
 Ether is removed from alkyl halides by shaking  The silver iodide thus form can be detected and
with conc. H 2 SO 4 . estimated. This is the basis of Zeisel method for the
 Ethers can be distinguished from alkanes with detection and estimation of alkoxy group in a compound.
the help of this reaction. (iv) Action of PCl5
(iv) Reaction with Lewis acids : Being Lewis R  O  R  PCl 5   2 RCl  POCl 3 .
heat
There is
bases, ethers form complexes with Lewis acids such as no reaction in cold.
BF3 , AlCl 3 , FeCl 3 , etc. These complexes are called (v) Reaction with acetyl chloride
etherates.
CH 3 COCl  C 2 H 5  O  C 2 H 5  
 CH 3 COOC 2 H 5
ZnCl 2

CH 3 CH 2 .. CH 3 CH 2 .. Acetylchloride Diethyl ether heat Ethyl acetate

O :  BF3  O  BF3
CH 3 CH 2 CH 3 CH 2 (vi) Reaction with acid anhydride
Boron trifluoride etherate (complex)
CH 3 CO  O  OCCH 3  C2 H 5  O  C2 H 5
Acetic anhy dride Diethy l ether
Similarly, diethyl ether reacts with Grignard
reagent forming Grignard reagent etherate. 
2
 2CH 3 COOC 2 H 5
ZnCl
heat Ethy l acetate

R O(CH 2 CH 3 )2 (vii) Dehydration

2(CH 3 CH 2 )2 O  RMgX  Mg
(CH 3 CH 2 )2 O X
Grignard reagent etherate
C 2 H 5 OC 2 H 5   2CH 2  CH 2  H 2 O
Al 2 O3
300 o C
Due to the formation of the etherate, Grignard (viii) Reaction with carbon mono oxide
reagents dissolve in ether. That is why Grignard o
C 2 H 5 OC 2 H 5  CO   C 2 H 5 COOC 2 H 5
BF3 / 150 C
reagents are usually prepared in ethers. However, they Diethy l ether 500 atm. Ethy l propionate
cannot be prepared in benzene, because benzene has no
(ix) Action of bases
lone pair of electrons and therefore, cannot form  
complexes with them. L i C H 3  H  CH 2  CH 2  O  CH 2  CH 3
 
(3) Reaction involving cleavage of carbon-
 CH 4  CH 2  CH 2  L i O C 2 H 5
oxygen bond
(4) Ring substitution in aromatic ethers :
(i) Hydrolysis
Alkoxy group is ortho and para directing and it directs
(a) With dil. H 2 SO 4 : ROR  H 2O   2 ROH
H 2 SO 4
the incoming groups to ortho and para position. It
activates
.. the.. aromatic .. ring towards
.. electrophilic
..
C2 H 5 OC 2 H 5  H 2 O   2C2 H 5 OH
H 2 SO 4

Diethy l ether Ethanol substitution

:OR reaction.
:O – R +
OR +
OR +
OR
(b) With conc. H 2 SO 4 :

.. :
C 2 H 5 OC 2 H 5  H 2 SO 4  C 2 H 5 OH  C 2 H 5 HSO 4
C 2 H 5 OH  H 2 SO 4 C 2 H 5 HSO 4  H 2 O
..
C 2 H 5 OC 2 H 5  2 H 2 SO 4  2 C 2 H 5 HSO 4  H 2 O 
Diethy l ether Ethy l hy drogen sulphate I II III IV V

(ii) Action of hydroiodic acid

(a) With cold HI III, IV and V show high electron density at ortho
and para position.
C2 H 5 OC2 H 5  HI   C2 H 5 I  C2 H 5 OH
Cold

Diethyl ether Ethyl iodide Ethyl alcohol (i) Halogenation : Phenyl alkyl ethers undergo
usual halogenation in benzene ring.
OC2H5 OH
For example, Bromination of anisole gives ortho
and para bromo derivative even in the absence of iron
+ HBr + C2H5Br OCH3 catalyst.
(III) bromide OCH3 OCH3
 B

