Theme

Alcohols, Phenols and Ethers 11

Exercises

1. Write IUPAC names of the following compounds:

CH3
(i) CH3 — CH — CH — C — CH3
CH3 OH CH3
(ii) H3C — CH — CH2 — CH — CH — CH2 — CH3
OH OH C2H5
(iii) CH3 — CH — CH — CH3
OH OH
(iv) HO — CH2 — CH — CH2 — OH
OH
CH3
OH
(v)

CH3

(vi)

OH
CH3

(vii)

OH
CH3
CH3

OH
(viii)

CH3
(ix) CH3 — O — CH2 — CH — CH3
CH3
(x) C6H5 — O — C2H5
(xi) C6H5 — O — C7H15 (n –)
(xii) CH3 — CH2 — O — CH — CH2 — CH3
CH3

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Ans. (i) 2,2,4-trimethylpentan-3-ol
(ii) 5-ethylheptane-2,4-diol
(iii) Butane-2,3-diol
(iv) Propane-1,2,3-triol
(v) 2-methylphenol
(vi) 4-methylphenol
(vii) 2,5-dimethylphenol
(viii) 2,6-dimethylphenol
(ix) 1-methoxy-2-methylpropane
(x) Ethoxybenzene
(xi) 1-phenoxyheptane
(xii)2-ethoxybutane
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
(vii) Cyclohexylmethanol
(viii) 3-cyclohexylpentan-3-ol
(ix) Cyclopent-3-en-1-ol
(x) 4-chloro-3-ethylbutan-1-ol
CH3
1 2 3 4
Ans. (i) CH3 — C — CH2 — CH3
OH
2-Methylbutan-2-ol
1 2 3
(ii) CH2 — CH — CH3
OH
1-phenylpropan-2-ol

CH3 CH3
1 2 3 4 5 6
(iii) CH2 — CH2 — C — CH2 — C — CH3
OH OH OH
3,5-dimethylhexane-1,3,5-triol

OH
1
(iv) C2H5
2
3
C2H5
2,3-diethyl phenol
1 2 3
(v) CH3CH2 — O — CH2 — CH2 — CH3
1-ethoxypropane
1 2 3 4 5
(vi) CH3 — CH — CH — CH2 — CH3
OC2H5 CH3
2-ethoxy-3-methylpentane

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CH2OH
(vii)

Cyclohexyl methanol

OH
1 2 3 4 5
(viii) CH — CH — C — CH — CH
3 2 2 3

3-cyclohexylpentan-3-ol

OH
(ix) 1
2

3
Cylopent-3-en-1-ol
1 2 3 4 5
(x) OH — CH2 — CH2 — CH — CH2 — CH3
CH2Cl
3-chloromethylpentan-1-ol
3. (i) Draw the structures of all the isomeric alcohols of molecular formula C5H12O and give their IUPAC
names.
(ii) Classify the isomers of alcohols in question (a) primary, secondary and tertiary alcohols.
Ans. (i) The molecular formula C5H12O represents eight isomeric alkanols. These are:
5 4 3 2 1
(a) CH — CH — CH — CH — CH — OH
3 2 2 2 2
Pentan-1-ol
4 3 2 1
(b) CH3 — CH — CH2 — CH2 — OH
CH3
3-Methylbutan-1-ol
4 3 2 1
(c) CH3 — CH2 — CH — CH2 — OH
CH3
2-Methylbutan-1-ol
CH3
3 2 1
(d) CH3 — C — CH2 — OH
CH3
2,2-Dimethylpropan-1-ol
5 4 3 2 1
(e) CH3 — CH2 — CH2 — CH — CH3
OH
Pentan-2-ol
(f) CH — CH — CH — CH
3 3

CH3 OH
3-Methyl butan-2-ol
CH3
1 2 3 4
(g) CH — C — CH — CH
3 2 3
OH
2-Methylbutan-2-ol

