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25

ALCOHOLS, PHENOLS AND ETHERS


(CLASS XII CHEMISTRY)
Concepts
(d) From esters (with Grignard reagent) :

ALCOHOLS
(R OH)

General formula CnH2n+1OH


Methods of Preparation of Alcohols
(a) From alkyl halides :
aq KOH

RX

||

ethylformate

ROH + KX

2 alcohol

(ii)
Moist AgOH

Esters other than formic ester + RMgX


H O / H+

ROH + AgX

3 alcohol
OH

O
||

LiAlH 4

Aldehydes
1 alcohol

CH3CHO
CH3CH 2OH
acetaldehyde
ethanol

3 alcohol

(e) From alkenes :


(i) Hydration of alkene

LiAlH

4 2 alcohol
Ketone

OH

||

(i) dry ether

R - C - OC 2 H 5 + 2R MgX
R - C - R
(ii) Mg(OH)X

LiAlH 4

(ii)

(i) dry ether

H - C - OC 2 H 5 + 2R MgX H - C - R
(ii) - Mg(OH)X

(b) By reduction of carbonyl compounds, acids and esters:


(i)

H O / H+

2
Formic esters + 2RMgX
2 alcohol
OH

(i)
O

conc H 2SO4
RCH = CH 2 + H 2O
R - CH - CH 3
Anti Markownikoff rule

OH

LiAlH

4 CH - C - CH
CH3 - C - CH3
3
3

acetone

2-propanol

LiAlH4 / H2 - Ni

1 alcohol
(iii) Acid
LiAlH / Na - alcohol

4
(iv) Ester
mixture of alcohols

Rearrangement occurs during reaction because


reaction must proceed via most stable
carbonium ion.
Trans product are formed during reaction.
CH3
CH3
H
BH3

THF

LiAlH

4 RCH OH + R OH
RCOOR
2

(c) By reaction of Grignard reagent and carbonyl


compounds :
H2O / H+

(i)

1 alcohol
HCHO + RMgX

(ii)

Any other aldehyde + RMgX


H 2 O/ H+

2 alcohol
+

H 2O / H
(iii) Ketone + RMgX
3 alcohol

OH
H

1-methoxycyclohexene

Trans-2-methylcyclohexanol

The addition of water to alkene is syn.


(ii) Hydroboration Oxidation reaction
dry ether
Anti Markownikoff addition

RCH = CH 2 + B2 H 6

diborane

NaOH/H O

2 2
2(RCH 2CH 2 )3 B

Trialkylboron

RCH 2 CH 2 OH + 2H 3 BO 3

It
is
anti-Markownikoff
addition of H2O to alkene.
CH3OH cannot be prepared by Grignard reagent.

The addition of water to alkene is syn.


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2
(iii) Oxymercuration demercuration reaction
RCH

(CH3COO) 2 Hg, THF - H 2O


= CH 2

Markownikoff addition

NaBH4 / OH
R - CH - CH3

R - CH - C H 2
|

OH
OH HgOCOCH3

It is Markownikoff addition of water to alkene.

The addition of water to alkene is anti.


(iv) Oxo process (Carbomylation or hydroformylation
reaction)
[Co(CO) ]
D

propanol -1

By fermentation of carbohydrates : (Commercial


method)
(i) From molasses - It is solution left after
crystallisation of sugar from sugar cane juice.
Invertase

C12 H 22O11 + H 2 O C6 H12 O6 + C6 H12 O6


sucrose

glu cos e

fructose

Zymase

C6 H12O6
2C2 H5OH + 2CO2
ethyl alcohol

(ii) From starch Diastase

2(C6 H10 O5 )n + nH 2 O nC12 H 22O11


Maltose

Starch

H2 O / Maltase

C12 H 22O11
2C6 H12 O6
Maltose

glu cos e

Zymase

C6 H12O6
2C2 H5OH + 2CO2
glu cos e

ethyl alcohol

Properties of Alcohols
(i) Boiling point of alcohols are higher than those of
hydrocarbons and isomeric ethers of comparable
molecular mass due to intermolecular hydrogen
bonding.
(ii) Reactivity of alcohols

The reactions in which O H bond cleaves


1 > 2 > 3

The reactions in which C O bond cleaves


3 > 2 > 1

Alcohols are weak acids.


