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ALCOHOLS
Alcohols, generally indicated by R–OH, can be regarded as derivative of alkanes where one or
more of the hydrogens have been replaced by hydroxyl group (–OH)

R — H 
–H
+ OH
→ R — OH
Alkane Alcohol
CH3
H3C OH H3C
H3C
methanol OH
ethanol OH
propan-2-ol
CH3

H3C CH3

OH OH
2-Methyl-2-propanol

Structures and Geometry Of Alcohol

The hydroxyl oxygen includes two non-bonding pairs, it will adopt sp3 hybridisation with a
C—O—H bond angle of about 109°.
H3C
H3C O
H3C H

Both the C—O and O—H single bonds are quite strong. Because oxygen is considerably more
electro-negative than either carbon and hydrogen both these bonds are polarized towards oxygen
making alcohols reasonably polar molecules.

Nomenclature
Alcohols can be named by three methods.
1. Carbinol method: Alcohols are considered as derivatives of methyl alcohol also
known as carbinol.
Example:
H3C H3C
OH
H3C OH
H3C
OH H3C CH3
Methyl carbinol Dimethyl carbinol Trimethyl carbinol

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2. Common Names: (Radicofunctional Nomenclature) This method is most often used

for the simple alcohol. A common name consists simply of the name of alkyl group
followed by the word alcohol. e.g.

H3C H3C
OH
H3C
H3C
OH H3C OH CH3
Ethyl alcohol isobutyl alcohol tertbutyl alcohol

3. IUPAC system: In this system alcohols are called ‘alkanols’. The name of an alcohol
is derived by replacing the final ‘e’ from the name of the corresponding alkane by the
suffx-‘ol’. The longest chain containing the –OH group is selected as the parent chain
numbered in such a way that the carbon atom carrying the OH group gets the smallest
number. The substituents is then indicated by suitable numbers.

Example
H3C H3C CH3
H3C
CH3
OH
H3C OH CH3
H3C HO H3C OH HO
methanol propan-1-ol propan-2-ol 2-methylpropan-1-ol 2-methylpropan-2-ol

Classification of Alcohols
Alcohols are classified according to no. of hydroxyl groups present in their molecule. Alcohols
with one two and three hydroxyl groups are called monohydric, dihydric & trihydric alcohols
respectively. Alcohols which contains four or more hydroxyl groups are called polyhydric
alcohols.
OH OH

OH
H3C OH OH
HO
methanol ethylene glycol OH OH OH OH
glycerol butane-1,2,3,4-tetrol
Note: When two or more hydroxyl groups attached to the same carbon atom the compound is generally
unstable. The compound loses a water molecule and is converted into a stable compound.
Monohydric alcohols are further divided into three classes:
H3C
i) Primary alcohol: The hydroxyl group is
attached with primary carbon atom. They H3C
OH H3C OH
possess a characteristic group —CH2—OH. propan-1-ol 2-methylpropan-1-ol

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CH3
ii) Secondary alcohol: The hydroxyl group
attached to secondary carbon atom. They H3C
OH
possess >CH—OH group. OH
H3C H3C
iii) Tertiary alcohol: The hydroxyl group CH3
CH3
attached to tertiary carbon atom. They H 3C
H 3C
possess a characteristic group C—OH. CH3
HO OH CH3

Physical Properties of Alcohols’

The alcohols are neutral substance, the lower members are liquids and have a distinctive smell
and a burning test the higher members are solids and are almost odourless.

In a group of isomeric alcohols the primary alcohols has the highest boiling points and the
tertiary the lowest, with the secondary having an individuate value. The lower members are less
volatile than it is to be expected from their molecular weights and this is due to association
through hydrogen bonding extending over a chain of molecules, thus giving rise to a large
molecule the volatility of which would be expected to be low.

R R R R
— −−−O — H−−−O — H−−−O — H−−−O — H

The lower alcohols are very soluble in water and the solubility diminishes as the molecular
weight increases. Their solubility of water is to be expected. Since the oxygen atom of the
hydroxyl group in alcohol can form hydrogen bond with water molecule. In the lower alcohols
the hydroxyl group constitutes a lage part of the molecule. Whereas the molecular weight of the
alcohol increases the hydrocarbon character of the molecule increases and hence the solubility in
water decreases. This however is not a complete story, the structure of carbon chain plays also a
part e.g. n-butanol is fairly soluble in water but t-butanol is miscible with water in all
proportions.

Preparation of Alcohol
1. By hydrolysis of alkyl halide: Alkyl halide undergo hydrolysis when heated with
aqueous alkalies or moist silver oxide. The hydrolysis occurs by a nucleophilic
substitution reaction.
∆
R — X + KOH  → R — OH + HX
Aq. Alcohol

This method is not satisfactory as alkenes are formed as side product. However
satisfactory results are obtained by using moist silver oxide.

2. Acid catalysed hydration of alkenes: Alkenes add water in the presence of an

acid catalyst to yield alcohol. The addition takes palce according to markovnikov

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regioselectivity. The reaction is reversible and the mechanism for the acid-catalysed
hydration of an alkene is simply the reverse of that for the dehydration of an alcohol.
H
+ H2O
+ HA + A− + A- + HA
− H2O
+
alkene H O H O
H H Alcohol H

Acid catalysed hydration of alkene has limited synthetic utility. However because of
carbocation intermediate rearrangement may take place. Thus a mixture of isomeric
alcohols may result.

3. Oxymercuration Demercuration: Alkenes reacts with mercuric acetate in a

mixture of water and tetrahydrofuran (THF) to produce (hydroxyalkyl) mercury
compounds. These can be reduced to alcohols with sodium borohydride and water.

a) Oxymercuration
O
C = C + H 2 O + Hg(OCCH 3 ) 2 
THF
→ —C—C— + CH 3COOH

HO Hg — O — C — CH 3

O
b) Demercuration
O
—C — C — → — C — C — +Hg 2+ CH 3 — C — O
+ OH + NaBH 4 
HO Hg — O — C — CH 3 HO H

The net addition of H— and —OH takes place with markovnikov regioselectivity and
takes place without the complications of rearrangements.

4. Hydroboration-oxidation: An alkene reacts with BH3 : THF or diborane to

produce an alkylborane oxidation and hydrolysis of the alkylborane with hydrogen
peroxide and base yields an alcohol.
CH3 + enantiomer
H

BH 3 : THF
Anti Markovnikov
→
&syn addition + dialkyl & trialkyl borane
CH3
H
H B
H H

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CH3
− H
H
CH3 
H 2 O2 OH
Boron gr. is replaced
→ + enantiomer
with retention of
configuration
H H
B OH

H H

The net addition of H— and —OH occurs with anti-markonikov region-selectivity and
syn stereoselectivity.

5. Hydroxylation of alkenes:
→
KMnO 4
—C—C—
or
OsO4
NaHSO3 , H 2 O HO OH
syn-hydroxylation
OH
+

RCO3H
→ — C — C — 
H2O / H
→ —C—C—
O HO
anti--hydroxylation

6. Reduction of Esters: Like many organic compounds, esters can be reduced in two
ways: (a) by catalytic hydrogenation using molecular hydrogen, or (b) chemical
reduction. In either case, the ester is cleaved to yield (in addition to the alcohol or phenol
from which it was derived) a primary alcohol corresponding to the acid portion of the
ester.

RCOOR ′ 
reduction
→ RCH 2 OH + R ′OH
1° alchol

Hydrogenolysis (cleavage of hydrogen) of an ester requires more severe conditions than

simple hydrogenation of (addition of hydrogen to) a carbon-carbon double bond. High
pressures and elevated temperatures are required: the catalyst used most often is a mixture
of oxides known as copper chromite, of approximately the composition CuO.CuCr2O4.
For example

CH 3 (CH 2 )10 COOCH 3 

H 2 , CuO.CuCr2 O 4
150°, 5000/n/in 2
→ CH 3 (CH 2 )10 CH 2 OH + CH 3OH
(Methyl dedecanoate) (1− dodecanol)

Chemical reduction is carried out by use of sodium metal and alcohol, or more usually by
use of lithium aluminium hydride. For example:

CH 3 (CH 2 )14 COOC 2 H 5 

LiAlH 4
→ CH 3 (CH 2 ) 14 CH 2 OH
(Ethyl hexadecanoate) 1− hexadecanol

7. From organometallic compounds: Organolithium and organomagnesium

compounds (Grignard reagents) are useful compounds for preparation of all three types of
alcohols e.g. 1°, 2°, 3° alcohols).

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a) Primary alcohols can be prepared by treating the reagent with formaldehyde followed
by hydrolysis.

b) Primary alcohols higher than ethanol can be prepared by treating the reagent with
epoxides (oxiranes).

c) Secondary alcohols are prepared is from aldehyde other than formaldehyde or from
ester of formic acid with excess of Grignard reagent. However in second method the
2° alcohol will always have identical alkyl groups i.e. R2CHOH and not
RCHOH— R ′ .

d) Tertiary alcohols are prepared from (i) ketones (ii) from esters of monocarboxylic
acids other than formic acid with excess of Grignard reagent. However in second
method those 3° alcohol can be prepared which have at least two identical groups.

Grignard Reagent
Organomagnesium halides were discovered by French chemist Victor Grignard in 1900.
Grignard received the Noble prize for his discovery in 1912 and organomagnesium halides are
now called as Grignard Reagents in his honour. Grignard reagents have great use in organic
synthesis.

Grignard reagents are usually prepared by the reaction of an organic halide and magnesium metal
(turnings) in an ether solvent.

R — X + Mg 
Et 2 O
→ R — Mg — X 
 Grignard reagents
Ar — X + Mg 
Ether
→ Ar — Mg — X 

The order of reactivity of halides with magnesium is also RI > RBr > RCl (very few
organomagnesium fluorides have been prepared. Aryl Grignard reagents are more easily prepared
by Aryl bromides and aryl iodides than from aryl chlorides which reacts very sluggishly.

The general formula for Grignard reagents is R—Mg—X. Grignard reagents are seldom isolated
but are used for further reactions in ether solution.

A Grignard reagents forms are complex with its ether solvent, the structure of the complex can be
represented as

R R
O
R — Mg — X
O

R R

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Complex formation with molecules of ether is important factor in the formation and stability of
Grignard reagent.