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5 4 3 2 1
(h) CH — CH — CH — CH — CH
3 2 2 3
OH
Pentan-3-ol
(ii) Primary: (a), (b), (c) and (d); Secondary: (e), (f) and (h); Tertiary: (g)
4. Explain why propanol has higher boiling point than that of the hydrocarbon, butane?
Ans. The molecules of butane are held together by weak van der Waal’s forces of attraction while those of
propanol are held together by stronger intermolecular hydrogen bonding.
δ+ δ– δ+ δ– δ+ δ–
———H—O———H—O———H—O———
CH2CH2CH3 CH2CH2CH3 CH2CH2CH3
Therefore, the boiling point of propanal is much higher than that of butane.
5. Alcohols are comparatively more soluble in water than hydrocarbons of comparable molecular masses.
Explain the fact.
Ans. Water and alcohols both are polar in nature. When an alcohol is dissolved in water, it forms H-bonds with
water molecule by breaking the H-bond already existing between water molecules.
Hydrocarbons are non-polar in nature and do not forms H-bonds with water molecules. Therefore,
alcohols are readily soluble in water whereas hydrocarbons are not.
δ– δ+ δ– δ+ δ–
———R—O———H—O———H—O———
H H R
Hydrogen bonding among alcohol and water.
6. What is meant by hydroboration-oxidation reaction? Illustrate it with an example.
Ans. The addition of diborane to alkenes to form trialkyl boranes followed by their oxidation with alkaline
hydrogen peroxide to form alcohols is called hydroboration-oxidation.
For example, propan-1-ol is produced by the hydroboration-oxidation reaction of propene. In this reaction,
propene reacts with diborane (BH3)2 to form trialkyl borane as an addition product. This addition product
is oxidized to alcohol by hydrogen peroxide in the presence of aqueous sodium hydroxide.
CH3 — CH = CH2 + (H—BH2)2 (CH3—CH—CH2
Propane Diborane H BH2

CH3—CH = CH2

CH3—CH = CH2
(CH3—CH2—CH2)3B (CH3—CH2—CH2)2BH
–
H2O 3H2O2,OH

3CH3—CH2—CH2—OH + B(OH)3
Propan-1-ol
7. Give the structures and IUPAC names of monohydric phenols of molecular formula, C7H8O.
Ans. The three isomers are:
OH OH OH
CH3

CH3

2-methylphenol 3-methylphenol
CH3
o-Cresol m-Cresol
4-methylphenol
p-Cresol
8. While separating a mixture of ortho and para nitrophenols by steam distillation, name the isomer
which will be steam volatile. Give reason.

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Ans. Ortho-nitrophenol is steam volatile. The reason is chelation due to intramolecule 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.
O O
O — H --- O = N → O
N H

O→N = O — H --- O
o-nitrophenol p-nitrophenol
(Intramolecular H-bonding) (Interamolecular H-bonding)
9. Give the equations of the reaction for the preparation of phenol from cumene.
Ans. To prepare phenol, cumene is first oxidised in the presence of air to cumene hydroperoxide.
CH3 CH3
CH3—CH CH3—C—O—O—H

O2, 368 – 408 K

Cumene Cumene
[Isopropyl benzene] hydroperoxide
The cumene hydroperoxide thus formed, is treated with dilute acid to prepare phenol and acetone as by-
products.
CH3
CH3—C—O—O—H OH

H+
322 – 363 K + CH3COCH3

Cumene hydroperoxide Phenol Acetone

10. Write chemical reaction for the preparation of phenol from chlorobenzene.
Ans. Chlorobenzene is fused with NaOH (at 623 K and 320 atm pressure) to produce sodium phenoxide, which
gives phenol on acidification.
Cl ONa OH

623 K, 200 atm HCl

+2NaOH –NaCl, –H2O –NaCl

Chlorobenzene Sodium phenoxide Phenol

11. Write the mechanism of hydration of ethene to yield ethanol.
Ans. The mechanism of hydration of ethene to form ethanol involves three steps:
Step 1: Protonation of ethene to form carbocation by electrophilic attack of H3O+:
H2O + H+ → H3O+
H H
H H + + H
C=C +H—O—H H—C—C + H2O
H H H
H
Step 2: Nucleophilic attack of water on carbocation formed:
H H H H
+ H Slow +
H—C—C H—C—C—O—H
+ H2O
H
H H H

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Step 3: Deprotonation to form corresponding alcohols:
H H H H OH
+ Fast +
H — C — C — O — H + H2O → H — C — C — H + H O
3

H H H H
12. You are given benzene, conc. H2SO4 and NaOH. Write the equations for the preparation of phenol
using these reagents.
SO3H ONa OH

Ans. conc. H2SO4 NaOH H2SO4

∆ ∆

Benzene Benzene Sodium Phenol

sulphonic acid phenoxide
13. Show how will you synthesise:
(i) 1-phenylethanol from a suitable alkene.
(ii) Cyclohexylmethanol using an alkyl halide by an SN2 reaction.
(iii) Pentan-1-ol using a suitable alkyl halide?
Ans. (i) 1-phenylethanol can be prepared from ethenylbenzene by addition of H2O in the presence of dil.
H2SO4.
CH = CH2
Dil. H2SO4 CH —CH3
+ NaOH
OH
1-phenylethanol
(ii) Hydrolysis of cyclohexylmethyl bromide by aqueous NaOH gives cyclohexylmethanol.