Order of acidic strength 1 > 2 > 3
(iii)
Na

ROH

R'COCl/Pyridine

RONa + H2 (shows acidic nature of alcohol)


RCOOR' + HCl
ester

(RCO)2 O

RCOOR
ester

R'MgX

R H + Mg(OR')X
alkane

R COOH
conc H2SO4

2C2 H5OH
CH3CH 2 - O - CH 2 CH3 + H 2 O
diethyl ether

443 K
H 2SO 4

C 2 H 5 OH
H 2 C = CH 2 + H 2 O
ethene

Cu / D

CH3CH 2CHO
CH3CH 2CH 2 OH
(f)

413 K
H 2SO4

ethyl sulphate

1 alcohol Aldehyde

H2 / Ni

propanal

383 K
H 2SO4

C2 H5OH
(C2 H5 )2 SO4

(v) Reaction with Cu/D - (Dehydrogenation)

4
CH 2 = CH 2 + CO + H 2O

ethene

(iv) Reaction with conc H2SO4

RCOOR' + H2O

The order of ease of formation of ester


Primary alcohol > Secondary alcohol > Tertiary
alcohol.

Cu / D

2 alcohol Ketone
Cu / D

3 alcohol Alkene + H 2 O (dehydration)

(vi) Reaction with phosphorous halides: Phosphorous


halides convert alcohols to alkyl halides
ROH + PCl 5 RCl + POCl 3 + HCl
P / Br

2 3RBr + H PO
3 ROH + PBr3

3
3

P/I

2 3RI + H PO
3 ROH + PI 3
3
3

(vii) Reaction with thionyl chloride: Alkyl chlorides are


obtained
ROH + SOCl 2
RCl + SO 2 + HCl

(viii) Reaction with halogens: The reaction with halogens is


oxidation and halogenation.
CH 3 CH 2 OH + Cl 2
CH 3CHO + 2 HCl ( oxidation )

CCl3CHO + 3HCl (halogenation)


CH 3CHO + 3Cl2
Chloral

(ix) Reaction with (Al2O3) :


Al O

2 3
CH3CH2 O CH2CH3+ H2O
2CH3CH2OH
513-523K

Distinction between 1, 2 and 3 Alcohols


(i) Victor Meyer Test
Alcohol + P/I2 + AgNO2 + HNO2 + NaOH
Red colouration 1 alcohol
Blue colouration 2 alcohol
No colour 3 alcohol
(ii) Lucas test

Lucas reagent is anhydrous ZnCl2 + conc HCl


Alcohol + Lucas reagent
cloudiness appear immediately 3 alcohol
cloudiness appear after 5-10 minutes 2 alcohol
No cloudiness at room temperature 1 alcohol

PHENOLS

Phenols are compounds having OH group directly


attached to aromatic ring system. C6H5OH is simplest
phenol and is called carbolic acid.

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3
Methods of Preparation of Phenols
(i) From benzene diazonium chloride

N2Cl

OH
D

+ H2O
Diazonium salt

+ N2 + HCl
Phenol

(ii) From Grignard reagent


MgBr

OH

H 2O/HCl

+ 1/2 O2 (air)

+ MgBr(OH)
Phenol

(iii) From sodium benzene sulphonic acid


SO3Na
OH
Fuse and HCl

+ NaOH

+ Na2SO3

sod. benzene sulphonic acid

Properties of Phenols
(i) Physical properties: Phenol is a colourless crystalline solid
mpt. 42C and bpt 183C. It is deliquescent, becomes pinkish
on exposure to air due to oxidation sparingly soluble in cold
water.
(ii) Chemical properties of phenols :
(i) Acidity of phenols

Phenols are weak acids. They turn blue litmus


red. They are weaker acids than H2CO3.

Phenols are stronger acids than alcohols (due to


resonance) but weaker acids than carboxylic acids.

Electron withdrawing groups


increase
acidity of phenol

Electron donating groups


decrease acidity
of phenol

Phenols form the intermolecular hydrogen binding


and and their m.pt and b.pt are much higher than
hydrocarbons of the compound of the comparable
molecular weights
(ii) Alkylation of phenol

phenol

OH

(iv) From Cumene

CH3

OC2H5

OH
(i) O2

+ CH3COCH3

(ii) H2O, H2O2

Acetone

Phenetole
(ether)

Phenol

Cumene

(v) Dows process

(iii) Benzoylation
OH

Cl
+ NaOH
Chlorobenzene

573 623 K
200 atms

NaOH

+ NaCl + H2O

Benzoyl chloride

ONa

Phenol

OH
+ NaCl

Sod. phenoxide

Phenyl benzoate

(Schotten Beumann reaction)


