You are on page 1of 36

11 Alcohols,Phenols

Alcohols, Phenols
and Ethers and Ethers
Question 1.

303

Intext
IntextQuestions
Questions
Classify the following as primary, secondary and tertiary

alcohols.
CH 3

(i) CH 3 C CH 2 OH

CH 3

(ii) H 2 C == CH CH 2 OH
OH
CHCH3

(iii) CH 3 CH 2 CH 2 OH

(iv)

CH3

CHCOH
CH

CH2CHCH3

(v)

(vi)

OH

CH3

If CH2OH group is present, alcohol is 1 (primary), if CHOH group is


present is 2 (secondary) and if COH group is present, alcohol is 3. So
classify on this basis.

Solution.

(i)
(iii)
(v)
(vi)

Question 2.

Primary alcohol
Primary alcohol
Secondary alcohol
Tertiary alcohol

(ii) Primary alcohol


(iv) Secondary alcohol

Identify allylic alcohols in the above examples.

Following groups are included in allylic alcohols.


H

CH2 ==CH CH2 OH CH2==CH C OH


Primary (1 )

allyl alcohol
C

Secondary (2 )
allyl alcohol

Solution.

(vi)

(ii) H2C== CH CH2OH


CH3
CH

CHCOH
CH3

CH2 ==CH C OH

Tertiary (3 )
allyl alcohol

NCERT ClassXII ChemistrySolutions

304

Question 3. Name the following compounds according to the IUPAC


system.
CH 2 OH

(i) CH 3 CH 2 CH CH CH CH 3

CH 2 Cl
CH 3
CH 2 OH

(ii) H 3 C CH CH 2 CH CH CH 3

CH 3
OH
OH
(iii)
Br

(iv) H 2 C==CH CH CH 2 CH 2 CH 3

OH
(v) CH 3 C==C CH 2 OH

CH 3 Br
Prefix according to the C-chain; for alcohol add suffix ol; for double
bond ene; tell the position of substituents, double bond and functional
group (s).Then, given the name in the following manner.
Name of substituent with position (in alphabetical order) + parent
C-chain name + primary suffix (antiene etc.) + secondary suffix with
position (for main functional group).

Solution.
1

CH2OH
5
4
3
2
(i) CH3 CH2 CH CH CH CH3

CH3
CH2Cl
3-chloromethyl-2-isopropyl
pentan - 1-ol
1

CH2OH

2
5
4
3
6
(ii) CH3 CH CH2 CH CH CH3

OH
CH3
2,5 dimethylhexan-1,3-di-ol

Chemistry-XII

Alcohols, Phenols and Ethers

Alcohols,Phenols and Ethers

305

OH
1
2

(iii)

Br
3-bromocyclohexanol
1

(iv) H2C==CH CH CH2 CH2 CH3

OH
Hex-1-en-3-ol
4

(v)

CH3 C==C CH2OH



CH3Br
2-bromo-3-methylbut-2-en-1-ol

Question 4.

Show how are the following alcohols prepared by the


reaction of a suitable Grignard reagent on methanal?
CH2OH
(i) CH 3 CH CH 2 OH

CH 3

(ii)

HO
H

2
HCHO + RMgX
+ RCH2OH + Mg(OH) X. Form here, it is clear that

HCHO gives CH2OH groups, so R of Grignard reagent is the remaining


part of given alcohols. Thus, select the suitable Grignard reagent by
substituting the value of R.

Solution. (i)

Dry ether

HCHO + (CH3)2 CH MgBr

Methanal

Isopropyl
magnesium
bromide

[(CH3)2 CH CH2OMgBr]
Addition compound
Mg(Br)OH H2O/H +

(CH3)2CH CH2OH
Isobutyl alcohol

or

Chemistry-XII

2-methylpropan-1-ol

Alcohols, Phenols and Ethers

NCERT ClassXII ChemistrySolutions

306

MgBr
Dry ether

(ii) HCHO +

CH2OMgBr
Intermediate
product

Methanal Cyclohexyl
magnesium
bromide

H2O/H

CH2OH

Mg(OH)Br
Cyclohexyl
methanol

Question 5. Write structures of the products of the following reactions.


H O/H+

2
(i) CH 3 CH==CH 2
O
CH2COCH3

NaBH4

(ii)

NaBH

4
(iii) CH 3 CH 2 CH CHO

CH 3

(i) Acidic hydration of propene i.e., addition of H2O


(according to Markownikoffs rule) result in the formation of alcohol.
(ii) Reduction of

C ==O group (not in ester group) into OH.

(iii) Reduction of CHO group into CH2OH.

Solution.

H O /H

2
(i) CH3 CH == CH2
CH3 CH CH3
Markownikoff's
Propene

rule
OH

Propan-2-ol

2
1

(ii)

O
methyl-2-oxocyclohexyl
ethanoate

Chemistry-XII

OH

CH2COCH3

NaBH4
Reduction

CH2COCH3
O
Methyl (2-hydroxycyclohexyl)
ethanoate

Alcohols, Phenols and Ethers

Alcohols,Phenols and Ethers


4

307

NaBH

4
(iii) CH3 CH2 CH CHO
Reduction

CH3

2-methylbutanal

CH3 CH2 CH CH2 OH

CH3
2-methylbutan-1-ol

Question 6. Give structures of the products you would expect when


each of the following alcohol reacts with
(a) HCl ZnCl 2
(b) HBr and
(c) SOCl 2
(i) Butan-1-ol
(ii) 2-methylbutan-2-ol
Replacement of OH by (a) Cl (b) Br (c) Cl

Solution. (i) Reactions of butan-1-ol


4

HCl ZnCl

2
(a) CH3 CH2 CH2 CH2 OH

Heat (Lucas reagent)

Butan-1-ol(1)

CH3 CH2 CH2 CH2 Cl + H2O


1-chlorobutane

(b) CH3 CH2 CH2 CH2 OH


Butan-1-ol

HBr CH CH CH CH Br + H O

3
2
2
2
2
Heat

1-bromobutane
SOCl 2

(c) CH3 CH2 CH2 CH2 OH


Heat

CH3 CH2 CH2 CH2 Cl + SO2 + HCl


1-chlorobutane

(ii) Reactions of 2-methylbutan-2-ol


CH3
2
4
1
3
HCl ZnCl 2
(a) CH3 C CH2 CH3

Lucas reagent

OH
2- methylbutan-2-ol (3)

