You are on page 1of 44

A-49, Maulana Azad Sarani, City Centre, Durgapur -16, (WB) Call-7699999929

Response @ www.iitjeeguru.in
Alcohols are organic compounds containing a hydroxyl group attached to a saturated carbon atom and
having the general formula ROH, where R can be an alkyl or a substituted alkyl group.
Alcohols can be monohydric or polyhydric depending on whether they contain one or more hydroxyl
groups. Alcohols can also be classified as primary (1), secondary (2), or tertiary (3) depending on
whether the hydroxyl-bearing carbon atomis attached to one, two, or three carbon atoms.
Preparation of Alcohols
Alcohols are starting point for organic synthesis of a number of compounds and can be obtained from
organic raw materials in nature like petroleum, natural gas, coal, and biomass. Some important methods for
preparing alcohols are
1. Grignard Synthesis
C =O +R MgX
C OMgX
R
+
+
o+ o
H
2
O
R
C OH + Mg(OH)X
Mg(OH)X is a gelatinous material and is difficult to handle. It is converted to water-soluble magnesium
salts by mineral acids.
Mg(OH)X
Mg
2+
+X +H
2
O
H
+

Grignard synthesis is an example of nucleophilic additionthe characteristic reaction of aldehydes and


ketones. The class of alcohol obtained in the reaction depends upon the type of carbonyl compound
used. Formaldehyde yields primary alcohols, aldehydes with more than one carbon atomyield secondary
alcohols, and ketones yield tertiary alcohols.
C =O + R MgX
+
H C OMgX
R

H
H
2
O
R CH
2
OH
1 alcohol
H
H
Formaldehyde
C =O + R' MgX
+
R C OMgX
R'

H
H
2
O
RR' CH OH
2 alcohol
H
R
Higher aldehydes
C =O + R MgX
+
R' C OMgX
R

R''
H
2
O
R''
R'
Ketones
R' C OH
R
R''
3 alcohol
ALCOHOLS, PHENOLS
AND ETHERS
A-49, Maulana Azad Sarani, City Centre, Durgapur -16, (WB) Call-7699999929
Response @ www.iitjeeguru.in
A convenient synthesis of primary alcohol uses ethylene oxide, and the primary alcohol formed has
two more carbon atoms than the Grinard reagent.
H
2
C CH
2
+ R MgX H
2
C CH
2
R R CH
2
CH
2
OH
OMgX
1alcohol
O
Ethylene oxide
Organolithiumcan also be used for the synthesis of alcohols.
o+
C =O + R Li
Alcohol
C O

Li
+
H
2
O
C OH
R
o
Aldehyde/Ketone
The synthesis of alcohols by using organolithiums is a better method than by using Grignard reagents,
because organolithiumcompounds are less prone to unwanted side reactions and are more reactive than
Grignard reagents. Besides, organolithiums can be used to prepare alcohols fromhighly crowded carbonyl
compounds.
2. Hydrolysis of Alkyl Halides
This method involves nucleophilic substitution of a halide ion by a hydroxyl ion.
R X
aq. NaOH
R OH
or aq. KOH
S
N
l or S
N
2
Example:
aq. NaOH
CH
2
Cl CH
2
OH
3. Hydroxylation of Alkenes
1, 2 diols can be prepared by using this method.
C =C
Cold alk. KMnO
4
or OsO
4
RCO
3
H, H
+
(Peroxy acids)
C
OH
C
OH
C
OH
C
OH
Anti-hydroxylation
Syn-hydroxylation
A-49, Maulana Azad Sarani, City Centre, Durgapur -16, (WB) Call-7699999929
Response @ www.iitjeeguru.in
4. Oxymercuration-Demercuration
It involves anti-Markovnikovs addition of water to double bond without rearrangement.
C =C
C C
R
R
OH
Alkyl borane
Example:
CH
3
C =CH
2
CH
3

Hg(OAC)
2
CH
3
C CH
2
CH
3

Hg(OAC)
2
H
2
O
HgOAC
NaBH
4
C C
R
OH
H
Demercuration
Oxymercuration
H
2
O
OH HgOAC
NaBH
4
CH
3
C CH
3
CH
3

