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ALCOHOL, ETHER & PHENOL

Contents
1. Alcohols ..................................................................................................................... 1
2. Nomenclature........................................................................................................... 2
3. Methods of Preparation ........................................................................................ 3
4. Physical Properties ............................................................................................. 20
5. Chemical Properties ............................................................................................ 21
6. Miscellaneous Reactions .................................................................................... 25
7. Test for –OH Group .............................................................................................. 27
8. Methods of Distinction Between Alcohols..................................................... 28
9. Ethers ...................................................................................................................... 33
10. Structure................................................................................................................. 34
11. Nomenclature........................................................................................................ 34
12. Methods of Preparation ..................................................................................... 34
13. Physical Properties ............................................................................................. 36
14. Chemical Properties ............................................................................................ 37
15. Cyclic Ethers .......................................................................................................... 38
16. Preparation of Epoxides..................................................................................... 39
17. Reactions of Epoxides ......................................................................................... 39
18. Aryl Ethers ............................................................................................................. 40
19. Phenols ................................................................................................................... 45
20. Nomenclature........................................................................................................ 45
21. Methods of Preparation ..................................................................................... 46
22. Physical Properties ............................................................................................. 47
23. Chemical Properties ............................................................................................ 48
24. Level – 1 (Main) .................................................................................................... 59
25. Level – 2 (Main) .................................................................................................... 61
26. Level – 3 (Advanced) ........................................................................................... 67
27. Level – 4 (Comprehension & Match the Column) ........................................ 73
28. Level – 5 (Subjective Type) ................................................................................ 82
29. Level – 6 (Previous Years Main & Advanced) ............................................... 85
30. Level – 7 (NCERT Corner)................................................................................... 91
31. Answer Sheet ......................................................................................................... 98
ALCOHOL, ETHER & PHENOL
1. Alcohols
The organic compounds containing one or more than one hydroxyl group(s) attached to sp3 hybridised carbon
atom(s) are called alcohol. Alcohols are bent molecules. In alcohols, the carbon atom linked with ‘O’ atom of –OH
3 3
group is sp hybridised. The central ‘O’ atom is also sp hybridised and the bond angle is 105.

(sp3-sp3) 
O


105
H3C H

(sp3-sp) 
Structure of Methyl alcohol
Compounds in which the hydroxyl group is attached directly to a sp2 hybridised carbon atom are known as enols or
phenols (in case of aromatic compounds).
For example,
OH CH3
CH 3 CH 2 CH CH OH CH 3 C CH3 H2C=CH
CH 2OH
But l en l ol OH Allyl alcohol
(Phenol) (enol) tert-Butyl alcohol

OH CH 2 CH 2 CH 2 CH CH 2
CH 2OH
Cl OH OH OH OH
Benzyl alcohol Ethylene chlorohydrin
Cyclohexanol Glycerol
(  Chloroethyl alcohol)

Classification
Alcohols are classified as mono, di and trihydric alcohols accordingly as they contain one, two or three hydroxyl
3
groups. Alcohols which contains four or more hydroxyl groups attached to the sp hybridised carbon atoms are
called polyhydric alcohols.
CH3 OH CH2 OH
CH2 OH CH2 OH
Methyl alcohol CH2 OH
CH OH (CH-OH)4
Ethan-1-2-diol
(Dihydric alcohol) CH2 OH CH2 OH
Propan-1,2,3-triol Sorbitol or Mannitol
(Trihydric alcohol) (Polyhydric alcohol)

Again we can classify monohydric alcohols according to the kind of carbon that bears the –OH group. For example,
H R R
R C OH R C OH R C OH
H H R
Primary Secondary Tertiary
(1) (2) (3)
2 – ALCOHOL, ETHER & PHENOL – JEE

2. Nomenclature
For certain alcohols, common names are used extensively with respect to their IUPAC names. The common
names are derived by adding the suffix alcohol to the name of alkyl group. Common names of few alcohols are as
follows.
CH3 CHCH3 CH3
CH3 CH2OH
OH CH3 CHCH2 OH
Ethyl alcohol Isopropyl alcohol Isobutyl alcohol
CH3
H2C OH CH3
CH3 C OH CH3 C CH2 OH
CH3
CH3
tert-butyl alcohol Benzyl alcohol Neo-pentyl alcohol

The IUPAC naming rules of alcohols are as follows:


(a) Select as the parent structure, the longest continuous carbon chain that contains the –OH group, then consider
the compound to have been derived from this structure by replacement of hydrogen by various groups.

 The parent structure is known as ethanol, propanol, butanol, etc., depending upon the number of
carbon atoms. Each name is derived by replacing the terminal –e of the corresponding alkane name by
–ol.

(b) Indicate by a number, the position of the –OH group in the parent chain, generally using the lowest
possible number for this purpose.
(c) Indicate by numbers, the positions of other groups attached to the parent chain.
CH 3
CH 3OH
CH CH CHCH OH CH 2CH2OH
3 2 2
Methanol 2-Methyl-1-butanol 2-Phenylethanol
CH3 CH3
CH3 CH2 C CH3 CH3CHCHCH3 CICH2CH2OH CH3 CHCH=CH2

2-Chloroethanol OH
OH OH
3-Buten-2-ol
2-Methyl-2-butanol 3-Methyl-2-butanol
Alcohols containing two hydroxyl groups are called diols or glycols. They have both common

names and IUPAC names. Common names are given in parenthesis.
H
H H
CH2 CH2 CH3HC CH2 CH2 CH2 CH2 H
OH OH OH OH
OH OH H H H H
1,2-ethanediol 1,2-propanediol 1,3-propanediol
(Propylene glycol) (Trimethylene glycol) HO HO
(Ethylene glycol)
cis-1, 2-cyclopentanediol
H
H H
CH2 CH2 CH3HC CH2 CH2 CH2 CH2 H
OH OH OH OH
OH OH H H H H
1,2-ethanediol 1,2-propanediol 1,3-propanediol
(Propylene glycol) (Trimethylene glycol) HO HO
(Ethylene glycol) cis-1,2-cyclopentanediol
Illustration 1: Give the systematic (IUPAC) name for the following alcohol.
CH2I CH2OH

H3C CH2 CH CH CH CH3

CH3
Solution: The longest chain contains six carbon atoms, but it does not contain the carbon bonded to the
hydroxyl group. The longest chain containing the carbon bonded to the –OH group is the one
indicated by the box, containing 5 carbon atoms.
The chain is numbered from right to left so as to give the hydroxyl bearing carbon atom the lowest
possible number.
CH2I CH2 OH

H3C CH2 CH CH CH CH3

CH3
The correct name for the compound is 3-iodomethyl-2-isopropyl-1-pentanol

3. Methods of Preparation
Alcohols are prepared by the following methods:
(1) Hydrolysis of Alkyl Halides: Alkyl halides react with aqueous sodium hydroxide to form alcohols.
H2O
R X + NaOH R OH + NaX
Alkyl halide  Alcohol
H2O
CH3CH2 Br + NaOH CH3CH2 OH + NaBr

Ethyl bromide Ethyl alcohol

(2) Hydration of Alkenes: Alkenes react with sulphuric acid to produce alkyl hydrogen sulphates (Markovnikov rule
is followed). Alkyl hydrogen sulphates on hydrolysis give alcohols. For example,
OSO 3H
+
CH3 CH CH2 + HOSO 3H CH3 CH CH3
Propylene Isopropyl hydrogen
sulphate
OSO3H H OH

CH3 CH CH3 O H
 CH3 CH CH3 + H2SO4
+
Isopropyl alcohol
The overall result of the above reactions appears to be Markovnikov addition of H2O (Hydration) to a
double bond.
OH
+
H CH3 CH CH3
CH3 CH CH2 + H OH

Propylene Isopropyl alcohol
It is not possible to make primary alcohols by this method (ethyl alcohol is the only exception).

(3) Hydroboration-Oxidation of Alkenes: Alkenes react with diborane, B2H6 to form trialkylboranes.
Diborane adds as borane, BH3. The positive part of BH3 is the boron, the negative part is hydrogen. For
example,
3CH CH CH + BH (CH3CH2CH2) 3B
3 2 3
Propylene Tripropylborane
4 – ALCOHOL, ETHER & PHENOL – JEE
Trialkylboranes are used for making primary alcohols by reaction with alkaline aqueous solution of
hydrogen peroxide.
OH
(CH3CH2CH2)3B + H2O2 3CH3CH2CH2OH + H3BO 3
n-Propyl alcohol
(1-Propanol)
The overall result of the above reactions appears to be anti-Markovnikov addition of H2O to a double bond.
(1) B2H6
CH3 CH CH2 CH3CH2CH2OH
(2) H2O/OH
Propylene n-Propyl alcohol

Hydroxylation
Synthesis of 1, 2 diols from alkene:
OSO 4, H2O 2
C C C C (syn hydroxylation)
or KMnO4.OH
cold dilute OH OH

Example
CH2CH3 CH2CH3 CH2CH3
H CH2CH3 H H
O OH
O -
KMnO 4 HO H OH
Mn H2O
O H OH
O OH
H CH2CH3 H H
CH2CH3 CH2CH3 CH2CH3
meso-3, 4 hexane
diol (60%)
O OH
R C OOH
C C C C (anti hydroxylation)
H2O
OH
CH2CH3 CH2CH3
H CH2CH3 H CH2CH3 H
OH H OH
HCO3H H2O
O
HO H
H CH2CH3 CH2CH3
H CH2CH3
HO H CH2CH3
(3S, 4S)-hexane-3, 4-diol

Organometallic Reagents
Organometallic compounds contain covalent bonds between carbon atom and metals. Organometallic reagents
are useful because they have nucleophilic carbon atoms, in contrast to the electrophilic carbon atoms of alkyl
halides. Most metals (M) are more electropositive than carbon and the C–M bond is polarized with a partial +ve
charge on the metal and partial negative charge on the carbon atom:
Grignard Reagents
Organometallic compounds of lithium and magnesium are most frequently used for synthesis of alcohols. The
organometallic halides of empirical formula R – Mg – X, are called Grignard reagents in honour of the French
Chemist Victor Grignard, who discovered this utility around 1905 and received the Nobel Prize in chemistry in
1912. Grignard reagents result from the reaction of an alkyl halide with magnesium metal.
This reaction is always carried out in an ether solvent, which is needed to solvate and stabilize the Grignard
reagent as it forms. Although we write the Grignard reagents as R – Mg – X, the actual species in solution usually
contains two, three, or four of these units associated together with several molecules of the ether solvent. Diethyl ether,
CH3CH2–O–CH2CH3, is the most common solvent for these reactions although other ethers are also used:
   
CH CH  O  CH CH
R  X  Mg 
3 2 2 3
 R  Mg X
organometallic halide (Grignard reagent)
(X = Cl, Br or I)
Grignard reagents may be made from primary, secondary and tertiary alkyl halides as well as from vinyl and aryl
halides. Alkyl iodides are the most reactive halides followed by bromides and chlorides. Alkyl fluorides generally do
not react.
Reactivity R – I > R – Br > R – Cl >> R – F
The following reactions show the formation of some typical Grignard reagents
CH3 – I + Mg  CH3 – Mg – I
ether

iodomethane methyl magnesium iodide


Br ether MgBr
+ Mg
H H
bromocyclohexane cyclohexyl magnesium bromide

CH2  CH – CH2 – Br + Mg  CH2  CH – CH2 – MgBr


ether

alkyl magnesium bromide

Organolithium Reagents
Like magnesium, lithium reacts with alkyl halides, vinyl halides, and aryl halides to form organometallic
compounds. Ether is not necessary for this reaction; organo lithium reagents are made and used in a wide variety
of solvents.
R – X + 2Li   Li+ X– + R – Li
Organo lithium reacts like R–: Li+

Example
CH3CH2CH2CH2 – Br + 2Li 
hexane
 CH3CH2CH2CH2Li + LiBr
n-butyl bromide n butyl lithium
CH2  CH – Cl + 2Li 
 CH2  CH – Li + LiCl
Pentane

vinyl chloride

Br + 2Li ether
Li + LiBr

bromobenzene phenyllithium

Preparation of alcohols by Grignard’s reagents: addition of organometallic reagents to carbonyl


compounds
Because the Grignard reagents resemble carbanions, Grignard and organolithium reagents are strong nucleophiles
as well as strong bases. Their most useful nucleophilic reactions are addition to carbonyl ( >C=O) groups. The
carbonyl group is polarized, with a partial +ve charge on carbon atom and a partial negative charge on oxygen. The
positively charged carbon is electrophile; attack by a nucleophile places a negative charge on oxygen atom.

 
R C O R C O

The product of this nucleophilic attack is an alkoxide ion, a strong base. The addition of water or a dilute acid
protonates the alkoxide ion to give the alcohol.

H O H R C OH + OH
R C O

alkoxide
Either a Grignard reagent or an organo metallic reagent can serve as the nucleophile in the addition to carboxyl
group. The following discussions refer to Grignard reagents, but they also apply to organometallic reagents.
6 – ALCOHOL, ETHER & PHENOL – JEE

R R
R + X
  + H3O
ether -
R' MgX + C O R' C O MgX R' C OH + Mg
R OH
R R
(i) Preparation of Primary Alcohols

(ii) Preparation of Secondary Alcohols


+
ether + - H3O
R MgX + R' CH O R' CH O MgX R' CH OH
Grignard's aldehyde
reagent R R
O OH
Br (1) ether
H3C Mg + C H C H
(2) H3O+
H2C CH3
ethyl magnesium benzaldehyde
bromide 1-phenylpropan-1-ol

(iii) Preparation of Tertiary Alcohols


+
Br H3O
H3C Mg +
ethyl magnesium O -
bromide H3C CH2 CH3 CH2 C O CH3 CH2 C OH

phenyl-ethyl ketone H2 C CH3 H 2C CH3


3-phenylpentan-3-ol
O R
(i) ether
R MgX + R' C R'' + R' C OH
ketone (ii) H 3 O
R''
tertiary alcohol
O OH
(1) ether
R MgX + R' C OR'' R' C R''
(2) H3O+
ester
R
tertiary alcohol
Addition of the first equivalent of the Grignard reagent produces an unstable intermediate that expels a chloride ion
(in the acid chloride) or an alkoxide ion (in the ester), giving a ketone. The alkoxide ion is a suitable leaving group
in this reaction because on leaving stabilizes a negatively charged intermediate in a strongly exothermic step.
Attack on an acid chloride
R'
R' R'
+ -+ -
R MgX C O R C O MgX C O + Cl
Cl R
Cl
acid chloride ketone
intermediate

Attack on an ester
R'
R' R' X
+ -+
R MgX C O R C O MgX C O + Mg
R'' O R OR
O R''
ester intermediate ketone
The ketone, thus produced reacts with a second equivalent of the Grignard reagent, forming the magnesium salt of
a tertiary alkoxide. Protonation gives a tertiary alcohol with one of its alkyl groups derived from the acid chloride or
ester, and the other two derived from the Grignard reagent.
R' R'
R' +
+ - + H3O
R MgX C O R C O MgX R C OH
Grignard R
ketone R R
(second alkoxide
intermediate tertiary alcohol
equivalent)

(iv) Addition of Grignard Reagents to Ethylene Oxide


Grignard reagents usually do not react with ethers, but epoxides are usually reactive ethers because of their ring
strain. Ethylene oxide reacts with Grignard’s reagents to give after protonation, primary alcohols with two additional
carbon atoms.

 The nucleophilic attack by Grignard reagents opens the ring and relieves the ring strain.

+
O O MgX OH
+ ether H3O
+
R MgX H2C CH2 R CH2 CH2 R CH2 CH2
ethylene oxide alkoxide primary alcohol

+
O O MgBr OH
+
(H3C)2HC MgBr + H2C CH2 H 2C CH2 H3O
H2C CH2
Propyl magnesium ethylene oxide
bromide CH(CH3)2 CH(CH3)2
3-methyl-butan-1-ol

Reaction with Acidic compounds


Grignard and organolithium reagents react vigorously and irreversibly with water. Therefore, all reagents and
solvents used in these reactions must be dry.

OH

R MgX + H O H R H + Mg
X
8 – ALCOHOL, ETHER & PHENOL – JEE
For example, consider the reaction of ethyl lithium with water.
 
CH3 CH2 Li + H +
O H CH3CH2 H + Li OH
ethane
The products are strongly favoured in the reaction. Ethane is a very weak acid (Ka of about 10–50). So the reverse
reaction (abstraction of a proton from ethane by lithium hydroxide) is unlikely. When ethyl lithium is added to water
ethane is instantly bubbled to the surface.
Why would we want to add an organometallic reagent to water? This is method for reducing an alkyl halide to an alkane.
OH
+ H2O
R X + Mg R MgX R H + Mg
ether
X
H2O
R X + 2Li R Li + LiX R H + LiOH
The overall reaction is a reduction because it replaces the electronegative halogen atom with hydrogen atom. In
particular, this reaction provides a way to “label” a compound with deuterium at any position where a halogen to present.

The Grignard reagent is a very powerful base as it contains a carbanion. Thus, it is not possible to

prepare a Grignard reagent from an organic compound that contains an acidic hydrogen atom.

For example, prepare Grignard reagent from a compound containing an –OH group, an –NH – group, an –SH group, a –
COOH group, or an –SO3H group. If we were to attempt to prepare a Grignard reagent from an organic alkyl halide
containing any of these groups, the formation of the Grignard reagent would simply fail to take place because the
Grignard reagent that would be produced on the 1st step, it would immediately react with an acidic group.
Since Grignard reagents are powerful nucleophiles, we cannot prepare a Grignard reagent from any organic halide
that contains a carbonyl, epoxy, nitro or cyano (–CN) group. Compounds containing the following groups can not
be used to prepare the Grignard reagent, –OH, –NH2, –NHR, –COOH, –SO3H, –SH, –C  C – H,
O O O O

CH, C R, C OR, C NH2 , – NO2, – C  N.

Planning a Grignard Synthesis


By using Grignard synthesis skilfully one can synthesize almost any alcohol. 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 special attention to the groups attached to the carbon atom bearing the –OH
group. Many time 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 compounds. Let us consider the following example.
Suppose we want to prepare the following compound.
CH3
H3C
CH
H3C
OH
2,3-dimethyl-2-phenyl butane-2-ol
This means we can synthesize this compound in several different ways.
(i) We can use a ketone with isopropyl group and methyl group (3-methyl 2 butanon) and allow to react with
phenyl magnesium bromide.
C6 H5 O
H3C
H3C CH C CH3  CH C CH3 + C6H5MgBr
CH3 OH H3C

(ii) We can use a ketone containing an propyl group and a phenyl group (propyl phenyl ketone) and allow it to
react with methyl magnesium bromide
C6 H 5 C 6 H5
H3C CH C CH3  CH3 CH C + CH3MgBr
CH3 OH CH3 O
(iii) We can use an ester of benzoic acid and allow it to react with one equivalent of methyl magnesium
bromide and one equivalent propyl magnesium bromide
C 6 H5
C 6H 5
H3C CH C CH3  + (CH3) 2CH Mg Br + CH3MgBr
CH3 OH O OCH 3

Illustration 2: Using an alcohol of no more than four carbon atoms as your only starting material, outline
a synthesis of A:
O
H3C CH CH2 C CH CH3
CH3 CH3
(A)

CH3 CH3
Solution: H3C  H3C CH2MgBr
CH3  + CH3
OH
CH3 O CH3 O
(C)
(B)

Synthesis
H3C O H3C
(1) Et2O CH3 H2CrO4
CH CH2 MgBr + H C CH CH3 CH CH2 CH HC (A)
H3C (2) H2O H3C CH3
CH3 OH

Illustration 3: Starting with bromobenzene and any other needed reagents, outline a synthesis of the
following ketone.
O

CH3

Solution:

Reaction of Grignard reagent to ,  unsaturated aldehydes and ketones


When Grignard reagents (RMgX) react  -  unsaturated aldehydes and ketones, they do so in two ways. They
may react by a simple addition that is one in which the nucleophile adds across the double bond of the carbonyl
groups; or they may react by a conjugate addition. These two processes resemble the 1, 2 and the 1, 4 addition
reaction of conjugated dienes.
O OMgBr
H3C CH CH C CH3 + CH3MgBr H3C CH CH C CH3
CH3 simple or 1, 4 addition
product (18%)
+
OMgBr
H3C CH CH C CH3
CH3
conjugate addition or 1, 2
addition product (72%)
10 – ALCOHOL, ETHER & PHENOL – JEE
When organolithium compounds made to undergo the afore-said reaction with conjugated aldehyde or ketone, they
yield 1, 2 addition product in much higher percentage (almost exclusively) as compared with the Grignard
reagents.

Alcohols by Reduction of Carbonyl Compounds


Primary and Secondary alcohols can be synthesized by reduction of variety of compounds that contain the
carbonyl group several examples are shown here,
O O R
[H] [H]
R CH2 OH C CH2 OH
C
 R R' R'
R H 1 alcohol
acetaldehyde ketone 2  alcohol
O O
[H] [H]
C R CH2 OH R CH2 OH + R'OH
C
R OH R OR'
Acid 1 alcohol ester 1 alcohol

The two most useful hydride reagents, sodium borohydride (NaBH4) and Lithium aluminium hydride (LiAlH4) reduce
carboxyl groups in excellent yields. These reagents are called complex hydrides because they do not have a
+ – + –
simple hydride structure such as Na H or Li H . Instead, their hydrogen atoms, bearing partial negative charges,
are covalently bonded to boron and aluminum atoms. This arrangement makes the hydride a better nucleophile
while reducing its basicity.
H H
+ +
Na H B H Li H Al H
H H
Of these reducing agents, lithium aluminium hydride (LAH) is much stronger and more difficult to work with LAH as
reacts explosively with water and alcohols, liberating hydrogen gas and sometimes initiates fires. Sodium
boronhydride reacts slowly with alcohols and with water as long as the pH is high (basic). Sodium borohydride is a
convenient and highly selective reducing agent.

(i) Uses of Sodium Borohydride


Sodium borohydride (NaBH4) reduces aldehydes to primary alcohols, and ketones to secondary alcohols. The
reactions take place in a wide variety of solvent including alcohols, ethers, and water. The yields are generally
excellent.

O O OH
CH2OH NaBH4
H NaBH4 H3C C CH2 CH3 H3C CH CH2 CH3
CH3OH
butan-2-one butan-2-ol
cyclohexanecarbaldehyde (100%)

Sodium borohydride is selective; it usually does not react with carbonyl groups that are less reactive than ketones
and aldehydes. For example, carboxylic acids and esters are unreactive towards borohydric reaction. Sodium
borohydride can reduce a ketone or an aldehyde in the presence of an acid or ester.
O
O
NaBH4 HO CH2 C OCH3
O CH2 C OCH3
H H

(ii) Uses of Lithium Aluminium Hydride


Lithium aluminium hydride (LiAlH4, abbreviated as LAH) is a much stronger reagent than sodium borohydride. It
easily reduces ketones and aldehydes and also the less reactive carboxyl groups e.g. those in acids, esters, and
other acid derivatives.
 LAH reduces ketones to secondary alcohols and aldehydes, acids and esters to primary alcohols.

LAH reduces both keto and ester group in a compound like;


O
O CH2 C OCH3

O
(1) LiAlH 4/ether HO CH2 CH2 OH
O CH2 C OCH3
(2) H2O+
H H

Catalytic hydrogenation of ketones and aldehydes.


O OH
Raney
C + H2 CH
Ni
The conversion of acetone or an aldehyde to an alcohol involves adding two hydrogen atoms across the C = O
group. This addition can be accomplished by catalytic hydrogenation commonly using Raney Nickel as the
catalyst. If any unsaturation (double bond) present in addition to aldehyde or ketone will get reduced by this
reagent.