Phenyl ethyl Phenol Ethyl bromide Br2 r +
ether
CS 2
(b) With hot HI Anisol o-
R  O  R   2 HI   RI  R I  H 2 O
heat e Bromoanisole Br
p-
Bromoanisole
(iii) Zeisel method : Para isomer is obtained in 90% yield.
RI  AgNO 3 (alc.)  AgI   RNO 3 (ii) Friedel craft reaction
OCH3 OCH3 OCH3
CH3
+ CH 3 Cl  
AlCl 3
+
Methyl chloride

Anisol Ortho
e CH3
Para
 1218 Alcohol, Phenol and Ethers
CH3OH > C2H5OH > (CH3)2CHOH > (CH3)3C – OH
HCOOH > CH3COOH > (CH3)2CH – COOH > (CH3)C –
COOH.
 Pinacol-pinacolone rearrangement : The
OCH3 OCH3 OCH3 reaction involves dehydration of diols through the
COCH3 formation of carbocation intermediate which
+ CH 3 COCl  

AlCl 3 rearranges to more stable compound.
+
OH OH O CH 3
| |  || |
Anisol o-Methoxy CH 3  C  C  CH 3 
H
 CH 3  C  C  CH 3
e acetophenon | |  H 2O |
COCH3
e CH 3 CH 3 CH 3
p Methoxy Pinacol Pinacolone
(iii) Nitration acetophenon
e  In general, acid strength increases as Cresols <<
OCH3 OCH3 OCH3 Phenol << p-chlorophenol << m-Nitrophenol << o-
NO3 Nitrophenol < p-Nitrophenol << Picric acid.
  
HNO 3 / H 2 SO 4 +  Glyceryl trinitrate is an inorganic ester.
 Glyceryl trinitrate is colourless, oily liquid
Methyl Methyl-2 insoluble in water and is called Nobel’s oil. Nobel’s
phenyl nitrophenyl NO2
ether ether Methyl-4
oil is also used in the treatment of anginapectoris
(Anisole) (o- nitrophenyl and asthma.
Nitroanisole) ether
(p-
 Ether peroxide formation is prevented by adding
 Ethers are relatively less reactive than phenol
Nitroanisole) a little Cu2O to it.
towards electrophilic substitution reaction.
 Di-isopropyl ether is used in the petrol as an
antiknock compound.
 The mixture of alcohol and ether is used as a
substitute for petrol under the trade name natelite.
 Ethers form soluble co-ordination complexes
with Grignard’s reagent i.e., why Grignard reagent is
usually prepared in ether.
 Methyl alcohol (CH3OH) is called wood spirit. It  Thio alcohols are known as mercaptans.
is obtained by destructive distillation of wood.
Drinking of methanol causes blindness.
 Ethyl alcohol (C2H5OH) is called grain alcohol. It
is used in preparation of various beverages by using
different percentages.
 An alcohol-water mixture containing 57.1% alcohol
by volume or 49.3% by weight is called proof spirit.
 Ethyl alcohol containing 5 to 10% methyl alcohol
is called methylated spirit. It is unfit for drinking
purpose. Widespread deaths due to liquor poisoning
occur mainly due to the presence of methyl alcohol.
It is also called denatured spirit. Denaturing can also
be done by adding 0.5% pyridine, petroleum
naphtha, rubber distillate (caoutchoucine) or CuSO4.
 Pyroligneous acid contains acetic acid (10%),
methyl alcohol (2.5%) and acetone (0.5%).
 Fusel oil is a mixture of n-propyl alcohol, n-butyl
alcohol, n-amyl alcohol and isoamyl alcohol.
 Tincture of iodine is 2-3% alcoholic solution of
iodine.
 In the esterification reaction, the water formed is
removed by Dean and stark apparatus. It should be
noted that bulkier the acid or alcohol, slower is the
rate (due to stearic hinderance). Decreasing order of
rate of reaction of different alcohols and acids is