CH3

CH3 C CH2 CH3 + H2O

Cl
2-chloro-2-methylbutane

Chemistry-XII

Alcohols, Phenols and Ethers

NCERT ClassXII ChemistrySolutions

308

CH3

CH3

HBr
(b) CH3 C CH2 CH3
CH3 C CH2 CH3
eat
H

Br
OH
2- methylbutan-2-ol

2-bromo-2-methylbutane

+ H2O
CH3
CH3
2
2
4
4
1
3
1
3
SOCl 2
(c) CH3 C CH2 CH3
CH3 C CH2 CH3
Heat

OH
Cl
2-chloro-2-methylbutane

+ SO2 + HCl
Note *Butan-1-ol, being primary alcohol requires heating with Lucas
reagent. 2-methyl butan-2-ol being tertiary alcohol reacts without heating.
*Lucas test is used to distinguish between primary, secondary and tertiary
alcohols.

Question 7.

Predict the major product of acid catalysed dehydration of


(i) 1-methylcyclohexanol
(ii) butan-1-ol
In acid catalysed dehydration process a molecule of water is liberated
according to Saytzeffs rule i.e., results in the formation of more
substituted alkene.

CH3

Solution. (i)

OH

H (Heat)
H2O

1-methyl
cyclohexanol

CH2

CH3
+
1-methyl
cyclohexene
(Major)

1-methylene
cyclohexane
(Minor)

H + , heat

(ii) CH3 CH2 CH2 CH2 OH


Butan-1-ol

H 2O

CH3 CH2 CH==CH2 + CH3 CH==CH CH3


But-1-ene
(Minor)

But- 2-ene
(Major)

Note *OH from -C atomand H from -C atomiseliminated.


(i) According
to
Saytzeffs
rule,
major
product
1-methyl-cyclohexene,sinceitismoresubstituted.

Chemistry-XII

is

Alcohols, Phenols and Ethers

Alcohols,Phenols and Ethers

309

(ii) Major product is but-2-ene due to rearrangement to give secondary


carbocation,whichismorestable.
CH3 CH2 CH2 CH2 OH
Butan-1-ol

H+
H2O

CH3 CH2 CH CH2


H
1 carbocation
(Less stable)

H ion
shift

CH3 CH CH CH3
H
2 carbocation
(More stable)
H+

CH3 CH

CH CH3

But-2-ene

Question 8. Ortho and para nitrophenols are more acidic than phenol.
Draw the resonance structures of the corresponding phenoxide ions.
Acidic strength depends on the relative stabilities of corresponding
phenoxide ions based on resonance.

Solution. (i) Phenoxide ion


O

Chemistry-XII

Alcohols, Phenols and Ethers

NCERT ClassXII ChemistrySolutions

310

(ii) o-nitrophenoxide ion

O
O
N

O
N

(iii) p-nitrophenoxide ion

N
O

O
O
Due to R effect of NO2 group, o- and p-nitrophenoxide ions
are more stable than phenoxide ion. Consequently, both o- and
p-nitrophenols are more acidic than phenol.
O

Note Structures in boxes have negative charge on that C-atom to which


electron withdrawing NO2 group is attached. So, these structures
contributemoretowardstheacidiccharacterthantheothers.

Chemistry-XII

Alcohols, Phenols and Ethers

Alcohols,PhenolsandEthers

311

Question 9.

Write the equations involved in the following reactions :


(i) Reimer-Tiemann reaction
(ii) Kolbes reaction
(i) It is the reaction of phenol with chloroform in the presence of sodium
hydroxide. As a result, CHO group is introduced at o-position of
benzene ring.
(ii) Reaction of phenol and NaOH, then with CO 2, a weak electrolyte.
Orthobenzoic acid is formed.

Solution. (i)

CHCl2

CHCl3 + aq. NaOH

Phenol

O Na

O Na

OH

CHO
NaOH

Intermediate

OH
CHO

Salicylaldehyde

OH

ONa
(i) CO2

NaOH

(ii)

OH

(ii) H

Sodium
phenoxide

Question 10. Write

the
2-ethoxy-3-methylpentane
pentan-2-ol.

COOH

2-hydroxybenzoic
acid
(Salicylic acid)

reactions of Williamson synthesis of


starting from ethanol and 3-methyl

(i) Reaction of 3-methylpentan-2-ol with sodium.


(ii) Reaction of ethanol with hydrogen bromide.
(iii) Reaction of product formed in (i) reaction with the product of (ii).
5

Solution. (i) CH3 CH2 CH CH CH3 + Na

CH3 OH

3-methylpentan-2-ol

CH3 CH2 CH CH CH3

CH3 ONa
Sodium-(3-methyl)-pentoxide

Chemistry-XII

Alcohols, Phenols and Ethers

312

NCERT ClassXII ChemistrySolutions

(ii) C 2H5OH + HBr

C 2H5Br

+ H2O

Bromoethane

(iii) CH3 CH2 CH CH CH3 + C 2H5Br

CH3 ONa
CH3 CH2 CH CH CH3

CH3 OC 2H5
2-ethoxy-3-methylpentane

Questions 11. Which of the following is an appropriate set of reactants


for the preparation of 1-methoxy-4-nitrobenzene and why?
ONa
Br
(i)

+ CH3Br

(ii)

+ CH3ONa

NO2
NO2
This reaction involves preparation of ether by Williamson synthesis. It
takes place by SN2 attack of an alkoxide ion on primary alkyl halide.

Solution.
ONa

(ii)

OCH3
+ CH3Br

+ NaBr

NO2

NO2

1-methoxy-4-nitrobenzene

Because here the alkyl halide used is primary. Moreover in


method (i) the C Br bond has some double bond character.