O CH3
CH3 H3C CH2 CH2
Raney OH
H2C CH2 CH2 C CH2
Ni CH3
CH3 H 2,2-dimethylpentan-1-ol
2,2-dimethyl-4-pentenal

NaBH4

CH3
H2C CH2 CH2 C CH2 OH
CH3
2,2-dimethylpent-4-en-1-ol

From Amines
When 1 aliphatic amines are treated with nitrous acid, the –NH2 group gets converted into –OH group and
alcohols are formed. Nitrous acid is very unstable and usually it is prepared by treating aqueous and dilute sodium
nitrite solution with dilute acids, HCl, H2SO4, acetic acid etc.
R NH2 + HNO2 R OH + N2 + H2O
12 – ALCOHOL, ETHER & PHENOL – JEE
+
NaNO2 + HCl HNO2 + NaCl; HO N O+ H

H
+ R NH2 +
R N N O NO H O N O
H H

+
H
+
H N2 +
R N N OH R N N OH 2 R
H2O:
+
H +
R OH R O H
H
However, carbonium ions being the intermediates of the reaction, several side products and rearranged products
are obtained as shown below.
HX+NaNO2 +
CH3CH2CH2 NH2 CH3CH2CH2 N N

H
H3C CH2 + H2O
+ H3C CH CH2 CH3 CH2 CH2 OH
H
CH2
+
H2C CH3CH2CH2X CH3 CH CH2
H2O + X
CH3CH(OH)CH3 CH3 CH CH3 CH3 CH(X)CH3
SN
Thus, in this reaction, isomeric alcohols are obtained through the nucleophilic attack by water on the carbonium
ions; they may undergo the nucleophilic attack by the X– to form inorganic esters. Isomeric alkenes also form
through the E1 reaction of the carbonium ions; alkenes and esters are the side products of the reaction. Besides
these, a small amount of cycloalkene is also obtained.

Illustration 4: Identify A, B and C


MgBr +
H3O H2 / Ni
RCO2ET + (CH2) 5 followed + A B C
MgBr H3O
MgBr CH2 CH2 R
followed by
Solution: RCO2ET + (CH2)5 + CH2 C
MgBr H3O CH2 CH2 OH
+
H3O

H2 / Ni
R R

O
(i) Et 2O
Illustration 5: Me CH CH2 + EtMgBr + ?
(ii) H
Solution: Addition EtMgBr will only be governed by the steric effects.
O OH
(i) EtMgBr
Me CH CH2 Me CH CH2 CH2 CH3 + Me CH CH2OH
+
3 2 1 (ii) H (1)
Et
(minor)
If the Et attack at 1-carbon atom, this will experience a smaller steric effects. Therefore product (1)
will be major product.

Illustration 6: Convert CHD2I into CHD2CH2OH. What alkenes would you expect to get by the acid
catalyzed dehydration of the alcohol? Explain.
Solution: CHD2I 
(C H ) O
 CHD2MgI
Mg in
2 5 2

(i) CH2O
(ii)H O 
 D2CH – CH2OH
3

Dehydration of this alcohol can occur in two ways:


 
D2C  CH2 (i)H
(ii) H2O
 D2CH – CH2OH 
(i)H
(ii) H2O
 DCH  CHD
(A) (B)
Since deuterium shows a kinetic isotope effect therefore removal of deuterium occur more slowly.
Thus (A) will be the major product and (B) will be the minor product.
14 – ALCOHOL, ETHER & PHENOL – JEE

Quiz – 1
1. What is the correct IUPAC name of the following structure?
OH
C CH3
CH3

(A) 2–phenylpropanol (B) 2–(2–hydroxy propyl)benzene


(C) 2–phenylpropan–2–ol (D) 2–(2–propyl alcohol)benzene
2. What is the correct IUPAC name of the following structure?
OH

H3C CH3
Br
(A) 3–bromo–6–heptanol (B) 5–bromo–2–hydroxy heptane
(C) 3–bromo–6–hydroxy heptane (D) 5–bromoheptan–2–ol
3. What is the correct IUPAC name of the following structure?
OH

CH3
(A) 4–methylcyclohex–3–en–1–ol (B) 1–methylcyclohexen–4–ol
(C) 4–hydroxy–1–methylcyclohexene (D) 3–hydroxy–6–methylcyclohexene
4. Which of the following is / are isomer/s of methoxyethane
O
(A) CH3 – CH2 – CH = O (B)

(C) CH3 – CH2 – CH2 – OH (D) CH 3 CH CH 2 CH 3


OH
5. Among the two conformers of ethane–1, 2–diol(ethylene glycol) the conformer which is more stable is:
OH OH
H OH H H

H H H H

H OH
(I) (II)
(A) conformer (II) is more stable than (I) because of least Vander Waal repulsion
(B) conformer (I) is more stable than (II) because of minimum torsional repulsion
(C) conformer (I) is more stable than (II) because of minimum Vander Waal repulsion
(D) conformer (I) is more stable than (II) because of stronger intramolecular hydrogen bonding
6. Which of the following compound does not form a stable Grignard reagent?
CH2Br
Mg / Et 2O Mg
(A) CH3 – CH2 – O – CH2 – Br 
 (B)  
Et2 O

N(CH3)2
Br
Br
Mg / Et 2O Mg / Et O
(C) 
 (D) 
2

COOH Me
7. In the given series of reactions ‘X’ can be:
CH3

Mg / Et O H CH COOC H
C5H10Br2 
2

 C5H10Mg2Br2 
3 2 5
  + C2H5OH
(i) ( X) (ii) (iii)
H3C
OH
CH3
(A) H3C CH CH2 CH2 CH2 (B) H2C CH2 CH CH2
MgBr MgBr MgBr MgBr
(C) H2C (CH2)3 CH2 (D) H2C CH2 CH CH2 CH3
CH3 MgBr MgBr MgBr

8. The product of the following organic reaction is:


O +
Mg H 2O / H
H C (CH2)3 CH2 Br 'P'
Et2O
OH O
O O
H C (CH2)3 CH2 H H C (CH2)3 CH2 OH

(A) (B) (C) (D)

CH3
+
(i) BH 3 / THF H 2O / H
9. C CH3 C CH CH2 A
(ii) H 2O2 / OH
CH3
(i) Hg(OCOCH 3)2, CH3COOH

(ii) NaBH 4, OH

B
CH3 CH3

A H3C C CH CH3 B H3C C CH CH3


(A)
CH3 OH OH CH3

CH3

C H3C C CH CH2 CH3

OH
CH3 CH3

A H3C C CH CH3 B H3C C CH CH3


(B)
OH CH3 CH3 OH

CH3

C H3C C CH2 CH2 OH

CH3
16 – ALCOHOL, ETHER & PHENOL – JEE
CH3 CH3

A H3C C CH2 CH2 OH B H3C C CH CH3


(C)
CH3 OH CH3

CH3

C H3C C CH CH3

CH3 OH
CH3 CH3

A H3C C CH2 CH2 OH B H3C C CH CH3


(D)
CH3 OH CH3

CH3

C H2C C CH2 CH2 CH3

10. C3H7 OH  C2H5MgBr  A  B


The hydrocarbon obtained in the above reaction
(A) can be hydrated to alcohol
(B) is a product of Kolbe's decarboxylation of CH3 COONa
(C) can be obtained when ethanal reacts with Clemmensen’s reagent
(D) is a dehydration product of C2H5 OH

11. Compound C3H5 Cl  X  reacts with magnesium in presence of dry ether to form compound (A). (A) on reaction
with formaldehyde forms (B) which when heated in presence of HF gives 1, 3-butadiene. Compound C3H5 Cl
is:
Cl CH3  C  CH2
CH3  CH  CH  Cl CH2  CH  CH2  Cl |
Cl
(A) (B) (C) (D)

12. When toluene is treated with Cl2 at high temperature without the use of any catalyst, the product obtained is
(A) o-chloro toluene (B) m-chlorotoluene
(C) mixture of ortho & para-chlorotoluene (D) benzyl chloride

13. The treatment of CH3OH with CH3MgI release 2.24 mL of a gas at STP. The mass of CH3OH added is
(A) 1.49 mg (B) 2.98 mg
(C) 3.2 mg (D) 4.47 mg

14. What is the product of the following reaction?

(A) (B) (C) (D)


15. What is the product of the following reaction?
H3C CH3 OsO4, (CH3)3COOH
C C -
H (CH3) 3COH,OH
H
(A) CH3CH = O
(B) Racemic (2R, 3R) and (2S, 3S)-2, 3-butanediol
(C) meso-2, 3-butanediol
(D) cis-2,3-eproxybutane

16. What of the following syntheses gives-3-methyl-1-hexanol?


O
Mg 1)
(A) 2-bromopentane
+
diethyl ether 2) H
Mg 1) H2C=O
(B) 2-bromohexane
+
diethyl ether 2) H
Mg 1) CH3CH=O
(C) 3-bromopentane
+
diethyl ether 2) H
O

Mg 1) CH3 C CH3
(D) 1-bromobutane
+
diethyl ether 2) H

17. Which compound below is the product expected from the following reaction?

(A) (B)

(C) (D)

18. What is the product from the following reaction?


O
CH2MgBr + ?

(A) O (B) CH3 CHCH2


CH2
OH
CH2OH
(C) (D)
OHCH2CH2CH2
CH3CH2
18 – ALCOHOL, ETHER & PHENOL – JEE
19. What is the product of the following reaction sequence?
K Cr O ,H SO CH OH( XS) (1) 2CH MgBr
CH3CH2CH2CH2OH 
2 2 7 2
HO
4

 
3
 
3
 
2 H (cat) (2)H3O

(A) (B) (C) (D)


2
20. Which of the following reagents would carry out the following transformation? (D = H, the mass-2-isotope
of hydrogen)
O OH
CCH3 ?
CCH3
D
(A) NaBD4 in CH3OH (B) NaBD4 in CH3OD
(C) LiAIH4’ then D2O (D) LiAID4’ then D2O

(1) BH3 THF


Y'
(2) H2O 2 / OH
EtO Dil. H 2SO 4
21. CH2 CH2 CH CH3 CH2 CH CH CH3 Y
(2)
(1) Hg(OAc)2 / H 2O
Br Ph Ph Y''
(X) (2) NaBH4
The incorrect statement about, Y, Y', Y'' is / are:
(A) Y' has one chiral centre
(B) Y'' has two chiral centres
(C) Y is optically active
(D) It the reactant is optically pure then Y'' is a mixture of two diastereomers

CH3 18
CH3ONa H 2O
22. B CH3 C CH2 A
CH3OH +
O H
A and B are
CH3 CH3 CH3 CH3
(A) CH3 CCH2 , CH3 C CH2 (B) CH3 C CH2 , CH3 C CH2
18OH OH OH OCH3 OH OH OH OCH3
18
CH3 CH3 CH3 CH3
(C) CH3 C CH2 , CH3 C CH2 (D) CH3 C CH2 , CH3 C CH2
OH OH OH OH 18OH OH OCH3OH
18 18 18 18

23. Rate of acidic hydration of


CH CH2 CH CHCH3 C CH2

CH3
I II III
will be in order:
(A) I < II < III (B) I < III < II
(C) II < I < III (D) III < II < I
Aq. KOH solution
(P)

24. (R)-2-Chlorobutane

(Q)
C2H5OH + H2O
Which of the product will be optically inactive?
(A) P (B) Q
(C) Both (D) None

25. Match the following


Reaction Alcohol as Product

O
MgBr
(A) + CH3 C C2 H5 (I)

O
C C 2 H5
(B) (II)
+ C2H5MgBr

OH
C C2 H5
(C) (III)
C2 H5

CH3
(D) (IV) CH3 C OH

CH3

OH
CH2 CH3 C C2H5
(E) O + CH3MgX (V)
CH2

CH3
(F) C O + CH3MgI (VI) CH3CH2CH2OH
CH3
(A) A-IV, B-III, C-I, D-II, E-VI, F-V (B) A-V, B-VI, C-II, D-I, E-III, F-IV
(C) A-V, B-IV, C-I, D-II, E-VI, F-III (D) A-V, B-III, C-II, D-I, E-VI, F-IV
20 – ALCOHOL, ETHER & PHENOL – JEE

4. Physical Properties
(1) Lower alcohols are colourless, toxic liquids. They have a characteristic smell.
(2) Boiling points of alcohols increase regularly with the increase in the number of carbon atoms.

BOILING POINTS OF SOME ALCOHOLS


Name Structure No. of Carbons bpC
Methanol CH3OH 1 64.5
Ethanol CH3CH2OH 2 78.3
1-Propanol CH3CH2CH2OH 3 97.0
1-Butanol CH3(CH2)2CH2OH 4 118.0
1-Pentanol CH3(CH2)3CH2OH 5 138.0

(3) Among isomeric alcohols, as branching increases the boiling points decrease. For example,
OH CH3
CH3CH2CH2 CH2 OH CH3 CHCH2CH3 CH3 C OH
1-Butanol 2-Butanol CH3
bp 118 C bp 99 C 2-Methyl-2-propanol
bp 83 C
(4) Boiling points of alcohols are much higher than those of the corresponding alkanes.

Explanation
The O–H bond of alcohols is highly polar because oxygen is electronegative. The oxygen carries a partial negative
charge (–). The hydrogen carries a partial positive charge (+). The polarity of the O–H bond gives rise to forces
of attraction between a partially positive hydrogen in one alcohol molecule and partially negative oxygen in another
alcohol molecule. These forces of attraction are referred to as Hydrogen Bonding. The reason that alcohols have
higher boiling points is that a great deal of energy (in the form of heat) is required to overcome these attractive
forces.
Alkanes, which have no –OH group, do not undergo hydrogen bonding. Therefore, their boiling points are low.
Hydrogen bond Hydrogen bond
           
H O H O H O H O H O H O
R R R H R H
Hydrogen bonding in alcohol molecules Hydrogen bonding between alcohol
and water molecules
(5) Lower alcohols (C1 to C3) are completely soluble in water. As we go higher in the series, the water
solubility falls rapidly.

A compound that forms hydrogen bonds between its own molecules can also form hydrogen bonds with water. These
alcohol-water hydrogen bonds are the cause of high solubility of lower alcohols in water.

 In higher alcohols, the nonpolar alkyl group becomes more important. They have less tendency to
form hydrogen bonds with water and hence are less soluble.
–1
(6) IR Spectrum: Alcohols show a strong broad band in the 3200-3600 cm region due to O–H stretching.
They show a broad band in the 1000–1200 cm–1 region due to C–O stretching.

Illustration 7: Explain the following:


(a) ROH’s with three or fewer C’s are H2O soluble; those with five or more C’s are
insoluble, and those with four C’s are marginally soluble.
(b) When equal volumes of ethanol and water are mixed, the total volume is less than
the sum of the two individual volumes.
(c) Propanol (MW = 60) has a higher point than butane (MW = 58)
Solution: (a) The water solubility of alcohols is attributed to intermolecular H– bonding with H2O. As
the molecular weights of the alcohols increase, their solubility in water decreases,
because greater carbon content makes the alcohol less hydrophilic. Conversely, their
solubility in hydrocarbon solvents increases.
(b) H– bonding between ethanol and water to water molecules.
(c) Alcohol molecules attract each other by relatively strong H– bonds and somewhat
weaker dipole – dipole interactions, resulting in a higher bp. Only weaker Vander Waals
attractive forces must be overcome to vaporize the hydrocarbon.

5. Chemical Properties
Alcohols are reactive compounds. They are attacked by polar or ionic reagents. 
This is because: H
(1) The C–O and O–H bonds of alcohols are polar since oxygen is highly
electronegative.
(2) The oxygen atom of alcohols is an electron-rich centre because it has 
C O
two unshared pairs of electrons.
Polar
REACTION DUE TO C – O BOND bonds
Polarization of the C – O bond makes the carbon atom partially positive so this

carbon would be susceptible to nucleophilic attack and if it were not for the fact that OH is a strong base and they are

very poor leaving group. Protonation of the alcohol converts a poor leaving group (OH ) into a good one. It also makes
the carbon atom even more positive (because OH2 is more electron withdrawing than –OH) and therefore, even
more susceptible to nucleophilic attack. Now, nucleophilic substitution reactions are possible in alcohols according to the
given mechanism.

Step 1:
H

C O H +H A C O+ H+ A

Alcohol Strong Protonated alcohol


Acid
Step 2:

H H

Nu + C O+ H Nu C + O H

Protonated alcohol

(I) Reaction with Hydrogen Halides


When alcohols react with a hydrogen halide, substitution takes place producing an alkyl halide and water.
R – OH + HX   R – X + H2O
The order of reactivity of the hydrogen halides is HI > HBr > HCl > HF (HF is generally unreactive), and the order of
reactivity of alcohols is 3 > 2 > 1 > methyl.

Mechanism
Secondary, tertiary, allylic and benzylic alcohols appear to react by a mechanism that involves the formation of a
carbocation and that now is recognized as an SN1 reaction.

CH3 CH3 H
+ Fast +
Step 1: CH3 C OH + H O H CH3 C O H + O H

CH3 H CH3 H
22 – ALCOHOL, ETHER & PHENOL – JEE
CH3 H CH3 H
Step 2: + Slow +
CH3 C O H CH3 C + O H
CH3 CH3
CH3
CH3
Step 3: + - Fast
CH3 C + Cl CH3 C Cl
CH3 CH3
For example,
Conc. HBr
CH3 CH CH3 CH3 CH CH3
or ( NaBr + H2SO4)
OH Br
Isopropyl alcohol Isopropyl bromide

HCl / ZnCl2
CH3CH2CH2CH2 CH2 OH CH3CH2CH2CH2 CH2 Cl

n-pentyl alcohol n-pentyl chloride
CH3 CH3
Conc. HCl
CH3 C CH3 CH3 C CH3
OH Cl
tert-Butyl alcohol tert-Butyl chloride
In SN1 reactions of alcohol, R may rearrange. Primary alcohols and methanol apparently react through a
mechanism that we recognize as an SN2 type.
H
H

X + C O+ H X C + O H

Illustration 8: Secondary and tertiary alcohol can be converted into the corresponding alkyl halide
with concentrated HBr or HI, but to convert primary alcohol into corresponding primary
alkyl chloride, ZnCl2 is needed. Why?
Solution: We have discussed earlier that the reactivity to primary alcohol is least among the different
types of alcohols namely primary, secondary and tertiary. Thus, the protonation of –OH group
is not sufficient enough to increase the polarity of C – O bond to the level of being attacked by
the nucleophile. Lewis acid like ZnCl2 is used as catalyst to increase the polarity of the C – O
bond, leading to the formation of carbonium ion.
-
+ Cl +
R CH2 O + ZnCl 2 R CH2 O ZnCl 2 R CH2 O ZnCl
H H H

-
R CH2 Cl Cl +
R CH2 + ZnCl(OH)
SN1
(it can rearrange)

Zn(OH)Cl+ HCl ZnCl2 + H2O

(II) Reaction with PX3 and PX5


Alcohols react with PX3 and PX5 to yield alkyl halides (PX3 = PBr3, PI3).
3ROH + PBr3 
 3RBr + H3PO3
(1 or 2)
ROH + PCl5 
 RCl + POCl3 + HCl
For example,
CH3 CH3
PBr 3
CH3CH2 CH CH2 OH CH3CH2 CH CH2 Br
PBr 3
C 6H 5 CH CH3 C 6H 5 CH CH3
OH Br

Mechanism of reaction with PX3


PX3 + 3R – OH 
 (RO)3P + 3HX
Trialkoxyl phosphite
(RO)3P: + HX 
 (RO)3P – H +

H H
SN2
Step 1: X + R O P OR RX + O P OR
OR OR
H H
Step 2: SN2 -
X + R O P OR RX + RO P O
O O
H H
- Proton transfer
O P OR + HX HO P O R + X
O
O

H
- SN2
RX + HO P O
O
H H
Step 3: -
HO P O + HX HO P OH + X
O O
Straight chain primary alcohols react with PX3 to give unrearranged alkyl halides, since reaction is purely SN2.

Mechanism of reaction with PX5


Cl Cl
Cl
Cl
R O + Cl P +
R O P
H Cl Cl Cl
H Cl
N
+
H

SN2
- Cl
Cl Cl
R O P R Cl + POCl 3
Cl
Cl

(III) Reaction with SOCl2


R – OH + SOCl2   R – Cl + SO2 + HCl
Mechanism
Thionyl chloride first forms alkyl chlorosulphite as intermediate which undergo intermolecular substitution in the
absence of base, but it can undergo SN2 reaction in the presence of base like pyridine. For example,
24 – ALCOHOL, ETHER & PHENOL – JEE

CH2
R O
R CH2 OH + Cl S O + HCl
Cl Cl S
O

R CH2 Cl + SO2
(retention of
configuration)
In the presence of pyridine,
CH2
R O
R CH2OH + Cl S O + HCl
Cl Cl S
O

N + HCl + NH Cl-

-
+ NH Cl + R CH2 OSOCl
SN2
O

+ N H+ R CH2 Cl + S
-
O Cl
Proton exchange
O
N + RCH2Cl + S
HO Cl
Chlorosulphurous acid

REACTIONS DUE TO CLEAVAGE OF O – H BOND


(I) Reaction with alkali metals
Active metals (Na, K, Mg, Al, etc) when treated with alcohols give hydrogen gas. In this reaction, order of reactivity of
alcohols is CH3OH > 1 > 2 > 3. This reaction shows the acidic character of alcohols.
RO – H + Na   RO Na + ½ H2– +

In –OH group of alcohols, oxygen is more electronegative than hydrogen, this results in polarization of O – H bond
due to which acidic nature arises in alcohols.
Reaction of active metals with alcohols shows that alcohols are acidic in nature with the possible exception of methanol;
they are weaker acids than water, but stronger acids than acetylene or ammonia.

RO Na
+
+ HOH   NaOH + ROH
Stronger Stronger Weaker Weaker
base acid base acid
The order of acidity for some compounds is
H2O > ROH > HC  CH > NH3 > RH
The order of basicity is R > NH2 > HC  C > OR < OH
– – – –

The above order is based on reactions of alcohols with other species.


(II) Esterification
The third type of replacement of hydroxylic hydrogen by an acyl group is the formation of an ester. An acyl group
(RCO –) is derived commonly from acid chloride, acid anhydride or a carboxylic acid. They react with an alcohol to
form ester.
O O
R O H + Cl C R R O C R + HCl
R O H+ R CO
O R O CO R + RCOOH
R CO
R O H + HO OCR R O CO R + H2O

The reaction of an alcohol with carboxylic acid called “esterification reaction” is acid–catalysed

reaction and reversible.
R – COOH + ROH R – COOR + H2O

In order to have maximum yield of ester, the equilibrium has to be shifted to the right hand side. This can be done
in two ways
(a) by using one of the reactants in excess
(b) by removing the water formed as quickly as possible. Here highly volatile ester is removed by constant
distillation.
Mechanism of this reaction have been dealt in the topic “Carboxylic acids and their derivatives”

Illustration 9: (i) *CH3 – COOH 


Me3 C* -OH
H+
 (A)
(ii) CH3 – CO – O
18
–H 
CH3OH
H+
 (B)
14
* indicates C isotope.
Solution: (i) *CH3COOH 
Me3C*-OH
H+
CH3 – CO – OC*Me3 (A)

(ii) CH3 – CO – O
18
–H 
CH3OH
H+
 CH3 – CO – O – CH3 (B)

(III) Formation of ether


In the above reactions, we have seen that the hydroxylic hydrogen is replaced by active metal. Another
replacement reaction involves the formation of ether.
R–O–H 
- H
+R
 R–O–R
R1 – OH + R2 – X   R1 – O – R2 + HX
The direct reaction is not possible because OH is a poor leaving group (stronger base). Alkoxides are strong
nucleophiles and easily undergo nucleophilic substitution reaction with alkyl halides by SN2 mechanism, forming
ether by Williamson’s etherification process.
-
R O +R X R O R +X
Thus sodium ethoxide forms ethyl methyl ether with methyl bromide.
-
C2H5O + CH3 Br C2 H5 O CH3 + Br

(IV) Reaction with RMgX


Alcohol is a weak acid. A Grignard reagent, quite a strong base, is able to abstract hydrogen from (OH) group of an alcohol.
CH3 – O – H + CH3MgI 
 CH3 – OMgI + CH4

6. Miscellaneous Reactions
(I) Dehydration of Alcohols
Alcohols may be dehydrated to alkenes which may be done
1. By heating the alcohols with conc. H2SO4 or
2. By heating the alcohols with phosphoric acid at 200 – 250C or
3. By passing the vapours of alcohol over alumina at 350 – 400C.
The ease of dehydration of alcohols is tertiary > secondary > primary.
(a) Primary alcohols are dehydrated by conc. sulphuric acid at about 170C and alkenes are obtained.
H2SO4 /170 C
CH3CH2 OH CH2 CH2 + H2O
or Al2O3 / 350 C
26 – ALCOHOL, ETHER & PHENOL – JEE
(b) Secondary alcohols are dehydrated easily to alkenes. Secondary alcohols are dehydrated according to
Saytzeff’s rule (more substituted alkene is more stable).