(iv) Distillation with Zn
OH

Phenol

Cl

distil

+ Zn

(vi) Raschigs process: Developed in Germany

+ HCl + O2

COOC6H5

+ C6H5COCl

HCl

+ ZnO
Benzene

Phenol

(v) Kolbes reaction

Cu/Fe

+ H2O

OH

ONa

OH

Cl
+ H2O

Steam

+ HCl

Phenol

Sod. phenoxide

OCOONa
OH

V2O5

+ CO 2 400 K
4 7 atm

+ NaOH

425C
(vii) Oxidation of benzene:

Anisole
(ether)

C2H5I

CH3
C

+ NaI

Phenol

Propene

Benzene

+ CH3I

H3PO4

+ CH3 CH = CH2

OCH3

OH
HCl

2
+ HCl
Sod. salicylate
Salicylic acid
315C
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+ O2

COOH

(CH 3CO)2O

OH

+ CH3COOH

+ conc H2 SO4

COOH

(viii) Elbs persulphate reaction :


OH
OH

OCOCH3
COOH

OH

K2S2 O8

Catechol
(Minor)

OH

OH

Quinol
(Major)

COOC6H5

C6H 5OH + POCl3

alkaline solution

Aspirin
(2-acetoxy benzoic acid)

Salicylic acid

OH

(ix) Phthalein reaction :


Phenyl salicylate
(salol)

OH

CO

OH

COOCH3

CH3 OH (reflux)

OH

Phenol

conc. H2SO4

O
C

CO

Phthalic anhydride

Methyl salicylate
(oil of winter green)

Aspirin is used as analgesic and antipyretic.


Salol is used as antiseptic.
Oil of winter green is used in perfumery, as
flavouring agent in food and drinks. Also used as
analgesic in rheumatism and sciatica pain.
(vi) Reimer-Tiemann reaction
ONa

ONa

ONa
CH

CHCl2
+ CHCl3

NaOH, 340 K
NaCl, 2H2O

OH

OH

NO

NOH

NaNO2
Conc H2SO4

NOH + H

ONa
CHO

OH

(x) Libermanns nitroso reaction

OH
OH

2NaOH
NaCl

OH

OH

Phenolphthalein

H2SO4
H2O

OH

H2 O

CHO

Dil HCL
NaCl

OH

Indophenol (red)
If CCl4 is used instead of CHCl3 salicylic acid is
formed.
OH

ONa
+ CCl4

Phenol

ONa
CCl3

2NaOH,

H2O NaOH

NaCl,
2H2 O

3NaCl
H 2O

ONa

OH
COOH

dil. HCl

COOH

(xi) Electrophilic substitution reactions of phenol

Phenolic OH is o, p - directing group.


(i) Bromination

NaCl

OH

OH

OH
+ Br2

O 2/CrO 3
Phenol

+ Br2(aq)

Benzoquinone
(pink colour)

C 2H 5N 2Cl
Coupling reaction

C6H5 N = N C6H5OH
p hydroxyazobenzene
(Orange red dye)

ONa

Sodium salt of Indophenol

Salicylic acid

(vii)

C(OH)3

3NaOH,

OH
Br

OH
Br

CS2

+
Br
(Major)
p-bromo phenol

Br

Br

2, 4, 6 tri bromophenol
(white ppt)

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(Minor)
o-bromo phenol

5
(ii) Sulphonation
OH

OH

OH

H2SO4

H2SO4

373 K

293 K

SO3H

Phenol

SO3H
(iii) Nitration
OH

OH

OH
NO2

OH

dil HNO3

conc HNO 3

H 2SO 4

H 2SO 4

NO2

NO2

NO2

NO2

2, 4, 6 trinitrophenol
(picric acid)

Distinction between Alcohol and Phenol


(i)
(ii)
(iii)
(iv)
(v)

Test
Litmus test
Neutral FeCl3 test
Br2 + H2O
C6H5N2Cl
Liberman nitroso test
(H2SO4 + NaOH)

Phenol
Blue
red
Blue or violet colouration
White ppt
Orange red dye
Red colouration changing to
green and again red on dilution

Alcohol
No change
No change
No change
No change
No change
(ii) 1, 2 splitting products of glycol by reaction (oxidation)
with different compounds :