Question 12. Predict the products of the following reactions :


(i) CH 3 CH 2 CH 2 O CH 3 + HBr
OC2H5

(ii)

+ HBr
OC2H5

(iii)

Conc. H2SO4
Conc. HNO3

HI
(iv) (CH 3 ) 3 C OC2H 5

Chemistry-XII

Alcohols, Phenols and Ethers

Alcohols,PhenolsandEthers
Alcohols,PhenolsandEthers

313
313

(i) and (ii) RO R + H X ROH + R X i.e.,


(i) and
(ii) RO R + H X ROH + R X i.e.,
formed.
formed.
(iii) Nitration (introduction of NO 2 group) takes
(iii) p-positions.
Nitration (introduction of NO 2 group) takes
p-positions.
(iv) Tertiary iodide and primary alcohol are formed.
(iv) Tertiary iodide and primary alcohol are formed.

primary halide is
primary halide is
place at o- and
place at o- and

Solution. (i) CH3 CH2 CH2 O CH3 + HBr


Solution. (i) CH3 CH2 CH2 O CH3 + HBr
Methoxy propane
Methoxy propane

CH3 CH2 CH2 OH + CH3Br


CH3 CH2
CH2 OH + CH3Br
Propanol
Propanol

OC2H5
OC2H5
+ HBr
+ HBr

(ii)
(ii)

Ethoxy benzene
Ethoxy benzene

OH
OH
+ C2H5Br
+ C2H5Br
Phenol
Phenol

OC2H5
OC2H5 Conc. H2SO4

2 OC2H5
2 OC2H5
1
1

Conc. H2SO4
Conc. HNO3
Conc. HNO3

(iii)
(iii)
Ethoxy benzene
Ethoxy benzene

NO2
NO2

2-ethoxy2-ethoxynitrobenzene
nitrobenzene

+
+
O2N
O2N

1
1

4 OC2H5
4 OC2H5
3
3

2
2
4.-ethoxy4.-ethoxynitrobenzene
nitrobenzene

HI

(iv) (CH3)3C OC 2H5


(CH3)3C I + C 2H5OH
HI
(iv) (CH
OC
t butyl
(CH3)iodide
3C I + C
2H5OH
3 )3 Cethyl
2H5
Ethanol
t butyl
ether
t butyl ethyl ether

t butyl iodide

Ethanol

Exercises
Exercises
Exercises

Question 1. Write IUPAC names of the following compounds.


Question 1. Write IUPAC names of the following compounds.
CH 3
CH 3

CH
(i) CH 3 CH CH C
(i) CH 3 CH CH C CH 33

CH
CH
3
3 OH
CH 3 OH CH 3

(ii) H 3 C CH CH 2 CH CH CH 2 CH 3
(ii) H 3 C CH
CH 2 CH
CH
CH 2 CH 3

OH
OH
CH
OH
OH C22H 55

Chemistry-XII

Alcohols, Phenols and Ethers

314

NCERT ClassXII ChemistrySolutions

(iii) CH 3 CH CH CH 3

OH OH
(iv) HO CH 2 CH CH 2 OH

OH
CH3

CH3
OH

(v)

(vi)
OH

CH3

CH3
OH

(vii)

(viii)
OH

CH3

CH3

(ix) CH 3 O CH 2 CH CH 3

CH 3
(x) C6H 5 O C2H 5
(xi) C6H 5 O C7 H15 ( n)
(xii) CH 3 CH 2 O CH CH 2 CH 3

CH 3
Prefix according to the carbon chain; for alcohol (OH) use suffix -ol; tell
the position of substitutents and functional group. For ether ( O ),
prefix alkoxy is used. For OH group attached directly to benzene ring,
suffix phenol is used.
So, give the name of alcohol as substituent with position (in alphabetical
order) + prefix of carbon chain + primary suffix (ane, ene, yne) + ol with
position and give the name of ether as alkoxy alkane (where alkoxy
smaller R group and alkane is main chain)

CH3
1
2
Solution. (i) CH3 CH CH C CH3

CH3 OH CH3
5

2, 2, 4-trimethyl pentan-3-ol

Chemistry-XII

Alcohols, Phenols and Ethers

Alcohols,PhenolsandEthers
1

315
6

(ii) H3C CH CH2 CH CH CH2 CH3

OH
OH C 2H5
5-ethyl heptane-2, 4-diol
1

(iii) CH3 CH CH CH3

OH OH
Butane-2, 3-diol
1

(iv) HO CH2 CH C H2 OH

OH
Propane-1, 2, 3-triol

CH3

CH3

OH

(v)

(vi)

2
1

OH

2-methylphenol

4-methyl phenol

CH3

CH3

(vii)

(viii)

3
2

OH
1

2 CH
3
3
2,6-dimethyl phenol

OH

CH3
2,5-dimethyl phenol
1

(ix) CH3 O CH2 CH CH3

CH3

(x)

C 6H5 O C 2H5
Ethoxybenzene

1- methoxy-2-methyl propane

(xi) C 6H5 O C 7H15 (n )


1-phenoxy heptane
2

(xii) CH3 CH2 O CH CH2 CH3

1
CH3
2-ethoxybutane

Question 2. Write structures of the compounds whose IUPAC names


are as follows.
(i) 2-methylbutan-2-ol
(ii) 1-phenylpropan-2-ol
(iii) 3, 5-dimethylhexane-1,3, 5-triol (iv) 2, 3-diethylphenol
(v) 1-ethoxypropane
(vi) 2-ethoxy-3-methylpentane

Chemistry-XII

Alcohols, Phenols and Ethers

316

NCERT ClassXII ChemistrySolutions

(vii) Cyclohexylmethanol
(ix) Cyclopent-3-en-1-ol

(viii) 3-cyclohexylpentan-3-ol
(x) 3-chloromethylpentan-1-ol

(i) Draw the main carbon chain according to the root word of carbon
chain and then attach the other groups according to the positions
mentioned.
(ii) Suffix al represents OH group and prefix alkoxy repersents RO
group.

CH3

Solution. (i) CH3 C CH2 CH3

OH

2-methylbutan-2-ol
1

(ii) C 6H5 CH2 CH CH3

OH
1-phenylpropan-2-ol

CH3
OH

1
2
4
6
3
5
(iii) CH2 CH2 C CH2 C CH3

OH
OH
CH3
3, 5-dimethylhexane-1, 3-5-triol

OH
1

2 C2H5
1

(iv)

(v) C 2H5O CH2 CH2 CH3

C2H5

1-ethoxypropane

2,3-diethyl phenol
1

(vi) CH3 CH CH CH2 CH3

OC 2H5 CH3
2-ethoxy-3-methyl pentane

OH
1

CH2OH

(vii)

(viii) CH3CH2CCH2CH3

Cyclohexyl methanol

3-cyclohexylpentan-3-ol

Chemistry-XII

Alcohols, Phenols and Ethers

Alcohols,PhenolsandEthers

317

OH

(ix)

1
2
3
Cyclopent-3-en-1-ol
1

(x) HO CH2 CH2 CH CH2 CH3

CH2Cl
3-chloromethylpentan-1-ol

Question 3. (i) Draw the structures of all isomeric alcohols of molecular


formula C5H12 O and give their IUPAC names.
(ii) Classify the isomers of alcohols in question 3. (i) as primary,
secondary and tertiary alcohols.
(i) Make different isomers by varying the number of C-atoms in
continuous chain, the position of CH3 and OH groups.
(ii) Primary ( 1 )alchols have CH2 OH; group Secondary ( 2 ) have
CH OH; group and Tertiary ( 3 ) have C OH.