OH
5. Hydroboration-Oxidation
It involves anti-Markovnikovs addition of water to a double bond without rearrangement.
C =C + (BH
3
)
2
C C
B
R
H
2
O
2
R
C C +B(OH)
3
R
H
H
OH

OH
Alkyl borane
Example:
CH
3
C =CH
2
CH
3

(BH
3
)
2
H
2
O
2
/OH

CH
3
CH CH
2
OH
CH
3

Diborane
6. Reduction of Carbonyl Compounds
Aldehydes can be reduced to primary alcohols and ketones to secondary alcohols by using chemical
reducing agents.
RCHO
H
2
/Ni
RCH
2
OH 1 alcohol
C =O
R
R
LiAlH
4
or NaBH
4
R
R
CHOH 2 alcohol
Carboxylic acids can be reduced to primary alcohols by using LiAlH
4
.
4R COOH +3LiAlH
4
4H
2
+2LiAlO
2
+(R CH
2
O)
4
AlLi
4RCH
2
OH
1alcohol
H
2
O
A-49, Maulana Azad Sarani, City Centre, Durgapur -16, (WB) Call-7699999929
Response @ www.iitjeeguru.in
Acyl chlorides can also be reduced by LiAlH
4
.
LiAlH
4
R C Cl
O
R CH
2
OH
1 alcohol
In the chemical reduction of esters, the acid part is reduced to primary alcohol.
RCOOR' R CH
2
OH +R'OH
Reducing Agent
Copper chromite, CuO.CuCr
2
O
4
, can be used for reducing esters at a high pressure and temperature.
Example:
CH
3
CH
2
COOCH
3
H
+
LiAlH
4
CH
3
CH
2
CH
2
OH
H
2
, CuO.CuCr
2
O
4
high T, P
CH
3
CH
2
CH
2
OH +CH
3
OH
In o, |unsaturated carbonyl compounds, if the double bond is to be protected while reducing the
carboxyl group to an alcohol, special catalysts can be used.
C =C C
O
LiAlH
4
or NaBH
4
C =C CH OH
(unsaturated alcohol)
For reducing a double bond, hydrogenation can be carried out in the presence of Ni or Pt.
C =C C
O
H
2
Ni/Pt
C C CH
H H OH
(saturated alcohol)
Physical Properties
1. Alcohols have a higher boiling point than hydrocarbons or alkyl halides of comparable molecular weights.
This is because alcohols are capable of hydrogen bonding to their fellow alcohol molecules.
R O H O
H O H O
R
R
R H
The boiling point increases with an increasing number of carbon atoms and branching for a given number of
carbon atoms reduces the boiling point.
A-49, Maulana Azad Sarani, City Centre, Durgapur -16, (WB) Call-7699999929
Response @ www.iitjeeguru.in
2. Alcohols are highly soluble in water, because of the ability of alcohol molecules to formhydrogen bonds
with water.
R O
H
H O
H
The solubility decreases with an increase in the number of carbon atoms.
Chemical Properties
The chemical properties of an alcohol are characteristic of the hydroxyl group. The reactions of alcohols
can either involve breaking of a COH bond with the removal of an OH group or breaking of a
OH bond with the removal of a proton, H
+
.
(I) Reactions Involving COH Bond Cleavage
1. Reaction with phosphorus halides or SOCl
2
3ROH +PX
3 3R X +H
3
PO
3
(PX
3
=PBr
3
, PI
3
)
ROH +PX
5 R X +POX
3
+HX
(PX
5
=PCl
5
)
ROH +SOCl
2 R Cl +SO
2
+HCl
2. Reaction with hydrogen halides
R OH +HX R X +H
2
O
The reaction is catalysed by acids. The order of reactivity of alcohols towards HX is
allyl, benzyl >3 >2 >1 <CH
3
The mechanismfor the reaction is S
N
l:
(a)
Fast
R OH +HX R OH
2
+:X
+
+
(b)
Slow
R OH
2
R
+
+H
2
O
+
(c)
Fast
R
+
+:X

R X
Rearrangement can occur in this mechanismsince carbocation intermediates are involved.
Primary alcohols react by S
N
2 mechanism:
:X