OH H2SO 4 / More than 170 C


CH3 CH2 CH CH3 CH3 CH CH CH3
or Al2O3 / 250 C
2-Butanol But-2-ene(Major)
+
CH3 CH2 CH CH2
But-1-ene (Minor)
OH
H , 
PhCH2 CH CH3 PhCH CHCH3 + PhCH2 CH CH2
1-phenyl-2-propanol 1-Phenylprop-1-ene 3-Phenylprop-1-ene
(Major) (Minor)
CH3 CH3 CH3
OH
Al 2O 3
+
260
(Minor) (Major)
(c) On dehydration, tertiary alcohols also give alkenes. In dehydration of 3 alcohols two alkenes are obtained,
of which the more substituted alkene is major product.
OH 
H2SO4 / less than 170 C
CH3 CH2 C CH3 CH3 CH C CH3 + CH3 CH2 C CH2
Al2O3 /150 C
CH3 CH3 CH3
(2-Methyl but-2-ene) (2-Methyl but-1-ene)
(Major) (Minor)
(II) Oxidation
Primary, secondary and tertiary alcohols behave differently towards oxidising agents. Of the many reagents that
can be used to oxidise alcohols, we can consider only the most common of these like KMnO4 and K2Cr2O7.
(a) Primary Alcohols: These are easily oxidised first to aldehydes and then to carboxylic acids, both having the
same number of carbon atoms as the parent alcohol.
RCH2OH 
K 2Cr2O7
H2SO 4
 R – CHO 
K 2Cr2O7
H2SO 4
 RCOOH
RCH2OH 
Alkaline KMnO 4
Purple
 (RCOO– K+)
(Solution in H2O)
(Brown colour due to formation of MnO2)
(b) Secondary Alcohols: Secondary alcohols are oxidised to ketones by chromic acid, aq. K2Cr2O7, CrO3 in
glacial acetic acid, CrO3 in pyridine etc.

 If there is a possibility to form different types of acid after the oxidation of ketones, lowest
molecular weight carboxylic acid will be produced.
CH3CH2COCH3 
Acid KMnO4
 2CH3COOH
 O
CH3COCH2CH2CH3   CH3COOH + CH3CH2COOH
OH
Alk. KMnO4 Acidic
CH3 CH CH3 CH3 CO CH3 CH3COOH + HCOOH
KMnO4
Isopropyl alcohol Acetone Acetic Formic
Acid acid
OH
Alk. KMnO4 Acid
CH3 CH2 CH CH3 CH3CH2 CO CH3 2CH3COOH
KMnO4
2-Butanol Butan-2-one Acetic acid
(c) Tertiary Alcohols: Tertiary alcohols are not oxidised at all under alkaline conditions. If acid is present,
they are rapidly dehydrated to alkenes, which are then oxidised. Tertiary alcohols are most difficult to
oxidise among the three classes of alcohols.

(III) Iodoform Test: An alcohol containing CH3CH(OH) –group or CH3OC group when treated with I2/OH– or
(NaOI), yellow precipitate of iodoform is obtained. This is known as iodoform test.
OH
I 2/OH
R CH CH3 RCOO + CHI3
Main steps involved in the mechanism are given below.
OH O
(a) I 2 (Oxidation)
R CH CH3 R C CH3
O O
(b) I 2 (Iodination)
R C CH3 R C CI 3
O O
OH (NaOH) -
R C CI3 R C O + CHI 3
(c)
Iodoform
(yello precipitate)
Aldehydes or ketones having at least three  hydrogen (in case of alcohol,  hydrogen) give this test only when
treated with iodine and alkali solution.
For example,
OH
CH3 I 2/OH CH3
CH3 CH CH CHI3 + CH COO
CH3 (yellow ppt.) CH3
Although iodoform reaction is a test for CH3CO– or CH3CH(OH)– group but the compounds containing more acidic
hydrogen than that of the terminal hydrogens will not give positive iodoform test. Thus CH3 – COCH2 – COOEt will
not give positive iodoform test because, it contain active methylene group which is not terminal.
CH3CO – CH2 – COOEt   CH3 – CO – CI2 – COOEt
2 I
NaOH
(No iodoform)
But -keto acids give iodoform test because they first decarboxylate to form acetone, which give positive iodoform
test.
O O
OH
CH3 C CH2 C O H CH3 C CH3 + CO2
O
CH3 – CO – CH2CH2COOH under the cold conditions will give positive iodoform test, but under the heated
conditions, it will not respond positive by to iodoform test because of the formation of Angelica lactone.
O O CH3
HO CH3
C CH3 C CH3 
OH O
O H2O
-
C OH C O
O O O
O (Angelica
lactone)

7. Test for –OH Group


The following three tests may be used to detect the presence of an –OH group in organic compounds. For these tests,
take the liquid compound or a solution of the solid compound in an inert solvent such as dry ether or benzene.

1. Add to it small pieces of Sodium metal. If bubbles of hydrogen gas are given off, the compound contains an
–OH group.
2R OH 2Na 2R ONa H2
28 – ALCOHOL, ETHER & PHENOL – JEE
2. Add to it Phosphorus pentachloride. If the mixture becomes warm with evolution of HCl gas, the given
compound contains an –OH group.
R OH PCI5 R Cl POCl 3 HCl
3. Add Acetyl chloride or Benzoyl chloride to the substance. The separation of an oily layer of the ester and
evolution of HCl gas indicates the presence of an –OH group. It may be noted that if the compound was
taken in an organic solvent, the oily ester may dissolve in it and thus limiting the test to the evolution of HCl
gas only.

8. Methods of Distinction Between Alcohols


Primary, secondary and tertiary alcohols can be distinguished by any one of the following methods, viz,
(I) Oxidation method (II) Luca’s test (III) Victor Meyer’s test

(I) Oxidation method: Primary alcohols on oxidation give aldehydes and then acids, both containing
same number of carbon atoms as the original alcohol. Secondary alcohol on oxidation give. Ketones which either
do not undergo further oxidation or break down, under drastic conditions, to give a mixture of acids, each
containing fewer carbon atoms than the original alcohol. Tertiary alcohols, on vigorous treatment with acidic
oxidizing agents, give a mixture of ketones and acids, each containing fewer carbon atoms than the original
alcohol.
[O]
R  CH2OH  Cr2 O 72 3+
 RCH  O
-Cr

 Cr2 O72 [O]


O

R C
OH
OH O
[O] [O]
CH3 CH CH3   CH3 C CH3   CH3COOH  HCOOH
CH3 CH3
H
CH3  [O] [O]
CH3 C  CH3 C CH2   CH COCH  HCHO   CH3CO2H  2HCO2H
H O 3 3
OH 2
(II) Luca’s Test: It consists in treating the alcohols with Luca’s reagent, that is a mixture of conc. Hydrochloric
acid and anhydrous zinc chloride. Appearance of cloudiness in the reaction mixture will indicate the formation of the alkyl
chloride. A tertiary alcohol reacts immediately, a secondary alcohol reacts within five minutes and a primary alcohol does
not react appreciably at room temperature. This is because of the fact that in the presence of anhydrous ZnCl2 , the
reaction proceeds by SN 1 mechanism in which carbocations are formed.

 More stable is the carbocation formed, more easily the reaction occurs and thus the cloudiness.
anhydrous ZnCl
R3C  OH  HCl 
2  R C  Cl  H O
3 2

tert alkyl chloride


(immediate precipitation)

anhydrous ZnCl
R2CH  OH  HCl 
2  R CH  Cl  H O
2 2

sec alkyl chloride


(precipitation after 5mins.)

anhydrous ZnCl
RCH2OH  HCl 
2  RCH  Cl  H O
2 2

(No precipitation at)


room temperature)
Benzyl alcohol is although a primary alcohol gives immediate turbidity just like tertiary alcohols. This is due to the
fact that benzyl carbocation is extensively resonance stabilized. Allyl alcohols also reacts immediately with Luca’s
reagent, but turbidity does not appear, as allyl chloride formed is soluble in Luca’s reagent.

CH3 HCl
Illustration 10: (i)
OH
CH3

HCl
(ii) CH CH OH

CH3

Solution: (i)
CH2Cl
Cl
(ii)
CH CH CH3
CH3

Illustration 11: Convert


H3C CH3
(i) n CH 3CH 2CH2OH C C
H
H
O O OH OH
(ii)

(iii) n – CH3CH2CH2CH2OH 
 MeC  C – Me

Solution: (i) H3C nCH3CH2CH2MgBrH3O


+

OH PCC
H3C CHO

CH3
conc.
CH3 H3C
H3C H2SO4
OH
(ii) O O OH
CH3MgBr(excess) OH

(iii) OH CH2
conc.
n H3C
H2SO 4
Hg(OAC) 2
H2O
NaBH 4
CH3
CH3 conc.
H3C
H3C H2SO 4
Br 2 OH

Br CH3
CH3 NaNH2 H3C
H3C
Br
30 – ALCOHOL, ETHER & PHENOL – JEE

Quiz – 2
1. Identity the correct order of boiling points of the following compounds:
CH3CH2CH2CH2OH, CH3CH2CH2CHO, CH3CH2CH2COOH
1 2 3
(A) 1>2>3 (B) 3>1>2 (C) 1>3>2 (D) 3>2>1
OH OH
2. H2SO 4
'A'
Conc.
The organic product ‘A’ is:
O O O

(A) (B) (C) (D)


( + ) 2-butanol

NaH TsCl

3.
CH3Cl CH3OH

A A'
The relation between organic product A and A are:
(A) same organic product (B) pair of enantiomer
(C) pair of diastiomers (D) pair of structural isomers

Y X
4.
HO OH HO OH
Select X and Y out of
I : MnO4 / OH II : HCO3H
X Y
(A) I II
(B) II I
(C) I I
(D) II II
Me Me Me Me
OH OH
5. HO H H Cl H OH + HO H
(H) (I)
Et Et Et Et
Step (I) and (II) are
(A) both SN1 (B) both SN2
(C) (I) : SN1, (II) : SN2 (D) (I) : SN2, (II) : SN1
CH3
6. H C alkaline KMnO 4
A
H C
CH3
Which is true about this reaction?
(A) A is meso 1, 2-butan-di-ol formed by syn addition
(B) A is meso 1, 2-butan-di-ol formed by anti addition
(C) A is a racemic mixture of d and 1, 1, 2-butan-di-ol formed by anti-addition
(D) A is a racemic mixture of d and 1, 1, 2-butan-di-ol formed by syn-addition
7. Ethyl acetate is treated with double the molar quantity of C2H5MgBr and the reaction mixture is hydrolysed
with water. The product is:
H5 C 2 O
H5 C2 OH H3C
H5C2 OH OH O
H 5 C2 H3C C2 H5
H 5C 2
(A) (B) (C) (D)
O H
COOH
8. Identify the strongest Hydrogen bonding in the compound

H O O
O H O H O H
O H C C O H
O O O H O
C C H O
C H
O H O O
(A) (B) (C) (D)
CH3
H2SO 4 Conc.
9. H3C C CH2 OH 'A'

CH3
The rearranged organic product ‘A’ is:
CH3
(A) CH3 C CH CH3 (B) CH2 C CH2 CH3
CH3
CH3
(C) H3C C CH2 CH3 (D) H3C CH CH CH2
OH CH3

CH3 CH3
HCl
10. Cl C CH CH OCH3 'A'
Conc.
CH3 OH
The organic product ‘A’ is:
CH3 CH3 CH3
Cl C CH CH OCH3
(A)
Cl
CH3 CH3
Cl C CH2 C OCH3
(B)
CH3 Cl
CH3 CH3
(C) Cl C CH CH Cl
CH3 OH
Cl CH3
(D) H3C C CH CH OCH3
CH3

Cl
32 – ALCOHOL, ETHER & PHENOL – JEE
11. The products X and Y of the following reaction can be
H
H
Cl NaOH 
 (X)   (Y)
Br (1 eq.)
D
D
OH OH H
D Cl
Cl
(A) X is H (B) X is H
D D
H D
OH
OH
H H H
(C) Y is (D) Y is
O H D
D D D

Mg / (C 2H5) 2O O CH
SOCl 2
12. A B C
+
H
D
HO
H
Identify the compound C.

D
D HO
D CH OH D
H
H CH C
Cl
H OH Ph PhH

(A) (B) (C) (D)

13. Compound ‘P’ (C10H12O) evolves H2 with Na metal. It reacts with Br2 / CCl4 to give ‘Q’ (C10H12Br2O). With I2 /
NaOH it forms iodoform and an acid ‘R’ (C9H8O2). ‘P’ has geometrical and optical isomers. The structure of ‘P’
should be:
H
O HO C CH3
CH CH C CH3
(A) (B)

HC CH2
OH
CH CH CH CH3 CH CH CH3
(C) OH (D)

+
14. H
A + B
O CH2OH
Major product (A) in the above reaction is

(A) (B) (C) (D)


O O O O CH3

15. How many alkenes would be formed in the following reaction?


CH3

H3C C CH CH2 CH3 OH


E1
CH3 Br
(A) one (B) two (C) three (D) four
16. The reaction: F3 C  CHCl2 
base
 F2C  CCl2 ; Will occur via
(A) SN1 (B) E1
(C) E1Cb (D) E2

17. The treatment of a compound with HIO4 produces CH3CHO and CH3CH2CHO. The probable compound is
(A) CH3CH = CH2CH3 (B) CH3CH(OH)CH(OH)CH2CH3
(C) CH3CH = CHCH = CH2 (D) CH3CH(OH)CH2CHO

18. Which can be cleaved by HIO4?


O O OH O
(A) CH3CH2 CCH2 C CH3 (B) CH3CH C CH2CH3
O O
(C) (D) CH3C CH2 CHCH2 C CH3
HO OH OH

19. Dehydration of the alcohols

will be in order
(A) IV > III > II > I (B) I > II > III > IV
(C) IV > II > III > I (D) II > IV > I > III

+
H 3O HBr Mg / ether HCHO HI
20. CH3MgBr + A B C D E
+
H3 O
O
E is:

(A) (B)
I
H3C CH2I CH3
CH3
I
(C) (D)
I
CH3

9. Ethers
Ethers are a class of compounds which contain an oxygen atom bonded to two alkyl groups. They are further
designated as Symmetrical Ethers or Unsymmetrical Ethers according as the two alkyl groups attached to the
oxygen atom are same or different.
R O R R O R'
Symmetrical ether Unsymmetrical ether
The functional group of ethers is C–O–C

 Ethers may be considered as derivatives of water in which both hydrogen atoms have been
replaced by alkyl groups. They may also be considered to be derivatives of alcohols in which the
hydroxyl hydrogen has been replaced by an alkyl group.
H O H R O R' R O H
Water Ether Alcohol
34 – ALCOHOL, ETHER & PHENOL – JEE

10. Structure
3 3 3
In ethers, the oxygen atom is sp hybridized. The two C–O  bonds are formed by sp –sp overlap. The two
3
unshared pairs of electrons on oxygen occupy sp hybrid orbitals. The C–O–C angle is very close to 110.
Unshared
electron pairs
R in sp3 orbitals
R

sp
3
-s
p
3
 110 O
O

-s 3
p
sp 3
R

R
Orbital structure of an ether molecule.

11. Nomenclature
(1) Common System: The two alkyl groups attached to oxygen are named in alphabetic order and the word
ether is added. If the two alkyl groups are same (R–O–R), the prefix di- is used. Although the prefix di- is
often omitted, it is better to include it to avoid confusion.
CH3CH2–O–CH2CH3 CH3–O–CH2CH3
Diethyl ether Ethyl methyl ether
(Ethyl ether)

(2) IUPAC system: In this system, ethers are named as Alkoxyalkanes. The larger of the alkyl groups is
considered to be the alkane. The name of the alkane is prefixed by the name of the alkoxy group and position
number.
Ethoxy
Methoxy

CH3
OCH2CH3
CH3O CH CH3
CH3 CH CH2 CH3
2-Methoxypropane 2-Ethoxybutane
Names of some common alkoxy groups (RO–) are given below:
CH3O– Methoxy CH3CH2CH2O– n-Propoxy
CH3CH2O– Ethoxy (CH3)2CHO– Isopropoxy

12. Methods of Preparation


Ethers are obtained by the following methods:
(1) Dehydration of Alcohols: Symmetrical ethers are prepared by heating an excess of alcohol with
concentrated H2SO4 at 140C.
H2SO4
R OH + H OR R O R + H2O
Alcohol (2 molecules) 140C
Ether
H2SO 4
C2H5 OH + H OC 2H5 C2H5 O C2H5 + H2O
140C
Ethanol Ethanol Diethyl ether
The starting alcohol in the above reaction must be primary and the reaction temperature must be kept at
140C. This is because alkene formation is favoured at higher temperatures and with secondary or tertiary
alcohols.
MECHANISM
The acid-catalysed dehydration of ethanol to give diethyl ether involves four steps:
Step 1: Protonation of ethanol.

+
+
CH3CH2 O H + H CH3CH2 O H
H
Ethanol (from H2SO4) Protonated alcohol

Step 2: Elimination of H2O molecule to form a stable carbonium ion.


+ +
CH3CH2 O H CH3CH2 + H2O
H Carbonium ion

Step 3: Carbonium ion attacks another molecule to give an oxonium ion.


H
+ +
CH3CH2 + CH3CH2 O H CH3CH2 O CH2CH3
Ethanol Oxonium ion

Step 4: Oxonium ion loses a proton to yield diethyl ether.


H
+ +
CH3CH2 O CH2CH3 CH3CH2 O CH2CH3 + H
Diethyl ether

(2) Williamson Ether Synthesis: This involves the treatment of a sodium alkoxide with an alkyl halide.
Sodium alkoxides are obtained by treating alcohols with sodium metal (ROH + Na 
 RONa + H2).
Both symmetrical and unsymmetrical ethers can be made by this method.
+
R ONa + R' X R O R' + NaX
Sod alkoxide Alkyl halide Ether
+
CH3 ONa + C2H5 Br CH3 O C2H5 + NaBr
Sod methoxide Bromoethane Ethyl methyl ether
+
C2H5 ONa + C2H5 Br C2 H5 O C2H5 + NaBr
Sod ethoxide Bromoethane Diethyl ether

Mechanism
The Williamson synthesis involves a displacement of halide ion from an alkyl halide by an alkoxide. It follows S N2
mechanism.

+ SN2
CH3CH2O Na + CH3CH2 Br CH3CH2 O CH2CH3 + NaBr

Sodium ethoxide Bromoethane Diethyl ether

The alkyl halide used in this reaction must be primary. If secondary or tertiary alkyl halides are used, the reaction
leads mainly to alkene formation.
36 – ALCOHOL, ETHER & PHENOL – JEE
(3) Action of diazomethane on Alcohols: Methyl ethers can be obtained by treatment of primary or
secondary alcohols with diazomethane. Fluoroboric acid (HBF4) is used as a catalyst.

HBF4
R – O – H + CH2N2  R – O – CH3 + N2
CH3CH2 – O – H + CH2N2   CH3CH2 – O – CH3 + N2
HBF4

Ethyl alcohol Ethyl methyl ether

(4) Addition of alcohols to alkenes: Addition is catalysed by acid


CH3 CH3
CH3OH
C CH2 CH3 COCH3
H2SO 4
CH3
CH3
Intermediate is carbocation. There can be 1,2-hydride or 1,2–methyl shift to attain greater stability of
carbocation.

+ CH3CH2 + ROH CH3CH2OR


CH2 CH2 + H CH3CH2
nucleophile
H
CH3 CH3
+
CH3CH2OR + CH3CH2OR H
H CH3CH2CH CH2 + CH3CH2OH CH3CCH2CH3

H OCH2CH3

Illustration 12: Reaction of ethanol with sulphuric acid under suitable conditions can lead to the
formation of:
Solution:
C2H5OH 
H SO
2 4
C H HSO
2 5 4
383 (Ethyl hydrogen sulphate)


H2SO4
 CH3CH2OCH2CH3
413K (Diethyl ether )


H2SO4
 CH2  CH2
443K (Ethylene)

13. Physical Properties


1. Dimethyl ether and ethyl methyl ether are gases. All others are colourless liquids with pleasant odours.
2. Lower ethers are highly volatile and very flammable.
3. Boiling points of ethers show a gradual increase with the increase in molecular weight.

BOILING POINTS OF SOME ETHERS

Compound Formula bp(C)


Dimethyl ether CH3OCH3 – 25
Ethyl methyl ether CH3OC2H5
Diethyl ether C2H5OC2H5 35
Diisopropyl ether (CH3)2CHOCH(CH3)2 91
4. Ethers have lower boiling points than isomeric alcohols. This is because ether molecules cannot form hydrogen
bonds with each other as they have no –OH groups. The boiling points of ethers are close to the boiling points
to alkanes. For example, diethyl ether (MW = 74) boils at 35C; n-pentane (MW = 72) boils at 36C.
5. Ethers are slightly soluble in water. This is because they can form hydrogen bonds with water.
–1
6. IR Spectrum. Ethers show a strong, broad band due to C–O stretching in the 1060–1300 cm range.

14. Chemical Properties


Ethers are comparatively unreactive compounds. The ether linkage is quite stable towards bases, oxidizing agents
and reducing agents. As far as the ether linkage is concerned, ethers undergo just one kind of reaction, cleavage
of C – O – C bond.
(I) Salt formation: Though ethers are neutral compound but these form oxonium salts with inorganic acids.
H5 C 2 H5 C 2

+ O
O H Cl H Cl

H 5C 2 H 5C 2

Diethylether hydrochloride
This reaction is due to lone pair of electron on oxygen of ether functional group.
(II) Cleavage by acids
HX
R O R'HX R X R' OH R' X H 2O
Reactivity of HX: HI > HBr > HCl
Cleavage takes place only under vigorous conditions i.e. concentrated acids (usually HI or HBr) and at
high temperatures.
A dialkyl ether yields initially an alkyl halide and an alcohol. The alcohol may react further to form a second
mole of alkyl halide. For example,
(CH3 )2 CH  O  CH(CH3 )2 48%HBr
 2(CH3 )2 CH  Br
130 140 C

Diisopropyl ether Isopropylbromide

Mechanism
The oxygen of atom an ether is basic, like the oxygen of an alcohol. The initial reaction between an ether and an
acid is undoubtedly formation of the protonated ether. Cleavage then involves nucleophilic attack by halide ion on
this protonated ether, with displacement of the weakly basic alcohol molecule.
H SN2
R O R' HX R O R' X R X R'OH
or SN1

Protonated Weak base
ether (good leaving group)
Such a reaction occurs much more readily than displacement of the strongly basic alkoxide ion from the neutral
ether.
R O R' X R X R'O
Strong base
(poor leaving group)

Reaction of a protonated ether with halide ion, like the corresponding reaction of a protonated alcohol, can proceed
either by an SN 1 mechanism,
H
slow + + fast
(1) R O R' R R'OH (2) R X R X

or by an SN 2, mechanism.
38 – ALCOHOL, ETHER & PHENOL – JEE
H
H
 
R O R' X X R O R' R X R'OH

Whether the reaction proceeds in the direction of SN 1 or SN 2, depends on the conditions employed and the
structure of the ether. As one might expect, a primary alkyl group tends to undergo SN 2 displacement, whereas a
tertiary alkyl group tends to undergo SN 1 displacement.

 In ether of the type R – O – R’ where R are 1 alkyl group, lower alkyl halides are formed. If one of the alkyl
group is 3, SN1 reaction takes place and an alkyl halide having the 3 alkyl group is formed.

Action of HI
(a) At room temperature

CH3 O C 2 H5 CH3I C 2H5OH

H I

CH3  O  C(CH3 )3  HI CH3 OH  (CH3 )3 C  I


(b) At 100 C (excess of HI)
I H

CH3 O C2 H5 CH3I C 2H5I H 2O

H I
Thus the metameric ethers can be easily identified by the cleavage with HI.

(III) Action of PCl5 or SOCl2


Cl PCl3 Cl
+ 2C2H2Cl + POCl 3
C 2 H5 O C 2 H5

CH3 O CH2CH2CH3
CH3Cl CH3CH2CH2Cl SO2
Cl SO Cl

Thus the reaction of PCl5 or SOCl2 can be used to identify the metameric ethers.