Grignard reagents are very strong bases. They reacts with any compounds that has a hydrogen
atom attached to an electronegative atom such as oxygen, nitrogen or sulphur.
–δ +δ
R — MgX

The reactions of Grignard reagents with water and alcohol are nothing more than acid-base
reactions, they lead to the formation of the weaker conjugate acid and weaker conjugate base.
The Grignard reagents behaves as if it contains a anions of an alkane as if it contains carbanian

−δ +δ
R : MgX + H OH 
→ R : H + HO + Mg +2 + X −
G.R. water Alkane Hydroxide ion
(stronger base) (stronger acid) (wea ker (wea ker base)
acid)

–δ +δ
→ R : H + RO + Mg +2 + X −
R : MgX + H OR 
stronger stronger wea ker wea ker
base acid acid base

Grignard reagents are strong bases as well as powerful nucleophiles. Reactions in which
Grignard reagents acts as a nucleophile are by far the most important

Grignard reagents carry out nucleophilic attack at a saturated carbon they when reacts with
oxiranes. The nucleophilic alkyl group of the Grignard reagents attacks the partially positive
carbon of the oxirane ring. Because it is highly strained, the ring opens and the reaction leads to
the salt of primary alcohol. Subsequent acidification produces the alcohol.
δ– +δ δ+ δ+ +2
R : MgX + H 2 C— CH 2 
→ R — CH 2 — CH 2 — O MgX
O
δ– H 3O +

R — CH 2 — CH 2 — OH
primary alcohol

e.g.
C6 H 5 MgBr + CH 2 — CH 2 
Ether
→ C6 H 5 — CH 2 — CH 2 OMgBr
O
H 3O +

C6 H 5 — CH 2 — CH 2 — OH

Grignard reagent reacts primarily at the less substituted ring carbon atom of substituted oxiranes.
The most important reactions of Grignard reagents are those in which these reagents acts as a

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nucleophiles and attacks on unsaturated carbon especially the carbon the carbon of a carbonyl
group.

Reaction

R : Mg — X + C = O  i) ether

ii) H O + , X-
→ R — C — O — H + MgX 2
3

Mechanism
+2
R : MgX + → R — C — O Mg X −
C = O 
δ– δ+ δ+ δ–

R — C — O Mg +2 X − + H — O — H → R — C — O — H + O — H + MgX 2
+X−
H H

Product of Grignard Reagent

a) Reaction with formaldehyde

H
C6 H 5 MgBr + O 
Et 2 O
→ C 6 H 5 — CH 2 — OMgBr
Phenyl mag.
bromide
H
H 3O +
C6 H5 — CH 2 — OH
Benzylalcohol (90%)

b) Reaction with higher aldehyde

CH3
CH3

CH 3 — CH 2 — MgBr + H O 
Et 2 O
→ H3C
OMgBr
H

H 3O +
CH3

H3C OH
butan-2-ol

c) Reaction with ketone

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CH3
CH3
H3 C
CH 3 — CH 2 — CH 2 — MgBr + H3C O 
Et 2 O
→
OMgBr
H3 C

H 3O +

H3 C CH3

OH

CH3
2-methylpentan-2-ol

d) Reaction with ester

H3 C H3C CH3

CH 3 — CH 2 — Mg — Br + O 
Ether
→ OMgBr − C 2 H5 OMgBr
 →
H5C 2 O O
H5 C2

CH3
H3C

O 
CH3 —CH 2 MgBr
→
H
H3C OMgBr CH3
CH3
H
H 2O NH 4 Cl
CH3

H3C OH CH3
3-methylpentan-3-ol

Planning a Grignard Synthesis: By using Grignard synthesis skillfully, we can

synthesize almost any alcohol we want. In planning a Grignard synthesis we must simply choose
the correct Grignard reagent and the correct aldehyde, ketone, ester or epoxide. We do this by
examining the alcohol we wish to prepare and by paying special attention to the groups attached
to the carbon atom bearing the —OH group. Many times there may be more than one way of
carrying out the synthesis. In these cases our final choice will probably be dictated by the
availability of starting compound.

Suppose we want to prepare 3-phenyl 3- pentanol. We examine its structure and we see that the
groups attached to the carbon atom bearing the –OH are a phenyl group and two ethyl group.

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C 6 H5

H3C OH CH3

3-phenylpentan-3-ol

We can synthesize this compound in different ways.

1. We can use a ketone with two ethyl group (3-pentanone) and allow it to react with
phenylmagnesium bromide.
C6 H 5
CH3 — CH 2 — C — CH 2 — CH 2 
→ CH 3 — CH 2 — C — CH 2 — CH3 + C6 H5 MgBr
OH O

Synthesis
C6 H 5

C6 H 5 MgBr + CH 3 — CH 2 — C — CH 2 — CH 3 
i) ether
ii) H O+

→ CH 3 — CH 2 — C — CH 2 — CH 3
3

O OH
3− phenyl − 2 − pen tan ol

2. We can use a ketone containing an ethyl group and a phenyl group and allow it to react
with ethyl magnesium bromide.
C6 H 5
C6 H5
CH3 — CH 2 — C — CH 2 — CH 3 
→ CH3 — CH 2 — C + CH3CH 2 — MgBr
O
OH

Synthesis
C6 H 5 C6 H 5
CH3CH 2 MgBr + CH 3 — CH 2 — C 
i) ether
ii) NH 4 Cl
→ CH 3 — CH 2 — C — CH 2 — CH 3
O H2O
OH
3− phenyl −3− pen tan ol

3. We can use an ester of benzoic acid and allow it to react with two molar equivalents of
ethyl magnesium bromide.
CH3 C6H5

H3C 
→ + 2CH 3 — CH 2 MgBr
C 6H 5 O O
HO
CH3
Synthesis

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O C6 H 5
2CH3CH 2 MgBr + C6 H5 — C — O CH3 
i) ether
ii) NH 4 Cl
→ CH3 — CH 2 — C — CH 2 — CH3
H2 O

OH
3− phenyl −3− pen tan ol

All of these methods will be likely to give us our desired compound in yields greater
than 80%.

Restriction of the use of Grignard Reagents

a) The Grignard reagent is a very powerful base, in effect it contains a Carbanion. Thus it is
not possible to prepare a Grignard reagent from an organic group that contains an acidic
hydrogen.

b) Grignard reagents are powerful nucleophiles we can’t prepare a Grignard reagent from
any organic halide that contains a carbonyl, epoxy, nitro or cyano group.
This means that we prepare Grignard reagents, we are effectively limited to alkyl halide
or to analogous organic halide containing carbon carbon double bonds; internal triple
bonds, ether linkage and —NR2 group.
Grignard reagents are so sensitive to acidic compounds so when we prepare a Grignard
reagent we must take special care to exclude moisture from our apparatus and we must
use an anhydrous ether as our solvent.

Chemical Properties of Alcohols

1. Acidic character: Alcohols are very weak acids (Ka = 10–16 – 10–18) even feeble than
water (Ka = 10–14) and they do not turn blue litmus red. Alcohols behaves as acid because
of the presence of polar O—H group. Due to greater electro negativity of oxygen atom
the shared pair between `O’ and H is drawn towards the oxygen atom helping in release
of H+ ion. However the release of H+ ion in alcohol does not takes place with ease and
hence the alcohols acts as very weak acids. This can be explained on the basis of electron
releasing nature of alkyl group present in alcohol. This electron releasing tendency of
alkyl group increases electron density around the oxygen atom due to which polarity of
O—H bond decreases. In addition the alkoxide ion formed is also destabilized due to
concentration of negative charge on oxygen atom by electron releasing inductive effect of
alkyl group. Thus the release of H+ ion is difficult. This explains the weak acidic
characters of alcohols.

R−O−H R − O + H+
Alcohol Alkoxide ion

The order of acidic strength among various types of alcohols is

Primary > Secondary > Tertiary

The order can be explained in terms of electron releasing inductive effect of alkyl groups.
Greater is the number of alkyl group attached to carbon carrying —OH group lesser shall
be polarity of —OH group and hence lesser will be acidic character. In tertiary alcohols

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the carbon atom carrying –OH group is attached to three alkyl groups. Due to which
electron density on oxygen is minimum in their case and hence the loss of H+ is most
difficult. Thus tertiary alcohols are least acidic; whereas primary alcohols are most acidic
H R R
↓ ↓
R → C → OH > R → C → OH > R → C → OH
↑
H H R
1° Alcohol 2° Alcohol 3° Alcohol

Alcohol’s reaction with metal

1
→ 2RO + Na − + H 2 ↑
ROH + Na 
2
Note: Alcohols do not react with NaOH (due to low acidic character)
ROH + R ′MgX 
→ R ′H + Mg(OR)X
Strong acid Weaker acid

2. Dehydration:

a) Dehydration to alkene: Heating of most of alcohols with a strong acid causes a

loss of water molecule to form alkenes.
+
—C — C — 
H
→ C=C + H 2O
∆

H OH

i) The reaction is an elimination and is favoured at high temperature most commonly

used acids in the laboratory are H2SO4 and H3PO4 while alumina is often used in
industries.

ii) The order of dehydration among three types of alcohol is 3° > 2° > 1°. Thus
dehydrating conditions becomes milder as we proceed from 1° to 3° alcohols.
CH3 — CH 2 — OH →
conc. H 2SO4
180° C
CH 2 = CH 2 + H 2 O
OH


85% H3 PO4
→ + H 2O
165 −170°C

(CH 3 )3 COH 

20% H 2SO4
85° C
→ (CH 3 ) 2 C = CH 2 + H 2 O

This behaviour is related to relative stabilities of carbocations (3° > 2° > 1°).

iii) Since carbocations are formed as intermediate rearranged olefins, where possible
are formed.

iv) Whenever dehydrations produces two different alkenes major product is formed
according to Saytzaff’s rule.

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CH3 CH3 CH3


H 3 PO 4
→ +
∆

OH
Major Minor

Such reaction which can produce two or more structural isomers but one of then
is greater amount than the other are called regioselective. In case if only one
product is formed, a reaction is termed as regiospecific.

b) Intra-molecular Dehydration to ether: Primary alcohols when heated in

presence of an acid catalyst (usually H2SO4) undergo intermolecular dehydration to
form ether.
+
R — OH + HO — R 
H heat
→R —O—R.

Dehydration to ether takes place at a lower temperature than dehydration to alkene.

CH 2 = CH 2 ←
excess of H 2SO 4
180° C
CH 3 — CH 2 — OH →
excess of ethanol
H 2SO4 ,140° C

CH 3CH 2 — O — CH 2 — CH 3
This method is not useful for the preparation of unsymmetrical ethers because
reaction leads to mix. of products.
+
R—O—H + HO— R ′ 
H
→ R—O— R ′ + R—O—R + R ′ —O— R ′

3. Reaction with phosphorus trihalide or thionyl chloride

3R — OH + PX 3 
→ 3R — X + H 3 PO3
(1° or 2° ) (X = Br or I) phosphorous acid

Phosphorus is a water soluble and may be removed by washing the alkyl halide with
water or dilute aqueous base.

←
PBr3
 
P & I2
→

H Br H OH H I
Cyclopentyl bromide Cyclopentanol Cyclopentyl iodied

Mechanism: The mechanism for the reaction involves attack of alcohol group on the
phosphorus atom displacing a bromide ion and forming protonated alkyl
dibromophosphite.
Br

Br P Br
+
O + Br P 
→ O + Br

H Br H

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In second step a bromide ion acts as a nucleophile to displace HOPBr2 a good leaving
group due to the electronegative atoms bonded to the phosphorus.
Br
P Br

Br + O
+

→ Br + HO PBr2

R — OH + SOCl 2 
→ R — Cl + SO 2 ↑ + HCl ↑
(1° or 2° )

i) Since tertiary alcohols are readily converted into tertiary halides phosphorous trihalide
and thionyl chloride are mainly used for preparing primary and secondary halide.

ii) Since carbocations are not formed as intermediates the reactions with both the
reagents occurs without rearrangement.