+R OH
2
[X-----R-----OH
2
]
o+
o+
R

X +H
2
O
+
Primary alcohols do not undergo this type of rearrangement, because no carbocation intermediates
are involved.
A-49, Maulana Azad Sarani, City Centre, Durgapur -16, (WB) Call-7699999929
Response @ www.iitjeeguru.in
Reactivity of hydrogen halides: HI >HBr >HCl >HF
Hydrogen chloride is quite unreactive and requires the presence of ZnCl
2
for reaction with primary and
secondary alcohols.
Example:
CH
3
CH
2
CH
2
CH
2
OH
dry HBr
or
CH
3
CH
2
CH
2
CH
2
Br
NaBr, H
2
SO
4
, A
CH
3
CH
2
CH
2
OH
HCl +ZnCl
2
A
CH
3
CH
3
CH
2
Cl
CH
3
C CH
3
CH
3
OH
conc. HCl
room temp.
CH
3
C CH
3
CH
3
Cl
3. Dehydration: Acid catalysed
C C
OH H
acid
C =C +H
2
O
Reactivity of ROH : 3 >2 >1
Dehydration of alcohols in E
1
mechanisminvolving carbocation intermediate has the posibility of
rearrangement.
(II) Reactions involving OH Bond Cleavage
1. Reactions as acids: with active metals
RO H +M RO

M
+
+
1
2
H
2
(M =Na, K, Mg, Al etc.)
Reactivity of ROH CH
3
OH >1 >2 >3
When alcohols react with active metals, hydrogen gas is released; this is because of the acidic
nature of alcohols. Alcohols are weaker acids than water as shown by the reaction where a
stronger acid (H
2
O) displaces a weaker acid (alcohol) from its salt.
RO

Na
+
+ H OH Na
+
OH + ROH
stronger
base
stronger
acid
weaker
base
weaker
acid

Relative acidities: H
2
O >ROH >NH
3
>RH
Relative basicities: OH

<OR

<NH
2

<R

A-49, Maulana Azad Sarani, City Centre, Durgapur -16, (WB) Call-7699999929
Response @ www.iitjeeguru.in
Example:
CH
3
CH
2
OH
Na
CH
3
CH
2
O
-
Na
+
+
1
2
H
2
CH
3
C OH
Al
H
CH
3
CH
3
CH O

3
Al
CH
3
Aluminimum
isopropoxide
potassium tert-butoxide
K
(CH
3
)
3
C OH
(CH
3
)
3
CO

K
+
2. Ester formation
R OH +R' C
O
H
+
OH
R' C
O
OR
+H
2
O
R OH +R' C
O
Cl
R' C
O
OR
+HCl
Alcohol Acid
R OH +
S Cl
CH
3
O
O
CH
3
O
O
S OR +HCl
Tosyl chloride
Alkyl tosylate
(TSOR)

TS =
O
CH
3
S

Cl
O
Reactivity of alcohols in esterfication: CH
3
OH >1 >2 >3
(III) Miscellaneous Reactions
1. Oxidation
A primary alcohol containing two ohydrogens can either lose one of themto forman aldehyde or
both of themto form a carboxylic acid.
R CH
2
OH
Pyridinium chlorochromate
KMnO
4
R C =O (An aldehyde)
R COOH (A carboxylic acid)
or K
2
Cr
2
O
7
C
5
H
5
NH
+
CrO
3
Cl

H
(1)

R CH
2
OH + KMnO
4
1 alcohol Purple
RCOO K +MnO
2
+KOH
Brown
+
A-49, Maulana Azad Sarani, City Centre, Durgapur -16, (WB) Call-7699999929
Response @ www.iitjeeguru.in
A secondary alcohol can lose its only ohydrogen to form a ketone.
RCHOH
(2)
or CrO
3
R
K
2
Cr
2
O
7
R C =O
R
Prolonged oxidation or oxidation under harsh conditions oxidises secondary alcohols to carboxylic
acids involving breaking of carbon-carbon bonds.
CH
3
CHCH
2
CH
3
alk. KMnO
4
OH
CH
3
CCH
2
CH
3
O
CH
3
COOH +CH
3
COOH
acid. KMnO
4
A tertiary alcohol contains no o-hydrogens and is not oxidised. Under harsh conditions
(e.g., acidic oxidising agent), a tertiary alcohol dehydrates to an alkene which can further be
oxidised to acids having a lesser number of carbon atoms than the parent molecule.
2. Reaction with Reduced Copper
Primary and secondary alcohols are dehydrogenated to formaldehydes and ketones respectively,
whereas tertiary alcohols are dehydrated to form olefins.
CH
3
CH
2
OH
reduced Cu
OH
Primary alcohol
300C
CH
3
CHO