15. Cyclic Ethers


If oxygen atom is a part of hydrocarbon ring, ethers are called as cyclic ethers. Cyclic ethers have the general
formula (CH2 )n O, where n = 2,3,4,5 and 6.
O
O
O O O

n=2 n=3 n=4 n=5 n=6


Oxirane Oxetane Oxolane Oxane Oxepane
Three membered cyclic ethers are considered as oxides of the parent alkene. This type of ring is also called as epoxide.
CH2 CH2 CH2 CH CH2 CH3
O O
ethylene oxide 1,2-Butene oxide
(Epoxyethane) (1,2-Epoxybutane)
16. Preparation of Epoxides
Three membered cyclic ethers can be prepared either by an internal SN 2 reaction of a chlorohydrin or by
epoxidation

Cl CH2 CH2 OH OH Cl  Cl
CH2 CH2   CH2 CH2

O O

Peroxyacids, RCOOH will oxidize alkenes to epoxides. For example, trans 2–butene in the presence of
peroxyacids, adds an oxygen atom across the double bond to form an epoxide. This reaction is called epoxidation.
O O

C C
R H
R

O H O

 O
O
H O RCO2H
H H
Me Me Me
Me Me
Me
H
H H

17. Reactions of Epoxides


The highly strained three–membered ring in epoxides makes them much more reactive towards nucleophilic
substitution than other ethers.
 Acid catalysis assists epoxide ring opening by providing a better leaving group (an alcohol) at the
carbon atom undergoing nucleophilic attack. This catalysis is especially important if the
nucleophile is a weak nucleophile such as water or an alcohol.

Mechanism of Acid–Catalyzed Ring Opening


+
C C H O H C C H2O

O H O
H
Epoxide Protonated epoxide
H

O H O
H 2O +
C C O H C C C C H O H
+
O H O O H H
H H
Protonated Protonated Glycol
epoxide glycol
Epoxides can also undergo base –catalyzed ring opening. Such reactions do not occur with other ethers, but they
are possible with epoxides (because of ring strain), provided that the attacking nucleophile is also a strong base
such as an alkoxide ion or hydroxide ion.
Mechanism of Base–Catalyzed Ring Opening

H OR
R O C C RO C C O  RO 
C C OH RO

Strong O
An alkoxide ion
nucleophile Epoxide
40 – ALCOHOL, ETHER & PHENOL – JEE
If the epoxide is unsymmetrical, in base–catalyzed ring opening, attack by the alkoxide ion occur primarily at the
less substituted carbon atom since the reaction follows pure SN2 pathway. For example, methyloxirane reacts with
an alkoxide ion mainly at its primary carbon atom.

CH3CH2O H2 C CHCH3 CH3CH2OCH2 CHCH3 


CH3 CH2 OH

O O

Methyloxirane CH3CH2OCH2 CHCH3+ CH3CH2O

OH
1-Ethoxy-2-propanol

In the acid–catalyzed ring opening of an unsymmetrical epoxide, the nucleophile attacks primarily at the more
substituted carbon atom. For example,
CH3 CH3
H
CH3OH CH3 C CH2  CH3 C CH2OH
O OCH3
The reason is that in the protonated unsymmetrical epoxide, the oxygen is positively charged (electron deficient),
which compensates for its deficiency by pulling electron density more effectively from highly substituted carbon, as
a positive charge (developed due to electron pulling by O+) on this carbon would be stabilized more by the +I effect
of alkyl groups. Now, when the nucleophile attacks, it will be attracted more towards positively charged atom,
thereby attacking at highly substituted carbon atom. The reaction takes place by an SN2 pathway as the
nucleophile attacks from the position opposite to that of the leaving group but the transition state has considerable
SN1 characters due to positively charged carbon. It happens because the bond breaking exceeds bond making, as
the nucleophile is a poor one while the leaving group is a good one.
H

H3C H3C H3C O CH3 OCH3


  H3C
CH2  C H
H
CH2 

CH3OH
C C CH2   C CH2
H3C H3C H3C  H3C
O O
O OH
H H
Transition
state
Alkyl magnesium bromide also reacts with ethylene oxide by SN2 reaction in which the alkyl group of the Grignard
reagent acts as the nucleophile while MgBr coordinates with oxygen.

R Mg Br + CH2 CH2 R CH2 CH2O


+
(MgBr)

O
H3O
  R CH2 CH2 OH + MgBr(OH)
This reaction is a sort of intermolecular Williamson synthesis. It serves as a method for extending the R group of
organometallic by CH2  CH2  OH. So, this reaction is used to ascend the homologous series by two carbon
atoms in a single step.

18. Aryl Ethers


Phenols are converted into alkyl aryl ethers by reaction in alkaline solution with alkyl halides. For the preparation of aryl
methyl ethers, dimethyl sulfate, (CH3 )2 SO4 is frequently used instead of the more expensive methyl halides. For example,

+
OH O Na OCH3

NaOH
 + CH3 Br + NaBr

Anisole
OH + OCH 3
O Na
NaOH + CH3OSO 2ONa
 + CH3 OSO 2OCH 3

Anisole

The latter method is a better method to prepare anisole because with respect to Br, methylsulphonates (mesylate)
are better leaving group, which causes faster substitutions. Secondly, with respect to CH3Br , dimethyl sulphate is
less expensive, so cost effectiveness is also there.

+
OH O Na CH2 Br
NaOH O CH2
 + + NaBr

Benzyl phenyl ether

+
OH O Na OC2H5

NaOH + C2H5OSO 2ONa


 + C2 H5 OSO 2OC2H5

Phenetole

The mechanism of the above reaction can be outlined as follows. In alkaline solutions, phenol exist as phenoxide ion
which acts as a nucleophilic reagent and attacks the alkyl halide (or the dialkyl sulfate) and displaces halide ion (or
sulfate ion).
ArO + R X ArO R+ X
ArO + CH 3 OSO 3CH3 ArO CH3+ OSO 3CH3

The above reaction is familiar Williamson synthesis which can even be used for the preparation of unsymmetrical
ethers like alkyl aryl ethers.
Since phenoxides are prepared from phenols, and since alkyl halides are conveniently prepared from alcohols,
alkyl aryl ethers (like dialkyl ethers) are ultimately synthesized from two hydroxy compounds.
Aryl halides cannot be used in the Williamson synthesis because of their low reactivity towards nucleophilic
substitution. For the preparation of any alkyl aryl ether, there can be two combinations of reactants, but one
combination can usually be rejected out of hand. For example,
+
CH3CH2CH2Br + Na O Feasible

CH3CH2CH2 O

 CH3CH2O
+
Na + Br Not Feasible
42 – ALCOHOL, ETHER & PHENOL – JEE

Quiz – 3
1. Product of the following reaction is:
Conc. H 2SO 4
CH2 CH2 'P'
140 C
OH OH
O

(A) CH2 = CH2 (B) (C) O O (D) CH3 C H


O

2. Which among the following reaction process is ideal way to prepare tertbutyl methyl ether and why?
CH3
H3C C Cl
CH3 CH3 CH3
Na CH3Cl Na CH3
(i) H3C C OH H3C C OCH 3 (ii) CH3OH H3C C OCH3
CH3 CH3 CH3
(A) (i) process is ideal because tert butoxide is better nucleophile then methoxide ion
(B) (ii) process is better process as methoxide ion is an better nucleophile than that butoxide
(C) (i) process is a better process as there is no chance of elimination
(D) (ii) process is a better process as there is no chance of elimination

HI
3. Ph – O – CH3  A+B
excess
Products ‘A’ and ‘B’ are respectively
(A) PhOH, CH3OH (B) Ph – I, CH3I
(C) Ph – OH, CH3I (D) Ph – I, CH3OH

+
H2O/H
4. O CH3

OH

O + CH3OH OH , CH3OH O + CH3OH


O CH3

(A) (B) (C) (D)

+
H / CH 3OH
5. 'A'
O
The organic product ‘A’ is:

OCH3
(A) (B) (C) (D)
OH O
O O CH2 OH O OCH3 H

CH3
6. HI
H3C C OCH3 A
Conc.
CH3
HI / DMF

B
Organic products ‘A’ and ‘B’ are respectively
CH3 CH3
(A) H3C C I + CH3OH ; H3C C I + CH3OH
CH3 CH3
CH3 CH3
H3C C OH + CH3I ; H3C C I + CH3OH
(B)
CH3 CH3
CH3 CH3

H3C C I + CH3OH ; H3C C OH + CH3I


(C)
CH3 CH3
CH3 CH3

H3C C OH + CH3I ; H3C C OH + CH3I


(D)
CH3 CH3

7. The ether can be synthesized by bimolecular dehydration as shown to the right. Which of the following
compounds is most likely to be a significant byproduct in such a sythesis?
CH3 CH3 CH3
H2SO 4
2 HC OH HC O CH
heat
CH3 CH3 CH3
CH3 CH3 CH3 CH3
H3C C CH3 H2C CH
HC O O CH HC O C OH
O CH3
CH3 CH3 CH3 CH3
(A) (B) (C) (D)

8. Which of the following ethers could not be synthesized by a Williamson synthesis?


CH3 CH3
H3C–O–CH2CH3 CH3CH2 O O HC O CH
CH3 CH3
(A) (B) (C) (D)

9. What reagent would you use to effect the transformation shown to the right?
H H
?
H3C C CH2 Br H3C C CH2
OH O
(A) H2SO4 (B) NaBH4
(C) KOH (D) Na2CrO4

10. What is the product of the following reaction?


HBr (xs)

O
Br Br
(A) (B)
O Br
Br OH
(C) (D)
OH Br
44 – ALCOHOL, ETHER & PHENOL – JEE
11. What is the product of the following reaction?
O
H CH2CH3 CH
+ 3 COOH
H3C H
H CH2CH3 H H
(A) + enantiomer (B)
+ enantiomer
H3C O H H3C O CH2CH3
HO CH2CH3 HO H
H CH2CH3 + enantiomer
(C) + enantiomer (D)
H H OH
H3C OH H3C

12. The reaction shown below can be described as an:


OH O
NaOH, H 2O
H3C CH CH2Br H3C CH CH2
(A) acid-base reaction followed by an intramolecular Williamson ether synthesis
(B) acid-base reaction followed by an intramolecular SN1 reaction
(C) E2 reaction followed by an addition reaction to a double bond
(D) SN2 reaction followed by an intramolecular Williamson ether synthesis

13. What is the product of the following reaction?


O
NaOH, H 2 O
H
CH3
(A) (S)-1, 2-propanediol (B) Racemic mixture of 1, 2-propanediol
(C) (R)-1, 2-propanediol (D) 1, 3-propanediol

H2O / H
14. N CH CH2 + CH3 CH CH2 'P'
O
OH
OH
CH3 CH CH2 OH
N CH2 CH2 CH2 CH CH3 O
CH2 CHO
OH
CH3
(A) (B) (C) (D)

O
(i) NaOH / CaO
15. CH3 CH CH C OH A + CO2
(ii) H2 O / H
O
The product of the reaction
(A) CH3 CH CH3 (B) CH3 CH CH2
OH O
O
(C) CH3 CH2 CHO (D) CH3 C CH3
19. Phenols
Compounds that have a hydroxyl group directly attached to a benzene ring are called phenols. Thus phenol is the
specific name for hydroxy benzene and it is the general name for the family of compounds derived from hydroxy
benzene. Phenols do posses like aliphatic alcohols an –OH group but it is attached to a sp 2 hybridised carbon
atom, while in aliphatic alcohols the –OH group is attached to sp 3 hybridised carbon atom.

 A phenolic OH is characterized by appearance of violet, red or green colouration with neutral FeCl 3
solution.

20. Nomenclature
IUPAC names of few of the phenols are mentioned below. The names given in the parenthesis are common names.
OH
OH OH OH
CH3

CH3 CH3
Phenol o-methylphenol m-methylphenol p-methylphenol
(Carbolic acid) (o-cresol) (m-cresol) (p-cresol)

OH
OH OH
OH

OH OH
o-Dihydroxybenzene m-dihydroxybenzene p-dihydroxybenzene
(Catechol) (Resorcinol) (Hydroquinone)
OH
8 1 8 1 OH
7 2
7 2
6 3 6 3
5 4 5 4
1-Naphthol 2-Naphthol
(  -naphthol) (  -naphthol)
While naming substituted phenols, groups like CO2H,CHO,SO3H have priority over OH while for others OH have
priority over them. For example,
HO HO HO
1 NO2 1
2 2
3 3
4 4 CH3
OCCH3 HC= CH2 H2C(CH2)4CH3
2-nitro-4-acetyl phenol p-vinyl phenol 4-n-hexyl resorcinol

HO C O 2H CHO
1 OH
1 1 OH
2 2
2
3
3 C6 H5
CH2CH = CH2
m-allyl phenol 2-hydroxy-3-phenyl o-hydroxy
benzoic acid benzaldehyde
(Salicyaldehyde)
46 – ALCOHOL, ETHER & PHENOL – JEE

21. Methods of Preparation


(I) Hydrolysis of chlorobenzene
In this process chlorobenzene is heated at 350C under high pressure with aqueous NaOH. The reaction produces
C6H5 ONa  (sodium phenoxide) which on acidification yields phenol. This reaction is called as Dow’s process.
+ HO
Cl O Na

NaOH / 350 C
  
acidification


(HighPr essure) H

 Although aryl halides such as chlorobenzene and bromobenzene do not react with most
nucleophiles under ordinary circumstances, they do react under highly forcing conditions. These
reactions takes place through an elimination-addition mechanism that involves the formation of an
interesting intermediate called benzyne or dehydrobenzene.

(II) Nucleophilic Substitution of Aryl Halides by SN Ar Mechanism


When aryl halides containing strongly electron withdrawing groups at ortho and para positions are treated with
nucleophile like OH then substitution takes place to give corresponding phenols.
Cl OH
Cl OH NO2 NO2
NO2 NO2

NaOH


NaOH
 150C,5 atm
300 C,10 atm NO2 NO2

(III) Alkali fusion of Sodium Benzene Sulphonate


In this method sodium benzene sulphonate is melted (fused) with sodium hydroxide to produce. Sodium phenoxide
which after acidification gives phenol.
+ +
SO 3 Na O Na OH
H
NaOH / 350C
 
Na2SO3

This procedure can be used for the preparation of p-cresol as


CH3 CH3 CH3

NaOH(72%)KOH(28%) 
  
H
300  330 C
+ +
SO 3 Na O Na OH
(p-Methyl phenol) or p-cresol

(IV) From Cumene Hydroperoxide


Following steps takes place in the formation of phenol from cumene.
(a) Preparation of Cumene: Cumene is prepared by the Friedel–Craft alkylation of benzene with propene in the
presence of H3PO4 at 250C .
CH(CH3) 2

250 C
+ CH2 = CHCH 3 
H PO

3 4

Isopropyl benzene
(Cumene)
(b) Oxidation of Cumene: Cumene is oxidised to cumene hydroperoxide by the oxygen of air at 95  135C .
CH3 CH3
95 135C
C 6H 5 CH + O 2  C 6H 5 C O OH

CH3 CH3
Cumene hydroperoxide
The hydroperoxide results from a free radical substitution at the active benzylic carbon.
(c) Rearrangement to give phenol: When cumene hydroperoxide is treated with sulphuric acid, it undergoes a
hydrolytic rearrangement to yield phenol and acetone in quantitative yield. That is why, this method is used for the
commercial preparation of phenol as well as acetone.
CH3
H ,H O
2  C6H5OH + CH 3COCH3
C 6H 5 C O OH 
CH3 Phenol Acetone
This acid catalysed rearrangement requires the intermediacy of a positively charged oxygen atom at which phenyl anion
migrates. This leads to the generation of a carbocation, at which H2O (nucleophile) attacks, giving a hemiacetal which
decomposes in the presence of acid to give phenol and acetone. The steps involved in the mechanism are
H3C Ph H3C Ph
H
H3C Ph
H  H O: ~Ph:
C O O H  C O O H 
2 
C O  
H3C H3C H3C
oxonium ion Intermediate
H3C H3C OH 2 H3C H3C
OH
H O 
H H C = O PhOH
C O Ph 
2  C O Ph   C 
H3C H3C H3C OPh H3C
carbocation Acetone Phenol
Hemiacetal

H3C
C = O Ph
H3C
The migration of Ph group may be synchronous with the loss of H2O molecule. It should be noted that the Ph
migrates in preference to Me because Ph has greater migratory aptitude than that of Me.

(V) Hydrolysis of Diazonium Salts: When a diazonium sulphate solution is steam–distilled, phenol is
produced.
N+2HSO 4 OH

+ H 2O distill
  + N2 + H 2SO4

(VI) By Distillation of Phenolic Acid: When phenolic acids are heated with soda lime, decarboxylation takes
place producing phenols.

OH O Na
+
OH
COOH

NaOH(CaO),
  
H
Na2CO3

22. Physical Properties


1. Most pure phenols are colourless liquids or solids, although they are often found to contain a red tint owing
to the presence of oxidation products.
2. Phenols have a characteristic ‘Carbolic’ odour, which in case of phenol itself is highly toxic.
3. The boiling points of phenols are higher than aliphatic alcohols of comparable molecular weights. This is
due to stronger intermolecular hydrogen bonding in phenols relative to alcohols.
Compound MW bpC
Phenol 94 182
Cyclohexanol 100 162
1-Hexanol 102 157
48 – ALCOHOL, ETHER & PHENOL – JEE
The introduction of a hydroxy group into an already substituted aromatic ring, especially in the para position to methyl,
halogen, or nitro group, produces a marked increase in the boiling point. The effect on nitrophenol is shown below:
Compound mpC bpC
Phenol 42 181
Nitrobenzene 5.5 210
o-Nitrophenol 45 217
m-Nitrophenol 96 –
p-Nitrophenol 114 245
The greater volatility of the ortho isomer is due to intramolecular hydrogen bonding whereas the higher boiling
point of the para isomer is due to intermolecular hydrogen bonding.
O
H
+
N O
O
Intramolecular hydrogen
bonding in o-Nitrophenol

H O O
+
O N O +
N
O H O

Intermolecular hydrogen bonding in p-Nitrophenol

Also, p-nitrophenol is more soluble in water than o-nitrophenol. This is because p-nitrophenol can associate with
itself and also with water molecules. o-Nitrophenol cannot form intermolecular hydrogen bonds.
H

O H O O
+ +
N H O N
O
O
Intermolecular hydrogen bonds between
water and p-Nitrophenol
The low solubility and higher volatility of o-nitrophenol enables it to be easily separated from p-nitrophenol by
steam distillation.

23. Chemical Properties


Phenol exhibits two types of chemical reactions:
(1) Due to –OH group (2) Due to aromatic ring.

REACTIONS DUE TO –OH GROUP


(I) Acidic character
Although phenols are structurally similar to alcohols, they are much stronger acids than alcohols. The acidity of
phenol owe itself primarily to an electrical charge distribution in phenol that causes the –OH oxygen to be more
positive, therefore the proton is held less strongly and the conjugate base (phenoxide ion) formed by the loss of
proton is stabilized by resonance more than that of phenol.

(a) Acidity of phenol and alcohol: When phenol is dissolved in water, a proton is released and phenoxide ion is
formed. In the resonating structures of phenol, there is charge distribution created in the uncharged phenol.
O H O H O H O H O H
This means that such charged contributing structures are of higher energy, less contributing to the stability and
hence phenol reacts with water producing more stable phenoxide ion.
+
PhOH PhO + H
The phenoxide ion has a number of resonating structures.
O O O O O

The negative charge is dispersed over the whole phenoxide ion. More dispersal means greater stability. So
phenoxide ion is more stabilized than that of phenol since it involves greater charge dispersal. So the equilibrium
lies more in the forward direction making it considerably acidic. When alcohol is dissolved in water, alkoxide ion

and H are formed.
+
R O H R O +H
This alkoxide cannot be stabilized like that of phenoxide, so it ionizes only to a very small extent. As
phenoxide ion is stabilized more, so corresponding phenols are more acidic than alcohols.

(b) Influence of substituents on acidity of phenol: There are two types of substituents–(i) electron withdrawing
and (ii) electron releasing. Let us consider the effect of these on the acidity of phenol one by one.

(i) When electron withdrawing groups are present in phenol: When electron withdrawing groups like –
NO2 group, Cl atom, CN group etc. are present irrespective of their position in phenol, acidity increases. Let us take
the case of o–nitro, m–nitro and p–nitro phenols. In o–and p–nitrophenols, the negative charge of the phenoxide ion
is dispersed more by – NO2 group through resonance (–R ). More dispersal means greater stability which increases
the acidity. o–Nitrophenol is less acidic than p–nitrophenol due to intramolecular hydrogen bonding.

O O
O

N (o-Nitrophenol)
O
o
p-Nitrophenol
m–Nitrophenol is a weak acid than the o– or p–isomer. This is because in m–isomer there is no resonance effect of
– NO2 group but only inductive effect (–I) operates. So the order of acidity of nitrophenols should be
Phenol < m–nitrophenol < o–nitrophenol < p–nitrophenol
When two or more –NO2 groups are present, acidity increases greatly. In 2,4,6–trinitrophenol, acidity is comparable to
mineral acids. It dissolves in NaHCO3 (phenol does not). On this account, it is also called picric acid.
+
OH O Na
O2N O 2N NO 2
NO 2
+ NaHCO3 + H2CO3
NO 2 NO 2
(Picric acid) (Soluble)
Chlorophenols are stronger acids than phenols but weaker than nitrophenols. This is because in the chlorophenols there
is no resonance effect. Only inductive effect operates which make the chlorophenoxide ions stable. We know that
inductive effect fades away as the distance increases from the source. So the order of acidity of chlorophenols is.
Phenol < p–chlorophenol < m–chlorophenol < o–chlorophenol
50 – ALCOHOL, ETHER & PHENOL – JEE
(ii) When electron releasing group is present in phenol: When electron releasing group like alkyl group is
present, they by virtue of electron releasing effect intensify the negative charge of phenoxide ion, thus destablises
the ion and thereby decreases the acid strength. Thus o–, m and p–cresols are all weaker acids than phenols.
(II) Reactions related to acidic character
1. Because phenols are more acidic than water, the following reaction goes essentially to completion and
produces water–soluble sodium phenoxide. So, phenols are soluble in aq. NaOH solution.
PhOH + NaOH H2 O
 PhO Na  + H2 O
Stronger Stronger Weaker Weaker
acid base base acid
2. Most of the phenols are not soluble in aqueous sodium bicarbonate since H2CO3 is a stronger acid than
most phenols.

PhOH + NaHCO3
 PhONa  +
H2CO3
Weak acid strong acid
3. The fact that phenols dissolve in aqueous sodium hydroxide, whereas most alcohols with six carbon atoms
or more do not, gives us a convenient means for distinguishing and separating phenols from most
alcohols.

ROH + NaOH
 RO Na  + H2O
Weak acid strong acid
Alcohols will also not be soluble in aq. NaHCO3 solution. This is because H2 CO3 is a considerably
stronger acid than alcohols.
4. Carboxylic acids are soluble in aq. NaOH as well as in aq. NaHCO3 Solution.
RCO2H + NaOH RCO 2Na + H2O
strong acid weak acid
RCO2H + NaHCO3 RCO 2Na + H2CO3
strong acid weak acid
Thus aqueous NaHCO3 test provides a method for distinguishing and separating most phenols from carboxylic acids.
(III) Ester formation
Phenols reacts with carboxylic acid anhydrides or acid chlorides in the presence of alkali to form esters.
OH O COR
(RCO)2O / OH
  + RCOO

OH O COR
RCOCl / OH

 + Cl

(IV) Schotten – Baumann Reaction


When alkaline solution of phenol is shaken vigorously with benzoyl chloride, it forms phenyl benzoate. This is
known as Schotten – Baumann reaction.
O O
NaOH
C6H5 
C6H5OH + Cl C  C6 H5 O C C6H5
Phenol Benzoyl choride Phenyl benzoate

(V) Reaction with Zn dust


When phenols are heated with Zn dust, these are reduced to aromatic hydrocarbons.
Zn/ 
C6H5 OH  C6H6  ZnO
or H /MnO at1atm
2 2

(VI) Action of ferric chloride


When phenols are treated with neutral ferric chloride solution, they form coloured complexes. The colour of the
complex may be violet, red, blue or green. This is a characteristic reaction of compounds having enolic group.
(=C –OH). All enols respond to this test.
Illustration 13: Identify A and B on the following reactions are also
OH
conc. HBr
A B
HNO 3

OH O OH

conc. HBr
Solution: A B
HNO3
Br
O OH
benzo-1,4-quinone

Illustration 14: Find the product and explain the mechanism


HO CH3
+
H
?
H 3C
O
Solution: OH OH
HO CH3 HO CH3 HO CH3
CH3 CH3
+
H
H

H 3C H3C H3C H3C


OH OH OH
O OH

REACTIONS DUE TO BENZENE RING


(I) Bromination
OH OH
Br Br
H2O
+ 3Br2 + 3HBr
Br

Monobromination of phenol can be achieved by carrying out the reaction in a solvent of low polarity as
CS2 ,CHCl3 ,CCl4 ect. at low temperature.