Solution.

(i) Molecular formula C 5H12O represents eight isomeric


alkanols. These are :
5

(a) CH3 CH2 CH2 CH2 CH2 OH


Pentan-1-ol
2

(b) CH3 CH CH2 CH2 OH

CH3
3-methyl butan-1-ol
4

(c) CH3 CH2 CH CH2 OH

CH3
2-methyl butan-1-ol

CH3

(d) CH3 C CH2 OH

CH3
2, 2-dimethyl propan-1-ol
5

(e) CH3 CH2 CH2 CH CH3

OH
Pentan-2-ol

Chemistry-XII

Alcohols, Phenols and Ethers

318

NCERT ClassXII ChemistrySolutions


CH3

(f) C H3 C H C H C H3 (g) CH3 C CH2 CH3

OH
CH3 OH
2-methyl butan-2-ol

3-methyl butan-2-ol
5

(h) CH3 CH2 CH CH2 CH3

OH
Pentan-3-ol

(ii) Primary : (a), (b), (c) and (d); Secondary (e), (f), (h) Tertiary : (g).

Question 4. Explain why propanol has higher boiling point than that of
the hydrocarbon, butane?
Boiling point is directly proportional to the intermolecular forces existing
in a compound.

Solution. Although butane and propanol have comparable molecular


masses (58 and 60 respectively) but, in propanol, polar OH group is
present, due to which strong intermolecular hydrogen bonding exists
between its molecules. Whereas in butane weak van der Waals forces
of attraction are the only forces between the molecules. Therefore,
propanol has higher boiling point (391 K) as compared to that of butane
(309 K).
+

H O H O H O

C 3H7
C 3H7
C 3H7

Question 5. Alcohols are comparatively more soluble in water than


hydrocarbons of comparable molecular masses. Explain this fact.
Consider polar nature of water as well as alcohol; presence of hydrogen
bonding.

Solution. Water and alcohols both are polar in nature. When an alcohol
is dissolved in water, it forms hydrogen bonds with water by breaking
the H-bonding already existing between the water molecules.
Hydrocarbons are non-polar in nature and do not form H-bonds with
water molecules. Therefore, alcohols are readily soluble in water
whereas hydrocarbons are not.

R O H O H O
+

H
R
H
Hydrogen bonding among alcohol and water

Chemistry-XII

Alcohols, Phenols and Ethers

Alcohols,PhenolsandEthers

319

Question 6. What is meant by hydroboration-oxidation reaction?


Illustrate it with an example.
Addition of diborane to alkenes followed by oxidation.

Solution. The addition of diborane to alkenes to form trialkyl boranes


followed by their oxidation by alkaline H2O2 to form alcohols is known
as hydroboration-oxidation reaction. For example
CH3 CH==CH2 + (H BH2)2 CH3 CH CH2
Propene
Dibroane

H
BH2
CH3 CH== CH2
3H 2O 2 , OH

CH CH ==CH

3
2
(CH3 CH2 CH2)3 B

H 2O
(CH3 CH2 CH2)2 BH

3 CH3 CH2 CH2 OH + B(OH)3


Propan-1-ol

Boric acid

Alcohol formed by this reaction appears as it has been formed by


addition of water in a way contrary to the Markownikoffs rule.

Question 7. Give the structures and IUPAC names of monohydric


phenols of molecular formula, C7 H 8 O.
Ortho (1, 2); para (1, 4); meta (1, 3) Draw these isomers according to the
mentioned positions of OH and CH3 groups.

Solution. Following three isomers are formed from C 7H8O.


OH

OH

OH

2 CH3

CH3
2-methyl phenol
or
o- cresol (I)

3-methyl phenol
or
m cresol (II)

CH3
4-methyl phenol
or
p-cresol (III)

Question 8.

While separating a mixture of ortho and para nitrophenols by


steam distillation, name the isomer which will be steam volatile. Give reason.
Isomer, which is steam volatile is less strongly bonded. The other one is
strongly bonded by H-bonding.

Solution. Ortho-nitrophenol is steam volatile. The reason is chelation


due to intramolecular H-bonding. So, it can be separated by steam
distillation from p-nitrophenol. Para-nitrophenol is not steam volatile
due to presence of intermolecular H-bonding.

Chemistry-XII

Alcohols, Phenols and Ethers

320

NCERT ClassXII ChemistrySolutions


Intramolecular H-bonding

N+

O
H
O

o-nitrophenol
+

HO

NO

HO

NO

O Intermolecular

H-bonding
p-nitrophenol

Question 9. Give the equations of reactions for the preparation of


phenol from cumene.
Oxidation of cumene into cumene hydroperoxide, then acidic hydrolysis.

CH3

Solution.

CH3

H3CCH

H3CCOOH
+

O2

Cumene
or
(Isopropyl benzene)

H
H2O
Cumene
hydroperoxide

OH
O
+

CH3CCH3

Phenol

Propanone
(Acetone)

Note This method is employed for the preparation of phenol on


commercial scale, as the by product is also an important reagent.

Question 10. Write chemical reaction for the preparation of phenol from
chlorobenzene.
Reaction of chlorobenzene with
acidification of the product formed.

Chemistry-XII

sodium

hydroxide

followed

by

Alcohols, Phenols and Ethers

Alcohols,PhenolsandEthers
Solution.

321

Cl

O Na
+ NaOH

OH

623 K

HCl

300 atm

Chlorobenzene

Sodium
phenoxide

Phenol

Question 11. Write the mechanism of hydration of ethene to yield


ethanol.
The steps involved in this process are
1. Protonation of alkene.
2. Nucleophilic attack of water on carbocation.
3. Deprotonation to form an alcohol.