+H
2
CH
3
CH(OH)CH
3
reduced Cu
Secondary alcohol
300C
CH
3
CCH
3
+H
2
O
C
CH
3
CH
3
CH
3
reduced Cu
300C
C =CH
2
+H
2
O
CH
3
CH
3
Tertiary Alcohol
3. Action of Chlorine or Bromine
Chlorine and bromine, being mild oxidising agents, oxidise primary and secondary alcohols
to aldehydes and ketones respectively, which then undergo halogenation on o-carbon.
CH
3
CH
2
OH
Chloral
Cl
2
CH
3
CHO
3Cl
2
CCl
3
CHO
CH
3
CH(OH)CH
3
1, 1, 1 Tribromo propanone
Br
2
CH
3
COCH
3
3Br
2
CBr
3
COCH
3
A-49, Maulana Azad Sarani, City Centre, Durgapur -16, (WB) Call-7699999929
Response @ www.iitjeeguru.in
Tests For Alcohols
Primary, secondary, and tertiary alcohols can be distinguished by the following methods:
(I) Lucas Test
This test is based on different reactivities of alcohols towards Lucas reagenta mixture of concentrated
hydrochloric acid and anhydrous zinc chlorideat room temperature.
ROH +HCl
ZnCl
2
RCl +H
2
O
Formation of alkyl halides which are insoluble is indicated by the appearance of turbidity in the reaction
mixture. Since the reaction involves carbocation intermediate, the order of reactivity of alcohols is
benzyl, allyl > 3 > 2 > 1 > CH
3
OH.
Tertiary alcohols (benzyl and allyl alcohols as well) produce turbidity immediately, secondary alcohols
give turbidity within 5-10 minutes, and primary alcohols do not give turbidity at all.
(II) Oxidation
Primary alcohols on oxidation give aldehydes which are further oxidised to carboxylic acid having the
same number of carbon atoms as in alcohol.
Secondary alcohols are oxidised to ketones which on prolonged oxidation or under drastic conditions
give carboxylic acids containing lesser carbon atoms than alcohol. Tertiary alcohols cannot be oxidised
but under drastic conditions dehydrate to alkenes which are oxidised to a mixture of ketones and acids
containing lesser carbon atoms.
(III) Victor-Meyer Test
This test involves the following steps:
(i) Alcohol is treated with concentrated hydriodic acid or red phosphorus and iodine to form the
corresponding alkyl iodide.
(ii) Alkyl iodide is reacted with silver nitrite to form nitroalkane.
(iii) Nitroalkane formed is treated with nitrous acid (HONO).
(2NaNO
2
+H
2
SO
4
2HONO +Na
2
SO
4
)
and then with alkali (NaOH or KOH). Different products are obtained for different alcohols.
Primary alcohols produce blood red colour, secondary alcohols produce blue colour, and tertiary
alcohols produce no colour.
Some other tests to determine definite linkages in alcohols are:
(iv) Iodoformtest
This test is given by methyl ketones which on treatment with iodine and sodiumhydroxide (sodium
hypoiodite, NaOI) yields a yellow precipitate of iodoform(CHI
3
).
R C CH
3
+3NaOI
O
R C CI
3
+3NaOH
O
R C CI
3
+NaOH
O
RCOO

Na
+
+CHI
3
Iodoform
yellow precipitate
A-49, Maulana Azad Sarani, City Centre, Durgapur -16, (WB) Call-7699999929
Response @ www.iitjeeguru.in
Alcohols of the structure