OH OH OH
Br
0C
+ Br2   +
CS
2
o-Bromophenol Br
p-Bromophenol

(II) Nitration
When phenol is treated with dilute nitric acid, it gives o and p–nitrophenol and with concentrated nitric acid and
sulphuric acid it forms 2,4,6–trinitrophenol (Picric acid).
OH OH HO
NO2
dil HNO

3 +
20C
o-Nitrophenol NO2
Conc.HNO3 p-Nitrophenol
HO
+ Conc.H2SO4 NO2 NO2

2,4,6-trinitrophenol
NO2
52 – ALCOHOL, ETHER & PHENOL – JEE

However, picric acid is best prepared by first treating phenol with concentrated H2 SO4 at 100C when a mixture of
o– and p– phenol sulphuric acid is formed. This mixture is then heated with concentrated HNO3 to form picric acid.
In this reaction, sulphonic acid group is replaced by nitro group.
(III) Nitrosation
When phenol is treated with nitrous acid (NaNO 2  H2 SO4 ) at 280 K, it forms p–nitrosophenol which when oxidized
with dil HNO3 yields p–nitrophenol in good yield.
HO OH OH
(NaNO H SO ) dil HNO

2 2 4  3
280K
NO NO2
p-Nitrosophenol p-Nitrophenol
In the above reaction, electrophile is NO  (nitrosonium ion).
+
HNO2 H H O N O H2O N O
H
(IV) Sulphonation
When phenol is heated with conc. sulphuric acid, phenol forms either o– or p– isomer depending upon the
temperature of the reaction. In general, low temperature favours the formation of o–isomer and high temperature
favours the formation of p–isomer.
OH
H2SO 4, 298 K SO 3H
OH (o-phenol sulphuric acid)
-H2O
OH
H2SO 4, 373 K
-H2O (p-phenol sulphuric acid)
SO 3H

(V) Friedel Craft’s Alkylation and Acylation


Phenol undergo these reaction to form mainly p–isomer.
OH OH OH OH
OH OH
CH3 COR
AlCl
+ RCOCl 
AlCl3
+ CH3Cl 
3
 + +
CH3 COR
But the yields are not very high, as the reactivity of the phenol is decreased by the formation of a complex with AICI3.
H O AlCl 3

This electropositive oxygen withdraws the electron density from the ring, thus destabilizing the ring towards
Friedel–Craft’s alkylation and acylation.
(VI) Kolbe’s–Schmidt Reaction
When carbon dioxide gas is passed through sodium phenoxide at 400K under 6–7 atomospheric pressure, it forms
sodium salicylate which on acidification forms salicylic acid, although some para isomer is also formed.
O
O O
O HO HO
H
H C CO 2 CO 2 H
Tautomerize +
O O CO 2 H

(isolated) (Salicylic acid)


The product is almost exclusively sodium o–hydroxybenzoate (salicylate) and only traces of the p–isomer is obtained. If
the reaction is carried out at high temperature, p–isomer is the main product. However, if the reaction is carried out with
potassium phenoxide, the salt of the p–acid becomes the major product. It has been suggested that the preferential o–
attack with sodium phenoxide may result from stabilization of the intermediate through chelation by Na  in the ion–pair.
Na
 
O O

 C O

+
The K cation is larger and is less effective in stabilizing the intermediate, so the attack on the p–position becomes
more competitive. Salicylic acid is used for preparing Aspirin, Salol and oil of winter green.
OH OCOCH 3

CO2H CO 2H
(CH CO) O

3 2 
NaOH

Aspirin
Aspirin is acetyl salicylic acid and is an important analgesic and antipyretic.
OH OH

CO2H CO2C6H5
C H OH

6 5 
POCl
3

Salol
Salol is phenyl salicylate and is used as an internal antiseptic.
OH OH

CO 2H CO 2CH3
conc.H SO
 2 4
CH OH
3

Oil of winter green


Oil of winter green is methyl salicylate and used as a flavouring agent with a very sweet smell. It is used in the
preparation of iodex and balm.

(VII) Reimer–Tiemann reaction


This reaction is carried out by refluxing an alkaline solution of phenol with chloroform and distilling off the excess of
chloroform, acidifying the residual liquid with sulphuric acid and then steam distilling it. Unchanged phenol and o–
hydroxy benzaldehyde distills over, leaving behind p–hydroxy benzaldehyde.
The reaction involves an aryl carbanion / enolate anion, and also CCl3 derived from the action of strong bases on
HCCl3 , though the latter has only a transient existence decomposing to CCl2 , a highly electron–deficient
electrophile that attacks the aromatic nucleus.
OH O

CHO
+ CHCl3 + 3NaOH 330340K + 3NaCl+ 2H2O
 

Mechanism
Cl Cl
OH or OR Cl 
H C Cl C Cl   Cl C Cl
-H2 O dichloro carbene
Cl or - ROH Cl
54 – ALCOHOL, ETHER & PHENOL – JEE

O O O O

H CCl 2 H
CHCl 2
IMPE
O CCl 2

O O OH

CHO CHO
CHCl 2
2OH H
H2O

(more stable) (isolated)


The product from phenoxide ion after acidification gives largely the o–aldehyde (salicyldehyde) plus just a small
amount of the p–isomer. If both o–positions in the initial phenoxide anion are blocked, the reaction then yields the
p–aldehyde. Phenols with blocked p–position gives normal o–aldehydic product and cyclohexadienones containing
the dichloro methyl group.
O O O O HO

H CHCl 2 CHO
H
CCl 2 CCl 2 2OH H
+

-H2O

Me Me Me Me
Me
(isolated)

O O O

+
CCl2 H

Me Me CCl 2 Me CHCl 2
In addition to the expected o–aldehyde, it is also possible to isolate the unhydrolysed dichloro compound. Attack by
CCl2 at the p–position yields the intermediate which, unlike the intermediate for o–attack, has no H atom that can
be lost (as H+ ) to allow the ring to re–aromatise. So, on final acidification, it acquires a proton to yield the
dichloromethyl product. The dichloro compound owes its resistance to hydrolysis partly to its insolubility in the
aqueous base medium and also the sterically hindered, neopentyl–type system.

 In the Reimer–Tiemann reaction, the o–isomer predominates but if one of the o–position occupied,
the aldehyde group tends to go to the p–position.
For example, guaiacol on Reimer–Tiemann reaction gives vanillin.
OH OH
OCH 3 OCH 3
CHCl3 H
NaOH
Guaiacol CHO Vanillin

When catechol is reacted with CHCl3 and NaOH, protocatechol (3,4–dihydroxy benzaldehyde) is obtained.
OH OH
OH CHCl3 OH
H
NaOH

CHO
When phenol is reacted with CCl4 in the presence of NaOH, salicylic acid is obtained.
HO OH
CO 2H
+ CCl 4 + 4NaOH + 4NaCl + 2H2O

(VIII) Coupling with diazonium salts


Phenols couple with diazonium salts in the presence of an alkali to form azo dyes.

C6H5N+2Cl +C 6H5OH 


0  5 C
C6H5 N N C6H5OH
pH9 10
p-Hydroxy azobenzene (An orange dye)
The attack of the diazonium cation (as electrophile) occurs only on the highly activated rings i.e. rings with
OH,  NH2 ,  NHRand  NR 2 groups.

(IX) Gattermann’s reaction


Phenol when treated with liquid hydrogen cyanide and gaseous HCl in the presence of anhydrous aluminium
chloride yields a product which on hydrolysis mainly gives p–hydroxy benzaldehyde.
HCl HCN   HN CHCl
AlCl3

OH OH HO

HN CHCl 
AlCl3 / HCl
 
H2O

NH3

HC NH CHO
p-Hydroxy Benzaldehyde

(X) Condensation Reactions


Phenol on combining with phthalic anhydride in the presence of concentrated sulphuric acid produces
phenolphthalein.
O O
OH
C C
O 2 
conc.H2SO 4
 O
H2O
C C
O

OH
HO
Phenolphthalein
Phenol condenses with formaldehyde in the presence of dilute acid or alkali producing a plastic polymer called
bakelite.

OH
OH
Illustration 15: Convert CH (Not more than 3 steps)

OH
OH OH

CHO OH
Solution: CHCI3
MgBr

NaOH + HO CH
H3O
56 – ALCOHOL, ETHER & PHENOL – JEE
Illustration 16: Give the mechanistic steps of the following reaction.
O
OH
OH

OH
+ CCI4 1. NaOH/ 
2. H3O+

Solution:
OH
O O O

OH

O O O O
OH
OH
CI
H
CI
H OH
CI CI CI CI CI HO

CI CI

OH O O
+
CI H3O OH

O O O

OH O OH
Quiz – 4
1. 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

2. Phenol on treatment with dil. HNO3 at room temperature gives:

(A) (B) (C) (D)


3. When phenol is treated with excess bromine water, it gives
(A) m-bromophenol (B) o and p-bromophenol
(C) 2,4-dibromophenol (D) 2,4,6-tribromo phenol
4. Phenol and ethanol can be distinguished by using
(A) NaOH (B) anhy. AlCl3
(C) FeCl3 (D) Benzoic acid

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


OH
AlCl 3/CS 2
OCOCH 3 COCH3
heat
(a)
HO COCH3

(b)
(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
(A) III and IV (B) I and III (C) II and IV (D) I and II

6. Phenol is less acidic than


(A) ethanol (B) methanol (C) o-nitrophenol (D) p-cresol

7. That o-nitrophenol is more volatile than p-nitrophenol is best explained by:


(A) hyperconjunction (B) intramolecular H-bonding
(C) intermolecular H-bonding (D) resonance
8. Which one of the following tests provides a simple method of distinguishing between the two compounds
shown below?
OH CH2OH

and
CH3
(A) Reaction of each with sodium metal
(B) Reaction of each with acetic anhydride and catalytic sulfuric acid
(C) Solubility test of each in water
(D) Solubility test of each in aqueous sodium hydroxide
58 – ALCOHOL, ETHER & PHENOL – JEE
9. Phenol reacts with bromide in carbon disulfide solution at low temperature to give as a major product:
(A) m-bromophenol (B) o-and p-bromophenols
(C) p-bromophenol (D) 2, 4, 6–tribromophenols
10. 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
11. A mixture of benzoic acid and phenol may be separated by treatment with:
(A) NaHCO3 (B) NaOH
(C) NH3 solution (D) KOH
12. In the Libermann test for phenols, the blue or green colour produced is due to the formation of:

(A) NO OH (B) O NOH

+
(C) O N OH (D) O N ONa

+
CH3 CH2 CH2 Cl/ AlCl 3 O 2, H 3O
13. P Q + Phenol

What are P and Q.


CH2 CH2 CH3 O CH 2 CH 2 CH3 O
(A) + CH
3 C CH3 (B) + CH
3 CH 2 C H

CH3 CH3
O CH O
CH
CH3 CH3 + CH
(C) + CH
3 CH2 C H (D) 3 C CH3

14. The structure of the compound that gives a tribromo derivative on treatment with bromine water is:
CH2OH CH3 CH3 CH3
OH
(A) (B) (C) (D)
OH
OH
15. Direct the nature of the product in the following reaction:
OCH2CH=CH2
D D
200C
  Pr oduct

OH OH
D CH2CH=CH2 D D
(A) (B)

CH2CH=CH2
OD OD
D CH2-CH=CH2 CH2CH=CH2
(C) (D)
24. Level – 1 (Main)
1. tert–Butyl chloride on treatment with sodium alkoxide yields:
(A) an ether (B) an alkene
(C) an alcohol (D) an alkane

2. Methanol and ethanol can be distinguished by:


(A) Lucas test (B) Iodoform test
(C) Victor Meyer’s test (D) All of these

3. Which of the following compounds should be least soluble in water?


(A) Phenol (B) Ethanol
(C) Benzoic acid (D) Chlorobenzene

4. An alcohol on vigorous oxidation is found to give ethanoic acid and propanoic acid. The alcohol may be:
(A) 1-Pentanol (B) 2-Pentanol
(C) 1-Butanol (D) 2-Butanol

5. Which of the following compounds reacts fastest with Lucas reagent?


(A) 1-Butanol (B) 2-Butanol
(C) 2-Methyl-2-propanol (D) 2-Methyl-1-propanol

6. The compound with formula C4H10O yields a compound C4H8O on oxidation, the compound C4H10O is:
(A) an aldehyde (B) an alcohol
(C) a ketone (D) an anhydride

7. An organic liquid A containing C, H and O has a pleasant odour with a b.p. of 78C. On boiling A with conc.
H2SO4 a colourless gas is produced which decolourises bromine water and alkaline KMnO4. One mole of
this gas also takes one mole of H2. The organic liquid A is:
(A) C2H5Cl (B) C2H5CHO
(C) C2H6 (D) C2H5OH

8. Williamson’s synthesis of ethers is an example of:


(A) nucleophilic substitution reaction (B) nucleophilic addition
(C) electrophilic addition (D) none of above

9. When diethyl ether is heated with sulphuric acid it forms:


(A) Propanoic acid (B) Acetic acid
(C) Ethyl alcohol only (D) Ethyl hydrogen sulphate and ethanol

10. Ethers in contact with air for a long time form peroxides. The presence of peroxide in ether can be tested
2+
by adding Fe ions followed by the addition of:
(A) KCNS (B) SnCl2
(C) HgCl2 (D) KI

11. Which of the following is the strongest base?


(A) tert-Butoxide (B) Ethoxide
(C) Iso-Propoxide (D) Methoxide

12. When the degrees of dissociation of benzoic acid, salicylic acid and 2, 6-dihydroxy benzoic acid are
compared, it will be found that the degree of dissociation of:
(A) Benzoic acid is the highest
(B) Salicylic acid is the highest
(C) 2, 6-dihydroxy benzoic acid is the highest
(D) 2, 6-dihydroxy benzoic acid is roughly equal to that of benzoic acid

13. Identify Z in the series CH2 = CH2 


 X 
HBr
 Y AqKOH

Na2CO3
 Z.
I2 excess
(A) C2H5I (B) C2H5OH
(C) CHI3 (D) CH3CHO
60 – ALCOHOL, ETHER & PHENOL – JEE
14. Which of the following is Williamson synthesis reaction?
CH3
(A) Zn - Hg
C O CH3 CH2 CH3
conc, HCl
CH3
dil.
(B) NaOH
CH3CHO H2O CH3 CH CH CHO

(C) C2H5I + C 2H5ONa C2 H5 O C2H5 + NaI


NaOH
(D) HCHO HCOONa + CH 3OH

15. Which of the following reaction is possible?


(A) C2H5Cl + C2H5ONa — C2H5OC2H5 (B) C2H5Cl + alc. KOH — alcohol
(C) C2H5Cl + dry Ag2O — alcohol (D) All

16. An organic compound with molecular formula C7H8O dissolves in NaOH and gives characteristic colour
with FeCl3. On treatment with Br2 it gives tribromo product C7H5OBr3. The compound is :
(A) p–Hydroxy benzene (B) 2–Methoxy–2–phenyl propane
(C) m–Cresol (D) p–Cresol.

17. Which of the following alcohol have maximum solubility in water?


(A) n-butyl alcohol (B) isobutyl alcohol
(C) tert-butyl alcohol (D) sec-butyl alcohol

18. Which compound has highest boiling point?


(A) CH4 (B) CH3OH (C) CH3Cl (D) CH3Br

19. Which of the following is easily dehydrated?

(A) OH (B) OH (C) OH (D) OH

20. Which of the following compound from a hydrocarbon to react with Grignard reagent?
(A) CH3CH2OH (B) CH3CHO (C) CH3COCH3 (D) CH3CO2CH3
H2 /Pt
21. CH3  CH  CH  CHO   A, product A is:
(A) CH3CH2CH2CHO (B) CH3  CH = CH  CH2OH
(C) CH3CH2CH2CH2OH (D) CH2  CH(CH3) - CHO

22. Which reagent is not suitable for the formation of alkyl chloride by alcohol?
(A) NaCl (B) HCl + ZnCl2
(C) PCl3 (D) SOCl2
23. Which of the following statement is correct for the stability of ions of ethyl alcohol and phenol:
(A) Delocalisation of -electrons in phenoxide ion
(B) Delocalisation of electrons in ethoxide ion
(C) Inductive effect of ethyl and phenyl group
(D) Localisation of -electrons in phenoxide ion
24. Ethers are not distilled to dryness for fear of explosion. This is due to the formation of:
(A) oxides (B) peroxides (C) alcohols (D) ketones
25. Which of the following reagent(s) cannot be used to distinguish between phenol and benzyl alcohol?
(A) NaOH (B) NaHCO3 (C) Br2/CCl4 (D) FeCl3
26. Methylphenyl ether can be obtained by reacting:
(A) Phenolate ions and methyl iodide (B) Methoxide ions and bromobenzene
(C) Methanol and phenol (D) Bromobenzene and methyl bromide
27. Which of the following will give positive iodoform test?
(A) pentanal (B) 1-phenylethanol
(C) 2-phenylethanol (D) 3-pentanol

28. Ethyl alcohol on oxidation with acidic K2Cr2O7 gives:


(A) acetic acid (B) acetaldehyde (C) formaldehyde (D) formic acid

29. Compound 'X' has molecular formula C4H8O3. It evolves CO2 with aq. NaHCO3. 'X' reacts with LiAlH4 to
give an achiral product. The structure of X is:
(A) CH3 CH2 CHCOOH (B) CH3CH COOH
OH OMe
(C) CH3 CHCH2 COOH (D) CH3 CH COOH

OH CH2 OH

30. Which of the following compound reacts with CH3MgI and gives p-alcohol?
(A) acetone (B) methyl cyanide
(C) ethylene oxide (D) ethyl acetate

25. Level – 2 (Main)


1. Butane-1, 4-diol reacts with conc. H2SO4 to give:
(A) CH2 = CH – CH = CH2 (B) CH3 – CH = CH – CH3
(C) CH3 – CH2 – CH = CH2 (D) none of these
2. Which compound form most stable carbonium ion on dehydration?
CH3

(A) CH3 CH CH2OH (B) CH3 C OH


CH3 CH3
(C) CH3–CH2–CH2–CH2OH (D) CH3 CH CH2 CH3
OH
3. Product of the following reaction is:
(i) BH3 / THF

(ii) H2O2, OH
(A) 1-Pentanol (B) 2-Pentanol (C) Pentane (D) 1, 2-Pentanediol
4. Compound that gives red colouration in Victor Meyer's test is:
(A) (CH3)2CH—CH2OH (B) (CH3)2CHOH
(C) (CH3)3C—OH (D) (B) and (C)

5. HBr reacts with CH2  CH  OCH3 under anhydrous conditions at room temperature to give:
(A) H3 C  CHBr  OCH3 (B) CH3CHO and CH3Br
(C) BrCH2CHO and CH3OH (D) BrCH2—CH2—OCH3

6. When ethylene glycol reacts with periodic acid, the products are:
(A) Formaldehyde (B) Acetaldehyde
(C) Formic acid (D) Acetic acid
7. Which of the following cannot be made by the reduction of ketone or aldehyde with NaBH4 in methanol?
(A) 1-butanol (B) 2-butanol
(C) 2-methyl-1-propanol (D) 2-mthyl-2-propanol

8. Which of the following reagents will convert cyclohexene into cis-1,2-cyclohexanediol?


(A) OsO4’(CH3)3COOH, (CH3)COH,OH (B) HIO4
(C) O3 followed by Zn/H2O (D) CH3CO3H (peroxyacetic acid)
62 – ALCOHOL, ETHER & PHENOL – JEE
9. What is the major organic product of the reaction shown?
O O
H C C OCH3
LiAIH4 H3O

O
HOCH 2 CH2OH H C CH2OH
(A) (B)

O O OH
HOCH2 C OCH3 H C CHOCH3
(C) (D)

10. Which conditions would you use to perform the following transformation?
OH

(A) (1) Hg(OAC)2’ H2O, (2) NaBH4 (B) (1) OsO4’ (2) NaHSO3
+
(C) (1) BH3’ (2) H2O2’ NaOH (D) (1) O3’ Zn, H
11. What will be the products of the following reaction?

(A) II and III (B) III and IV


(C) I and IV (D) I, II, III and IV

12. Consider the following reaction:

Which type of reaction mechanism best explains what has occurred?


(A) E1 (B) E2
(C) SN1 (D) SN1 with a 1, 2-hydride shift

13. What is the product of the synthetic sequence below?


NaBH4 HBr 1) Mg Et 2OO PCC
O 2) H2C=OC=O CH2CI2
CH3OH
3) H3OO
OH CH3
(A) CO 2H (B) (C) (D)
CHO CHO OH

14. Select major product of the following reaction.


1. (CF 3CO 2)Hg)Hg
HO–CH2CH3 +
2. NaBH44
O OCH2CH3 OCH2CH3
OH
OH
O OCH2CH3
(A) (B) (C) (D)
15. Why do alcohols undergo substitution reactions with hydrogen halides but not with halide salts?
(A) Halide salts are strongly bonded ion pairs and the halide ion is less available to act as a
nucleophile
(B) The acid protonates the OH group and charges the leaving group from a hydroxide radical to a
water molecule
(C) Substitution always need to be carried out a low PH values
(D) The acid protonates the OH group and changes the leaving group from a hydroxide ion to a water
molecule.

16. What is the best description of the mechanism of the following transformation?

(A)

(B)

(C)

(D)

17. What is the major product of the following reaction?


CH3

NBS, benzoyl peroxide NaOCH2CH3


CO 2' heat CH3CH2OH

Br
CH2Br
CH2OCH2CH3

(A) (B)

Br OCH2CH3
CH2OCH2CH2 CH3
Br

(C) (D)

OCH2CH3 OCH2CH3
64 – ALCOHOL, ETHER & PHENOL – JEE
18. What is the major product of the reaction sequence shown?
O
+
Mg, ether H2C CH2 H3O
CH3 CHCH3
Cl
(A) (CH3)2CHCH2CH2OH (B) (CH3)2CHCHOHCH3
(C) CH3CH2CH2CH2CH2OH (D) CH3CH2CH2CHOHCH3

CH2 OH
+
H
(A)
19. 
Product (A) is:
CH3

(A) (B) (C) (D)

CH3
Conc. H2SO 4
20. In the given reaction CH3 A
OH OH
The product (A) is:
CH3 CH3
(A) (B)
CH3 CH3
O
CH3 CH3
(C) (D) CH3
COOCH3
O

OH
+
H
21. (A)

Product (A) is:

(A) (B)

(C) (D)

+
H
22. (A)

HO
Product (A) is:

(A) (B) (C) (D)


23. What is the major product of the following reaction?
CH3
CH3 + HBr ?
OH
CH3 CH3 CH3 CH3
CH3 Br CH2Br (IV) CH3
(I) (II) (III)
Br CH3
Br
(A) I (B) II (C) III (D) IV

24. When the optically active alcohol below is oxidized by H2CrO4, the major product is ……….
OH

CH3
(A) a ketone which is meso and optically inactive
(B) an optically active ketone
(C) a racemic mixture of ketones which is optically inactive
(D) an aldehyde which is meso and optically active

25. Which of the following is the best method for preparing aspirin,
COOH
O
OCCH3
COOH O O CCH3
(I) + HO C CH3 (II) O + HCOOH

COOH COOH O
O
(III) + CH3Cl (IV) + H3C C NH2
O CCl OH
(A) I (B) II
(C) III (D) IV

OH O O
(i) CO 2, NaOH H3C C O C CH3
26. (A) (B);
+
(ii) H
Aspiring Product (B) is:
O
OH O C Me OMe OH O
CHO COOH COOH C OCH3
(A) (B) (C) (D)

+
H3O
27. O
Product of above reaction is:
O OH O
(A) (B) CH3CHO
, ,
O O O O
(C) H, H (D) ,
66 – ALCOHOL, ETHER & PHENOL – JEE
28. What is the product of the following reaction sequence?
O +
CH3MgBr H3O
C CH ?