4. Reaction with hydrogen halide

R—OH + HX 
→ R—X + H2O.

The reactivity of the hydrogen halide is HI > HBr > HCl (HF is generally unreactive) and
the order of reactivity of alcohols is 3° > 2° > 1° < CH3.

The least reactive hydrogen halide i.e. HCl generally requires the presence of ZnCl2 for
reaction with 1° and 2° alcohols, however the highly reactive 3° alcohol do not require
ZnCl2.
dry HBr
or NaBr + H 2SO4
CH3—CH2—CH2—OH  → CH3—CH2—CH2—Br

Chloride ion is a weaker nucleophile than bromide and iodide ion. HCl does not react
with less reactive 1° and 2° alcohol unless some good Lewis acid like ZnCl2 is added to a
reaction mixture. Primary alcohol being least reactive requires some heat in addition to
ZnCl2. Zinc chloride a good Lewis acid for a complex with alcohol. This complex
provides a better leaving group for the reaction than H2O

Except with most primary alcohols rearrangement of the alkyl group occurs.
Cl

OH →
HCl

5. Oxidation of Alcohols
a) Oxidation of primary alcohols

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O O
R
→ R — CH → C
[O]
[O]

OH R OH
Primary alcohols can be oxidized by potassium permanganate. The reaction is usually
carried out in basic aqueous solution from which MnO2 precipitates as the oxidation
taken place. After the oxidation is complete filtration allows removal of the MnO2 and
acidification of filtrate gives the carboxylic acids.
→ RCO −2 K + + MnO 2
R—CH2—OH + KMnO4 
H 3O +

RCO2 H

b) Oxidation of secondary alcohols to ketones

R — CH — R ′ [O]
→ R — C — R′

OH O
Secondary alcohols can be oxidized by chromic acid (H2CrO4). Oxidation of
secondary alcohols are generally carried out in acetone or acetic acid.
R R
3. CH — OH + 2H 2 CrO 4 + 6H + → 3. C = O + 2Cr +4 + 8H 2 O
R R
OH O
e.g. [O]
→

c) With no hydrogen attached to carbonyl carbon, tertiary alcohols are not oxidized at all
under alkaline conditions. If acid is present they are rapidly dehydrated to alkenes
which are then oxidized. Tertiary alcohols are most difficult to oxidize among the
three classes of alcohols.

Dehydrogenation of alcohol by copper at 573 K: This reaction is also

considered as oxidation. In this reaction primary alcohols give aldehyde and
secondary give ketone. While tertiary alcohol undergo dehydration to form alkene.
CH 3 — CH 2 — OH 
Cu
573° C
→ CH 3 — CHO
Aldehyde

(CH 3 ) 2 — CHOH 
→ (CH 3 ) 2 CO
ketone

(CH 3 )3 COH 
→ (CH 3 ) 2 C = CH 2
alkene

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Tests for Alcohols

Alcohols dissolve in cold concentrated sulfuric acid. This property they share with alkenes,
amines, practically all compounds containing oxygen, and easily sulfonated compounds.
(Alcohols, like other oxygen-containing compounds, form oxonium salts, which dissolve in the
highly polar sulfuric acid.)

Alcohols are not oxidized by cold, dilute, neutral permanganate (although primary and secondary
alcohols are, of course, oxidized by permanganate under more vigorous conditions.). However,
as we have seen, alcohols often contain impurities that are oxidized under these conditions, and
so the permanganate test must be interpreted with caution.

Alcohols do not decolorize bromine in carbon tetrachloride. This property serves to distinguish
them from alkenes and alkynes.

Alcohols are further distinguished from alkenes and alkynes-and, indeed, from nearly every other
kind of compound-by their oxidation by chromic anhydride, CrO3, in aqueous sulfuric acid:
within two seconds, the clear orange solution turns blue-green and becomes opaque.

ROH + HCrO −4 
→ Opaque, blue green
1° or 2° clear, orange

Tertiary alcohols do not give this test. Aldehydes do, but are easily differentiated in other ways.

Reactions of alcohols with sodium metal, with the evolution of hydrogen gas, is of some use in
characterization; a wet compound of any kind, of course, will do the same thing, until the water is
used up.

The presence of the –OH group in a molecule is often indicated by the formation of an ester upon
treatment with an acid chloride or anhydride. Some esters are sweet-smelling; others are solids
and sharp melting points, and can be derivatives in identifications. (If the molecular formulas of
starting material and product are determined, it is possible to calculate how many –OH groups are
present.)

Test Distinguishing 1°, 2° and 3° Alcohols

1. Lucas Test: Lucas reagent is a mixture of conc. HCl of zinc chloride reacts with alcohol
to form corresponding alkyl chlorides which are insoluble. Formation of a chloride from
an alcohol is indicated by cloudiness that appears when the chloride separates from the
solution. Hence the time required for cloudiness to appear is a measure of reactivity of the
alcohol. A tertiary alcohol reacts immediately, a secondary alcohol reacts within five
minutes and primary alcohol does not react appreciably at room temperature.

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R — O + ZnCl2 R — O — ZnCl2
H H

→ Cl — R + [Zn(OH)Cl2 ]−
Cl + R — O — ZnCl2 
H
H
ZnCl2 + H 2 O

2. Victor Mayor Test: This test is based upon the fact that the three types (1°, 2°, 3°) of
nitroalkane (formed by alcohols) reacts differently with nitrous acid followed by sodium
hydroxide. The three types of alcohol are first converted into corresponding nitro
compounds.

Nitro alkenes thus obtained is treated with first nitrous acid and then with sodium
hydroxide to get different colours at the end.

Primary alcohol Secondary alcohol Tertiary alcohol

R R R
R
OH R
P + I2
OH OH
R P + I2 R
R P + I2
I
AgNO3 R R
R
R I
AgNO3 I
NO2 R R
HNO 2 AgNO3

NO2 R
R
R (Nitrolic acid) NO 2 R
HNO 2
N
R NO2
HO NO 2 R
NaOH HNO 2
R
NO2 N
No reaction
R O
(Red colour) NaOH
N NaOH
+ -
Na O Blue colour Colourless

The primary alcohol give a red colour, secondary alcohols produce a blue colour while in
case of the tertiary alcohols, the solution remains colourless. This test is also referred to
as red-blue test.

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ETHERS

Introduction
Ethers are a class of compounds which contains an oxygen atom bonded to two alkyl groups
(same or different). When both the alkyl groups are same they are designated as simple or
symmetrical ethers and when both are different they are called mixed or unsymmetrical ethers.
R—O—R R—O— R ′
CH3—O—CH3 CH3—O—C2H5
C2H5—O—C2H5 CH3—O—C3H7
Simple ethers Mixed ethers.

Ethers from a homologous series with the general formula CnH2n+2O where the value of `n’ is
always more than 1; the functional group of ether is (—O—). Ethers may be regarded as
anhydrides of alcohol as they may be obtained by elimination of water molecule from two
alcohol molecules.

R — O H + HO — R 
→ R — O — R + H2O
Alchol Alchol Ether

Just as alcohol are considered as monoalkyl derivatives of water ethers may be considered as
dialkyl derivatives of water.

Structure: The oxygen atom is ethers is sp3 hybridized. Two of the hybrid orbital overlap with
hybrid orbital of two carbon atoms to form sigma bonds. The bond angle is 110°.

O
R R

Nomenclature
1. Common names: Ethers are named after the alkyl groups attached to oxygen atom
and adding the word ether. When both alkyl groups are same the prefix di is used. Incase
of unsymmetrical ethers the two alkyl groups are named in alphabetical order.

2. IUPAC: In this system ethers are named as alkoxy alkane. The smaller alkyl group plus
oxygen is called an alkoxy substituents.

Ether Common Name IUIPAC

CH3—O—CH3 Dimethyl ether Methoxy methane
CH3—O— C2H5 Ethyl methyl ether Methoxy Ethane

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Physical Properties of Ethers

1. Dimethyl ether and ethyl methyl ether are gases. All others are colourless liquids with
pleasant odour.

2. They are sparingly soluble in water but readily soluble in organic solvents. Solubility of
ether is water in presence of small amount of alcohol perhaps due to hydrogen bonding
between ether of water molecule.
R —O−−−H—O—H

3. Boiling points of ether show a gradual increase with increase in molecular weight. Ethers
have low boiling points than isomeric alcohols as there is no association between the
molecules in an alcohol due to hydrogen boding. The boiling points of ethers are close to
the boiling points of alkanes.

4. They are lighter than water lower ethers are highly volatile and very inflammable.

Preparation of Ethers
1. Williamson’s Synthesis: Heating of alkyl halide with sodium or potassium
alkoxide gives ether. This is a good method for preparation of simple as well as mixed
ethers.
R—X + Na—O— R ′  → R—O— R ′ + NaX.

The reactivity of primary (1°) alkyl halide is in the order CH3 > CH3—CH2 > CH3—
CH2—CH2 and the tendency of the alkyl halide to undergo elimination is 3° > 2° > 1°.
Hence for better yield the alkyl halide should be primary of the alkoxide should be
secondary or tertiary.

C2 H5 Br + NaO — C — 
→ C 2 H5 — O — C — + NaBr

This method is not applicable to tert. alkyl halides because the alkoxide ions being both
powerful nucleophiles and bases could being dehydrogenation of the tertiary alkyl halides
to form alkenes.
R — ONa R — O− + Na +

R — O — Na + R ′ — X 
→ R — O — R + NaX
R ′ — O — Na R —O—R
R—X+ →
Ar — O — Na R — O — Ar
Aryl Ether

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e.g. —OH + CH 3 — CH 2 — Br 

aq. NaOH
→ —O — CH 2 — CH3

2. Alkoxy mercuration Demercuration: Alkoxy mercuration Demercuration is

another method for syntherising ethers. The reaction of an alkene with an alcohol in the
presence of mercury salts such as mercuric acetate or trifluoro acetate leads to an alkoxy
mercuric intermediate which upon reaction with sodium borohydride yields an ether.
C=C + R — OH + Hg(OOCCF3 ) 2 
→ —C—C—
RO HgOOCCF3
NaBH 4

—C — C —

RO H
Ether

e.g.

i) Hg(OOCCF3 )2 HOCH(CH3 )2
ii) NaBH , HO−
→ —O — CH — (CH 3 ) 2
4

(98% yield)

Chemical Properties of Ethers

1. Salt formations: When ethers are treated with cold concentrated inorganic acids,
these form oxonium salts. The reaction between ethers and acid is a Lewis acid-base type
interaction.
R R
O + HCl  → O — H Cl
R R
Ether hydrochloride

2. Action of air and light: Reaction involving alkyl group leads to the formation of
peroxides.
OH
O

hν
H3 C O CH3 + O 2  → H3C O CH3
It is a free radical reaction and oxidation occurs at the C atom next to the etheral oxygen
to form hydroperoxides.