R C CH
3
H
OH
(R =H or alkyl or aryl group)
also give positive iodoformtest.
Hypohalites oxidise an alcohol having the above-mentiond structure to methyl ketone which gives a
positive iodoformtest.
R C CH
3
+NaOI R C CH
3
+NaI +H
2
O
O
gives positive
Iodoform test
H
OH
Example:
CH
3
CHOH, CH
3
CHCH
2
CH
2
CH
3
, C
6
H
5
CHCH
3
H
OH
OH
give positive iodoformtest.
(V) Analysis of 1, 2 Diols. Periodic Acid Oxidation
Compounds containing two or more =O or OH groups attached to adjacent carbon atoms undergo
oxidation with cleavage of carbon-carbon bonds. A C =O group is oxidised to carboxylic group,
C OH
H
group is oxidised to CHO (aldehyde) and if the carbon atomin COH group does not
have any hydrogen atom, it is oxidised to a ketonic group. Example:
R
OH
R C CH R' +HIO
4
O
RCOOH +R'CHO
OH
R C CH R'
OH
HIO
4
R
R C =O +R'CHO
R CH CH
2
CH R'
OH
no reaction
OH
HIO
4
A-49, Maulana Azad Sarani, City Centre, Durgapur -16, (WB) Call-7699999929
Response @ www.iitjeeguru.in
PHENOLS
Phenols are compounds having the general formula ArOH, where Ar is phenyl, substituted phenyl,
or some other aryl group like naphthyl group. Phenols have an OH group attached directly to the aromatic
ring. Some of the common phenols are
OH
0 Chlorophenol
Cl
OH
m Cresol
CH
3
OH
Catechol
OH
OH
Resorcinol
OH
OH
Hydroquinone
OH
OH
2 Napthol
OH
m Hydroxybenzoic acid
COOH
Preparation
(I) Dow Process
Chlorobenzene is treated with aqueous NaOH at a temperature of 360C under a high pressure. The
reaction involves nucleophilic substitution through elimination-addition mechanism involving benzyne
intermediate.
Chlorobenzene
+
Cl
NaOH, 360C
4500 1b/in
2
O Na

HCl
OH
Sodium phenoxide
Phenol
( I I ) Fr om Cumene ( I sopr opyl Benzene)
Cumene is converted by air oxidation into cumene hydroperoxide which is converted by aqueous acid
into phenol and acetone.
CH
3 CH
3
CH
3
O
CH
Cumene
CH
3
C O O H
Cumene hydroperoxide
OH
+CH
3
C CH
3
Phenol Acetone
O
2 H
2
O, H
+
The reaction involves rearrangement of hydroperoxides involving 1, 2shift to electron-deficient oxygen
through the following steps:
CH
3
C O O H
H
+
CH
3
CH
3
CH
3
C O OH
2
+
H
2
O
CH
3
C =O
CH
3
H
2
O
CH
3
C O
CH
3
OH
2
+
CH
3
H
CH
3
OH CH
3
C +
+
O
CH
3
C O
OH
H
+
A-49, Maulana Azad Sarani, City Centre, Durgapur -16, (WB) Call-7699999929
Response @ www.iitjeeguru.in
Acid converts the peroxide I into protonated peroxide which loses a molecule of water to forman intermediate
in which oxygen bears only six electrons. A 1, 2 shift of phenyl group fromcarbon to electron-deficient
oxygen yields carbocation II which reacts with water to yield hydroxy compound III, a hemiketal, which
breaks down to give phenol and acetone.
(III) Hydrolysis of DiazoniumSalts
Ar N
2
+
+ H
2
O Ar OH +H
+
+N
2
N
2
+
HSO
4
Cl
H
2
O, H
+
A
OH
Cl
+N
2

Diazoniumsalts can be obtained as follows:


HNO
3
NO
2
Reduction
NH
2
HONO
0C
(NaNO
2
, HCl)
N
2
+ Cl

RCO
+
Physical Properties
1. The simplest phenols are colourless liquids or low-melting solids.
2. Phenols have a high boiling point because of inter-molecular hydrogen bonding.
3. Phenol itself is soluble in water but most other phenols are essentially insoluble in water. However, the
salts of phenols are soluble in water.
ArOH ArO

phenol
(acid)
Insoluble in water
phenoxide ion
(salt)
soluble in water
Chemical Properties
Phenols are highly reactive compounds and show two kinds of reactions due to
(I) OH group
(II) electrophilic aromatic substitution on the ring
1. Acidic Nature of Phenols (Salt Formation)
Phenols are fairly acidic compounds. Aqueous hydroxides convert phenols into their salts and aqueous
mineral acids convert the salts back into free phenols.
OH