(A) C CH3 (B) C CCH2CH2OCH3

(C) C CCH2OCH2CH3 (D) C CCH2CH2OH

29. Which of the following is/are the major product(s) of the following reaction?
HI
+ ?

I I

I
(I) (II) (III)
(A) I (B) I and II
(C) I and III (D) II

30. Which compound below is the product expected from the following reaction?

(A) (B)

(C) (D)
26. Level – 3 (Advanced)
Single Choice
1. tert–Butyl chloride on treatment with sodium alkoxide yields:
(A) an ether (B) an alkene (C) an alcohol (D) an alkane

2. Methanol and ethanol can be distinguished by:


(A) Lucas test (B) Iodoform test (C) Victor Meyer’s test (D) All of these

3. Which of the following compounds should be least soluble in water?


(A) Phenol (B) Ethanol (C) Benzoic acid (D) Chlorobenzene

4. An alcohol on vigorous oxidation is found to give ethanoic acid and propanoic acid. The alcohol may be:
(A) 1-Pentanol (B) 2-Pentanol (C) 1-Butanol (D) 2-Butanol

5. Which of the following compounds reacts fastest with Lucas reagent?


(A) 1-Butanol (B) 2-Butanol
(C) 2-Methyl-2-propanol (D) 2-Methyl-1-propanol

6. The compound with formula C4H10O yields a compound C4H8O on oxidation, the compound C4H10O is:
(A) an aldehyde (B) an alcohol (C) a ketone (D) an anhydride

7. An organic liquid A containing C, H and O has a pleasant odour with a b.p. of 78C. On boiling A with conc.
H2SO4 a colourless gas is produced which decolourises bromine water and alkaline KMnO4. One mole of
this gas also takes one mole of H2. The organic liquid A is:
(A) C2H5Cl (B) C2H5CHO
(C) C2H6 (D) C2H5OH

8. Ethers are not distilled to dryness for fear of explosion. This is due to the formation of:
(A) oxides (B) peroxides (C) alcohols (D) ketones

9. Williamson’s synthesis of ethers is an example of:


(A) nucleophilic substitution reaction (B) nucleophilic addition
(C) electrophilic addition (D) none of above

10. When diethyl ether is heated with sulphuric acid it forms:


(A) Propanoic acid (B) Acetic acid
(C) Ethyl alcohol only (D) Ethyl hydrogen sulphate and ethanol

11. Ethers in contact with air for a long time form peroxides. The presence of peroxide in ether can be tested
2+
by adding Fe ions followed by the addition of:
(A) KCNS (B) SnCl2 (C) HgCl2 (D) KI

12. Which of the following is the strongest base?


(A) tert-Butoxide (B) Ethoxide (C) Iso-Propoxide (D) Methoxide

13. Identify the product Z in the following sequence of reactions:



CO2 H3 O
Phenol  X
NaOH
  Y   Z
4 7 atm, 410 K
(A) Aspirin (B) Salicylaldehyde
(C) Benzoic acid (D) Salicylic acid

14. When the degrees of dissociation of benzoic acid, salicylic acid and 2, 6-dihydroxy benzoic acid are
compared, it will be found that the degree of dissociation of:
(A) Benzoic acid is the highest
(B) Salicylic acid is the highest
(C) 2, 6-dihydroxy benzoic acid is the highest
(D) 2, 6-dihydroxy benzoic acid is roughly equal to that of benzoic acid
68 – ALCOHOL, ETHER & PHENOL – JEE

15. Identify Z in the series CH2 = CH2 


 X 
 Y HBr AqKOH

Na2CO3
 Z.
I2 excess
(A) C2H5I (B) C2H5OH (C) CHI3 (D) CH3CHO

16. Phenol, p-Methylphenol, m-Nitrophenol and p-Nitrophenol follows order of increasing acidic strength:
(A) Phenol, p-Methylphenol, p-Nitro phenol, m-Nitrophenol
(B) p-Methylphenol, phenol, m-Nitrophenol, p-Nitrophenol
(C) p-Methylphenol, m-Nitrophenol, Phenol, p-Nitrophenol
(D) m-Nitrophenol, p-Nitrophenol, Phenol and p-Methylphenol

17. A compound of the formula C4H10O reacts with sodium and undergoes oxidation to give a carbonyl
compound which does not reduce Tollen’s reagent, the original compound is:
(A) Diethyl ether (B) n-Butyl alcohol
(C) Isobutyl alcohol (D) sec-Butyl alcohol

CH3
CH3OH H2O18
18. B CH3 C CH2 +
A
CH3ONa H
O
A and B are:
CH3 CH3 CH3 CH3

(A) H3C C CH2 H3C C CH2 (B) H3C C CH2 H3C C CH2

OH 18 OH
18 OH OH OH OCH3 OH OCH3
(C) both are correct (D) none is correct

19. In the reaction sequence,


CH2OH
hypochlorous R
CH2 CH2 A
acid
CH2OH
A and R are respectively
(A) CH2 CH 2 and heat (B) CH3CH2Cl and NaOH
O
(C) CH3CH2OH and H2SO4 (D) CH2Cl.CH2OH and NaHCO3
20. 3, 3-Dimethyl-2-butanol, on reaction with conc. H2SO4 at 443 K will give ….. as the major product.
(A) 3,3-Dimethyl-1-butene (B) 2,3-Dimethyl-2-butene
(C) 2,2-Dimethyl-2-butene (D) 2,2-Dimethyl-1-butene

21. When anisole is treated with Br2 in CS2 the product formed is:
(A) Methyl bromide and Phenol (B) Bromobenzene
(C) Mixture of ortho and para-Bromoanisole (D) Methanol and Methyl chloride
OH
OC 2H5
22. + C 2H 5 I
Anhy. C 2H5OH
(A) C6H5 OC2H5 (B) C2H5 OC2H5 (C) C6H5 OC6H5 (D) C6H5I

23. In which of the following case configuration about chiral C is retained:


Me Na CH3Br Me CH3ONa
(A) Ph OH (B) Ph OH
TsCl
Et Et
Me PCl 5 CH3Br
(C) Ph OH (D) None of these
Et
+
. H
24. what would be (X)
OH
.
(A) (B)
OH O Me

(C) CH2CH3 (D)


O O CH3
+
H
25. The reaction CH2 gives
H 2O
CH3
(A) OH (B) OH

(C) CH3 (D) None of the above


OH
26. Write the final product of the following reaction:
OH Al 2O 3 i) HI
H3C A B
350 Co
ii) AgOH
Product (B) is:
OH O CH3
(A) H3C (B) H3C
CH3
(C) H3C O (D) H3C
CH3 CH2

27. Which one of the following will most readily be dehydrated in acidic solution?
OH
O OH
H3C CH3
(A) H3C CH3 (B)
O
OH O
CH3
(C) H3C CH3
(D) H3C
OH
OH

28. Which of the following decreasing order of rate of dehydration with H 2SO4 is correct for the alcohols.
OH OH
OH
C CH2 C (CH3) 2
CH3 (H3C)2 CH2 CH3 (H3C)2 CH
CH3
(A) (B) (C)
CH2 CH
H3C CH
(CH3)2
H3C
OH OH

(D) (E)
(A) C>B>D>A>E (B) E>A>D>B>C
(C) B>C>D>E>A (D) None of the above
70 – ALCOHOL, ETHER & PHENOL – JEE
29. When 2, 2, 6, 6–tetramethylcyclohexanol is reacted with acid, which of the following compounds would be
expected to be found in the reaction mixture?

(A) (B) (C) (D)

 1. B 2H6 1. O 3
H
30. C7H14O(X) C7H12 C7H14O(Z)
A 3 a lc o h o l 
2. H 2O 2/OH  A n 
2. Zn/H 2O
o
(Y) is o m e r o f X

CH3 CH3
CH3 CH3
OH
(A) (B) (C) (D) CH3
CH3 OH OH HO

Multiple Choice
OH   product.
HBr /Boiling
31.

Which of the following are possible products (in significant amount) -


(A) (B) Br

Br
(C) (D)

32. Which of the following compounds will give a yellow precipitate with iodine and alkali -
(A) 2-Hydroxypropane (B) Acetophenone
(C) Methyl acetate (D) Acetamide

33. Isobutylene is obtained when -


(A) sodium t-butoxide is treated with methyl iodide
(B) t-Butyl bromide is treated with sodium methoxide
(C) t-Butyl alcohol is treated with conc. H2SO4
(D) t-Butyl methyl ether is heated with conc. H2SO4

34. Which of the following reagent can be used to differentiate ethanol and phenol ?
(A) Treatment of metallic sodium (B) Treatment of aqueous KOH
(C) Treatment of Na2Cr2O7 / H2SO4 (D) Treatment of FeCl3

35. The product(s) possible in the following reaction (Z) is/are


OH
i-prMgBr 
CMe2Br [X] [Y]
C6H6
PhCO3H

[Z]
O
Me
O O
Me O
O Me
Me Br
O O
(A) (B) (C) (D) Me
Me
Me Me
OH

1 eqv.TsCl 4 LiAlH
36.   
 [X]    [Y]
C5H 5 N C5H 5 N

OH
The correct options are –
OTs OH

(A) X= (B) X=

OH OTs
OH

(C) Y= (D) Y=

OH Me

LiAlH4 CrO3
37. MeCH – CH2 [X] Acetic acid
[Y]
O
NH2OH
NH4Cl
[Z]
PCl5

H2O
[Q] [P]
The correct statement(s) are -
(A) Q = MeCONHMe (B) Y = MeCH2CHO
(C) Q = MeCONHCH2Me (D) Z = MeCMe
N–OH

38. The cyclic compounds,

OH & OMe can


O O
be differentiated by -
(A) Tollen's Reagent (B) H3O
(C) HI (D) Benedict's solution

H O
39. 2 [P] O

H
 [Q]
Me O Me H 2SO 4 
The correct option(s) are –
(A) P = CH3CCH2CH2CCH3 (B) P = OHC(CH2)4CHO
O O
O
O

(C) Q= (D) Q=
Me Me
72 – ALCOHOL, ETHER & PHENOL – JEE

2 Br H O
40. CH2 = CH – OCH3 
  [X] 3 
 [Y] + [Z] products
MeOH

The correct statements are [Y gives haloform reaction]


Br OMe
(A) X= (B) Y = MeOH
OMe
OMe
(C) Y = CH2BrCHO (D) X= Br
OMe

41. The ether O–CH2 when treated with HI produces

(A) –CH2I (B) –CH2OH

(C) –I (D) –OH

42. Which of the following are less acidic than phenol ?


CH3

(A) CH3OH (B) OH


NO2

(C) OH (D) H2O

43. Phenol can be converted into salicylic acid by using -


(A) CO 2 and alkali under pressure followed by acidic hydrolysis
(B) CCl4 and alkali at 340 K followed by acidic hydrolysis
(C) CHCl3 and alkali at 340 K followed by oxidation
(D) None of these

44. When phenol is treated with CHCl3 and NaOH followed by acidification, salicyaldehde is obtained. Which
of the following species are involved in the above mentioned reaction as intermediate ?
O OH OH O–
H CHCl2 H CHCl2
(A) – (B) (C) CHCl (D)
CCl 2

OH
Cl
CH2–C–Cl
OH NaOH O
45. 
 P Q

OH
O
O–C–CH2–Cl O–Na+
(A) P is (B) P is
O–Na+ O–Na+
O O
O
(C) Q is (D) Q is
O O
27. Level – 4 (Comprehension & Match the Column)
CMP: Epoxides are cyclic ethers with three membered rings. The IUPAC nomenclature of epoxides are oxiranes.
CH2 CH2
O
IUPAC name 
 Oxirane
Common name   Ethylene oxide
It is synthesized from alkenes with the help of peroxyacids
O
CH2 CH2 + R C OOH CH2 CH2 + RCOOH
O
The addition of oxygen to double is necessarily a Syn addition reaction.
Highly strained three membered ring in molecules of epoxides makes them more reactive towards
nucleophiles.
Epoxides gives primarily ring opening reaction, by two methods:
(a) Acid-catalyzed ring opening reaction:

+
OH2
+ 
H3C CH CH2 + H3O CH3 CH CH2 + H2O CH3 CH CH2
+
O O OH
H +
H
The attack is by SN2 mechanism,
however nucleophilic attack the 2 OH
carbon as it can bear the positive
charge better CH3 CH CH2
OH
(b) Base catalyzed ring opening reaction:
- H2O
CH3 CH CH2 + HO CH3 CH CH2 OH CH3 CH CH2 OH
-
O O OH
The attack is by SN2 reaction
and nucleophile attacks at the
less hindered carbon atom

OSO4, NaHSO3 The product A and B are respectively:


1. A

(i) RCOOH
(ii) H2O/H+

B
The product A and B are respectively:
OH OH
OH
(A) A= B= +
OH , OH OH
OH OH OH
(B) A= + B=
OH OH OH
OH OH OH
(C) A= B= +
OH , OH OH
OH OH
(D) A= B=
OH , OH
74 – ALCOHOL, ETHER & PHENOL – JEE
2. CH3
CH3OH / HA
CH3 C CH2 A
O

(i) CH 3O / CH 3OH

B
The product A and B are respectively:
CH3 CH3

(A) A = CH3 C CH2 OH , B = CH3 C CH2OCH 3

OH OH
CH3 CH3

(B) A = CH3 C CH2 OCH3 , B = CH3 C CH2OCH3

OCH3 OH
CH3 CH3

(C) A = CH3 C CH2 OH , B = CH3 C CH2 OCH3

OCH3 OH
CH3 CH3

(D) A = CH3 C CH2 OCH3 , B = CH3 C CH2 OH

OH OCH3

3. Product of the following reaction is:


CH2 CH CH3
Br (i)
Mg / ether O H2CrO7
A
(ii) H2O / H
OH O O
CH CH CH3
C CH3 CH2 C CH3 C CH2 CH3
CH3

(A) (B) (C) (D)

(i) Mg / ether
CH2 CH CH2 CH2 CH2 Cl A
4. +
(ii) H 2O / H
O
The product A is:
OH
CH2 CH CH2 CH2 CH3
(A) (B) CH2 CH CH2 CH2 CH3
O
OH
OH
OH
(C) (D) OH
(i) CH 3MgX
5. A
(ii) CH2 CH CH3
O
+
(iii) H 2O/H
The product ‘A’ is:
OH OH OH
CH3 CH CH2 OH
CH2 CH CH3 CH2 CH2 CH CH3 CH2 CH CH2 CH3

(A) (B) (C) (D)


O
6. (i) LiAlH 4/ether
CH3 CH CH2 A
(ii) H 2O

(i) LiAlH4 + AlCl3 / ether The product A and B are respectively:


(ii) H2O

B
(A) A = CH3 CH CH3 , B = CH3 CH2 CH2

OH OH
(B) A = CH3 CH2 CH2 OH , B = CH3 CH CH2

Cl OH
(C) A = CH3 CH2 CH3 , B = CH3 CH CH2 Cl

OH OH
(D) none of these

CH3 N /
7. CH3 CH CH2 A The product A is:
O

+
(A) CH3 CH CH2 N

OH CH3

+
(B) CH3 CH CH2 N
OH CH3
(C) CH3 CH CH2 N
OH
(D) CH3 CH CH2 N
CH2
OH
76 – ALCOHOL, ETHER & PHENOL – JEE

CMP: One of the industrial processes to synthesize ‘Phenol’ is by cumene hydroperoxide. Mentioned
below are the steps in the synthesis of phenol:
Step I:
CH3
H3PO 4 CH
+ CH 3 CH CH2 CH3
250C
Step II:
CH3
CH3
high pressure CH O OH
CH + O 2
95° - 130°C
CH3 CH3
cumene hydroperoxide

Step III:
CH3
+ CH3
H3O conc.
C O OH C6H5OH + C O
CH3
CH3
The step III involves rearrangement (phenyl migration) to cationic oxygen atom.
CH3 CH3
+ CH3
H3O +
C O OH C O OH C O
H2O
CH3 CH3 CH3

H2O

O CH3 H CH3
OH
+ +
+ CH3 C CH3 HO C O O C O
+
H H
CH3 CH3
H
Based on the following comprehension, answer the following question.
+
(i) H 3PO 4 O2 H3O
8. + CH CH2 A + B
200C 95  135C 50C

OH
The product A and B are respectively:
O O

OH CH2 C H
OH C CH3
(A) (B)
A= B=
A= B= ,
,
OH
O
OH CH2 CHO
OH C CH3
(C) (D) A= B=
A= B= ,
,
OH
OH OH
18
H2O /H
9. CH3 O CH CH2 A + B The product A and B are respectively:

O18 O
(A) (B) 18
A = CH3 OH , B = CH3 CH A = CH3 OH , B = CH3 CH

O O
18
(C) 18 (D)
A=H C H , B = CH3 CH2 OH
A=H C H , B = CH3 CH2 OH

+
H3O
10. O OH A The product A is:
50C
O O
OH O
(A) (B)

CH2 CH2 CH2 CH2 CHO CH CH2 CH2 CH2 CHO


(C) (D)
OH O

+
H3O /H+
11. O OH

O
(A) (B) CHO CH2 CH CH CHO

O OH
(C) (D) HOCH2 CH2 CH CH CHO

+
O H3O /H+
12. A
O
The product ‘A’ is:
H
OH
OH O O
O
OH O O
H
H
(A) (B) (C) (D)
78 – ALCOHOL, ETHER & PHENOL – JEE

CMP: Pinacele-Pinacelone is a characteristic reaction which involves carbocation rearrangement. A


mechanistic explanation of reaction is given below:
H H H H
+ H H
CH3 C C CH3 H /conc. +
CH3 C C CH3 CH3 C C CH3
OH OH +
OH OH2 OH
H shift

CH3 C CH2 CH3 + CH3 C CH2 CH3


H +
O OH
Based on above comprehension, answer the following question.

CH3 CH3
+
H /conc.
13. Ph C C Ph A

OH OH
Product ‘A’ is:
CH3 CH3 CH3

Ph C C Ph CH3 C C(Ph)2 Ph C C CH3

O CH3 O Both A and B O O


(A) (B) (C) (D)

OH OH
+
14. H /conc.
A
O O
HO
O
O
+

(A) (B) (C) (D)

dil H2SO4
15. A
HO CH2
CH3

(A) (B) (C) O (D)


CH2 CH CH3
HO OH 3 C H O
Match The Column
Answer Q. 16, Q.17 and Q.18 by appropriately matching the information given in the three columns of the following table.
Column 1 Column 2 Column 3
OH
OH
(I) (i) Conc. H2SO4 (P) Acid base followed by SN2
OH
OH O
nucleophilic addition
(II) (ii) (Q)
Cl elimination
(1 Meq)
OH (i) CO 2, NaOH
(III) HO
(iii) + (R) dehydration
OH (ii) H 3O
OH
(IV) (iv) NaOH, CH3 – CHI2 (S) Electrophilic reaction
OH
16. Which combination gives a product mixture containing three isomer?
(A) (III), (ii), (Q) (B) (I), (ii), (Q) (C) (II), (ii), (P) (D) (I), (iii), (Q)

17. Which combination gives a product which give a yellow ppt with Cl2(g) in alkaline medium?
(A) (I), (i), (R) (B) (IV), (i), (R) (C) (III), (i), (R) (D) (III), (i), (S)

18. Which combination gives the product which the strongest acid among all the products formed from all
possible combination?
(A) (I), (iii), (S) (B) (II), (iii), (S) (C) (II), (iii), (P) (D) (IV), (ii), (Q)

Answer Q. 19, Q.20 and Q.21 by appropriately matching the information given in the three columns of the following table.
Column 1 Column 2 Column 3
OH

(I) (i) Br2/H2O (P) dehydration

OH
OH
(II) (ii) Br2/CS2 (Q) oxidation
OH
OH

(III) (iii) K2Cr2O7 (R) electrophilic substitution

OH
OH
(IV) (iv) conc. H2SO4 /  (S) tautomerization
OH

19. Which combination gives a product which is a hydrocarbon and non polar?
(A) (III), (iv), (P) (B) (IV), (iv), (P) (C) (IV), (iii), (S) (D) (I), (iii), (Q)

20. Which combination gives tribromoproduct?


(A) (I), (ii), (Q) (B) (III), (i), (R)
(C) (II), (i), (R) (D) (IV), (i), (R)

21. Which combination gives a product which when subsequently reacted with HBr gives a monobrominated
product?
80 – ALCOHOL, ETHER & PHENOL – JEE
(A) (I), (iii), (Q) (B) (II), (iii), (Q)
(C) (IV), (iv), (P) (D) (III), (ii), (R)

22. Match the Column I with Column II.


Column I Column II
(A) Fries rearrangement (P) Resorcinol + Phthalic anhydride 
Conc.

 Fluorescein
H2 SO4

(B) Elbs persulphate oxidation (Q) AlCl3


Phenyl ethanoate   p-Hydroxy acetophenone

(C) Coupling reaction (R) K 2 S2 O8


Phenol   Quinol
(D) Phthalein reaction (S) Phenol + Benzene diazonium chloride  p-Hydroxy
azobenzene

23. Match the Column I with Column II.


Column I Column II
OH O
(A) (P) Conc. H2SO4
H3C CH CH3 H3C C CH3
OH
+
(B) (Q) I2/NaOH/H
H3C CH CH3 CH3COOH + CHI3
OH I
(C) (R) PDC
H3C CH CH3 H3C CH CH3
OH
(D) (S) NaI/Acetone
H3C CH CH3 H3C CH CH2

24. Match the Column I with Column II.


Column I Column II
H3C CH3
CH OH OH
(A) (P) H2CO3 more acidic than

Me +
O BF 3
(B) (Q) Acidic strength
+ F 3C C OH
Me Me
OH
OH
Me Me
(C) (R)
+ Na2CO3 No reaction
Me
OH OH CH3 H
+
NO 2 H3C O O H
(D) > (S)

NO 2

25. Match the Column I with Column II.


Column I Column II
OH
+ CH2 = CH – CH2 – Cl
(A) (P) Reactivity towards electrophilic substitution

AlCl3
 A  Product
OEt

OH
Me
(B) 
Zn/HCl
 Product (Q) Decreasing order of E reduction

N NPh
OH
-
O OH Me
(C) (R)
>
NH2
O

(D) O O > (S) Claisen rearrangement

26. Match the Column I with Column II.


Column I Column II
Br
(A) (P) RCOOOH

OH
(B) (Q) Carbocation

O CH2 CH2 CH2 Cl OH


CH2 CH CH2
(C) Alc. KOH (R) Epoxidation

RCH = CHR 
 RCH CHR
(D) (S) Elimination
O
82 – ALCOHOL, ETHER & PHENOL – JEE

28. Level – 5 (Subjective Type)


1. An organic liquid 'A' containing C, H and O with boiling point 78C, possessing a rather pleasant odour, on
heating with concentrated sulphuric acid gives a gaseous product 'B' with the empirical formula, CH2. 'B'
decolourises bromine water as well as alkaline KMnO4 solution and takes up one mole of H2 (per mole of
B) in the presence of finely divided nickel at high temperature. Identify the substances A and B.

2. A compound 'X' containing C, H and O is unreactive towards sodium. It does not add with bromine. It also
does not react with Schiff's reagent. On refluxing with an excess of HI, 'X' yields only one organic product
'Y'. 'Y' on hydrolysis yields a new compound 'Z' which can be converted into 'Y' by reaction with red
phosphorus and iodine. The compound 'Z' on oxidation with potassium permanganate gives a carboxylic
acid. The equivalent weight of this acid is 60. What are the compounds 'X', 'Y' and 'Z'? Write chemical
equations leading to the conversion of 'X' to 'Y'.

3. An alcohol A, when heated with conc. H2SO4 gives an alkene B. When B is bubbled through bromine water
and the product obtained is dehydro halogenated with excess of sodamide, a new compound C is
obtained. The compound C gives D when treated with warm dilute H2SO4 in presence of HgSO4. D can
also be obtained either by oxidizing A with KMnO4 or from acetic acid through its calcium salt. Identify A, B,
C and D.

4. Write down the reaction involved in the preparation of following using the reagents indicated against in
parenthesis. "Ethyl benzene from benzene". [C2H5OH, PCl5, anhyd. AlCl3]

5. Give reason in one or two sentences for the following:


"o-nitrophenol is steam volatile whereas p-nitrophenol is not."

6. Suggest a reason for the large difference between the boiling points of butanol and butanal, although they
have almost the same solubility in water.

7. A compound of molecular formula C7H8O is insoluble in water and dilute sodium bicarbonate but dissolves
in dilute aqueous solution hydroxide and gives a characteristic colour with aqueous FeCl3. On treatment
with bromine water, it readily gives a precipitate of C7H5OBr3. Write down the structure of the compound.

8. Give a chemical test to distinguish between methanol and ethanol.

9. How may be the following transformation be carried out (in not more than six steps)?
"Ethyl alcohol to vinyl acetate."

10. Complete the following with appropriate structures:


OH
?
OH CHO

11. Explain the following in one or two sentences only:


"Phenol is an acid, but it does not react with sodium bicarbonate."