3. Halogenation of Ether: When treated with chlorine or bromine, ethers undergo

substitution, the extent of which depends on the conditions. Hydrogen joined to the

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carbon directly attached to the oxygen atom is most readily replaced, e.g. diethyl ether
reacts with chlorine in the dark to from 1,1-dichlorodiethyl ether:

CH 3CH 2 OCH 2 CH 3 →

Cl 2
CH 3CHClOCH 2 CH 3 →
Cl2
CH 3CHClOCHClCH3

In the presence of light, perchlorodiethyl ether is obtained

(C 2 H 5 ) 2 O →
Cl 2
(C2 Cl5 ) 2 O

The reaction proceeds by a free-radical mechanism, and α-substitution occurs readily

because of resonance stabilization of the intermediate radical.

R1O − CH 2 R 2 
Cl
→ R1O − CHR 2 ←
→ R1O = CHR 2 →
Cl 2
R1O − CHClR 2 + Cl ; etc.

4. Reaction with Acid Chlorides: Acid chlorides react with ethers when heated in
the presence of anhydrous zinc chloride, aluminium chloride, etc.; e.g.
MeCOCl + AlCl3 MeCO + + AlCl4−
R O
+
R 2 O + MeCO + 
→
−
O MeCO 2 R + R + 
AlCl 2
→ RCl + AlCl3
R CH3
Acids anhydrides also split ethers to form esters:
R 2 O + (CH 3CO)2 O 
ZnCl2
→ 2CH 3CO 2 R

5. Cleavage by Acids: Ethers on reaction with acids (HX) in presence of heat undergoes
cleavage to form an alkyl halide and an alcohol. Alcohol on further reaction with HX
gives second molecule of alkyl halide.

R—O— R ′ + HX  → R—X + R ′ —O—H

R ′ —OH + HX  → R ′ —X + H2O.
Reactivity of HX towards ether is HI > HBr > HCl

Mechanism: In the first step ether is protonated by HX to give protonated ether. In the
second step halide ion acts as nucleophile and attacks protonated ether to undergo
cleavage. This step is favoured because the leaving group is weakly basic.
H
R — O — R + HX R — O — R + X−
protonated ether

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H H

R — O— R + X → X − − − R − − − O— R ′
SN 2
pathway
⊕ δ+

1
SN pathway

R ⊕ + R ′ — OH R — X + R ′ — OH
X
R—X
Reaction in second step can take the direction of SN1 or SN2 pathway depending upon the
condition employed and the structure of ether. When both the alkyl groups are methyl
or 1°. It will follow SN2 reaction and when at least one of the alkyl group is 3° the
reaction follows SN1 reaction.
H3C O H
+
CH3 
HI

one equvalent
→ H5 C 2 O + I−
H3C CH3
SN 2 pathway
H3C H
H5 C2 OH + CH 3 I +
O CH3 I
H3C

H3C H3C H
+
O + H — I 
→ O
H3C C(CH 3)3 H3C C(CH 3)3
SN 1
H3C
⊕
C(CH ) + 3 3
OH
H3C

I−
C(CH 3 )3 I

Aryl Ethers
Phenols are converted to alkyl aryl ethers by reaction in alkaline solution with aryl halide. For the
preparation of aryl methyl ethers, dimethyl sulphate (CH 3 )2 SO 4 is frequently used instead of
more expensive methyl halide.
+
OH ONa OCH3


NaOH
– H2O
→ + H3C Br 
→ + NaBr

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OH ONa O-CH3


NaOH
→ + CH3 — OSO2 OCH3 
→
– H 2O
+ CH3OSO2 ONa

The second method is better method to prepare anisole because methyl sulphoates are better
leaving group than which causes faster substitutions.
OH ONa CH2Br

+ NaBr

NaOH
– H2O
→ + 
→ O

Benzyl phenyl ether

OH ONa OC2H5


NaOH
– H 2O
→ + C2 H 5 — OSO 2OC2 H 5 
→ + C 2 H 5OSO 2ONa

phenetole

The mechanism of the above reaction can be outlines as follows. In alkaline solution phenol
exists as phenoxide ion which acts as nucleophile and attacks the alkyl halide and displaces
halide ion
ArO + R − X 
→ AR − O − R + X

ArO– + CH3—OSO2OCH3  → Ar—O—CH3 + OSO 2 OCH 3

Since phenoxides are prepared from phenols and since alkyl halide prepared from alcohols. Alkyl
aryl ethers are ultimately synthesized from two hydroxyl compounds.

Aryl halides can not be used in the williamson’s synthesis because o their low reactivity towards
the nucleophilic substitution.

Br
H3C + ONa

H3C
O
H3C
+ Br
ONa

Epoxides
If oxygen atom is a part of carbon skeleton in the ring, then such rings are called cyclic ethers.
The general formula is (CH2)nO.
O
O
O O

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There are two approved ways to name epoxide according to one method three membered oxygen
containing ring is called oxirane with oxygen atom occupying position 1. Alternatively an
epoxide can also be named as an alkane with epoxy substituents and the number of the carbons to
which carbon is attached immediately proceeding the alkane name. Example
CH3
O
2-ethyloxirane
Preparation of Epoxides: Epoxides can be prepared by oxidation of alkene using peroxy
acids
R
R — CH = CH 2 + RCO3 H 
→ + R ′CO 2 H
O

Reactions of Epoxides
The highly strained three membered ring is molecules of epoxides make them much more
reactive towards nucleophilic substitution than other ethers.

1. Acid catalysed ring opening of epoxide: Acid catalysis assists epoxide ring
opening by providing a better leaving group at the carbon atom undergoing nucleophilic
attack

—C — C — + H — O — H 
→ —C—C— + O—H
O O
H H
H
Protonated epoxide

O—H O—H O

—C — C — + O — H 
→ —C—C— 
H
→ —C—C—
O
H O O
H
H H

+ H—O—H

2. Base catahysed ring opening of Epoxides: Epoxides can also undergo base
catalysed ring opening such reactions do not occur with other ethers provided that the
attacking nucleophile is also a strong base such as alkoxide ion or hydroxide ion.

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R —O + — C — C — 
→ R O — C — C — O 
H —O—R
→
O
RO — C — C — OH + RO

If the epoxide is unsymmetrical, in base catalysed ring opening attack by the alkoxide
ions occurs primarily at the less substituted carbon atom.

CH 3 — CH 2 — O + H 2 C — CH — CH3 
→ CH3 — CH 2 — O — CH 2 — CH — CH3
O
O
CH3 — CH 2 OH

CH3 — CH 2 — O + CH3 — CH 2 — O — CH 2 — CH — CH3

OH
1-ethoxy-2-propanol

Because reaction is SN2 reaction and primary substrates reacts more rapidly in SN2
reaction because they are less sterically hindered. In the acid catalysed ring opening of an
unsymmetrical epoxide the nucleophile attacks primarily at the more substituted carbon
atom.
CH3 CH3
H3C δ+
e.g. H C OH + H3C CH2-OH
3
O
OCH3
H
H
The bonding in the protonated epoxide is unsymmetrical with more highly substituted
carbon atom bearing aconsiderable positive charge the reaction is SN1 like. The
nucleophile therefore attacks this carbon atom even though it is more highly substituted.
Which bears a greater positive charge because it resembles more stable tertiary
carbocation.

PHENOLS

Introduction
Compounds that have a hydroxyl group directly attached to benzene ring are called phenols.
Thus phenol is a specific name for hydroxybenzene and it is the general name for the family of
compounds derived from hydroxybenzene.

OH H3C OH

phenol 4-methyl phenol

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[Type text]

compounds that have a hydroxyl group attached to a polycyclic benzenoid ring are chemically
similar to phenols but they are called napthols.
7
6 8

5 OH
OH 9

8 1 OH 10
7 2 4

6 3 3 1
5 4 2
1-napthol 2-Napthol 9-Phenanthrol

Nomenclature of Phenols
Phenols are named as derivatives of simplest compound of this class i.e. phenol
OH
OH OH O2N NO2

phenol
Cl NO2
3-chlorophenol 2-4-6-trinitrophenol
(picric acid)

Methyl phenols are known as cresols

OH OH OH OH
CH3 H3C CH3

CH3
CH3
2-methyl phenol 3-methyl phenol 4-methyl phenol 2-6 dimethyl phenol
(o-cresol) (m-cresol) (p-cresol)

Some dihydric and trihydric phenols are given below:

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[Type text]
OH OH OH
OH

OH
1-2-Benzenediol 1-3-Benzenediol
(Catechol) (Resorchinol) OH
1-4 Benzenediol
(Qunol)

OH OH OH
OH

OH OH HO OH
OH
1-2-3 Benzenetriol 1-2-4 Benzenetriol 1-3-5 Benzene-triol
(pyrogallol (Hydroxyqionol) (Phloroglucinol)

But carboxyl and acyl group take precedence over the phenolic hydroxyl and hence it is treated
as a substitutent in these cases.
OH
3 2

HO COOH H3C 4 1 COOH

5 6
4-hydroxybenzoic acid 2-hydroxy-4-methylbenzoic acid

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[Type text]

Preparation of Phenol
1. Laboratory synthesis
Hydrolysis of arenediazonium salts
+
Ar — NH 2 
HONO
→ Ar — N 2 
Cu 2 O
Cu +2 H O
→ Ar — OH
2

Example
NH2 OH

Br Br

→
i) NaNO 2 , H 2SO 4
ii) Cu 2 O, Cu 2+ H 2 O

CH3 CH3
2-bromo-4-methylphenol

2. Industrial synthesis
Dow Process – Hydrolysis of chlorobenzene: Chlorobenzene is heated 350°C
under high pressure with aq. sodium hydroxide. The reaction produces sodium phenoxide
which on acidification yields phenol.

Cl ONa
+ 2NaOH 350° C
→ + NaCl + H 2O
(high pressure)

ONa OH

→
HCl + NaCl

Alkali fusion of sodium benzosulphonate

SO3Na ONa
350° C
+ 2NaOH  → + Na 2SO3 + H 2 O

H 3O +

OH

phenol

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[Type text]

From cumene hydroperoxide

H3C CH3

CH 2 = CH — CH 3 
H 3PO 4
250° C
→
propene
benzene isopropylbenzene (cumene)

CH3
95 – 135° C
+ O 2  → O
CH3 OH
CH3 H3C
+
O 
H 3O
50–90° C
→ OH + O
CH3 OH H3C
1-methyl-1-phenylethyl hydroperoxide phenol acetone

Physical Properties of Phenol

Physical properties of phenols are strongly influenced by hydroxyl group, which permits phenols
to form hydrogen bond with other phenol molecule causing high melting and boiling points and
also with water causing some (partial) solubility in water. This accounts why phenols have higher
melting and boiling points and are more soluble in water than arenes and alkyl halides of
comparable molecular weight. Phenol themselves are colourless solid (m.p. 41°C) the colour if
any associated with phenols is either due to the presence of some other functional group —NO2
or due to the presence of some oxidized product of phenol as impurity.

Comparative solubility and boiling point is observed in the three isomers (o-m- and p)
nitrophenols. p-nitrophenol is capable of forming intermolecular H bond between themselves and
with water too, hence it has higher m.p. and more solubility in water m-Nitrophenol also behaves
is the same way.
H
+ -
O O H O O + O H O
+ N O
N
+
N +
O
-
H
O
+
N - + O-nitrophenol (intramolecular H-bond
H O O O O H O H restricts intermolecular H bonding)

H
p nitrophenol (intermolecular H bond
between two molecules (intermolecular H-bond with water)

However o-nitrophenol is capable of forming intramolecular H bond. Due to intramolecular H

bond neither with its second molecule nor with water. Hence o-nitrophenl has low m.p. and low
solublility in water then the corresponding m- and p-isomer.