Solution. The mechanism involves 3 steps :


Step I : Protonation of alkene to form carbocation by electrophile
attack of H3O+ .
H2O + H+ H3O+
H
H
C

+H

+ H2O

Step II: Nucleophilic attack of water on carbocation formed.

H
C

H
+

+ H2O

H
C

Step III : Deprotonation to form corresponding alcohol.


H
C

H
C

H + H2O

OH

+ H3O

Question 12. You are given benzene, conc. H 2SO 4 and NaOH. Write the
equations for the preparation of phenol using these reagents.
(i) Sulphonation of benzene.
(ii) Reaction with NaOH and water.

Chemistry-XII

Alcohols, Phenols and Ethers

322

NCERT ClassXII ChemistrySolutions

SO3H

Solution.

H2SO4 (Conc.)

NaOH

Heat

H2O

Benzene

SO3 Na

Benzene
sulphonic
acid

Sodium benzene
sulphonate

NaHSO3, NaOH (Fuse)

OH

ONa
+

Phenol

Sodium phenoxide

Question 13. Show how will you synthesise :


(i) 1-phenylethanol formasuitable alkene.
(ii) Cyclohexylmethanol usinganalkylhalidebyan S N 2 reaction.
(iii) pentan-1-ol usingasuitablealkylhalide?
(i) Acidic hydration of ethenyl benzene.
(ii) Alkaline hydrolysis of cyclohexyl methyl bromide.
(iii) Alkaline hydrolysis of 1-bromopentane.
Dil.H SO

2
4
Solution. (i) C 6H5 HC == CH2 + H2O

Markownikoff's
rule

Ethenylbenzene
(Styrene)

C 6H5 CH CH3

OH
1-phenyl ethanol

CH2Br
(ii)

CH2OH

+ NaOH(aq)

+ NaBr

Cyclohexyl
methyl bromide
5

Cyclohexyl
methanol
1

(iii) CH3 CH2 CH2 CH2 CH2 Br + KOH CH3 CH2 CH2 CH2 CH2 OH
1-bromopentane

(aq )

Pentan-1-ol

+ KBr

Chemistry-XII

Alcohols, Phenols and Ethers

Alcohols,PhenolsandEthers

323

Question 14. Give two reactions that show the acidic nature of phenol.
Compare acidity of phenol with that of ethanol.
Reaction of phenol with Na and NaOH; comparing of acidity of phenol
and ethanol.

Solution. Following reactions show the acidic nature of phenol :


(i) Reaction with sodium H2 gas is produced.
OH
ONa

+ 2Na
Phenol

+ H2

Sodium phenoxide

(ii) Reaction with sodium hydroxide Forms sodium salt and water.
OH
ONa
+ NaOH
Phenol

+ H2O
Sodium phenoxide

Comparison of acidic character of phenol and ethanol


Phenol is more acidic than ethanol because after losing a proton
(H+ ), phenol forms phenoxide ion which is stabilised by resonance
whereas ethoxide ion is not.
O

II

III

IV

Question 15. Explain why is ortho nitrophenol more acidic than ortho
methoxyphenol?
(i) NO 2- electron withdrawing group. OCH3-electron releasing group.
(ii) Presence of electron withdrawing group increases the stability of
phenoxide ion while presence of electron releasing group decreases
its stability.
(iii) Higher is the stability of phenoxide ion formed, more is the acidic
character.

Chemistry-XII

Alcohols, Phenols and Ethers

324

NCERT ClassXII ChemistrySolutions

Solution. Nitro (NO2) group is electron withdrawing whereas methoxy


(OCH3) group is electron releasing in nature. o-nitrophenol produces
H+ ions easily but methoxyphenol does not. This is because
o-nitrophenoxide ion is stabilised due to resonance. This is not true with
o-methoxyphenoxide ion. The two negative charges repel each other
thereby destabilising it.
OH

O
NO2

NO2

+ H
o-nitrophenol

OH

O
OCH3

OCH3

+H

O
O

CH3

O
O

CH3

Note Also give resonating structures of o-nitrophenoxide ion for Q. 8


intext questions.

Question 16. Explain how does the OH group attached to a carbon of


benzene ring activate it towards electrophilic substitution?
Resonance effect due to OH group.

Solution. In the presence of attacking electrophile, OH group exerts


+R effect on the benzene ring. So, electron density in the ring increases
particularly at the ortho and para positions. When an electrophile
attacks, substitution takes place readily at these (o and p ) positions.
OH

OH

OH

OH

Chemistry-XII

OH

Alcohols, Phenols and Ethers

Alcohols,PhenolsandEthers

325

Question 17. Give equation of the following reactions.


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

Oxidationof propan-1-ol withalkaline KMnO4 solution.


Brominein CS2 withphenol.
Dilute HNO3 withphenol.
Treatingphenolwithchloroforminpresenceofaqueous NaOH.

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

Alcohol oxidises to carboxylic acid.


o-and p- bromophenol are formed.
Nitration (introduction of NO 2 group) at o- and p- positions.
Reimer-Tiemann reaction involves introduction of CHO group at
ortho position, salicylaldehyde is formed.
KMnO /OH

4
Solution. (i) CH3CH2CH2OH
CH3 CH2 CHO

(Oxidation)

Propan-1-ol

Propanal

KMnO 4 /OH

CH3CH2COOH
(Oxidation)

OH

OH
Br

Br2/CS2

(ii)

Propanoic acid

OH
+

HBr

Br
Phenol

o-bromophenol

OH

OH

OH
NO2
+

HNO3(dil.)

(iii)

p-bromophenol

H2O

NO2
Phenol

o-nitrophenol

OH

ONa
CHCl3/NaOH (aq)

(iv)

p-nitrophenol

OH
CHO
H2O/H

CHO

343 K
Phenol

Salicylaldehyde

Question 18. Explain the following with an example.


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

Kolbe's reaction.
Reimer-Tiemann reaction.
Williamsonethersynthesis.
Unsymmetricalether.

Chemistry-XII

Alcohols, Phenols and Ethers

326

NCERT ClassXII ChemistrySolutions


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

(Reaction of phenol with NaOH and CO 2), Salicylic acid is formed.