12. Arrange the following in increasing order of boiling point:


n-butane, n-butanol, n-butyl chloride, iso-butane.

13. Indicate steps which would convert:


(i) phenol to acetophenone
(ii) acetic acid to tert-butyl alcohol

14. Compound X (molecular formula, C5H8O) does not react appreciably with Lucas reagent at room
temperature but gives a precipitate with ammonical silver nitrate with excess of MeMgBr, 0.42 g of X gives
224 mL of CH4 at STP. Treatment of X with H2 in presence of Pt catalyst followed by boiling with excess
HI, gives n-pentane. Suggest structure for X and write the equation involved.
15. Arrange the following in order of their
(i) Increasing basicity
H2O, OH–, CH3OH, CH3O–
(ii) Increasing reactivity in nucleophilic substitution reactions
CH3F, CH3I, CH3Br, CH3Cl

16. When t-butanol and n-butanol are separately treated with a few drops of dilute KMnO 4 in one case only,
the purple colour disappears and a brown precipitate is formed. Which of the two alcohols gives the above
reaction and what is the brown precipitate?

17. 3, 3-dimethylbutan-2-ol losses a molecule of water in the presence of concentrated sulphuric acid to give
tetramethylethylene as a major product. Suggest a suitable mechanism.

18. A compound D(C8H10O) upon treatment with alkaline solution of iodine gives a yellow precipitate. The filtrate
on acidification gives a white solid E (C7H6O2). Write the structures of D, E and explain the formation of E.

19. An optically active alcohol A (C6H10O) absorbs two moles of hydrogen per mole of A upon catalytic
hydrogenation and gives a product B. The compound B is resistant to oxidation by CrO 3 and does not
show any optical activity. Deduce the structure of A and B.
+
20. 2, 2-dimethyloxirane can be cleaved by acid (H ). Write mechanism.

21. Which of the following is the correct method for synthesizing methyl-t-butyl ether and why?
(i) (CH3)3CBr + NaOMe  (ii) CH3Br + NaO-t-Bu 

22. Although phenoxide ion has more number of resonating structures than benzoate ion, benzoic acid is a
stronger acid than phenol. Why?

23. Give reasons for the following in one or two sentences.


"Acid catalysed dehydration of t-butanol is faster than that of n-butanol.

24. An ester A(C4H8O2), on treatment with excess methyl magnesium chloride followed by acidification, gives
an alcohol B as the sole organic product. Alcohol B, on oxidation with NaOCl followed by acidification,
gives acetic acid. Deduce the structures of A and B. Show the reactions involved.

25. Each of the following reactions gives two products. Write the structures of the products:
(i) C6H5CH2CHClC6H5  Alc. KOH, heat

 
HI excess
(ii) (CH3)2CH – OCH3 
heat

26. Explain briefly the formation of the products giving the structures of the intermediates.
H H2 H H2
C C HCl C C H2C
(a) (i) H2C C OH H2C C Cl + CH CH2 Cl + etc.
H2 H2 H2C
CH3 CH3
H H
C CH HCl C CH only
(ii) H2C C H C C
OH 2 Cl
H2 H2
NaNH2
(b) OCH3 OCH3
NH3
Br H2N

27. How would you synthesize 4-emthoxyphenol from bromobenzene in not more than five steps? State clearly
the reagents used in ach step and show the structures of the intermediate compounds in your synthesis
scheme.
84 – ALCOHOL, ETHER & PHENOL – JEE
28. Cyclobutylbromide on treatment with magnesium in dry ether forms an organometallic compound (A). The
organometallic reacts with ethanal to give an alcohol (B) after mild acidification. Prolonged treatment of
alcohol (B) with an equivalent amount of HBr gives 1-bromo-1-methylcyclopentane (C). Write the
structures of (A), (B) and explain how (C) is obtained from (B).

29. Identify X, Y and Z in the following synthetic scheme and write their structures:
 i NaNH
CH3CH2C  CH  2
(ii)CH3 CH2Br
 X
H2 /Pd BaSO4
X  Y 
Alkaline
KMnO4
 Z

30. Convert,
OH

Asprin

31. A (C6H12) 


HCl
 BC
 C6H13 Cl 
B 
Alc. KOH
 D (isomer of A)
D 
Ozonolysis
E (it gives negative test with Fehling solution but respond to iodoform test)
A  F + G (both give positive Tollen's test but do not give iodoform test)
Ozonolysis

F + G  Conc. NaOH


 HCOONa + a primary alcohol.
Identify A to G.

H3C CH2
32.
OH
Write resonance structures of the given compound.
Cl


C2H5 ONa/ C2H5 OH SOCl2
33. 
KCN
DMF
 (A) 
C6H5 CHO/ 
 (B) 
H3 O

 (C) 
CH3 NH2
 (D)

Identify A to D.
O
OH

H / (i) O3
34.   X 
(ii) Zn/ CH3 COOH
 Y 
NaOH

Identify X and Y.
29. Level – 6 (Previous Years Main & Advanced)
JEE-Main
1. In the following reaction sequence:
KOH(aq.) (i) CH 3MgBr Anhy. ZnCl 2 + conc.HCl
I II III gives turbidity immediately
+
(C 3H6Cl 2) (ii) H 2O/H
The compound I is: (Online 2017)
Cl
(A) CH2 CH CH3 (B) CH3 C CH3
Cl Cl Cl
(C) Cl CH CH2 CH3 (D) CH2 CH2 CH2
Cl Cl Cl

2. The major product of the following reaction is: (Online 2017)


OH
(i) K 2CO 3
(ii) CH 3I (1 eq.)
OH
OCH 3 O
(A) (B)
OH
OCH 3 OH
(C) (D)
OCH3

3. The product of the reaction given below is: (Offline 2016)


(i) NBS / hv
X
(ii) H 2O/K 2CO 3

OH O CO 2H
(A) (B) (C) (D)

4. Consider the reaction sequence below: (Online 2016)


OCH 3

Succinic anhydride Clemmenson's


A X
AlCl 3 reduction
X is:
CH3O OH OH
H3CO
(A) (B)

OH OH
OCH 3
H3CO
(C) (D)
86 – ALCOHOL, ETHER & PHENOL – JEE

5. The most suitable reagent for the conversion of R–CH2–OH  R–CHO is: (2014)
(A) PCC (Pyridinium chlorochromate) (B) KMnO4
(C) K2Cr2O7 (D) CrO3

6. Arrange the following compounds in order of decreasing acidity. (2013)


OH OH OH OH

Cl CH 3 NO 2 OCH 3
(I) (II) (III) (IV)
(A) IV > III > I > II (B) II > IV > I > III
(C) I > II > III > IV (D) III > I > II > IV

7. Ortho-nitrophenol is less soluble in water than p-andm-nitrophenols because (2012)


(A) o-nitrophenol shows intramolecular H-bonding
(B) o-nitrophenol shows intermolecular H-bonding
(C) melting point of o-nitrophenol is lower than those of m- and p-isomers
(D) o-nitrophenol is more volatile in steam than those of m- and p-isomers

8. Which of the following reagents may be used to distinguish between phenol and benzoic acid?
(2011)
(A) Tollen's reagent (B) Molisch reagent
(C) Neutral FeCl3 (D) Aqueous NaOH

9. Phenol is heated with a solution of mixture of KBr and KBrO 3. The major product obtained in the above
reaction is: (2011)
(A) 3-Bromophenol (B) 4-Bromophenol
(C) 2, 4, 6-Tribromophenol (D) 2-Bromophenol

10. From amongst the following alcohols the one that would react fastest with conc. HCl and anhydrous ZnCl 2
is: (2010)
(A) 2-Methylpropanol (B) 1-Butanol
(C) 2-Butanol (D) 2-Methylpropan-2-ol

11. The major product obtained on interaction of phenol with sodium hydroxide and carbon dioxide is:
(2009)
(A) benzoic acid (B) salicylaldehyde
(C) salicylic acid (D) phthalic acid

12. -D-(+)-glucose and -D-(+)-glucose are: (2008)


(A) conformers (B) epimers
(C) anomers (D) enanitomers

+
OH O Na
13. + CHCl3 + NaOH 
CHO
The electrophile involved in the above reaction is: (2006)
+
(A) Dichloromethyl cation (C HCl2) (B) Dichlorocarbene (:CCl2)
 
(C) Trichloromethyl anion ( CCl3 ) (D) Formyl cation ( CHO )

14. The increasing order of the rate of HCN addition to compounds I–IV is: (2006)
(I) HCHO (II) CH3COOCH3 (III) PhCOCH3 (IV) PhCOPh
(A) I < II < III < IV (B) IV < II < III < I
(C) IV < III < II < I (D) III < IV < II < I
15. p-cresol reacts with chloroform in alkaline medium to give the compound A which adds hydrogen cyanide
to form the compound B. The latter on acidic hydrolysis gives chiral carboxylic acid. The structure of the
carboxylic acid is: (2005)
CH 3 CH 3 CH 3 CH 3
CH(OH)COOH CH 2COOH CH 2COOH

CH(OH)COOH
OH OH OH OH
(A) (B) (C) (D)
16. The best reagent to convert pent-3-en-2-ol into pent-3-en-2-one is: (2005)
(A) acidic permanganate (B) acidic dichromate
(C) chromic anhydride in glacial acetic acid (D) pyridinium chlorochromate
17. Among the following compounds which can be dehydrated very easily? (2004)
OH
(A) CH3CH2CH2CH2CH2OH (B) CH 3CH 2CH 2 CHCH 3
CH 3
(C) CH 3CH 2 CCH 2CH 3 (D) CH 3CH 2 CHCH 2CH 2OH
OH CH 3

18. The IUPAC name of the compound is: (2004)


HO
(A) 3,3-dimethyl-1-hydroxy cyclohexane (B) 1,1-dimethyl-3-hydroxy cyclohexane
(C) 3,3-dimethyl-1-cyclohexanol (D) 1,1-dimethyl-3-cyclohexanol

19. For which of the following parameters the structural isomers C2H5OH and CH3OCH3 would be expected to
have the same values? (Assume ideal behaviour) (2004)
(A) Heat of vaporization
(B) Vapour pressure at the same temperature
(C) Boiling points
(D) Gaseous densities at the same temperature and pressure
20. During dehydration of alcohols to alkenes by heating with concentrated H2SO4 the initiation step is:(2003)
(A) protonation of alcohol molecule (B) formation of carbocation
(C) elimination of water (D) formation of an ester
21. An ether is more volatile than an alcohol having the same molecular formula. This is due to (2003)
(A) dipolar character of ethers
(B) alcohols having resonance structure
(C) inter-molecular hydrogen bonding in ethers
(D) inter-molecular hydrogen bonding in alcohols

JEE Advance
Single Choice
22. The acidic hydrolysis of ether (X) shown below is fastest when (2014)

acid
OR OH + ROH

(A) one phenyl group is replaced by a methyl group


(B) one phenyl group is replaced by a para-methoxyphenyl group
(C) two phenyl groups are replaced by two para-methoxyphenyl groups
(D) no structural change is made to X
88 – ALCOHOL, ETHER & PHENOL – JEE
23. The compound that does not liberate CO2, on treatment with aqueous sodium bicarbonate solution, is:
(A) benzoic acid (B) benzenesulphoni acid (2013)
(C) salicylic acid (D) carbolic acid (phenol)

24. The major product of the following reaction is: (2011)


RCH2OH

O H (anhydrous)
(A) a hemiacetal (B) an acetal
(C) an ether (D) an ester

25. In the reaction HBr the products are (2010)


OCH3

(A) Br OCH3 and H2 (B) Br and CH3Br

(C) Br and CH3OH (D) OH and CH3Br

26. The increasing order of boiling points of the below metioned alcohols is: (2006)
(I) 1, 2-dihydroxy benzene (II) 1,3-dihydroxy benzene
(III) 1,4-dihydroxy benzene (IV) hydroxyl benzene
(A) I < II < IV < III (B) I < II < III < IV
(C) IV < II < I < III (D) IV < I < II < III

27. The best method to prepare cyclohexene from cyclohexanol is by using (2005)
(A) conc. HCl + ZnCl2 (B) conc. H3PO4
(C) HBr (D) conc. HCl

28. The product of acid catalysed hydration of 2-phenylpropene is: (2004)


(A) 3-phenyl-2-propanol (B) 1-phenyl-2-propanol
(C) 2-phenyl-2-propanol (D) 2-phenyl-1-propanol

OH

OC 2H5
29. + C2 H5 I ? (2003)
Anhydrous (C 2H5OH)
(A) C6H5OC2H5 (B) C2H5OC2H5
(C) C6H5OC6H5 (D) C6H5I

30. 1-Propanol and 2-propanol can be best distinguished by (2001)


(A) oxidation with alkaline KMnO4 followed by reaction with Fehling's solution
(B) oxidation with acidic dichromate followed by reaction with Fehling's solution
(C) oxidation by heating copper with acidic dichromate followed by reaction with Fehling's solution
(D) oxidation with concentrated H2SO4 followed by reaction with Fehling's solution

31. The compound that will react most readily with NaOH to form methanol is: (2001)
+ –
(A) (CH3)4N I (B) CH3OCH3
+ –
(C) (CH3)3S I (D) (CH3)3CCl

Multiple

32. The correct combination of names for isomeric alcoholic with molecular formula C 4H10O is/are (2014)
(A) tert-butanol and 2-methylpropan-2-ol
(B) tert-butanol and 1, 1-dimethylethan-1-ol
(C) n-butanol and butan-1-ol
(D) iso-butyl alcohol and 2-methylpropan-1-ol
33. The reactivity of compound Z with different halogens under appropriate conditions is given below:
mono halo substituted
OH derivative when X2 = I2
di halo substituted
derivative when X2 = Br2
C(CH3)3
Z tri halo substituted
derivative when X2 = Cl2
The observed pattern of electrophilic substitution can be explained by (2014)
(A) the steric effect of the halogen
(B) the steric effect of the tert-butyl group
(C) the electronic effect of the phenolic group
(D) the electronic effect of the tert-butyl group

34. The major product(s) of the following reaction is (are) (2013)


OH

aqueous Br 2 (3, 0 equivalents)


?

SO 3H
OH OH OH OH
Br Br Br Br Br

Br Br Br Br Br
SO 3H Br Br SO 3H
(P) (Q) (R) (S)
(A) P (B) Q (C) R (D) S

35. In the following reaction, the product(s) formed is (are) (2013)


OH
CHCl 3
- ?
OH

CH3
OH O OH OH
OHC CHO CHO

CH3 CH 3 CHCl 2 CH 3 CHCl 2 CH3


(P) (Q) (R) (S)
(A) P (major) (B) Q (minor)
(C) R (minor) (D) S (major)
OH
NaOH(aq)/Br
36. In the reaction the intermediate(s) is (are) (2010)

- - -
O O O O
Br
(A) (B) (C) (D)
Br
Br Br
Br Br
90 – ALCOHOL, ETHER & PHENOL – JEE
Comprehension
CMP: A tertiary alcohol H upon acid catalysed dehydration gives a product I. Ozonolysis of I leads to
compounds J and K. Compound J upon reaction with KOH gives benzyl alcohol and a compound
L, whereas K on reaction with KOH gives only M. (2008)
O
H3C Ph
M=
Ph H

37. Compound H is formed by the reaction of


O O
(A) + PhMgBr (B) + PhCH 2MgBr
Ph CH3 Ph CH3
O O Me
(C) + PhCH2MgBr (D) +
Ph H Ph H Ph MgBr

38. The structure of compound I is:


Ph CH3 H3C Ph
(A) (B)
H Ph H Ph
Ph CH 3 H3C CH 3
(C) (D)
H CH 2Ph Ph H

39. The structures of compound J, K and L, respectively are


– +
(A) PhCOCH3, PhCH2COCH, and PhCH2COO K
– +
(B) PhCHO, PhCH2CHO and PhCOO K
(C) PhCOCH3, PhCH2CHO and CH3COO–K+
– +
(D) PhCHO, PhCOCH3 and PhCOO K

CMP: Reimer-Tiemann reaction introduces an aldehyde group, on to the aromatic ring of phenol, ortho to
the hydroxyl group. This reaction involves electrophilic aromatic substitution. This is general
method for the synthesis of substituted salicylaldehydes as depicted below: (2007)

OH O Na OH
CHO CHO
aq. HCl
[I]
Intermediate
CH3 CH3 CH3
(I) (II) (III)
40. Which of the following reagents is used in the above reaction?
(A) aq. NaOH + CH3Cl (B) aq. NaOH + CH2Cl2
(C) aq. NaOH + CHCl3 (D) aq. NaOH + CCl4

41. The electrophilic in this reaction is:


+
(A) : CHCl (B) CHCl2
(C) : CCl2 (D) .CCl3

42. The structure of the intermediate I is:

O Na O Na O Na O Na
CH2Cl CHCl2 CCl3 CH2OH
(A) (B) (C) (D)

CH3 CH3 CH3 CH3


Match the Column
43. Match the chemical conversions in List I with the appropriate reagents in List II and select the correct
answer using the code given below the lists: (2013)
Column I Column II

(P) Cl (1) (i) Hg(OAc)2 (ii) NaBH4

(Q) ONa OEt (2) NaOEt

(R) OH (3) Et–Br

(S) (4) (i) BH3; (ii) H2O2/NaOH

OH
P Q R S
(A) 2 3 1 4
(B) 3 2 1 4
(C) 2 3 4 1
(D) 3 2 4 1

Single Integer
44. The number of hydroxyl group(s) in Q is: (2015)
+
H aqueous dilute KMnO4 (excess)
H P Q
heat o
HO 0 C
H3C CH3

30. Level – 7 (NCERT Corner)


1. (i) Draw the structures of all isomeric alcohols of molecular formula C5H12O and give their IUPAC
names.
(ii) Classify the isomers of alcohols as primary, secondary and tertiary alcohols.
Sol. (i) The structures of all isomeric alcohols of molecular formula, C5H12O are shown below:
(a) CH3 – CH2 – CH2 – CH2 – CH2 – OH (Pentan-1-ol (1))
(b) CH3 CH2 CH CH2 OH
CH3
2-Methylbutan-1-ol (1 o )
(c) CH3 CH CH2 CH2 OH
CH3
3-Methylbutan-1-ol (1 o )
CH3
(d) CH3 C CH2 OH
CH3
2,2-Dimethylpropan-1-ol (1 o )
CH3
(e) CH3 CH2 CH2 CH CH3
o
Pentan-2-ol (2 )
CH3 OH

(f) CH3 CH CH CH3


 
3  Methylbu tan 2  ol 2o
92 – ALCOHOL, ETHER & PHENOL – JEE
OH
(g) CH3 CH2 CH CH2 CH3
 
Pen tan 3  ol 2o
OH
(h) CH3 CH2 C CH3
CH3
2  Methylbu tan 2  ol 3o  
(ii) Primary alcohol: Pentan-1-ol; 2-Methylbutan-1-ol; 3-Methylbutan-1-ol; 2, 2−Dimethylpropan-1-ol
Secondary alcohol: Pentan-2-ol; 3-Methylbutan-2-ol; Pentan-3-ol
Tertiary alcohol: 2-methylbutan-2-ol

2. What is meant by hydroboration-oxidation reaction? Illustrate it with an example.


Sol. The addition of borane followed by oxidation is known as the hydroboration-oxidation reaction. 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 - BH 2) 2 CH3 CH CH2
Propene Diborane H BH2

CH3 CH CH2

CH3 CH CH2
 CH3  CH2  CH2 3 B  CH3  CH2  CH2 2 BH

H2O 3H 2O 2, OH

3 CH 3 CH2 CH2 OH + B(OH) 3


Propan-1-ol

3. Give the structures and IUPAC names of monohydric phenols of molecular formula, C7H8O.
OH OH OH
CH 3
Sol.
CH 3
2-Methylphenol
3-Methylphenol CH 3
(o-Cresol) 4-Methylphenol
(m-Cresol)
(p-Cresol)

4. While separating a mixture of ortho and para nitrophenols by steam distillation, name the isomer which will
be steam volatile. Give reason.
Sol. Intramolecular H-bonding is present in o-nitrophenol and p-nitrophenol. In pnitrophenol, the molecules are
strongly associated due to the presence of intermolecular bonding. Hence, o-nitrophenol is steam volatile.
Intramolecular
O O H-bonding
N H Intramolecular
O H-bonding
O HO N O
O HO N
O
o-Nitrophenol p-Nitrophenol
5. Give the equations of reactions for the preparation of phenol from cumene.
Sol. To prepare phenol, cumene is first oxidized in the presence of air of cumene hydroperoxide.
CH3 CH3
CH3 CH CH3 C O O H
O2, 368-408K

Cumene Cumene
(Isoprophylbenzene) hydroperoxide
Then, cumene hydroxide is treated with dilute acid to prepare phenol and acetone as byproducts.
CH3
CH3 C O O H OH
+
H
323-363 K + CH3COCH3

Phenol Autone
Cumene
hydroperoxide

6. Write chemical reaction for the preparation of phenol from chlorobenzene.


Sol. 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 HCl
+ 2NaOH
320 atm
Chlorobenzene Sodium phenoxide Phenol

7. Write the mechanism of hydration of ethene to yield ethanol.


Sol. 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:
H H H H
+
H +
H C C + H2O H C C O H
H
H H H
Step 3:
H H H H OH
+ +
H C C O H + H2O H C C H + H3O
H H H H

8. You are given benzene, conc. H2SO4 and NaOH. Write the equations for the preparation of phenol using
these reagents.
SO 3H ONa OH
Conc. H 2SO 4 NaOH H2SO 4
Sol.

Benzene Benzene Sodium
sulphonic acid phenoxide
94 – ALCOHOL, ETHER & PHENOL – JEE
9. 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?
Sol. (i) By acid-catalyzed hydration of ethylbenzene (styrene), 1-phenylethanol can be synthesized.
CH CH 2 + CH CH 2
H
+ H2O OH
Phenylethene 1-phenylethanol
(ii) When chloromethylcyclohexane is treated with sodium hydroxide, cyclohexylmethanol is obtained.
CH 2Cl CH 2OH

+ NaOH + NaCl

Chloromethylcyclohexane Cyclohexylmethanol
(iii) When 1-chloropentane is treated with NaOH, pentan-1-ol is produced.
CH3 CH2 CH2 CH2CH2 Cl  NaOH  CH3 CH2CH2 CH2CH2OH  NaCl
1Chloropentane Pantan1ol

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

+ Na + 1
H2
2
Phenol Sodium phenoxide
(ii) Phenol reacts with sodium hydroxide to give sodium phenoxide and water as byproducts.
OH ONa

+ NaOH + H2O

Sodium phenoxide
The acidity of phenol is more than that of ethanol. This is because after losing a proton, the phenoxide ion
undergoes resonance and gets stabilized whereas ethoxide ion does not.

O O O O O

11. 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 with phenol.
(iv) Treating phenol with chloroform in presence of aqueous NaOH.
alc. KMnO4
Sol. (i) CH3 CH2 CH2 OH   CH3 CH2 COOH
Propan1ol Propanoic acid
OH OH OH
Br
Br 2 in CS 2
+
(ii) 273 K
Phenol o-Bromophenol
Br
(Minor)
p-bromophenol
(Major)
OH OH OH
NO 2
(iii) dilute HNO 3
+

o-Nitrophenol
NO 2
p-Nitrophenol
+ +
OH ONa ONa OH
CHCl 2 CHO + CHO
CHCl 3 + aq. NaOH NaOH H
(iv)

Salicylaldehyde
Intermediate

12. Explain the following with an example.


(i) Kolbe’s reaction.
(ii) Reimer-Tiemann reaction.
(iii) Williamson ether synthesis.
(iv) Unsymmetrical ether.
Sol. (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 as the main product. This reaction is
known as Kolbe’s reaction.
OH ONa OH
COOH
NaOH (i) CO 2
+
(ii) H
Phenol Sodium phenoxide Ortho-hydroxybenzoic acid
(Saliclic 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
CHCl 2
CHCl 3 + aq. NaOH

Phenol
Intermediate
This reaction is known as the Reimer-Tiemann reaction. The intermediate is hydrolyzed in the
presence of alkalis to produce salicyclaldehyde.
+ +
ONa ONa OH
CHCl 2 CHO CHO
+
NaOH H

Salicylaldehyde
Intermediate
(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 O Na R O R + NaX
Akyl halide 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 O Na + CH3 Br CH3 O CH CH3 + NaBr
If the alkyl halide is secondary or tertiary, then elimination competes over substitution.
96 – ALCOHOL, ETHER & PHENOL – JEE
(iv) Unsymmetrical ether: An unsymmetrical ether is an ether where two groups on the two sides of an
oxygen atom differ (i.e., have an unequal number of carbon atoms). For example: ethyl methyl
ether (CH3−O−CH2CH3).