Chemical Properties

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1. Acidity of phenols: The most characteristic property of phenols is their acidity.

Phenols are more acidic that alcohols which are even more weakly acidic than water, but
phenols are less acidic than carboxylic acids.
R—COOH > Ar—OH > H—OH > R—OH
A summary of acidic character of phenols is given here.
i) Greater acidity of a phenol than an alcohol is due to possibility of resonance in phenol
which leads to electron-deficient oxygen atom. Presence of electron-deficient oxygen
+
atom (see structures II, III and IV) in turn weakens the — O — ← H bond, and thus
facilitates release of proton.
O—H O—H O—H O—H

I II III IV

Such structures are not possible in alcohols.

ii) Once hydrogen atom is removed from phenol, the ion (phenoxide) is very much
stabilized due to delocalization of its negative charge.
O O O O

V VI VII VIII
Resonance in phenoxide ion (note that structures VI to VIII are equivalent)

Remember that phenoxide ion is very much more stable than the parent compound
phenol because phenoxide ion does not involve charge separation, while in phenol
three equivalent resonanting structures (II to IV) involve charge separation.

iii) Electron-withdrawing substituents increase the acidity of phenols; while electron

releasing substituents decrease acidity. Thus substituents affect acidity of phenols in
the same way as they affect acidity of carboxylic acids; it is of course, opposite to the
way these groups affect basicity of amines.
OH O G withdraws electrons, thus disperses the –ve
charge of the ion, stabilizes it and hence
H+ +
increases ionization of the parent phenol.

G G
+
(where G = —NO2, —CN, —CHO, —COOH, — N R 3 , —X)

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[Type text]

OH O G releases electrons, thus intensifies the –ve

charge of the ion, destabilizes it and hence
H+ + decreases ionization of the parent phenol.
G G

(where G = —R, —OR, —NR2)

2. Ester formation: Phenols reacts with carboxylic acid unhydride and acid chloride to
form esters. These reactions are quite similar to these of alcohols.
O O
—OH 
(R —C—O)2 O
base
→ —O — C — R + R — COO

O O
—OH → R —C—Cl
base
—O — C — R + Cl

3. Phenol in Williamson’s Synthesis: Phenols canbe converted to ethers through

the williamson’s synthesis Because phenols are more acidic than alcohols. they can be
converted to sodium phenoxide through the use of sodium hydroxide.

Ar — OH 
NaOH
→ ArONa +  R—X
X = Cl,Br,I,OSO 2 R
→ Ar — O — R + NaX
e.g.
OH ONa + OCH 2 — CH 3


NaOH
→ 
CH3 —CH 2 —I
→ + NaI

CH 3 CH 3 CH 3

4. Reaction with Ammonia: Phenol is converted to aniline when heated with

ammonia under pressure or in presence of ZnCl2.

—OH + NH 3 
ZnCl2
→ —NH 2 + H 2O

5. Reaction with Zn dust: Phenol when treated with Zn dust it gives benzene.

∆
—OH + Zn  → C6 H 6 + ZnO

6. Fries Rearrangement: Phenyl acetate undergoes the Fries rearrangement with AlCl3
to form ortho and para hydroxyl acetophenone. The ortho isomer is separated from the
mixture by the steam-distillation.

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[Type text]
OH
O

O
O CH3 OH

CH3

AlCl3 (CS2 )
→ +
O CH3
1-(2-hydroxyphenyl)ethanone 1-(4-hydroxyphenyl)ethanone

Intramolecular Mechanism: If may be assumed to be Friedel-Craft’s acylation type

in which the acylium ion is supplied by the substrate, i.e.,. it is self-acylation.

First of all, AlCl3 complexes with the oxygen of the phenoxy group from which the
acylium ion is generated, the acylium ion then attacks the benzene ring as in the case of
Friedel-Crafts acylation.
O Cl O Cl Cl
Cl -
Al + Al Al
O CH3 O CH3
Cl O Cl O Cl
H O


AlCl3 (CS2 )
→ −[COCHF3 ]
 → 
COCH3
→
− Cl−
CH3

-
-HCl Cl

Cl
Cl
Al
OH O O O

CH3 CH3
←
H2O


Similar attack at p-position gives the para isomer.

7. Alkylation: When phenol is treated with allyl halide in the presence of NaOH
formation of aryl allyl ether takes place.
CH2
OH O

CH 2 = CH − CH 2 − Br
 NaOH
→

Allyphenyl ethers rearrange to o– allyl phenol when heated at 200°C.

γ
β CH2
OH
O α γ α
CH2
200°C
 → β

2-allylphenol

This rearrangement is known as Claisen rearrangement

If ortho position is free, only ortho rearrangement occurs. However, if both ortho
positions are substituted then rearrangement takes place at para position.

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[Type text]
CH2

CH3 OH
O H3C CH3
∆
 →
CH3

CH2
4-allyl-2,6-dimethylphenol

An interesting feature of the rearrangement is that when migration takes place to the ortho
position, the γ-carbon of allyl group attaches itself to the benzene ring. In other words,
there is an inversion of allylic chain. However, no such inversion of allylic chain takes
place with p-migration.
CH3
γ
CH3 β
β
γ
OH CH3
α
O
α γ
O OH
β H 3C CH3 H 3C CH3
∆
 → ∆
 →
CH2
α
α
β

γ
H 3C

Reactions Due To Benzene Ring

8. Bromination: The hydroxyl group is a powerful activating group and an o-p director
in electrophilic substitution. Phenol reacts with bromine in aqueous solution to yield
2,4, 6-tribromophenol.
OH OH
Br Br
+3Br2 
H2O
→ + 3HBr

Br
2,4,6-tribromophenol

Monobromination of phenol can be achived by carrying out the reaction in carbon

disulphide at a low temperature condition that reduce electrophilic reactivity of bromine.
The major product is para-isomer.
OH OH

5° C
+ Br2 
CO2
→ + HBr

Br
9. Nitration: Phenol reacts with dilute nitric acid to yield a mixture of o and p-
nitrophenol.

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[Type text]
OH OH OH
NO2

20% HNO3
25° C
→ +

NO2

But when phenol is treated with nitrating mixture it gives 2,4,6-trinitrophenol (picric acid)
OH OH
NO2 NO2
+ HNO3 → H 2SO4

conc.

NO2

10. Sulphonation: Phenol reacts with concentrated sulphuric acid to yield mainly the
orthosulphonated product of the reaction is carried out at 25°C and mainly the
parasulphonated product at 100°C.
OH
SO3H

OH 25°C


conc.
H 2SO 4
→

OH
100°C

SO 3H

11. Kolbe Reaction: Phenol in the presence of base NaOH, reacts with carbon dioxide at
high temperature and pressure to yield sodium salicylate which on acidification yields
salicylic acid. This reaction is electrophlic substitution reactionin which carbon dioxide
behaves as an electrophile. The reaction is known as Kolbe reaction.

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Na O O
C
H O
tautomerisation
O
+
Na
O

H H
O OH O O

O O
+ Na +
←
H3O


Salicyclic acid Sodium salicylate

The Kolbe reaction is usually carried out by allowing sodium phenoxide to absorb carbon
dioxide and then heating the product to 125°C under a pressure of several atmospheres of
carbon dioxide. The unstable intermediate undergoes a proton shift that leads to sodium
salicylate subsequent acidification of the mixture produces salicylic acid.

In this reaction substitution takes place only at ortho position.

12. Reimer-Tiemann reaction: This reaction is carried out by refluxing an alkaline

solution of phenol with chloroform at 60C, distilling off the excess of chloroform,
acidifying the residual liquid with sulphuric acid, and then steam-distilling it. Unchanged
phenol ando-hydroxy-benzaldehyde distill over, leaving behind p-hydroxybenzaldehyde.

The mechanism of the Reimer-Tiemann reaction is believed to involve the formation of

dichlormethylene.
O O Cl O O Cl O
Cl H Cl
H Cl− O
 →
CCl2 +

OH − ; H O 
H 2O
→ 
H
→ 
OH
→
2
Cl H2O

Phenols with blocked p-positions give cyclohexadienones containing the dichromethyl

group.
OH OH O

O

NaOH
CHCl3
→ +

CH3 CH3 H3C CH3

In the Reimer-Tiemann reaction, the o-isomer predominates, but if one of the o-positions
is occupied, the aldehyde group tends to go the p-positions; e.g., guaiacol forms vanillin

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[Type text]

OH OH

O O
CH3 CH3
→
NaOH
CHCl3

Test for Phenol: Phenol gives a violet colour with ferric chloride; this reaction is
characteristic of all compounds containing the grouping – C(OH) = C.

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Solved Problems
OBJECTIVE

Problem 1: Identify the product [C] in the given sequence of reaction

H3C HCl aq. KOH
+ NBS (X)
peroxide
(Y) (Z)
CH2 excess

HO
H3C OH
(a) (b)
H3C CH3
OH
OH
OH

(c) (d) None of These

OH
H3C
Cl
H3C
H3C H3C
Solution: HCl
+ NBS CH3
CH2 CH2 peroxide Br
Br (Y)
(X) OH aq. KOH
H3C

CH3 excess
OH
(Z)

OH
H3C CH3
Problem 2: 14
CH 2 = CH − CH 2 − Cl ∆
 →  →?
NaOH

What is the missing product?

OH
CH2
H3C CH3 HC
CH 2
O 14
(a) (b)
H3C CH3
CH2
HC 14
CH2

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[Type text]

14
CH2 OH
HC
H3C CH3
CH 2
(c) O (d)
H3C CH3
14
H2C CH CH2

14
O CH2 CH CH2 OH
Solution:
H3C CH3 H3C CH3
∆
 →

H2 C CH CH2
14
(After rearrangement)

Problem 3: Out of following alcohols, which one is most reactive for dehydration reaction
via E1 mechanism.
OH OH
(a) CH NO2 (b)
H3C CH2 H3C CHO
OH OH O
(c) CN (d)
H3C H3C H

Solution: (b)

Problem 4: 
NBS
→ 
Mg, either
→ 
CH 3CN
→ 
Acidic
Hydrolysis
→ final product is:

COMe OH

(a) (b)
COMe
COOH

(c) (d)
COMe

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[Type text]

H3C N
Br MgBr MgBr COMe

Solution:
 →
+
 →  →
NBS
 →
Mg, either CH 3CN H 3O

OH

Problem 5: CH3
O

H2O / H+
H3 C O CH3 A (an acid) + B
18
CH3
Where A and B are, respectively,
O O
18
(a) H3C and Me3C OH (b) H3 C and Me3C OH
OH OH
18
O O
18
(c) H3C and Me3C OH (d) H3 C and Me3C OH
18 18
OH OH

Solution:
OH
O
H+
CMe3 slow
CMe3 H3 C O
H3 C O 18
18
OH

+ Me3C 
H 2O
→ Me3C − OH + H +
H3 C O
18

The above mechanism of ester hydrolysis is known as alkyl-oxygen cleavage

unimolecular.