CH2Br CH2OH
+ H — OH ∆ + NaBr
SN2, hydrolysis

Cyclohexylmethyl bromide Cyclohexylmethanol

(iii) Hydrolysis of 1-bromopentane by aqueous NaOH gives pentan-1-ol.
∆
 → CH CH CH CH CH — OH + NaBr
CH3CH2CH2CH2CH2Br + NaOH SN 2, Hydrolysis 3 2 2 2 2
1-bromopentane Pentan-1-ol

14. Give two reactions that show the acidic nature of phenol. Compare acidity of phenol with that of
ethanol.
Ans. The acidic nature of phenol can be represented by the following two reactions:
(a) Reaction with sodium: Phenol reacts with sodium to give sodium phenoxide, liberating H2 gas.
OH ONa

2 + 2Na 2 + H2

Phenol Sodium
phenoxide
(b) Reaction with NaOH: Phenol reacts with NaOH to form sodium phenoxide and water as a by-
product.
OH ONa

2 + NaOH + H2O

Phenol Sodium
phenoxide

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Phenol is more acidic than ethanol. This is due to the reason that after the loss of a proton phenol form
phenoxide ion which is stabilized by resonance, while ethoxide ion formed after the loss of a proton from
ethanol, does not.
–
O H O

–H+

R R
Phenoxide ion
The resonating structures of phenoxide ion are shown as below:
– –
O O O O O

– –

–
The lone pair of electrons on oxygen delocalizes into the benzene (mesomeric effect) which reduces the
electron density in the O—H bond. The O—H bonds are weaker and therefore breaks easily whereas in
ethanol the electron releasing inductive effect of the alkyl group increases the electron density on the
O—H bond. This strengthens the bond so the bond does break not break easily. Therefore making ethanol
less acidic than phenol.
15. Explain why is ortho-nitrophenol more acidic than ortho-methoxyphenol?
Ans. OH OH
NO2 OCH3

o-nitrophenol o-methoxyphenol
The nitro group is an electron withdrawing group. The presence of the group in the ortho-position decreases
the electron density in the O–H bond. As a result, it is easier to lose a proton. Also, the o-nitrophenoxide
ion formed of the loss of proton is stabilised by resonance. Hence, ortho, nitrophenol is a stronger acid.
On the other hand, methoxy group is an electron releasing group. Thus, it increases the electron density
in the O–H bond and hence, the proton can not be given out easily.
For this reason, ortho-nitrophenol is more acidic than ortho-methoxyphenol.
–
O—H O
NO2 NO2
+ H+

o-nitrophenol
–
O—H O
OCH3 OCH3
+ H+

o-methoxyphenol

O– O–
CH3 – +
O CH3 O

16. Explain how does the – OH group attached to a carbon of benzene ring activate it towards electrophilic
substitution?

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Ans. Phenol may be regarded as a resonance hybrid of structures I-V, shown below:
OH OH + OH + OH + OH

– –

I II III IV V
As a result of +R effect of the –OH group, the electron density in the benzene ring increases thereby
facilitating the attack of an electrophile. In other words, presence of –OH group, activates the benzene ring
towards electrophilic substitution reactions. Further, since the electron density is relatively higher at the
two o-and one p-position, therefore electrophilic substitution occurs mainly at o-and p-positions.
17. Give equations of the following reactions:
(i) Oxidation of propan-1-ol with alkaline KMnO4 solution.
(ii) Bromine in CS2 with phenol.
(iii) Dilute HNO3 acid with phenol
(iv) Treating phenol with chloroform in presence of aqueous NaOH.