ArOH ArO

Phenol Phenoxide ion H


+
The acidity of various compounds vis--vis water and phenol is as follows:
Alcohols <Water <Phenols <Carbonic Acid <Carboxylic Acid
Both phenol and phenoxide ions are resonance stabilised but stabilisation is greater for phenoxide ions.
Thus, resonance shifts equilibriumtowards ionisation, making phenol more acidic than alcohol, which
does not show resonance.
A-49, Maulana Azad Sarani, City Centre, Durgapur -16, (WB) Call-7699999929
Response @ www.iitjeeguru.in

+
O H O H
+
O H O H
+

O H O O

O
O

Phenol
OH

H
+

Phenoxide ion
Electron-withdrawing substituents like X, or NO
2
tend to disperse the negative charge on phenoxide
ion, thereby increasing the acidity of phenols.
Electron-releasing substituents like CH
3
or OR tend to intensify the negative charge on phenoxide ion,
thereby decreasing the acidity of phenols.
Unlike alcohols, phenols are more acidic than water and thus dissolve in aqueous hydroxides.
ArOH + NaOH(aq) ArO

Na
+
+ H
2
O
Stronger acid
Weaker acid
However, being less acidic than carbonic acid, phenols are insoluble in aqueous bicarbonates or carbonates.
ArOH + NaHCO
3
(aq) no reaction
2. Ester Formation Fries Rearrangement
Phenols are converted into their esters by the action of acids, acid chlorides, or anhydrides.
ArO H
RCOCl
NaOH
Ar' SO
2
Cl
pyridine
(RCO)
2
O
RCO OAr
Ar'SO
2
OAr
RCO OAr
O
OH +
C Cl
NaOH
C O
O
Phenyl benzoate
Schotten Baumann
Reaction
When esters of phenol are heated with aluminimumchloride, the acyl group migrates from the phenolic
oxygen to an ortho or para position of the ring yielding a ketone. This reaction is called the Fries rearrangement.
A-49, Maulana Azad Sarani, City Centre, Durgapur -16, (WB) Call-7699999929
Response @ www.iitjeeguru.in
Example:
O C C
2
H
5
O
AlCl
3
CS
2
C C
2
H
5
O
OH
+
C C
2
H
5
OH
O
Phenyl propionate
0Hydroxy phenol
ethyl Ketone
pHydroxyphenyl
ethyl Ketone
The reaction involves self-acylation by the acyliumion, RCO
+
.
3. Ether Formation
ArO

+R X
ArO

R +X

(1)
Phenols are converted into alkyl-aryl ethers by reaction with alkyl halides in an alkaline solution, involving
a nucleophilic attack by a phenoxide ion on the alkyl halide, thereby displacing the halide ion.
CH
2
Br +HO
aq. NaOH
CH
2
O
Aryl-methyl ethers can be prepared using methyl sulfates, (CH
3
)
2
SO
4
.
OH +CH
3
OSO
2
OCH
3
aq.NaOH
OCH
3
+CH
3
OSO
3