GLYCOL : CH2OH
|

CH2OH
Viscous liquid due to extensive hydrogen bonding due to
presence of two OH groups.
Preparation
(1) Hydroxylation of ethylene
CH 2 OH
1% KMnO 4
|
CH 2 = CH 2 + H 2 O + O
alkaline
CH 2OH
Cis addition

H2C = CH2

RCOO.OH
Peracid

H2C = CH2 + HOCl

CH2

CH2

CH2OH

H2O
H

CH2OH

CH2OH

Ethylene chlorhydrin

1
+ O2
2

CH2

CH2OH

Catalyst CH2
Ag
CH2

H2O
dil. HCl

CH2OH
CH2OH

Ethylene oxide

Properties

Physical Properties : It is colourless viscous liquid,


b.p. = 197C, m.p. = 11.5C, miscible with water in all
proportions due to intermolecular hydrogen bonding.

Chemical properties :
(i)

CH 2 OH + HOOC

COOH

CH 2 OH

phthalic acid

+H3PO3

CH2I

CH2

I2

CH2I
ethylene iodide (unstable)

+NaCl+CO2

Industrial method
CH2

PI3

HO CH2 Anti addition


CH2OH

CH2Br
CH2Br

CH2OH

NaHCO3

CH2Cl

PBr3

Heat

CH2

600C

CH2

CH2
ethylene

O + H2O
Ethylene oxide

O
||
anhy. ZnCl2
Tautomeris ation
CH 3 . C - H
CH 2
D
||
CHOH
vinyl alcohol
acetaldehyde
Conc. H2SO4
or Conc. H3PO4

CH2

CH2

CH2

CH2

Dioxane
CH3CHO

CH2O

(HCl)

CH2O

CH.CH3

Cyclic acetal
O=C

CH3

CH2O

CH3

CH2O
CH3
Cyclic Ketal

Heat

Glycol

H SO

2 4 Dacron (terylene)

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CH3

6
(ii) Reaction with oxalic acid
HIO 4

CH2 OH

CH 2 OH
|
(COOH)2
CHO H
HCOOH +
383 K
formic acid
|
CH 2 OH

2HCHO + HIO3

formaldehyde

CH2 OH
glycol

HNO 3

COOH
|

+ COOH

CH 2 OH
glycollic acid
KMnO 4 / H 3O +

glycerol

COOH

503 K

CH 2 OH
CH 2 ONO2
|
|
conc H 2SO 4
CHO NO 2
CHOH
+ conc HNO3
|
|
CH 2 OH
CH 2 ONO2

oxalic acid

2HCHO + 2CH3COOH + (CH3 COO) 2 Pb


Acetic acid

Lead acetate

Glycol is used as an antifreeze for automobile radiators


and as an coolant for aeroplane fuel.
Glycerol
(CH2OH CHOH CH2OH)

Its common name is glycerine.


Preparation
(i) By saponification of oils and fats :
CH 2 OCOR
CH 2OH
|
|
CHOCOR + 3NaOH
CHOH + 3RCOONa
sod. salt of fatty acid
|
|
(soap)
CH 2 OCOR
CH 2OH
oil or fat

Nitroglycerine
or glycerol trinitrate
or Nobel's oil

(iv)

Propene

Bismuth
nitrate

Allyl Chloride

CH 2 I
|
- I2
CHI

|
CH 2 I

CH3
|
+ HI
- I2

CHI

|
CH 2 I

CH 2
||
CH
|
CH 2 I

allyl
iodide

CH3
CH3
|
|
HI
CH CHI
||
|
CH 2
CH 3

propene

Isopropyl
Iodide

COOH
|
CHOH
|
COOH

tartonic acid

COOH
|
+ CO2 + H2 O
COOH
COOH
|
CO
|
COOH

KMnO4

glycerol

(iii) By fermentation of sugars:


Yeast
C 6 H12 O 6
C 3 H 8 O3 + CH 3CHO + CO 2
Na 2SO3
Glucos e
Glycerol
acetaldehyde
Properties
(i) Reaction with HI with small amount of HI, allyl iodide
is formed but with excess of HI isopropyl iodide is
formed.