Reaction of phenol with CHCl3 + aq. NaOH salicylaldehyde.
Alkyl halide + sod. alkoxide Ether + Sod. halide.
Ethers containing two different alkyl/aryl groups.

Solution. (i) Kolbe's reaction When phenol reacts with sodium


hydroxide, reactive phenoxide ion is formed. So, electrophilic
aromatic substitution takes place with CO2 under a pressure of 4-7
atm followed by acidification and ortho hydroxybenzoic acid
(Salicylic acid) is formed. This is called Kolbe's reaction.
OH
ONa
OH
2
1 COOH
(i) CO2

NaOH

(ii) H
Phenol

2-hydroxybenzoic
acid
(Salicylic acid)

Sodium
phenoxide

(ii) Reimer-Tiemann reaction When phenol is treated with


chloroform in the presence of sodium hydroxide, CHO group is
introduced at ortho position of benzene ring. This is called
Reimer-Tiemann reaction.

O Na

OH

CHCl2

CHCl3 + aq. NaOH

Phenol

Intermediate

OH

O Na

CHO

CHO

NaOH

Salicylaldehyde

(iii) Williamson
ether
synthesis Ethers
(symmertical
and
unsymmertrical) are prepared by this method. It involves the
reaction of an alkyl halide with sodium alkoxide.
R X + RONa R O R + NaX
e.g., 1. (CH3)3 C ONa + CH3Br CH3OC (CH3)3 + NaBr
RX

2. C 6H5OH + NaOH C 6H5ONa C 6H5 O R


(iv) Unsymmetrical ether An ether in which alkyl or aryl groups
attached to the oxygen atom are different, is known as
unsymmetrical ether. For example, ethyl methyl ether
(C 2H5OCH3), methyl phenyl ether (CH3 O C 6H5) etc.

Chemistry-XII

Alcohols, Phenols and Ethers

Alcohols,PhenolsandEthers

327

Question 19. Write the mechanism of acid catalysed dehydration of


ethanol to yield ethene.
Step involved in acid catalysed dehydration are
(i) Protonation of alcohol.
(ii) Formation of carbocation.
(iii) Elimination of a proton.

Solution. Mechanism of acid catalysed dehydration of ethanol


Step I : Protonation of ethanol
H H
H H H


Fast
H C C O H + H+
H C C O+ H


H H
H H

Ethanol

Protonated ethanol
(Ethyl oxonium ion)

Step II : Formation of carbocation


H H H
H H
+
+
Slow
H C C O H
H C C + H2O


H H
H H
Step III : Elimination of a proton
H H

H
H
C ==C
H C C +
+H+
H
H

Ethene
H H
Note The acid used in Step I is released in Step III. To drive the
equilibrium to the right, ethene is removed as it is formed.

Question 20. How are the following conversion carried out?


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

Propene propan-2-ol.
Benzylchloride Benzylalcohol.
Ethylmagnesiumchloride Propan-1-ol.
Methylmagnesiumbromide 2-methylpropan-2-ol.

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

Acidic hydration of propene.


Alkaline hydrolysis of benzyl chloride.
Reaction with methanal in dry ether followed by acid hydrolysis.
Reaction with propanone in dry ether followed by acid hydrolysis .

Solution. (i) CH3 CH == CH2 + conc.H2SO4


Propene

CH CH CH
3
3

OSO3H

Isopropyl hydrogen sulphate

Chemistry-XII

H O

CH3 CH CH3 + H2SO4


Boil

OH

Propan-2-ol

Alcohols, Phenols and Ethers

328

NCERT ClassXII ChemistrySolutions


CH2Cl

CH2OH
+ NaOH (aq)
Hydrolysis

(ii)

+ NaCl

Benzyl
chloride

Benzyl
alcohol

OMgCl
O

Dry
(iii) CH3CH2MgCl + H C H C H
ether

Ethyl magnesium
H2CCH3
chloride
H
Methanal

Adduct

OH

H 1C H

2
CH23 CH3
H 2O / H +

Propan-1-ol

(iv)

CH3MgBr

Methyl magnesium
bromide

H3C C

CH3
Propanone (Acetone)

OMgBr

H3C C CH3

CH
3

H 2O / H +

Aduct

OH

3
H3C1 2C CH3

CH3
2 - methyl propan - 2 - ol

Question 21. Name the reagents used in the following reactions.


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

Oxidationofaprimaryalcoholtocarboxylicacid.
Oxidationofaprimaryalcoholtoaldehyde.
Bromination ofphenolto2,4,6-tribromophenol.
Benzylalcoholtobenzoicacid.
Dehydrationof propan -2-ol topropene.
Butan-2-one to butan-2-ol.

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

Chemistry-XII

Oxidising agent (strong)


Weak oxidising agent
Br2 / H2O
Strong oxidising agent
Dehydrating agent
Reducing agent.

Alcohols, Phenols and Ethers

Alcohols,PhenolsandEthers
Solution.

(i)

329

Acidified K 2Cr2O7 or neutral/acidic/alkaline KMnO4.

(ii) Pyridine chlorochromate (PCC) (C 5H5N + HCl CrO3) in CH2Cl 2.


(iii)
(iv)
(v)
(vi)

Bromine water (Br2 / H2O).


Alkaline KMnO4 or acidified KMnO4
85% H3PO4 at 440 K.
LiAlH4 or NaBH4.

Question 22. Give reason for the higher point of ethanol in comparison
to methoxymethane.
Presence of intermolecular H-bonding in ethanol, but not in ether.

Solution. Hydrogen bonding is present between the ethanol molecules


which is absent in the molecules of methoxymethane. So, a large
amount of energy is required to break these strong bonds in ethanol.

H O H O H O

C 2H5
C 2H5
C 2H5

Question 23. Give IUPAC names of the following ethers.


(i) C2H 5 OCH 2 CH CH 3

CH3
(iii) O2N C6H 4 OCH 3 ( p)
H3C CH3

(ii) CH 3 OCH 2 CH 2 Cl

(iv) CH 3 CH 2 CH 2 OCH 3

(v)

(vi)
OC2H5

OC2H5

Recall the rules of IUPAC nomenclature see solution 1 of excercise.

Solution.