Alk. KMnO CH3CH2COOH + H2O
Ans. (i) CH3CH2CH2OH + 2 [O]  Oxidation →
4

Propan-1-ol Propanoic acid

OH OH OH
Br
(ii)
Br2 in CS2
+ + HBr

Phenol (Minor)
2-Bromophenol Br
(Major)
4-Bromophenol

OH OH OH
NO2
(iii) Dil. HNO3
+ + H2O

Phenol (Major)
2-Nitrophenol NO2
(Minor)
2-Nitrophenol

OH ONa OH
CHO CHO
(iv) CHCl . NaOH, 343 K H+, H O
3 2

Phenol (Minor) 2-Hydroxybenzaldehyde

2-Nitrophenol (salicylaldenyde)
18. Explain the following with an example:
(i) Kolbe’s reaction.
(ii) Reimer – Tiemann reaction.
(iii) Williamson ether synthesis.
(iv) Unsymmetrical ether.
Ans. (i) Kolbe’s reaction: When phenol is treated with sodium hydroxide, sodium phenoxide is produced.
This sodium phenoxide when treated with carbon dioxide, followed by acidification, undergoes
electrophilic substitution to give ortho-hydroxybenzoic acid (salicylic acid) acid as the main product.
This reaction is known as Kolbe’s reaction.

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OH ONa OH
(i) CO
COOH
N
aOH
→ 2→
(ii) H+

Phenol Sodium phenoxide Ortho-hydroxybenzoic acid

(Salicylic acid)
(ii) Reimer-Tiemann reaction: When phenol is treated with chloroform (CHCl3) in the presence of
sodium hydroxide, a –CHO group is introduced at the ortho position of the benzene ring.
– +
OH ONa
CHCl2
CHCl + aq. NaOH

3
→

Phenol Intermediate
This reaction is known as the Reimer-Tiemann reaction.
The intermediate is hydrolysed in the presence of alkalis to produce salicylaldehyde.
–+ –+
ONa ONa OH
CHCl2 CHO +
CHO
H
NaOH
→ →

Intermediate Salicylaldehyde
(iii) Williamson ether synthesis: Williamson ether synthesis is a laboratory method to prepare
symmetrical and unsymmetrical ethers by allowing alkyl halides to react with sodium alkoxides.
R–X + R' – ONa → R – O – R' + NaX
Alkylhalide Sodium alkoxide Ether

This reaction involves SN2 attack of the alkoxide ion on the alkyl halide. Better results are obtained in
case of primary alkyl halides.
CH3 CH3
–+
CH3 — CH — ONa + CH3 — Br → CH3 — O — CH — CH3 + NaBr
If the alkyl halide is secondary or tertiary, then elimination competes over substitution.
(iv) Unsymmetrical ether: An ether in which alkyl or aryl groups attached to the oxygen atom are
different, is known as unsymmtrical ether. Example: Ethyl methyl ether (C2H5OCH3), methyl phenyl
ether (CH3—O—C6H5).
19. Write the mechanism of acid dehydration of ethanol to yield ethene.
Ans. The mechanism of dehydration of alcohols to form alkenes occur by the following three steps:
(a) Formation of protonated alcohol:
+ H
+
CH3CH2 — O — H + H CH3CH2 — O H
(Oxonium Salt)
(b) Formation of carbocation:
+ H Slow +
CH3CH2 — O H CH3CH2 + H2O
Ethylcarbocation
(c) Elimination of a proton to form ethene:
+ Fast
H — CH2 — CH2 CH2 = CH2 + H+
Ethane
20. How are the following conversions carried out?
(i) Propene to Propan-2-ol
(ii) Benzyl chloride to Benzyl alcohol
(iii) Ethyl magnesium chloride to Propan-1-ol
(iv) Methyl magnesium bromide to 2-Methylpropan-2-ol

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Ans. (i) When propene is allowed to react with water in the presence of an acid as a catalyst, then propan-2-ol is
obtained. The process of conversion of propene to propan-2-ol is also called as acid hydration.
H+
CH3 — CH2 = CH2 + H2O CH3 — CH — CH3
Propene
OH
Propan-2-ol
(ii) If benzyl chloride is treated with NaOH (followed by acidification) then benzyl alcohol is produced.
CH2Cl CH2ONa CH2OH