glyceric acid

Cl2
CH3 - CH = CH 2
500C ClCH 2 - CH = CH 2

glycerol

CH2 OH
|
CHOH
|
COOH

dil HNO3

CH2 OH
|
CHOH
|
CH2 OH

(ii) From propene

CH 2OH
|
3HI
CHO H

|
CH 2OH

allyl alcohol

(iii) Reaction with H2SO4 and HNO3

COOH + 2H2 O

Formic acid

glycerol
(It is regenerated)

(COOH)2

CH 2 = CH - CH 2 OH + 2H2 O + 2CO2

oxalic acid

COOH

(CH 3COO) 4 Pb

CH 2OH
|
CHO H
|
CH 2OH

Meso oxalic acid

FeSO4 + H2O2
(Fenton's reagent)
or Br2 NaOH

CH2 OH
|
CHOH
|
CHO

glycreralaldehyde

(v)

C H2 OH
|
+ CO
|
CH2 OH
dihydroxy
acetone

CH 2 OH
|

CHOH + 2HIO4
|
CH 2 OH
glycerol

2HCHO + HCOOH + 2HIO 3 + H 2O

(vi) CH 2 OH
|
KHSO 4 or H 2SO 4
CHOH
or only ZnCl2
|
CH 2 OH
glycerol

CH 2
||
CH
|
CH 2

acrolein
(Bad smelling)

The reaction is used as test for glycerol.

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7
Uses of Glycerol
(i) Used in manufacture of dynamite, high quality soaps
and cosmetics.
(ii) Sweetening agent in beverages and confectionary.
(iii) As medicines. In treatment of heat disease and asthma.

RX

Methods of Preparation of Ethers


(i) From alcohol
2
4
2ROH

R - O - R + H 2O

alcohol

(ii)

ether

2RX + Ag 2 O (dry)
R - O - R + 2AgX

ONa + Cl CH 3

ether

(iii) Williamsons synthesis


RX +

RONa

alk. halide sod. alkoxide

mixed ether

The alkyl halide should be primary as 2 and 3


halides undergoes elimination to give alkenes.
Mixed and simple both ethers are prepared by
this method.
To prepare alkyl aryl ether, sodium phenoxide
and alkyl halide should be used.
No reaction takes place if aryl halide is reacted
with sodium alkoxide due to lesser reactivity of
aryl halides.

ETHERS (ROR OR ROR)

conc H SO , 413 K or
Al2 O3 , 633 K

+ R ONa
R - O - R + NaX

alk. halide sod. alkoxide

methyl
chloride

sod. phenoxide

CH3+ NaCl
methyl phenyl ether

R - O - R + NaX
simple ether

Properties of Ethers
+ [R 2 O H ] Cl

HCl formation of oxinium salts

dialkyl oxonium chloride

+ [ R 2 O H] H S O 4

H2SO4

dialkyl oxonium hydrogen sulphate

peroxide formation
air or O3
Cleavage by HX

R - O- R
HX / D
R - X + R OH. R X
Excess
X attaches itself to small R.Reactivly of HX
HI > H Br > HCl

R O R

F
Coordination complex
BF3

R
R

..
O

RMgX

R
R

..
O

Grignards reagent
H2O / dil. H2SO4

BF

F
Addition product
R
Mg
X

..
O

R
(R = C2H5)
R

ROH + ROH

Hydrolysis
PCl5 D
CH3COCl
Anhy. AlCl3

2RCl + POCl3
O
||
CH 2 - C - OR + RCl
Ester
alkyl chloride

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8
O
||
2 CH 3 - C - OR + RCl

(CH3CO)2O
Anhy. AlCl3

Ester

Dehydration

Alkene + H2 O

Al2O3 300C
R O R'

Cl2 / dark

Cl

2
CH 3 - CHCl - O - CH 2 - CH 3

a-Chloro diethyl ether

Cl

Cl

Cl

Cl
|

CH 2 - CH - O - CH 2 CH 3 + CH 3 - CH - O - CH - CH 3
a,b -dichloro diethyl ether

..
Cl5C2 O
.. C2Cl5

Cl2
light

Perchlorodiethyl ether

AROMATIC ETHER : Anisole


OH
Preparation

a,a '-dichloro diethyl ether

OCH3
CH2N2

+N2
OH

Properties
HI
OCH3

+ CH3 I
OCH3

OCH3
NO2 +

Nitration Conc HNO3


H2SO4
Anisole

o-nitro anisole

OCH3

OCH3
Bromination Br2/CS2

NO2
p-nitro anisole

Br

o-bromo anisole

+
Br
p-bromo anisole

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