Na
+
Anisole (Methoxy benzene)
4. Ring Substitution Reactions
A phenolic group powerfully activates an aromatic ring towards electrophilic aromatic substitution and
therefore special precautions are needed to prevent polysubstitution or oxidation.
(a)Nitration
OH
Phenol
conc. HNO
3
diluate HNO
3
OH
NO
2
NO
2
O
2
N
2, 4, 6 - Trinitrophenol
OH
NO
2
OH
NO
2
+
0Nitrophenol
pNitrophenol
20C
A-49, Maulana Azad Sarani, City Centre, Durgapur -16, (WB) Call-7699999929
Response @ www.iitjeeguru.in
(b) Sulfonation
H
2
SO
4
15 20C
OH
100C
OH
OH
SO
3
H
H
2
SO
4
, 100C
0-Phenolsulfonic acid
SO
3
H
p-Phenolsulfonic acid
(c) Halogenation
Treating phenols with an aqueous solution of bromine results in the displacement of every hydrogen,
ortho or para, to the OH group and may even cause displacement of certain other groups.
Br
2
, H
2
O
OH
4, 6 Dibromo 2methyl phenol
CH
3
Br
OH
CH
3
Br
Br
2
, H
2
O
OH
Br
OH
Br SO
3
H
Br
2, 4, 6 Tribromo phenol
If halogenation is carried out in a solvent of low polarity like chloformor carbon disulfide, the reaction
can be limited to monohalogenation.
OH
Br
2
, CS
2
OH
Br
OC
+
OH
Br
(Major product)
(d) Friedel-Crafts Alkylation/Acylation
Friedel-Crafts alkylation of phenols yields alkyl phenols; however, the yield is poor. This is because
AlCl
3
, instead of generating a carbocation, gets involved in forming a complex with electron-rich
phenol.
OH
+AlCl
3
O AlCl
3
+
A positively charged oxygen is electron-withdrawing, thereby decreasing the reactivity of ring towards
electrophilic substitution reactions.
Friedel-Crafts acylation of phenols also has a low reactivity and behaves the same way.
A-49, Maulana Azad Sarani, City Centre, Durgapur -16, (WB) Call-7699999929
Response @ www.iitjeeguru.in
(e)Nitrosation
Phenols are one of the few compounds reactive enough to undergo attack by nucleophilic nitrosonium
ion,
+
NO.
Nitrous acid converts phenols into nitrosophenols.
NaNO
2
, H
2
SO
4
OH
7 8C
OH
NO
(f) Coupling with diazonium salts
HO
OH
weakly
alkaline
+
+
Phenol
N =N
Diazonium salt
p-Hydroxyazobenzene
N
2
(g)Carbonation: Kolbe reaction
Treatment of salt of phenol with carbon dioxide brings about substitution of carboxyl group for hydrogen
in ring.
o

O Na
+
o

OH
NaOH
+ C
O
o
+
O
125C, 47 atm
OH
COONa
Sodium salicylate
(major product)
H
+
OH
COOH
Salicylic acid
Some p-hydroxybenzoic acid is also formed but it can be easily separated by fractional distillation. If
the reaction is carried out on potassium phenoxide, the salt of p-acid becomes the major
product.
Salicylic acid is used to produce a number of important derivatives used as medicines.
OH
COOH
Salicylic acid
CH
3
OH, H
+
C
6
H
5
OH, H
+
(CH
3
CO)
2
O
H
+
OH
COOCH
3
OH
COOC
6
H
5
OCOCH
3
COOH
Methyl salicylate
(Oil of winter green)
(flavouring agent)
Phenyl salicylate
Salol
(internal antiseptic)
Acetyl salicylic acid
(Aspirin)
(an analgesis and antipyretic)
A-49, Maulana Azad Sarani, City Centre, Durgapur -16, (WB) Call-7699999929
Response @ www.iitjeeguru.in
(h)Reimer-Tiemann reaction
+

OH
Salicyladehyde
CHCl
3
aq. NaOH
CHO
O Na
H
+
/H
2
O
OH
CHO
+

OH
Salicylic acid
CCl
4
aq. NaOH
COOH
O Na
H
+
/H
2
O
OH
COOH
The reaction involves electrophilic substitution of dichloro carbene, :CCl
2
on the highly reactive
phenoxide ring.
:CCl
3

CCl
3
+ OH
H
Chloroform

+H
2
O Cl

+CCl
2
Dichlorocarbene
O

CHO
O : :
..
O : :
:
CCl
2
..
O
CCl
2
H
O

CHCl
2
OH
OH
CHO
H
+
Phenoxide ion
The product is largely 0-aldehyde with a small amout of the p-isomer. If both O-position in phenoxide ion
are substituted the reaction yields p-isomer.
(i) Reaction with formaldehyde
Phenol reacts with formaldehyde in the presence of an acid or alkali forming 0