H / Pt
Problem 6: B ←
4
 NaBH —CH=CH—CHO →
2
A

A and B are:
(a) —CH2CH2CHO, —CH=CH—CH2OH

(b) —CH2CH2CH2CHOH, —CH=CH—CH2OH

(c) —CH=CH—CH2OH in both cases

(d) —CH2CH2CH2OH in both cases

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[Type text]

Solution: NaBH4 clearly reduces carbonyl group, protecting the double bond.
∴ (b)

Problem 7: Dipole moment of CH3CH2CH3(I), CH3CH2OH (II) and CH3CH2F(III) is in

order
(a) I < II < III (b) I > II > III
(c) I < III < II (d) III < I < II

Solution: Higher the electronegativity between C–X higher will be the dipole moment
∴ (a)

Problem 8: The strongest acid among the following aromatic compounds is

(a) p-chlorophenol (b) p-nitrophenol
(c) m-nitrophenol (d) o-nitrophenol

Solution: Nitro is strongly electron withdrawing group, at ortho position intra-molecular

hydrogen bond reduces the acidic strength.
∴ (b)

Problem 9: The boiling points to isomeric alcohols follow the order

(a) primary > secondary >tertiary (b) tertiary > secondary > primary
(c) secondary > tertiary > primary (d) does not follow any order

Solution: Vander Waal forces are responsible for boiling point.

∴ (a)

Problem 10:
Reaction of with RMgX
O
Followed by hydrolysis will lead to produce
(a) RCHOHR (b) RCHOHCH3
(c) R2CHCH2OH (d) RCH2CH2OH
+
Solution: RMgX + 
→ H3C 
H2 O / H
→ R
O
O MgX OH
∴(d)

Problem 11:
NaBH4
B←  O 
H 2 / Pt
→A

OH
A and B are:

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[Type text]

(a)
O ,

OH OH
(b) ,

OH OH

(c) in both cases

OH

(d) in both cases

OH

Solution: NaBH4 clearly reduces carbonyl group, protecting the double bond.
∴ (b)

Problem 12: Phenol can be distinguished from alcohol with

(a) Tollens reagent (b) Schiff's base
(c) Neutral FeCl3 (d) HCl

Solution: Phenol gives violet colour with neutral FeCl3

∴ (c)

Problem 13: Which of the following is a primary alcohol?

(a) Butan –2-ol (b) Butan –1-ol
(c) Propan -2-ol (d) 2-Dimethylhexane-4-ol

Solution: Consider the structure

∴ (b)

CH3
Problem 14: H3C
18

O 
H2O
H+
→ A, A is
CH3 CH3

H3C H3C

18OH OH OH OH
(a) (b) 18
CH3 CH3

H3C H3C

OH O CH3 OH O CH3

(b) Both are correct (c) None is correct

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Solution: In acidic medium nucleophile attacks that carbon which is more sterically
hindered.
∴ (a)

Problem 15: Reaction of CH2 – CH2 with RMgX followed with hydrolysis produces

O
(a) RCHOHR (b) RCH2CH2OH
(c) RCHOHCH3 (d) RCH = CHOH

Solution: ∴(b)

Problem 16: 1, 2, 3-trihydroxybenzene is also known as

(a) Pyrogallol (b) Phloroglucinol
(c) Resorcinol (d) Quinol
[MP PET 1991]
Solution: (a)

Problem 17: Which of the following are isomers

(a) Methyl alcohol and dimethyl ether
(b) Ethyl alcohol and dimethyl ether
(c) Acetone and acetaldehyde
(d) Propionic acid and propanone
[AFMC 2005; BCECE 2005]
Solution: (b)

Problem 18: The structural formula of cyclohexanol is

CH 2 CH 2
H 2C CHOH H 2C CHOH
(a) (b)
H 2C CH 2 H 2C CH 2
CH 2 CH 2
CH2OH
(c) (d)

[Bihar CEE 1995]

Solution: (a)

Problem 19: CH2 = CH2 + B2H6 

NaOH
H 2 SO4
→
Product in above reaction is
(a) CH3CH2CHO (b) CH3CH2OH
(c) CH3CHO (d) none of these
[Bihar CEE1980]
Solution: (b)

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[Type text]

Problem 20: Which compound is formed when CH3OH reacts with CH3 – Mg - X
(a) Acetone (b) Alcohol
(c) Methane (d) Ethane
[Bihar CEE 1980]
Solution: (c) CH3 – OH + CH3MgX → CH4 + CH3O - MgX

Problem 21: Methyl alcohol can be distinguished from ethyl alcohol using
(a) Fehling solution
(b) Schiff’s reagent
(c) Sodium hydroxide and iodine
(d) Phthalein fusion test
[KCET 1984; BHU 2000]
Solution: (c) C2H5OH 
→ CHI3 (yellow ppt)
NaOH / I 2
IodoformTest

CH3OH 
NOH / I 2
→ No ppt.

Problem 22: An alcohol on oxidation is found to give CH3COOH and CH3CH2COOH. The
structure of the alcohol is
(a) CH3CH2CH2OH (b) (CH3)2C(OH)CH2CH3
(c) CH3CH2CHOHCH3 (d) CH3CH(OH)CH2CH2CH3
[BIT 1990]
Solution: (d)

Problem 23: An aromatic amine (A) was treated with alcoholic potash and another
compound (Y) when foul smelling gas was formed with formula C6H5NC. Y
was formed by reacting a compound (Z) with Cl2 in the presence of slaked lime.
The compound (Z) is
(a) C6H5NH2 (b) C2H5OH
(c) CH3OCH3 (d) CHCl3
[BIT 1990]
Solution: (b)
NH2 N C

+ 3KOH + CHCl3 + 3KCl + 3H2O

(A) (Y)
C2H5OH + Cl2 
Ca ( OH ) 2
→ CH3CHO 
Cl2
→ CCl3CHO 
Ca ( OH ) 2
→ CHCl3
(Z) (y)

Problem 24: The reagent which easily reacts with ethanol and propanol is
(a) Fehling solution (b) Grignard reagent
(c) Schiff’s reagent (d) Tollen’s reagent
[MP PET 1989]
Solution: (b) C2H5OH + R - Mg - X → RH + C2H2OMgX
C3H7OH – R - Mg - X → RH + C3H7OMgX

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Problem 25: CH3 – CH = CH – CH(OH) – CH3 

Jon ' s
reagent
→ X,
Product X is
(a) CH3CH2CH2CH(OH)CH3 (b) CH3CH = CHCOCH3
(c) Both (a) and (b) are correct (d) CH3CH2CH2COCH3
[RPET 2000]
Solution: (b)

Problem 26: The compound which gives the most stable carbonium on dehydration is

CH3
|
(a) CH 3 − C H − CH 2 OH (b) CH3 − C − OH
| |
CH3 CH3
(c) CH3 – CH2 – CH2 – CH2OH (d) CH3 − CH − CH 2 − CH 3
|
OH
[MNR 1995]
Solution: (b)

Problem 27: The reaction of C2H5OH with H2SO4 does not give
(a) Ethylene (b) Diethyl ether
(c) Acetylene (d) Ethyl hydrogen sulphate
[MP PET 1996]
Solution: (c)
1100C C2H5HSO4 + H2O
H2SO4 1370C
C2H5OH C2H5OC2H5 + H2O
0
170 C
C2H4 + H2O

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[Type text]

Problem 28: Match the Column – I and Column – II

Column I Column II (reagents used for the desired

product in major amount)
OH OH

(a) (p) CHCl3/NaOH

COOH
OH OH
COOH
(b) (q) CCl4/NaOH

Cl

(c) (r) NaOH followed by CO2

N
N
H
OH OH
CHO
(d) (s) KOH followed by CO2

Solution: (a – q, s), (b – q, r), (c – p), (d – p)

Write-up - I
Lithium aluminium hydride (LiAlH4) and sodium borohydride (NaBH4) are both hydride ion
donor and this property of theirs is utilized in reduction of carbonyl compounds to alcohols.
LiAlH4 being a strong hydride ion donor can reduce any carbonyl function like aldehydes,
ketones, esters (cyclic or non-cyclic), acid chloride, acid anhydride etc. While NaBH4 is a weak
hydride ion donor and it can reduce only aldehydes and ketones. LiAlH4 can reduce even carbon-
carbon double-bond conjuaged with phenyl ring and carbonyl group both. The reaction scheme
may be shown to occur in the following way.
LiAlH 4 
→H → H−
NaBH 4 
H H
δ+ δ−
−
O + H 
→ O 
acidification
→ OH

The attack of H ion being the slow step, the rate constant of the reaction depends upon the
electrophilicity of carbonyl carbon. Though the rate constant of reduction taking carbonyl
function other than aldehydes and ketones, is very small it is the concentration of hydride ion
( H ) that matters in determining the rate of reduction.

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[Type text]

1. O
O O
Ph
NaBH4
B←  
LiAlH 4
→A

Where A and B are, respectively

OH OH
OH OH O O
(a) Ph Ph
and

OH OH
OH OH OH OH
(b) Ph Ph
and

OH OH
OH OH O O
(c) Ph Ph
and

OH OH
O O O
(d) Ph Ph
and

2. The rate of reduction of the following carbonyl compounds by NaBH4

CH3
CH3 O C2H5 O O O
H3C CH3
CH3
H C2 H5 H

CH3
CH3 C2H5 O2N
(I) (II) (III) (IV)

(a) IV > I > II > III (b) I > II > IV > III
(c) III > II > I > IV (d) II >I > III > IV

3. The incorrect statement amongst the following is:

(a) The order of reduction reaction by LiAlH4 and that of the reduction by NaBH4 each is
two
(b) Al–H bond is more ionic than B–H bond and hence LiAlH4 can produce larger
concentration of hydride ion than that of NaBH4
(c) LiAlH4 cannot reduce –NO2 group
(d) Inspite of very small rate constant of reduction of any carbonyl function other than
aldehydes and ketones, the rate of reduction with LiAlH4 becomes appreciable due to
large concentration of hydride ion.

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[Type text]

Solution: 1. (c) 2. (a) 3. (c)

Write-up II

An optically active compound, C6H12O (A) gives a positive test with 2-4-
dinitrophenylhydrazine but a negative test with Tollen’s reagent. A on treatemnt with
NaBH4⋅H2O produces ‘B’ and on treatment with N2H4, EtO–, at high temperature
produces C.