+
+ NaOH → 
H→
– HCl

Benzyl chloride Benzyl alcohol

(iii) When ethyl magnesium chloride is treated with methanal in the presence of dry ether, an addition
product is obtained which gives propan-1-ol on hydrolysis.
– – OH
H CH2 — OMgCl +
C = O + C2H5 — MgCl → H2O/H
→ Mg(OH)Cl + C3H7 — OH Or CH2
H C2H5 Propan-1-ol
Adduct CH2 — CH3
(iv) When methyl magnesium bromide is treated with propane in the presence of dry ether, an adduct is
obtained which gives 2-methylpropan-2-ol on hydrolysis.
CH3 OH
H3C –+ H O/H+
C = O + CH3 — MgBr → CH3 — C — OMgBr 2 ฀ Mg(OH)Br + CH3 — C — CH3
HC
3
Propane
CH3 CH3
Adduct (2-Methylpropan-2-ol)
21. Name the reagents used in the following reactions:
(i) Oxidation of a primary alcohol to carboxylic acid.
(ii) Oxidation of a primary alcohol to aldehyde.
(iii) Bromination of phenol to 2,4,6-tribromophenol
(iv) Benzyl alcohol to benzoic acid.
(v) Dehydration of propan-2-oI to propene.
(vi) Butan-2-one to butan-2-ol .
Ans. (i) Acidified potassium dichromate or neutral/acidic/alkaline potassium permanganate.
–
(ii) Pyridinium chlorochromate (PCC), (C5H5NH) + ClCrO3 in CH2Cl2
or Pyridinium dichromate (PDC), [(C5H5NH)2]2+ Cr2O72– in CH2Cl2
(iii) Aqueous bromine, i.e., Br2/H2O.
(iv) Acidified or alkaline potassium permanganate.
(v) 85% H2SO4 at 440 K.
(vi) Ni/H2 or NaBH4 or LiAlH4.
22. Give reason for the higher boiling point of ethanol in comparison to methoxymethane.
Ans. Hydrogen bonding is present between the ethanol molecules which is absent in molecules of methoxy
methane. So, a large amount of energy is required to break these strong bonds in ethanol.
δ– δ+ δ– δ+ δ–
–––H—O–––H—O–––H—O–––
CH CH CH2CH3 CH2CH3
2 3
23. Give IUPAC names of the following ethers:
(i) C2H5OCH2 — CH — CH3
CH3
(ii) CH3OCH2CH2Cl
(iii) O2N — C6H4 —OCH3

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(iv) CH3CH2CH2OCH3
H3C CH3

(v)

OC2H5
(vi)

OC2H5
Ans. (i) 1-Ethoxy-2-methylpropane
(ii) 2-Chlorlo-l-methoxyethane
(iii) 4-Nitroanisole
(iv) 1-Methoxypropane
(v) 1-Ethoxy-4-4 – dimethyl cyclohexane
(vi) Ethoxybenzene
24. Write the names of the reagents and equations for the preparation of the following ethers by
Williamson’s synthesis :
(i) 1-Propoxypropane
(ii) Ethoxybenzene
(iii) 2-Methoxy-2-methylpropane
(iv) Methoxyethane.
Ans. (i) CH3CH2CH2Br + CH3CH2CH2ONa → CH3CH2CH2OCH2CH2CH3 + NaBr
1-Bromopropane Sod. propoxide 1-Propoxypropane
ONa OC2H5
(ii)
+ C2H5Br + NaBr

Sod. phenoxide Bromoethane Ethoxybenzene

CH3 CH3
(iii) CH3 — C — ONa + CH3Br CH3 — C — OCH3 + NaBr

CH3 CH3
Sod-2-methyl-2-propoxide Bromomethane 2-methoxy-2-methylpropane

(iv) C2H5ONa + CH3Br → C2H5 —O —CH3 + NaBr

Sod. ethoxide Bromomethane Methoxyethane
25. Illustrate with examples the limitations of Willamson synthesis for the preparation of certain types of
ethers.
Ans. Williamson’s synthesis is a versatile method for the synthesis of both symmetrical and unsymmetrical
ethers. However, for the synthesis of unsymmetrical ethers, a proper choice of reactants is necessary.
Since Williamson’s synthesis occurs by SN2 mechanism and primary alkyl halides are most reactive in SN2
reaction, therefore, best yields of unsymmetrical ethers are obtained when the alkyl halides are primary
and the alkoxide may be primary, secondary or tertiary. For example, tert-butylethyl ether is prepared by
treating ethyl bromide with sodium tert-butoxide.
CH3 CH3
δ+ δ– ∆
CH3 — C — O–Na+ + CH3CH2 — Br CH3 — C — OCH2CH3 + Na+Br–
CH3
CH3
(3°Alkoxide)