(i) C 2H5 O CH2 CH CH3

CH3
1-ethoxy-2-methylpropane
1

OCH3

(ii) CH3 O CH2 CH2 Cl

2-chloro-1-methoxyethane

(iii) O2N C 6H4 OCH3 (p)


4-nitroanisole

or

3
4

NO2
4-nitroanisole

Chemistry-XII

Alcohols, Phenols and Ethers

330

NCERT ClassXII ChemistrySolutions


3

(iv) CH3CH2 CH2OCH3


1-methoxypropane

H3C

CH3

(v)

(vi)

2
1

OC2H5

OC2H5

1-ethoxy-4,4-dimethyl
cyclohexane

Ethoxy
benzene

Question 24. Write the names of reagents and equations for the
preparation of the following ethers by Williamsons synthesis.
(i) 1-propoxypropane
(ii) Ethoxybenzene
(iii) 2-methoxy-2-methylpropane
(iv) 1-methoxyethane
Williamson's
synthesis

(i) R X + RO Na
R O R + Na X
(ii) Alkyl halide should be primary.

Solution.

Heat

(i) CH3CH2CH2O Na+ + CH3CH2CH2 Br

Sodium propoxide

1-bromopropane

CH3CH2CH2 O CH2CH2CH3 + NaBr


1-propoxypropane

O Na

(ii)

+ CH3CH2Br
Sodium
phenoxide

Heat

Bromoethane

OCH2CH3
+

NaBr

Ethoxybenzene

Chemistry-XII

Alcohols, Phenols and Ethers

Alcohols,PhenolsandEthers

(iii)

CH3

CH3 C O Na+

CH3

331

C H3 Br

Heat

Bromomethane

Sod. tert-butyl-alkoxide

CH3

CH3 C OCH3 + NaBr

CH3
2-methoxy-2-methylpropane

(iv) CH3CH2 ONa+ +

CH3 Br

Heat


CH3CH2 O CH3

Bromomethane

Sodium ethoxide

1-methoxyethane

+ NaBr

Question 25. Illustrate the examples the limitations of Williamsons


synthesis for the preparation of certain types of ethers.
Tertiary alkyl halides readily give elimination product with strong bases
like alkoxide ions. The CX bond of alkyl halide does not possess double
bond character i. e., should not be in conjugation with multiple bond.

Solution. (i) In Williamsons synthesis reaction for the preparation of


ether, the alkyl halide used must be primary as tertiary halides
readily undergo elimination with strong bases like C 2H5ONa. This
is be best understood by taking the example of preparation of
ethyl tertiary butyl ether. For which the reactants used are ethyl
bromide and sodium tertiary butoxide, but not the tertiary butyl
chloride and sodium ethoxide.
CH3
CH3

C 2H5Br
+ Na+O C CH3 C 2H5 O C CH3

Ethyl bromide

CH3
CH3
tertiary butyl ethyl ether

Sodium tertiary butoxide

+ NaBr
CH3

H3C C Br

CH3
Tert. butyl bromide

+ Na O C 2H5 CH3 C== CH2


Sodium ethoxide

CH3
2-methyl propene
(Ether is not formed)

+ NaBr + C 2H5OH
(ii) Aryl halides and vinyl halides cannot be used as substrates
because they are less reactive in nucleophilic substitution.

Chemistry-XII

Alcohols, Phenols and Ethers

332

NCERT ClassXII ChemistrySolutions

Question 26. How is 1-propoxypropane synthesised from propan-1-ol?


Write mechanism of this reaction.
(i) Williamsons synthesis or
(ii) Dehydration of propan-1-ol.

Solution. Any one of the following two methods can be employed


(i) Williamsons synthesis
(a) 3CH3CH2CH2OH + PBr3 3 CH3CH2CH2Br + H3PO3
1-bromopropane

Propan-1-ol

(b) 2 CH3CH2CH2OH + 2Na 2 CH3CH2CH2O Na + H2


Propan-1-ol

Sodium propoxide

Reaction mechanism

Dry ether

CH3CH2CH2 ONa+ + CH3CH2 CH2 Br


Sod. propoxide

Heat

1-bromopropane

CH3CH2CH2 O CH2CH2CH3 + NaBr


1-propoxypropane

or
(ii) By dehydration of 1-propanol with conc. H 2SO4 at 413 K.
H SO

2
4

CH3CH2CH2 O+
CH3CH2CH2OH + H+

Propan-1-ol

H
H

Protonated 1-propanol

CH3CH2CH2 O H + CH3CH2CH2 O+

H
H

Propan-1-ol

413 K


H 2O,
+

CH3CH2CH2 O CH2CH2 CH3

H
CH3CH2CH2 O CH2CH2CH3
H+ ,

1-propoxypropane

Question 27. Preparation of ethers by acid dehydration of secondary or


tertiary alcohols is not a suitable method. Give reason.
Due to steric hindrance, alkenes are formed by SN1 mechanism.

Solution. Ethers are formed as a result of acid dehydration by S N 2


mechanism (from primary alcohols). If secondary or tertiary alcohols are
used, due to steric hindrance, alkenes are formed and not ethers.

Chemistry-XII

Alcohols, Phenols and Ethers

Alcohols,PhenolsandEthers

333

Conc. H SO

2
4 CH CH==CH
CH3 CH OH

3
2
413 K
Propene

(major)
CH3

Propan-2-ol
(2 alcohol)

CH3
CH3

+ CH3 CH O CH CH3
Di-isopropyl ether
(minor)

CH3
CH3

Conc. H 2SO 4
CH3 C OH
CH3 C== CH2 + H2O
413 K

CH3

Tert. butyl alcohol


(3)

Question 28. Write the equation of the reaction of hydrogen iodide


with : (i) 1-propoxypropane (ii) methoxybenzene and (iii) benzyl ethyl
ether.
Alcohols and alkyl or aryl iodides are formed. Generally primary halide
(or lower halide) is formed in this reaction.

Solution.

HI
(i) CH3CH2CH2 O CH2CH2CH3

1-propoxypropane

373 K

CH3CH2CH2 OH + CH3CH2CH2 I
Propan-1-ol

OCH3
HI, 373 K

(ii)

Iodopropane

OH

Methoxybenzene

+ CH3I
Phenol

CH2OC2H5

Iodomethane

CH2I
HI, 373 K

(iii)
Benzyl ethyl ether

+ C2H5OH
Benzyl iodide

Ethanol

Question 29. Explain the fact that in aryl alkyl ethers


(i) the alkoxy group activates the benzene ring towards electrophilic
substitution.
(ii) it directs the incoming substituents to ortho and para positions in
benzenering.