1. Which of the following is correct?

(a) ‘B’ is opticaly inactive whereas C is optically active.
(b) Both ‘B’ and ‘C’ are optically acitve
(c) ‘C’ is optically inactive whereas ‘B’ is optically active
(d) Both ‘B’ and ‘C’ are optically inactive
−
2. A 
SeO 2
→ B 
OH
→ C. probable structure of ‘C’ is
OH H O OH H

(a) CHO (b)

-
H CH3 CH3 O H CH3 CH3

HO OH H O O

(c) (d)
CH3
H CH3 CH3 H3C

3. O H OH H
H3C
A= B=
H3C CH3 CH3 H CH3 CH3
optical active optical active
H
H3C
C=
H3C
CH3

4. O
H O OH H
O H
O

SeO 2
→ 
OH
→
- H CH3 CH3
H3C CH3 CH3 H H3C O
CH3

[Type text]
[Type text]

SUBJECTIVE

Problem 1: Write the mechanism of the given reaction

H+
CH2OH
O O
+ + +
+ -H2O -H -H
Solution: CH2OH2 +
CH2
O O O O

Problem 2: The following compounds are commercially available for use as water - soluble
solvents. How could each be made?
a) CH3CH2—O—CH2CH2—O—CH2CH2—OH carbitol
b) C6H5—O—CH2CH2—O—CH2CH2—OH phenyl carbitol

Solution: We can start with oxiranes of the central part

CH2 CH2 CH2OH
H+ CH CH OH
O  → O⊕—H →
3 2

CH2 + −H
CH2 CH2OCH2CH3
CH2OH
CH2—O—CH2CH2OH
/H+
CH2OH
CH2—O—CH2CH3
carbitol
CH2 CH2 CH2OH
H+ C6H5OH
O  → O —H 
⊕
+
→
CH2 CH2 −H CH2—O—C6H5
CH2OH
CH2—O—CH2CH2OH
/H+
CH2OH
CH2—O—C6H5
–H2O
Phenyl carbitol

Problem 3: Complete the following reaction:

18
Hg2+ PhCO3H
H3C C C A B
dil. H2SO4

Cl

[Type text]
[Type text]

O
Solution: (A) H3C C CH2

Cl
Cl
18
(B) H3C O C CH2
O

Problem 4: Write the mechanism for the following transformation:

H3C CH3
H3C conc. H2SO4 CH3
+ H2O
CH3 Heat
CH3
OH

Solution: H3C conc. H2SO4

CH3 Heat +
CH3
CH
CH3 CH3
OH
CH3

1,2 Methyl shift

H3C CH3
CH3 +
H
+
C
CH3
CH3 CH3
Problem 5: Identify the compound A and B:
+
H
A.
(a) HO CHO
OH OH

Ph Ph
+
(b) H
B

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[Type text]

O OH
Solution: (a)

A
+ O
OH OH OH OH2 Ph

Ph Ph Ph
Ph Ph
+ -
H Ph
(b)
Shift

(B)
O

Problem 6: The reaction of ethylene oxide with acidic water gives ethylene glycol,
HOCH2CH2OH. By constrast, when ethylene oxide at high concentration is
treated with OH–, a polymer known as polyethylene glycol (trade name
Carbowax) is formed. Deduce the structure of polyethylene glycol and show the
mechanism by which it is formed.

Solution: This is an example of an anionic polymerization:

O O
– –
HO HO — CH 2 — CH 2 — O
HO — CH 2 — CH 2 — O — CH 2 — CH 2 — O −
 →  →  → HO — (CH 2 — CH 2 —) n — O — H
The properties of the resulting polymer depend on the value of n, which is
determined by the reaction conditions.

Problem 7: What significance can you attach to the following observation?

CH3 CH3
→
1 equiv. mCPBA
O
CH3 CH3

Solution: Even through it is more sterically hindered, the more highly substituted double
bond is epoxidized in preference to the less substituted one. this indicates that in
the epoxidation reaction steric effects are less important than the electron-donating
effects of the alkyl groups, making the tetrasubstituted double bond more
nucleophilic than the disubstituted one.

Problem 8: Identify the products A and B giving proper explanation:

CH3
H3C
+|
+ H 2 O18 →
H
A
O

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[Type text]

CH3
H3C
+ H3C OH 
CH3ONa
→B
O
Solution: CH3 CH3 CH3
H3C H3C
+ 18
→
H

H 2O
→ H3C
+
O O 18
OH OH
H
(A)
(nucleophile attacks the more substituted
cabron in acid-cataysed reaction

CH3 CH3 CH3

H3C
− + +

CH3O Na

→ H3C 
H
(CH OH)
→ H3C
2
O
O O CH3 18 OH O CH3
(nucleophile attacks the less substituted carbon in base-catalysed reaction)

Problem 9: Predict the product

C6H5
Bayer's reagent HIO 4 dil. NaOH,
(A) (B) (C)

C6H5
C6H5 C6H5 C O
dil. NaOH,
Solution: OH H O
OH O
(A) (B) (C)

Problem 10: Identify the major products in the following reactions

NO2 OH
i) ii)
CH3
→
HNO3
A
 →B
H SO
2 4 Bromine
O Water

CH3
Solution: CH3
O Br

O 2N OH
A= B=
Br CH3
NO2

Problem 11: An organic liquid with sweet smell and b.pt 78°C contains C, H and O. On
heating with conc. H2SO4 gives a gaseous product (B) of empirical formula
(CH2)n. Compound (B) decolourises bromine water and alk. KMnO4. (B) also
reacts with one mole of H2 in presence of Ni. What are (A) and (B)?

[Type text]
[Type text]

Solution: Compound (empirical formula CH2) decolourizes Br2 water, reacts with alk.
KMnO4 and adds one mole of H2 and so (B) is alkene.
Compound (B) is obtained from (A) by the action of H2SO4 and so (A) is alcohol.
A has b.pt. 78°C. So (A) is ethanol
Conc.H2SO4
Reactions: i) C2 H5OH  → C2 H 4
Ethanol Ethylene

ii) C2 H 4 + Br2 water → decolourises (C2H4Br2)

(B)
C2 H 4 + KMnO 4 → decolourises (HCOOK) Pot. formate
(B)
iii) C2H4+ H2 → C2H6

Problem 12: Predict the product

(a) H3C CH CH CH3 Mg
Br OCH3
O
(b) ZnCl2, HCl

Solution: (a) CH3 CH CH CH3 + MgBrOCH3

Cl
(b)
Cl

Problem 13: Suggest a synthetic route to produce each product below starting with the
indicated material and any other reagents you need.
i) H H

OH D
ii)
H2C = CH2 O O

Solution: i) H
 →
PBr3
H H
  →
Mg / ether
Pyridine
OH Br MgBr

D2O

[Type text]
[Type text]
− +
ii) CH2 = CH2  → HOCH2CH2.OH 

MnO 4
KOH
→ HOCH2.CH2CH2.O.CH2.CH2.OH
H
−H2 O
H /∆
+
Intramoelcualr
dehydration – H2O

O O

Problem 14: Give the mechanistic step of the following reactions

OH OH
CO2H
1. NaOH / ∆
+ CCl4   
+
→
2. H3 O

Solution: OH O– O
Cl
| H
−
→
OH
+ CCl3 → CCl3

O– O– O– O–
−
− H2 O
← OH
← ← OH−

CO2– CO2H C(OH)3 CCl3

OH
H3O⊕

COOH

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Assignments (New Pattern)

SECTION – I Single Choice Questions

LEVEL - I

1. HBr reacts fastest with

(a) 2-methylpropan-2-ol (b) Propan-2-ol
(c) Propan-2-ol (d) 2-methylpropna-1-ol

2. Choose the correct statement(s) for the reaction

OH
O
O
O HO
→
AlCl3 / CS2
heat
CH3 CH3
CH3
O (b)
(a)
(a) (b) is formed more rapidly at higher temperature
(b) (b) is more volatile than (a)
(c) (a) is more volatile than (b)
(d) (a) is formed in higher yields at lower temperature

3. The end product C for the following reaction is

Na CH3I
(C6H5)2CHCH2OH  → X  → Y
(a) (C6H5)2C=CH2 (b) (C6H5)2CHCH2ONa+
O
||
(c) (C6H5)2CHCH2O— C —S–Na+ (d) (C6H5)2CHCH2OCH3

4. Which of the following compounds is oxidised to prepare methyl-ethyl ketone?

(a) 2-Propanol (b) 1-Butanol
(c) 2-Butanol (d) ter-Butyl alcohol

5. Dehydration of cyclopentyl carbinol with conc. H2SO4 forms

(a) Cyclopentene (b) Cyclohexene
(c) Cyclohexane (d) None of these

6. Order of reactivity of HX towards ROH is

(a) HI > HBr > HCl (b) HCl > HBr > HI
(c) HI > HBr < HCl (d) HI < HBr > HCl
+
7. H3O
Ester A (C4H8O2) + CH 3 MgBr  → B ( C4 H10O ) .
(2 parts) (alcohol)

Alcohol B reacts fastest with Lucas reagent. Hence A and B are:

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O CH3 O H3C
H3C , H C H ,
OH OH
(a) O
3
(b) O
CH3 H3C
H5C 2 H7 C 3
O OH O CH3
H3C , H3C H , H3C OH
(c) (c) O CH3
(d) O
CH3
H5 C 2 H 7C 3

CH3
8.
 cold
alkaline KMnO
→ A 
CrO3
AcOH
→ B. A and B are
4

CH3 CH3 CH3 CH3

OH OH -
OH C O
(a) , (b) ,
OH O OH O
CH3
CH3
OH
, (d) No formation of a and b
(c) OH OH

9. Hydrogen bonding is maximum in

(a) Ethanol (b) Diethyl ether
(c) Ethyl chloride (d) Triethyl amine

CH3
10. CH3
H3C 
HBr
→ A (predominant)

CH3 OH

A is:
CH3 Br Br CH3

(a) H3C (b) H3C

CH3 CH3 CH3 CH3

(c) Both (d) None is correct

11. Phenol is heated with chloroform and alcoholic KOH when salicyladehyde is produced.
This reaction is known as
(a) Fridel-Crafts reaction (b) Reimer-Tiemann reaction
(c) Rosenmund reaction (d) Sommelet reaction

12. The reaction of elemental sulphur with Grignard reagent followed by acidification leads
to the formation of
(a) Mercapton (b) Sulphoxide
(c) Thioether (d) Sulphonic acid

13. A mixture of benzoic acid and phenol may be separated by treatment with
(a) NaHCO3 (b) NaOH
(c) NH3 solution (d) KOH

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14. Phenol does not react with NaHCO3 because

(a) phenol is a weaker acid than carbonic acid
(b) phenol is a stronger acid than carbonic acid
(c) phenol is as strong as carbonic acid
(d) phenol is insoluble in water.