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The above ether cannot be prepared by treating sodium ethoxide with tert-butyl chloride or bromide since
under these condition an alkene, i.e., isobutylene is the main product.
CH3
(CH3)3 — C — Br + C2H5O– Na+ CH3 — C = CH2 + NaBr + C2H5OH
2-Methylpropene
Aryl and vinyl halides cannot be used as substrates because they are less reactive in nucleophilic
substitution.
26. How is 1-propoxypropane synthesised from propan-1-ol? Write mechanism of the reaction.
Ans. Any one of the following methods can be used for the synthesis of 1-propoxypropane from propan-1-ol.
(i) By Williamson’s synthesis
The halogen derivative such as bromoderivative and sodium salt of the alcohol take part in the
Williamson’s synthesis.
(a) 3 CH3—CH2—CH2—OH + PBr3 → 3 CH3—CH2—CH2—Br + H3PO3
Propan-1-ol 1-Bromopropane
– +
(b) CH3—CH2—CH2—OH + Na → CH3—CH2—CH2—O Na + 1/2H2
Propan-1-ol Sodium propoxide
– + SN2
CH3—CH2—CH2—ONa + CH3—CH2—CH2—Br
Sodium propoxide 1-bromopropane

CH3—CH2—CH2—O—CH2—CH2—CH3 + NaBr
1-Propoxypropane
(ii) By dehydration of propan-1-ol with conc. H2SO4 at 413 K
+ (Slow) +
CH3—CH2—CH2—O—H + H+ CH3—CH2—CH2—O—H –H2O
CH3—CH2—CH2
Propan-1-ol H 1°Carbocation
Protonated alcohol
The primary carbocation attacks another molecule of propan-1-ol by SN1 mechanism.
+ +
(Fast)
CH3CH2CH2 + OCH2CH2CH3 CH3CH2CH2O —CH2CH2CH3
H H
Protonated ether

(Fast) —H+

CH3CH2CH2OCH2CH2CH3
1-Propoxypropane
27. Preparation of ethers by acid dehydration of secondary or tertiary alcohols is not a suitable method.
Give reason.
Ans. Ethers are formed as a result of acid dehydration by SN2 mechanism (from primary alcohols). If secondary
or tertiary alcohols are used, due to steric hinderance, alkenes are formed and not ethers.
CH3 CH3
Conc. H2SO4
CH3—CH—OH 413 K
CH3—CH = CH2 + CH3—CH—O—CH—CH3

CH3 Propane Di-isopropyl ether

Propan-2-ol (Major) (Minor)
(2° alcohol)
CH3 CH3
Conc. H2SO4
CH3—C—OH 413 K CH3—C = CH2 + H2O
CH3
Butyl alcohol
(3° alcohol)

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28. Write the equation of the reaction of hydrogen iodide with (i) 1-propoxypropane (ii) methoxybenzene,
and (iii) benzyl ethyl ether. HI
 → CH CH CH — OH + CH CH CH I
Ans. (i) CH3CH2CH2OCH2CH2CH3 373 K 3 2 2 3 2 2

1-propoxypropane Propan-1-ol Iodopropane

OCH3 OH

(ii) HI, 373 K

+ CH3—I
Iodomethane
Methoxybenzene Phenol
CH2—O—C2H5 CH2I

(iii) HI, 373 K + C H OH

2 5

Benzyl ethyl ether Benzyl Iodide

29. Explain the fact that in alkyl aryl ethers:
(i) Alkoxy group activates the benzene ring towards electrophilic substitution.
(ii) It directs the incoming substituents towards ortho and para positions in benzene ring.
Ans. (i) 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.
O—R + O—R + O—R + O—R O—R