Chemistry-XII

Alcohols, Phenols and Ethers

334

NCERT ClassXII ChemistrySolutions


Consider + R effect of the alkoxy group and more electron density at oand p-positions.

Solution. In aryl alkyl ethers, +R effect of the alkoxy group ( OR)


increases the electron density in the benzene ring thereby activating
the benzene ring towards electrophilic substitution reactions.
OR

OR

OR

OR

OR

IV

III

II

Electron density is more at o- and p-positions so o- and p-products are


mainly formed during electrophilic substitution reactions.
e.g.,
OCH3
OCH3
OCH3

Br

Br2

CH3COOH

Br
Anisole

o-bromo-anisole
(minor)

p-bromo-anisole
(major)

Question 30. Write the mechanism of the reaction of HI with


methoxymethane.
Steps involved in this process are
(i) protonation
(ii) formation of methanol and iodomethane.

Solution. When equimolar amounts of HI and methoxymethane are


taken, a mixture of methyl alcohol and iodomethane are formed.
Mechanism

Step I CH3 O CH3 + H I

H
+
Protonation
CH3 O CH3 + I

fast

Dimethyl oxonium ion

H
+
SN 2
StepII I + CH3 O CH3

Slow

CH3 I
Iodomethane

+ CH3OH
Methanol

If HI is present in excess, CH3OH formed in step II is further


converted into CH3I.

Chemistry-XII

Alcohols, Phenols and Ethers

Alcohols,PhenolsandEthers

335

H
+
Protonation
StepIII CH3 O H + H I CH3 O H + I

fast

Protonated methanol

H
+
SN 2
StepIV I + CH3 O H

CH3 I

Slow Iodomethane

+ H2O

Question 31. Write equations of the following reactions.


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

Friedel Craftsreactionalkylation of anisole.


Nitrationof anisole.
Bromination of anisole in ethanoic acidmedium.
Friedel Crafts acetylation of anisole.
OCH3 group is o/p directing.
(i) Alkylation (i.e., introduction of R group ) at o- and p-positions.
(By anhyd. AlCl3 CS2 ).
(ii) Nitration (i.e., introduction of NO 2 group) at o- and p-positions
(By H2SO4 HNO 3 ).

(iii) Bromination (introduction of Br2 group) at o- and p-positions


(By Br2 in CH3COOH).
(iv) Acetylation (introduction of RCO-group) at o- and p-positions
(By CH3COCl-anhydrous AlCl3).

Solution. (i) Friedel Crafts reaction (Alkylation)


OCH3

OCH3
+ CH3Cl
Anisole

Anhyd. AlCl3

Chloromethane

OCH3
CH3
+

CS2

2-methoxy toluene
(Minor)

CH3

4-methoxy toluene
(Major)

(ii) Nitration of anisole


OCH3

OCH3
H2SO4

OCH3
NO2
+

HNO3
Anisole

2-nitroanisole
(Minor)

NO2
4-nitroanisole
(Major)

Chemistry-XII

Alcohols, Phenols and Ethers

336

NCERT ClassXII ChemistrySolutions

(iii) Bromination of anisole


OCH3

OCH3

OCH3
Br

Br2 in

Ethanoic acid
Anisole

o-bromo
anisole (Minor)

Br
p-bromoanisole (Major)

(iv) Friedel Crafts acetylation of anisole


OCH3
+ CH3COCl
Anisole

Anhyd. AlCl3

Ethanoyl
chloride

OCH3

OCH3
COCH3

+
2-methoxy
acetophenone
(Monor)

COCH3
4-methoxy acetophenone
(Major)

Question 32. Show how would you synthesise the following alcohols
from appropriate alkenes?
CH3

(i)

OH

OH

(ii)

OH

(iii)

(iv)

OH

By hydration (addition of H2O)of appropriate alkenes in accordance with.


Markownikoffs rule.

Chemistry-XII

Alcohols, Phenols and Ethers

Alcohols,PhenolsandEthers

337

Solution.
CH3
(i)

CH3

CH3

H2O

OH
H

1-methyl
cyclohexene

Tert. carbocation

CH3

H+

OH

1-methylcyclo-hexan-1-ol

OH

(ii)

+ HOH
4-methyl hept-3-ene

H
Markownikoff's
rule

4-methyl heptan-4-ol

OH
+

(iii)

+ HOH
Pent-1-ene

Penan-2-ol

(iv)

4
H2O
H

2-cyclohexylbut
-2-ene

OH
2-cyclohexyl
butan-2-ol

Question 33. When 3-methylbutan-2-ol is treated with HBr, the


following reaction takes place
Br

HBr
CH 3 CH CH CH 3 CH 3 C CH 2 CH 3
Br

CH 3
CH 3 OH
Give a mechanism for this reaction.
The secondary carbocation formed in the process rearranges to a more
stable tertiary carbocation by a hydride ion shift from 3rd carbon atom.

Chemistry-XII

Alcohols, Phenols and Ethers

338

NCERT ClassXII ChemistrySolutions

Solution. Mechanism
H2O

HBr

CH3 CH CH CH3
CH3 CH CH CH3
Br

CH3 O H
CH3 OH

3-methylbutan-2-ol
H
H

H ion shift
CH3 C CH CH3

CH3
2 carbocation
(Less stable)

Br

CH3 C CH2 CH3 CH3 C CH2 CH3

CH3
CH3

Br

3 carbocation
(More stable)

2-bromo-2-methyl
butane

Selected NCERT ExemplarProblems


ShortAnswersType
Question 1. What is the structure and IUPAC name of glycerol?
Solution. CH2 CH CH2

OH

OH

OH

Propane-1,2,3-triol

Question 2. Write the IUPAC name of the following compounds.


NO2
3
6

(i) CH 3 CH CH CH CH CH 3

CH 3 OH C2H 5 OH

Solution.

(ii)

2
1

OCH3

(i) 3-ethyl -5- methylhexane-2, 4,-diol.


(ii) 1-methoxy-3-nitrocyclohexane

Question 3. Write the IUPAC name of the compound given below.


5

CH 3 CH 2 C ==C OH

1
CH 3 CH 2 OH

Solution.

Chemistry-XII

3-methylpent-2-ene-1, 2-diol.

Alcohols, Phenols and Ethers