15. Predict the product of reaction below

O

OH + H3C 
Pyridine
→

Cl
O
O
(a) CH3
(b)
OH
O
O

(d) CH3
(c) CH3

16. Predict the product of the reaction below

O

OH + H3C 
AlCl3
→

Cl
OH
OH O

(a) CH3 (b)

H3C O
O

O CH3
(d) Both (a) and (b)
(c)

17. The correct decreasing order of acidic strength is

(a) C6H5OH > C6H5CH2OH > C6H5COOH > C6H5SO3H
(b) C6H5CH2OH > C6H5OH > C6H5SO3H > C6H5COOH
(c) C6H5COOH > C6H5CH2OH > C6H5OH > C6H5SO3H
(d) C6H5SO3H >C6H5COOH > C6H5OH > C6H5CH2OH

18. The acidic character of 1°, 2°, 3° alcohols, H2O and RC≡CH is in the order
(a) H2O > 1° > 2° > 3° RC≡CH (b) RC≡CH > 3° > 2° > 1° > H2O
(c) 1° > 2° > 3° > H2O > RC>CH (d) 3° > 2° > 1° > H2O > RC≡CH

19. Which of the ether(s) below is (are) not likely to form peroxides when exposed to air?
(a) H 3C O CH3 (b)
O

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H3C

O O
CH3 (d)
(c) H3C
H3C CH3
CH3
H3C

20. H3C

CO, H2 [CoH(CO)4 ]
125°, pressure
→ →
H2
Cu − Zn
product
CH2
This represents Oxo method of alcohol synthesis. Product can be:
CH3

(a) H3C OH (b) OH

H 3C
(c) Both are true (d) None is true

LEVEL – II

1. Butanonitrile may be prepared by heating

(a) Propyl alcohol with KCN (b) Butyl alcohol with KCN
(c) Butyl chloride with KCN (d) Propyl chloride with KCN

2. Reaction of ethanol with sulphuric acid and suitable conditions can lead to the
formation of
(a) C2H5HSO4 (b) Ethene
(c) Ethoxyethane (d) All of them

3. The dehydration of 1-butanol gives

(a) 1-Butene as the main product (b) 2-Butene as the main product
(c) Equal amounts of 1-butene and 2-butene (d) 2-methyl propene

4. —CH3 Cold CrCO

 → A 
3
→ B; A and B are
alkaline KMnO4 AcOH

CH3 CH3 CH3 CH3

(a) OH , OH (b) OH , =O
—OH =O —OH =O
CH3 CH3
(c) OH , (d) No formation of A and B
—OH —OH

5. 3-methyl-3-hexanol can be prepared by

(a) CH3MgI and 3-hexanone, followed by hydrolysis
(b) C2H5MgI and 2-pentanone, followed by hydrolysis
(c) C3H7MgI and 2-butananone, followed by hydrolysis
(d) Any of the method above

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6. Predict the major product

+ excess HI →
O
(a) HO – CH2 – CH2 – CH2 – CH2 – I (b) HO – CH2 – CH2 – CH2 – CH2 – OH
(c) I – CH2 – CH2 – CH2 – CH2 – I (d) No reaction

7. The relative order of acidity of alcohols in comparison to H2O and HC ≡ CH is

(a) H2O > ROH > HC ≡ CH (b) H2O > HC ≡ CH > ROH
(c) ROH > H2O > HC ≡ CH (d) ROH > HC≡ CH > H2O

8. 1° alcohol can be converted to 1° aldehyde by using the reagent

(a) Pyridinium chlorochromate (b) Potassium dichromate
(c) Potassium permanganate (d) Hydrogen peroxide

9. CH3
conc.H 2SO4
CH3——C——CH—CH3  → A (predominant)

CH3 OH
A is :
(a) (CH3)3C—CH=CH2 (b) (CH3)2C=C(CH3)2
(c) CH2=C—CH2—CH2CH3 (d) none is correct
|
CH3

10. Glycerol has:

(a) one 1° and one 2° alcoholic groups (b) one 1° and two 2° alcoholic groups
(c) two 1° and one 2° alcoholic groups (d) two 2° alcoholic groups

SECTION – II More than one choice

O
1. i)
Me NH CH3
O 
Br2 / Fe
→P ii)

Mononitration
→Q
NO2
iii) H5C6
+ Cl 
Anh. AlCl3
→ R 
mononitration
→S
O
Where P, Q, R and S are all major products of the respective reactions:
Now choose the correct choice (s) from the following:

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Me O
O Br and
(a)
(P) (R)
O O

HN CH3 HN CH3
O2 N O
(b) or and
NO2 NO2
NO2
NO2
(Q) (S)
Br
Me O
O and
(c)
(P) (R)

Br
Me O

(d) O and
NO2
(P) (S)

2. Which among the following is/are true about properties of monohydric alcohols?
(a) In strongly acidic medium, alcohols exist as alkyloxonium ions (RO+H2)
(b) Alcohols are weaker acids than water
(c) The decreasing order of basic strength of alcohol is 3° > 2° > 1°
(d) The decreasing order of acidic strength of alcohol is 3° > 2° > 1°
3. Which of the following statements are correct?
(a) An SN1 reaction proceeds with inversion of configuration
(b) An SN2 reaction proceeds with stereochemical inversion
(c) An SN2 reaction follows second order kinetics
(d) The reaction of ter. butyl bromide with −OH follows first order kinetics

Et
4. D Br
H2 O

Me
(a) racemisation takes place by SN1 (b) inversion takes place by SN2
(c) racemisation in both SN1 and SN2 (d) inversion of both SN1 and SN2

5. Chromic anhydride in H2SO4 is turned blue by

(a) 1° alcohol (b) 2° alcohol
(c) 3° alcohol (d) OH

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CH3 CH3 CH3 H

6.
C C C C
H H H CH3
per acid per acid

A C
+ +
H /H2O H /H2O

B D
Which of the following statements is/are true:
(a) B is a single compound and optically inactive
(b) D is a single compound and optically inactive
(c) B is an equimolar mixture of two enantiomeric compounds
(d) D is an equimolar mixture of two enantiomeric compounds

D
SOCl2
7. CH3 C
OH (A)
H
(i) SOCl2 (ii)
N
(B)
(a) Retention of configuration takes place in A
(b) Inversion of configuration takes place in B
(c) Retention of configuration takes place in B.
(d) Inversion of configuration takes place in A.
8. Characteristic dark colouration with neutral FeCl3 solution is given by
OH
OH O
(a)
(b) CH3 C CH C OC 2H5
OH

(c) (d) CH3CH2CH2OH

CH3

9. Which of the following will be soluble in sodium bicarbonate solution?

OH
O2N NO2 COOH
(a) (b)

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OH SO3H

(c) (d)

10. Cl NaBH 4
(A)

LiAlH 4

(B)

The product(s) is/are

(a) (A) is an alcohol (b) (B) is an alcohol
(c) (A) is an acid (d) (B) is an acid
SECTION – III Comprehension Type Questions

Write-up I
Oxidation of alcohol is the most useful and widespread area of oxidation, as it
encompasses the alcohol → aldehyde → carboxylic acid sequence that is used so
often in organic synthesis.

1. In the given reaction

CH 3 − C = CH − CH 2 OH →
Reagent
CH 3 − CH = CH − CHO
the reagent may be:
(a) Jones reagent (b) Sarret reagent
(c) Pyridinium dichromate (PDC) (d) All of these

2. The given reaction

C6 H 5 − CH = CH − CH 2 − CH 2 OH →
DMSO /(COCl)2
Et 3 N / CH 2 Cl2
C6 H 5 − CH = CH − CH 2 − CHO
is known as:
(a) Oppenaur oxidation (b) Swern reaction
(c) Malaprade oxidation (d) Baeyer-Villigar oxidation

3. In the given reaction:

CH3
NaOH / ∆

CAN
→(A)  →(B)

HO
the product is:

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CH3 CH3 CH3

and
(a) (b)

HO O HO HO
CH3
O

(c) (d)

O O

Write-up II
Reaction of a compound with a solvent is generally referred to as a solvolysis. Tert-Butyl
bromide was solvolysed under two different conditions.
Reaction – I: tert-Butyl bromide was refluxed with ethanol containing a small amount of
sodium ethoxide. The reaction was exceedingly rapid with a half life of only a few
minutes and resulted two products A an ether and B(C4H8). The rate of this reaction is
given by the expression.
rate = k1[tert-BuBr] + k2[tert-BuBr] [C2H5O–]
Reaction – II: In the second reaction, tert-Butyl bromide was refluxed with a mixture of
solvents containing 70% ethanol and 30% water.

4. The two rate constants k1 and k2 respectively for the first reaction stand for
(a) SN1 and SN2 (b) SN1 and E2
(c) E1 and SN2 (d) E1 and SN1

5. In the second reaction which of the three prodcuts would be formed in maximum amount
and which in the minimum
Maximum Minimum
(a) (CH3)COH (CH3)3COC2H5
(b) (CH3)3COC2H5 (CH3)3COH
(c) (CH3)3COH (CH3)2C = CH2
(d) (CH3)3COC2H5 (CH3)2C = CH2

6. The three compounds Me3COC2H5, Me2C = CH2 and Me3COH respectively are formed
by which mechanism?
(a) SN1, E1, SN1 (b) SN1, E2, SN1
(c) SN1, E2, SN2 (d) SN2, E2, SN1

Write-up III
Although chlorobenzene is inert to nucleophilic substitution, it gives quantitative yield of
phenol when heated with aq. NaOH at high temperature and under high pressure. Phenol,
so formed, is a weaker acid than the cabroxylic acid; hence it dissolves only in strong
bases like NaOH, but not weak like NaHCO3. It reacts with acid chlorides and acid

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anhydrides in the absence of AlCl3 to form esters. As far as electrophilic substitution in

phenol is concerned, the –OH is an activating group, hence its presence enhances the
electrophilic substitution in the o- and p-positions.
Condensation with formaldehyde is one of the important property of phenol. The
condensation may take place in presence of acids or alkalis and leads to the formation of
bakelite, an important industrial polymer.

7. The o-acylation of phenols with acid anhydrides can be catalysed by

(a) sulphuric acid (b) NaOH
(c) both (d) none

8. Phenol undergoes electrophilic substitution more readily than benzene

(a) the intermediate carbocation is a resonacne hybrid of more resonating structures than
that from benzene.
(b) the intermediate is more stable as it has positive charge on oxygen, which can be
better accommodated than on carbon.
(c) in one of the canonical structures, every atom (except hydrogen) has complete octet
(d) the –OH group is o, p-directing which like all other o,p-directing groups is activating

9. Phenol undergoes electrophilic substitution more readily in presence of alkali than the
phenol itself because
(a) of the formation of a more stable carbocation as an intermeidate
(b) of the formation of a more stable carbanion as an intermediate
(c) of the formation of a more stable neutral intermediate
(d) in presence of alkali, a stronger electrophile is produced

Answers to Assignments
SECTION - I

Level - I
1. (a) 2. (c) 3. (d) 4. (c)
5. (b) 6. (a) 7. (a) 8. (a)
9. (a) 10. (b) 11. (b) 12. (a)
13. (a) 14. (a) 15. (a) 16. (d)
17. (d) 18. (a) 19. (c) 20. (c)

Level - II

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1. (d) 2. (d) 3. (b) 4. (a)

5. (d) 6. (c) 7. (a) 8. (a)
9. (b) 10. (c)

SECTION - II

1. (a), (b) 2. (a), (b), (c) 3. (b), (c), (d) 4. (a), (b)
5. (a), (b), (d) 6. (b), (c) 7. (a), (b) 8. (a), (b)
9. (a), (b), (d) 10. (a), (b)

SECTION - III

1. (d) 2. (d) 3. (a) 4. (c)

5. (b) 6. (b) 7. (c) 8. (c)
9. (d) 10 (a) 11. (d) 12. (b)
13. (c) 14. (b) 15. (d)

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SECTION - V

1. (d) 2. (b) 3. (b) 4. (b)

5. (c) 6. (b) 7. (c) 8. (c)
9. (c)

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