– –

–
As the ortho and para positions in the ring become points of high electron density, the electrophiles
prefer to attack these positions.
(ii) The alkoxy group directs the incoming group which is an electrophile towards the ortho and para
positions in the ring. As a result, a mixture of isomeric products is formed.
30. Write the mechanism of the reaction of HI with methoxymethane.
Ans. The mechanism of the reaction of HI with methoxymethane involves the following steps:
Step 1: Protonation of methoxymethane:
H
+
CH3 — O — CH3 + H — I CH3 — O — CH3 + I–
Step 2: Nucleophilic attack of I–, this in case of primary and secondary alkyl halides follows SN2 mechanism.
–
H H
+ +
I– + CH3 — O — CH3 → I – – – CH3 – – – O – – – CH3 → CH3 — I + CH3 — OH
Iodomethane Methanol
Step 3: When HI is in excess and the reaction is carried out at a high temperature, the methanol formed in
the second step reacts with another HI molecule and gets converted to methyl iodide.
H
+
CH3 — O — H + H — I CH3 — O — H + I–
+
I– + CH3 — OH2 → CH3 — I + H2O
31. Write equations of the following reactions:
(i) Friedel-Crafts reaction -alkylation of anisole
(ii) Nitration of anisole.
(iii) Bromination of anisole in ethanoic acid medium
(iv) Friedel-Craft’s acetylation of anisole.

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120 | CBSE NCERT Question Chemistry – XII
OCH3 OCH3 OCH3
CH3
Ans. (i) Anhyd. AlCl3
+ CH3Cl +
CS2
Anisole 2-Methoxytoluene
(Major)
CH3
4-Methoxytoluene
(Major)

OCH3 OCH3 OCH3

NO2
(ii) H2SO4
HNO3
+

Anisole 2-Nitroanisole
(Minor) NO2
4-Nitroanisole
(Major)
OCH3 OCH3 OCH3
Br
Br2 in
(iii) +
Ethanoic acid
Anisole o-Bromoanisole
Br (Minor)
p-Bromoanisole
(Major)
OCH3 OCH3 OCH3
COCH3
(iv) Anhyd. AlCl3
+ CH3COCl +
Ethanoyl
Anisole chloride 2-Methoxy-
acetophenone
COCH3
(Minor)
4-Methoxy-
acetophenone
(Major)
32. Show how will you synthesise the following alcohols from appropriate alkenes:
CH3
(i)
OH

(ii) OH

(iii) OH

(iv)
OH

Ans. All the given alcohols can be synthesised by the acid-catalysed hydration of alkenes in the acidic medium.
The addition follows Markovnikov’s rule.
CH3 + CH3 CH3 CH3
(i) H+ H2O
O—H
–H+
OH
+
H
1-Methylcyclohexene 1-Methylcyclohexan-1-ol
(ii) 4-Methylpent-3-ene upon hydration in the acidic medium will give the desired alcohol.

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 Alcohols, Phenols and Ethers | 121
H

H+ H2O O—H –H+ OH

+ +

4-Methylhept-3-ene 4-Methylheptan-4-ol
(iii) Pent-2-ene gives the desired alcohol upon hydration in the presence of acid.
H
OH
+ O—H
H+ H2O + –H+

Pent-2-ene Pentan-2-ol
(iv) The cyclic alkene used in this reaction is 2-cyclohexylbut-2-ene.
+
H+ H2O –H+
+ O—H OH
H
2-cyclohexylbut-2-ene 2-Cyclohexlbutan-2-ol
33. When 3-methylbutant 2-ol is treated with HBr, the following reaction takes place:
Br
HBr
CH3—CH—CH—CH3 CH —C—CH
3
—CH
2 3

CH3 OH CH3
Give a mechanism for this reaction.
(Hint: The secondary carbocation formed in step II rearranges to a more stable tertiary carbocation by
a hydride ion shift from 3rd carbon atom.)
Ans. The mechanism of the given reaction involves the following steps:
Step 1: Protonation
H+
CH3 — CH — CH—CH3 CH3 — CH — CH — CH3
CH3 OH CH OH
3 + 2
3-Methylbutan-2-ol
Step 2: Formation of 2° carbocation by the elimination of water molecule
+
CH3 — CH — CH—CH3 –H2O CH3 — CH — CH — CH3
CH3 OH2 CH3
+
2° Carbocation
Step 3: Re-arrangement by the hydride-ion shift
H
+ 12-hydride shift +
CH3 — C — CH—CH3 CH3 — C — CH2 — CH3
CH3 CH3
(less stable) 3° Carbocation (more stable)
Step 4: Nucleophilic attack
Br
+
CH3 — C — CH2—CH3 Br– CH3 — C — CH2 — CH3
CH3 CH3
2-Bromo-2-methylbutane
rr

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