13. Write the equation of the reaction of hydrogen iodide with:


(i) 1-propoxypropane (ii) methoxybenzene and (iii) benzyl ethyl ether.
Sol. (i) C2H5 CH2  O  CH2 C2H5  HI 373 K
 CH3 CH2CH2  OH  CH3CH2CH2  I
1Propoxypropane Propan1ol 1Iodopropane
OCH 3 OH

(ii) + HI + CH 3 I

Methoxybenzone Phenol Iodomethane


CH 2 O C2 H 5 CH 2I

(iii) + HI + C2H5 OH

Benzyl ethyl ether Benzyl iodide Ethanol

14. 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.
OCH 3 OCH 3 OCH 3
CH 3
Anhyd. AlCl 3
Sol. (i) + CH 3Cl +
CS 2
Anisole 2-Methoxytoluene
CH 3 (Minor)
4-Methoxytoluene
(Major)
OCH 3 OCH 3 OCH 3
NO 2
H2SO 4
(ii) +
HNO 3
Anisole 2-Nitroanisole
NO 2
(Minor)
4-Nitroanisole
(Major)
OCH 3 OCH 3 OCH 3
Br
Br2 in
(iii) +
Ethanoic acid
Anisole o-Nitroanisole
Br
(Minor)
p-Bromoanisole
(Major)
OCH 3 OCH 3 OCH 3
COCH 3
Anhyd.
(iv) + CH 3COCl +
AlCl 3
Anisole Ethanoyl chloride 2-Methoxy-
COCH 3
actophenone
4-Methoxy-
(Minor) acetophenone
(Major)
15. Show how would you synthesise the following alcohols from appropriate alkenes?
CH3 OH
(i) OH (ii)

OH
(iii) (iv) OH
Sol. (i) The given alcohols can be synthesized by applying Markovnikov’s rule of acid-catalyzed hydration
of appropriate alkenes.
CH 3
+ H 2O +
H
CH 3
1-Methylcyclohexene OH
+
H
CH 2 1-Methylcyclohexan-1-ol
+ H 2O

Methylenecyclohexene
+ OH
H
(ii) + H2O

4-Methylhept-3-ene 4-Methylheptan-4-ol
OH
+
H
(iii) + H2O
Pent-1-ene Pentan-2-ol
Acid-catalyzed hydration of pent-2-ene also produces pentan-2-ol but along with pentan-3-ol.
OH
+
H
+ H2O +
Pent-2-ene Pentan-2-ol
OH
Pentan-3-ol
Thus, the first reaction is preferred over the second one to get pentan-2-ol.
+
H
(iv) + H2O OH

2-Cyclohexylbut-2-ene 2-Cyclohexylbutan-2-ol
98 – ALCOHOL, ETHER & PHENOL – JEE

31. Answer Sheet


Quiz – 1
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15

C D A C D C B A BC C C B B C B

16 17 18 19 20 21 22 23 24 25

A C C D A C A A B D

Quiz – 2
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15

B B B A D A C A A B C B C A C

16 17 18 19 20

C B B A D

Quiz – 3
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15

C C C B C C D C C C A A A B C

Quiz – 4
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15

B B D C A C C D B D A D D D C

Level – 1 (Main)
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15

B B D B C B D A D A A C C C A

16 17 18 19 20 21 22 23 24 25 26 27 28 29 30

C C B D A C A A D B A B A D C
Level – 2 (Main)
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15

A B A A A A D A A C C D C C D

16 17 18 19 20 21 22 23 24 25 26 27 28 29 30

A A A B D A B B B A B B D A C

Level – 3 (Advanced)
Single Choice
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15

B B D B C B D B A D A A D C C

16 17 18 19 20 21 22 23 24 25 26 27 28 29 30

C C A D B C A A D C A A A D B

Multiple Choice
31 32 33 34 35 36 37 38 39 40

BC AB BCD BD BC BD AD AD AD AC

41 42 43 44 45

AD ABD AB ABD BD

Level – 4 (Comprehension & Match the Column)


1 2 3 4 5 6 7 8 9 10 11 12 13 14 15

C C C C B A D C A A B B B C C

16 17 18 19 20 21

A B B B B A

22. A–Q, B–R, C–S, D–P 23. A–R, B–Q, C–S, D–P 24. A–S, B–R, C–P, D–Q

25. A–S, B–R, C–P, D–Q 26. A–Q, B–QS, C–S, D–P

Level – 5 (Subjective Type)


1. Since hydrocarbon 'B' decolourise Br2 water as well as alkaline KMnO4 solution, so it is an unsaturated
hydrocarbon.
Since 'B' takes only one mole of H2, it contains only one double bond. Hence, compound 'B' is ethene.
C2H4  H2 Ni
High T
C2H6
(B)

Compound 'B' decolourise bromine water as well as alkaline KMnO 4 solution as follows
Alk. KMnO4 CH2OH
C2H4  4H2 O  [O]  
(B) CH2OH
C2H4  Br2  CH2Br  CH2Br
(B)

Ethyl alcohol on heating with conc. sulphuric acid gives ethene, thus the organic liquid 'A' is ethyl alcohol.
100 – ALCOHOL, ETHER & PHENOL – JEE
Conc. H2 SO4
C2H5 OH   C2H4  H2 O
'A' 'B '
 ethyl alcohol   ethene
2. Since the compound 'X' does not react with sodium, so it is neither and acid, nor an alcohol (–OH group
absent). Compound 'X' does not react with Schiff's reagent, so it is not an aldehyde.
Compound 'X' yields only one product with excess of HI, so it may be an ether and last product of the given
sequence of reactions is an acid with molecular weight 60, so the acid is acetic acid (CH3COOH) and the
ether is diethyl ether.
(because acid is a 2C compound, so ether contains 4 carbons.)
HI Hydrolysis
C2H5OC2H5 C2 H5 I C2H5OH
excess
'X' 'Y' 'Z'
KMnO 4
Read P, I 2
CH3COOH

3. (i) Since D is also obtained by distillation of calcium acetate as well as oxidation of A by KMnO4.
Hence, D is acetone and A is propan-2-ol.
CH3COO Distillation
2 Ca 2CH3COCH3 + 2CaCO3
CH3COO
acetone
calcium acetate (D)
[O]
H3C CH CH3 CH3COCH3
KMnO 4
OH acetone
(D)
Propan-2-ol
(A)
(ii) A on treatment with conc. H2SO4 gives B
Conc. H2SO4
H3C CH CH3 H3C CH CH2
H2 O
OH propene
(B)
(iii) B reacts with Br2 and subsequent dehydrobromination by NaNH2 produces C.
Br2
H3C CH CH2 H3C CH CH2
Br Br
1, 2-dibromopropane
NaNH2
H3C CH CH2 H3C C CH
2HBr
Br Br propyne
(C)

(iv) C with dil. H2SO4 in presence of HgSO4 gives D.


H2SO 4
H3C C CH + H2O CH3COCH3
HgSO4
acetone
(D)

4. C2H5OH + PCl5  C2H5Cl + POCl3 + HCl


C2 H5
Anhy. AlCl 3
C2H5Cl
+ + HCl
ethyl chloride
benzene ethyl benzene

5. o-nitrophenol has lower boiling point, so it is more volatile and is less miscible with steam than p-
nitrophenol due to intramolecular hydrogen bonding, and hence, can be separated by steam distillation.
6. Butanol has greater capacity for inter molecular hydrogen bonding than butanal.
7. C7H8O has following isomeric compounds:
CH2OH CH3 CH3 CH3
OH

OH
benzyl o-cresol m-cresol
OH
alcohol
p-cresol
Since, the compound is insoluble in water and NaHCO 3 but dissolve in NaOH and gives characteristic
colour with FeCl3, hence it must be phenol ie, o-, p- or m-cresol.
OH
CH3 3Br2 Br Br
C6 H 5
CH3 3HBr
CH3
m-cresol
Br
(C7H5OBr 3)
Thus, the compound may be a m-cresol.

8. Ethanol give iodoform test, while methanol does not.


C2H5OH + 4I2 + 6NaOH  CHI3  + 5NaI + HCOONa + 5H2O
iodorom

CH2 CH2
Br Br  CH COO 
9. CH3CH2OH Conc. H2 SO4

CH2  CH2 
Br2

Alc. KOH
 CH  CH 
3
CH3 COOH
2

ethylene acetylene
H2 O

CH2  CH  O.COCH3
vinyl acetate

OH
CHCl3/NaOH
10. OH CHO

phenol salicylaldehyde

11. Phenol is a very weak acid, hence it does not react with sodium bicarbonate.

12. iso-butane < n-butane < n-butyl chloride < n-butanol.


13. (i) Phenol to acetophenone:
CH3 COCl
C6H5 OH 
Zn dust
 ZnO
 C6H6 
anhydrous AlCl3
 C6H5 COCH3
phenol benzene HCl acetophenone

(ii) Acetic acid to tertiary butyl alcohol:


+
H3C CH3 H2O(H ) H3C CH3
PCl5 CH3 Cl CH3 MgI
CH3 COOH 
 CH3COCl  CH3COCH3 
 C
OH
C
acetic acid acetyl chloride acetone
H3C O MgI H3C OH
H OH Mg
I tert. butyl alcohol
Lucas reagent
14. Compound 'X' No reaction at room temperature
(Mol. formula (C 5H8O))

Ammoniacal Excess (i) H 2/Pt


Precipitates CH4 n-pentane
AgNO 3 MeMgBr (ii) Boil with excess HI
Hence, in compound X, five C-atoms are present in straight chain. It gives methane with excess Grignard
reagent, so in it acidic hydrogen is present. It gives precipitates with ammoniacal AgNO 3, therefore it must
have acidic hydrogen in form of alkynic group. It does not give any reaction with Lucas reagent, therefore it
has a p-alcoholic group.

Thus, on the basis of above properties, the possible structure of compound X is given as follows:
HC  C – CH2 – CH2 – CH2OH (mol. formula C5H8O)
102 – ALCOHOL, ETHER & PHENOL – JEE
Reaction
(i) HC  C – CH2 – CH2 – CH2OH 
Lucas reagent
at room temperature
 No reaction
(ii) HC  C – CH2CH2 – CH2OH + AgNO3 + NH4OH  AgC  C CH2  CH2  CH2 OH  NH4NO3 + H2O
White ppt.

(iii) H – C  C – CH2 – CH2 – CH2OH + 2MeMgBr  BrMg – C  C – CH2 – CH2 – CH2O – MgBr + 2CH4
(iv) HC  C – CH2 – CH2 – CH2OH + 2H2  Pt
 CH3 – CH2 – CH2 – CH2 – CH2OH
 Boil HI
 I2 , H2 O  CH3  CH 2  CH2  CH2  CH3
n  pen tan e

Compound 'X' is HC  C – CH2 – CH2 – CH2OH.


– –
15. (i) The increasing order of basicity is: H2O < CH3OH < OH < CH3O
(ii) The increasing order of reactivity in SN reaction is: CH3F < CH3Cl < CH3Br < CH3I

16. t-butanol is not oxidized with dil. KMnO4, so it does not give brown precipitates. n-butanol is oxidized with dil.
KMnO4, so it is able to disappear the purple colour of KMnO4 and to give the brown precipitate of MnO2.
3CH3 – CH2 – CH2 – CH2OH + 2KMnO4  CH3 – CH2 – CH2 – CHO + 2MnO2  + 2KOH + 2H2O
brown ppt.

CH3 CH3 CH3


Conc. H2SO 4
17. CH3 C CH CH3 CH3 C C CH3 + H2O

CH3 OH (major product)
Mechanism of above reaction is represented as follows:
CH3 + CH3
H
CH3 C CH CH3 CH3 C CH CH3
+
CH3 OH CH3 OH2
CH3 H CH3 + CH3 CH3
+ + H
CH3 C C CH3 CH3 C CH CH3 CH3 C C CH3 (Major product)
H2O
CH3 CH3
(more stable) (less stable)
I2 NaOH
18. Compound D   CHI3   compound (filterate) 
 C7H6 O2   Compound E
Acid

 C8 H10 O   yellow ppt.


Thus, this reaction indicates the presence of – COCH3 group or presence of – CHOH – CH3 group in given
compound D. On the basis of molecular formula of compound D and above reaction, the possible structure
is given below:

CH CH3
OH
Thus, this compound gives iodoform test as in following reaction. (in first step this compound on oxidation

with I2 gives COCH3)

CH CH3 + 3I 2 + NaOH COONa + 3NaI + 3H2O + CHI3


OH yellowish
(D) crystalline
solid
Acidification
COONa COOH
(other compound) benzoic acid
(filterate) (C7H6O 2)
Hence, compounds
D= CH CH3 (C8H10O2)
OH

C O H
E= (C7H6O2)
O
CrO3
19. C6H10 O  2H2 
Catalyst
 C6H14 O   No reaction
 optically active  compound B
compound A  optically inactive
Compound A is unsaturated monohydric alcohol and it has either two C = C bonds or one triple bond.
Compound A is optically active and after hydrogenation optically inactive compound 'B' is obtained which is
not oxidized with CrO3. Hence, in it –OH group is attached with tertiary C-atom ie, it is a tertiary alcohol.
Thus, the possible structure of A is given as below:
OH
CH *C C CH
3
CH2 CH3
*C  Asymmetric C-atom and due to presence of it, it shows optical activity.
OH OH
* Catalyst *
CH C C CH + 2H
3 CH 2 C CH CH 3 2 3
CH2 CH3 CH2 CH3
Compound A Compound B
(optically active) (optically inactive)
20. The oxirane ring is cleaved by the following mechanism:
OH 2
H3C + H3C OH
H H2O H3C   CH2 H3C C CH2 +
+
H
H3C O H3C + C
O H3C 
O CH3 OH
H H
transition state
(intermediate state)
21. In these two methods, method (ii) is the correct method for the formation of ether because in method (i),
alkene is formed in place of ether.
(i) (CH3)3C – Br + Na – O – Me  CH3 C CH2 + NaBr + CH3OH
CH3
iso-butene
CH3 CH3
(ii) CH3Br + Na O C CH3  H3C C O CH3 + NaBr
CH3 CH3
This reaction is called as Williamson's synthesis and it is based upon SN2 reaction mechanism.
22. The resonating structure of phenoxide is given as below:
O O O O O

(I) (II) (III) (IV) (V)

Resonating structures of phenoxide ion


104 – ALCOHOL, ETHER & PHENOL – JEE
- -
O O O O
C C

Resonating structures of benzoic ion


Resonating structure of phenoxide ion
In resonating structure of phenoxide, negative charge is present on C-atom (which is less electronegative)
while in benzoate ion, negative charge is present on more electronegative atom. Hence, in ionic structure,
if negative charge is present on more electronegative atoms, therefore it is more stable in comparison to
that ion which have negative charge on less electronegative atoms.
Thus, due to higher stability of benzoate ion, it is able to provide more H+, so it is more acidic.
C6H5 OH    C6H5 O  H
less stable

C6H5 COOH    C6H5 COO   H


more stable

So, order of acidic strength C6H5COOH > C6H5OH

23. Due to formation of more stable 3-carbonium ion with t-butanol than 1-carbonium ion in n-butanol.
+
H + +
CH3 CH2 CH2 CH 2OH CH3 CH2 CH2 CH2 CH3 CH2 CH CH3
H2O
n-butanol 1  carbonium ion
o

although it ischanged in 2o  carbonium ion


CH3 + CH3
H +
CH3 C OH CH3 C (3o  carbonium ion)
CH3 CH3

Ester  A  
 3
Alcohol B  
i CH MgBr NaOCl
24. ii acidification CH3 COOH
 C4H8 O2 
Hence, compound B is secondary alcohol because it gives CH3COOH which contains lesser number of C-atom
w.r.t. alcohol. So, compound A is formate ester (because other esters with excess Grignard reagent give t-
alcohol).
CH3 + CH3
Step (i) H2O/H Step (ii) CH 3MgBr
H C OC 3H7 + CH3MgBr H C OC 3H7 H C
(-C3H7O-MgBr) (excess)
O O MgBr O
A
+ CH3
4[O] [O] H3C H2O/H
CH3COOH CHOH H C CH3
H2O + CO 2 + CH3COOH (-Mg(OH)Br)
NaOCl H3C
(-H2O) 'B' O MgBr
+
H2O/H H3C OH
C3H7 O MgBr CHOH + Mg
H3C Br
'B'
CH3
Hence, C3H7 group is CH
CH3
CH3
Thus, compound A is H C CH
CH3
O
Compound B is CH3 – CHOH – CH3
Cl
Alc. KOH C6H5 C C H +
C6 H 5
C C
C 6 H5
25. (i) C6H5 CH2 CH C6H5
 H C6 H 5 H H
trans-isomer of stibene (major) cis-isomer of stibene (minor)
H3C HI H3C
(ii) CH O CH3 CHI + CH3I + H2O
excess
H3C H3C
isopropyl iodide

26. (a)
+ 3 1 +
CH2 H Cl
CH 4 CH 2 CH2 + CH CH2 CH CH2
(i) H2C OH of HCl H2C OH2 H2O H2C of HCl H2C Cl
CH2 CH2 CH2 CH2
(first product)
The reaction occurs by SN2-mechanism but has considerable SN1-mechanism also because
leaving group is good one and nucleophile is poor (weak). Therefore, C1 develops partial positive
charge due to which thus C3-atom leading to cyclisation.
+
CH CH2 CH2 CH2
+ Cl
H2C CH2 CH2 CH Cl CH2 CH
CH2 CH2
(second product)

CH3 +
CH3 CH3 CH3
H H2O + Cl
(ii) CH CH CH CH CH CH CH CH
of HCl + of HCl
H2C CH2 OH H2C CH2 OH2 H2C CH2 H2C CH2 Cl
Here, positive charge of such C-atom is decreased by +I effect of –CH3 group. So, cyclisation is
not possible. Hence, here cyclic product is not formed.

NH2
(b) OCH 3 O CH3 O CH3
+ of NaNH 2
Br + H
H Br H benzyne derivative

NH3
OCH 3 O CH3
(-NH 2)
H2N H2N
(major final product) (major intermediate product)

Br OH OMe OMe
NaOH Me 2SO 4 conc. H2SO 4
27. at higher -MeHSO 4 higher temp.
pressure and temp. (-H2O)
bromo benzene phenol anisol
SO 3H
p-methoxy benzene
sulphonic acid
OMe OMe
+
H3O Fuse with NaOH
(-Na2SO 3, -2H2O)

OH ONa
4-methoxy phenol sodium salt of
4-methoxy phenol
106 – ALCOHOL, ETHER & PHENOL – JEE

H OH
H3C
H3C C O MgBr
28. C O H
Br Mg MgBr H
Dry ether (ethanal)
cyclobutyl bromide cyclobutyl magnesium
bromide (A)

Br CH3 H3C
+
HBr C OH H2O/H
H
-Mg(OH)Br
1-bromo 1-methyl
cyclopentane (C) 1-cyclobutyl ethanol
(B)
Mechanism of formation of compound 'C' from B
H3C H3C +
H3C +
C O H C OH 2 C H3C H
H + H H C
H H2O +
H
'B' (oxonium ion) (for stabilization) secondary
carboniumion
CH3
Br CH3 +
C Br H C Shifting of H ion
H
'C'
H2 /Pd BaSO4
 ii CH3  CH2Br  X  Y 
CH3 – CH2 – C  CH  Z
(i) NaNH2 Alkaline
29. KMnO4

The nature of Z may be identified as follows:


 i NaNH  3 2 ii CH CH Br
CH3 – CH2 – C  CH 
 NH3   CH3 – CH2 – C  C – Na 
2
 NaBr   CH3  CH2  C  CCH2  CH3
Compound ' X '

OH OH
CH3 CH2 C C CH2 CH3
CH3 CH2 C C CH2 CH3
H H
cis-hexene-3 H H
H2 /Pd BaSO4 compound 'Y'  
H O O compound 'Z'

Partial hydrogenation
  2
with alkaline KMnO4

 hydroxylation 
Hence, 'Z' is meso-isomer for optical active compound. Thus, 'Z' is optically inactive due to internal
compensation (which is due to presence of plane of symmetry).
OH OH OH OCOCH3
COONa COOH (CH CO) O COOH
NaOH + CO2 HCl 3 2
30.
o
at 140 C 4-12 atm CH3COOH
phenol pressure aspirin
(Kolbe's reaction)

31. A(C6H12) 


HCl
 BC
 C6H12 Cl
B Alc. KOH
 D
D 
Ozonolysis
E (it gives negative test with Fehling solution but responds to iodoform test)
A  F + G (both give positive Tollen's test but do not give iodoform test)
Ozonolysis

F + G  Conc. NaOH


 HCOONa + A primary alcohol
In F and G, both are aldehyde because they give positive Tollen's test and do not give iodoform test. These
aldehydes give cross Cannizaro's reaction, so they do not have -hydrogen atom. In cross Cannizaro's
reaction, HCOONa is formed along with p-alcohol. So in these, an aldehyde is HCHO and another is
(CH3)3CCHO, F and G are obtained by ozonolysis of A, therefore, compound A is CH2 = CH – C(CH3)3
Structure of compound A is
H3C
H3C C CH CH2
H3C
Compound A on reaction with HCl gives compound B and C which have C6H13Cl molecular formula. Thus,
CH3 CH3 CH3
HCl
CH3 C CH CH2 CH3 C CH CH3 CH3 C CH2 CH2Cl
CH3 CH3 Cl CH3
Compound A Compound B Compound C

Compound B gives D on dehydrohalogenation with alc. KOH


CH3 CH3 CH3
Alcoholic KOH + + CH3 +
H3C CH3
CH3 C CH CH3 CH3 C CH CH3 CH3 C CH H
C C
boil (-Cl ) CH3 H3C CH3
CH3 Cl CH3
(sec. carbonium ion) Compound D

Compound D on ozonolysis give compound E


H3C CH3 Ozonolysis
C C 2 CH3 C CH3
H3C CH3
O
Compound E

Compound E has methyl ketonic group (–COCH3), so it gives positive iodoform test and does not give the
test with Fehling solution due to absence of –CHO group.

Compound A on ozonolysis gives compound F and G as follows:


CH3 CH3
Ozonolysis
CH3 C CH CH2 CH3 C CHO + CH2O(HCHO)
CH3 CH3 Compound F
Compound A Compound G

Compound G and F give crossed Cannizaro's reaction with conc. NaOH solution.
CH3 CH3
CH3 C CHO + CH2O + conc. NaOH HCOONa + CH3 C CH2OH
CH3 Compound F CH3
Compound G primary alcohol
CH3 CH3
Hence, Compound A = CH3 C CH CH2 , B = CH3 C CH CH3,
CH3 (C H
6 12 ) CH3 Cl
CH3 O
C = CH3 C CH2 CH2Cl , D = CH3 C C CH3, E = CH3 C CH3,
CH3 CH3 CH3
O CH3
F=H C H (CH2O), G = CH3 C CH2OH
CH3

32. Resonating structures


H3C CH2 H3C + CH2

OH OH
(I) (II)
Resonating Structure
108 – ALCOHOL, ETHER & PHENOL – JEE
CN
Ph CH C
CH2Cl CH2CN +
KCN Na O Et
33.
DMF EtOH
(A) PhCHO,  (B)
COOH
O Ph CH C +
H3O 
C NH CH3 (i) SOCl 2
Ph CH C
(ii) CH 3NH2
(C)

(D)
Note: 1. In the second step involving formation of B from A initially.
OH CN
Ph CH CH

1. is formed which on heating dehydrates to


CN
Ph CH C

2. In the last step involving formation of D from C initially


C
C Cl
Ph CH C

is formed which afterwards converted to D.

+ H +
OH O CH2
+ H +
34. H  Ring + H
H2O expansion
(X)
CH3
O (i) O 3
H C O
(ii) Zn + CH3COOH

(Y)
Level – 6 (Previous Years Main & Advanced)
1 2 3 4 5 6 7 8 9 10

B A B D A D A C C A

11 12 13 14 15 16 17 18 19 20

C C B C B C C C D A

21 22 23 24 25 26 27 28 29 30

D C D B D C B C B C

31 32 33 34 35 36 37 38 39 40

A ACD ABC B BD AC B A D C

41 42 43 44

C B A 4

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