or p-hydroxy methyl
phenol.
Basic Catalysis
O : :
..
H
O
CH
2
O

CH
2
OH
OH
+
C =O
H
o+ o
H
H
2
O
H
+
Acidic Catalysis
OH :
..
H
Protonated
aldehyde
+
C =OH
H
CH
2
OH
OH
H H
2
O
CH
2
OH
OH
+
+
A-49, Maulana Azad Sarani, City Centre, Durgapur -16, (WB) Call-7699999929
Response @ www.iitjeeguru.in
Analysis of Phenols
Phenols react with neutral ferric chloride solution and form coloured complexes (red, blue, green, and
violet). This reaction is also shown by enols (e.g., CH
2
=CHOH).
Phenols can also be identified by their unique acidic strength. They are soluble in aqueous hydroxides but
insoluble in aqueous carbonates or bicarbonates.
ETHERS
Ethers are compounds of the general formula R O R, Ar O R or Ar O Ar, where Ar is
an aromatic group. An ether is symmetrical if the two groups attached to the oxygen atomare the same, and
it is unsymmetrical if the groups are different.
CH
3
CH
2
CH
2
CHCH
2
CH
3
OCH
3
3-Methoxyhexane
CH
3
CH
2
OCH
2
CH
2
CH
3
1-Ethoxypropane
Preparation
1. Dehydration of alchols
2R O H
H
2
SO
4
A
R O R +H
2
O
A water molecule is lost for every pair of alcohol molecules. Dehydration is limited to the preparation of
symmetrical ethers, because a combination of two different alcohols yields a mixture of three ethers.
Alcohols can also dehydrate to alkenes, but dehydration to ethers is controlled by the choice of reaction
conditions.
Example:
CH
3
CH
2
OH
140C
180C
C
2
H
5
OC
2
H
5
CH
2
=CH
2
Diethyl ether
Ethene
Conc.
H
2
SO
4
Ether formation by dehydration is an example of nucleophilic substitution: protonated alcohol is the
substrate and the second molecule of alcohol is the nucleophile.
The reaction is S
N
1
for 2 and 3 alcohols and S
N
2
for 1 alcohol.
R OH
2
R OH

+H
H
2
O
R'OH
R
+

[R' O ---R----OH
2
]
+
R OH
2
(Protonated alcohol)
R'OH
R O R'
H
+
H
+
+ R O R'
+
R' O R
H
+
R' O R +H
+
o+
H
o+
+
alcohols)
S
N
1(3 & 2
S
N
2(1 alcohols)
A-49, Maulana Azad Sarani, City Centre, Durgapur -16, (WB) Call-7699999929
Response @ www.iitjeeguru.in
2. Williamson synthesis
RX
R'O Na
+
ArO

Na
+
R OR'
R OAr

Yield from RX: CH


3
>1 >2 >3
The reaction involves the nucleophic substitution of an alkoxide (or phenoxide) ion for a halide ion. This
method can be used for preparing symmetrical as well as asymmetrical ethers.
(CH
3
)
2
CH(OH)
Na
(CH
3
)
2
CHO

Na
+
+CH
3
CH
2
CH
2
Br CH
3
(CH
2
)
2
O CH(CH
3
)
2
OH +CH
3
CH
2
Br
aq. NaOH
O CH
2
CH
3
Ethoxybenzene
The reaction gives the best yield with 1 alkyl halides. With tertiary alkyl halides, elimination becomes an
important reaction and no ether is obtained.
CH C Br + C
2
H
5
OH
CH
3
CH
3
aq.NaOH
CH
3
C =CH
2
CH
3
Physical Properties
1. The C O C bond angle in ethers is not 180 and the dipole moments of the two C O bonds do
not cancel each other. Hence, ethers possess a small net dipole moment.
R
net dipole moment
R
O
110
2. The boiling point of ethers are the same as those of alkanes of comparable molecular weights. The
boiling points of alcohols are much higher than those of ethers, as ethers are incapable of intermolecular
hydrogen bonding.
3. The solubility of ethers in water is comparable to that of alcohols, because ethers can formhydrogen
bonds with water molecules.
R O ------ H O
H
R
A-49, Maulana Azad Sarani, City Centre, Durgapur -16, (WB) Call-7699999929
Response @ www.iitjeeguru.in
Chemical Properties
Ethers are unreactive compounds. The ether linkage is quite stable towards bases, oxidising, and reducing
agents.
1. Cleavage by acids
R O R' +HX R X +R'OH
R' X
HX
Reactivity of HX: HI >HBr >HCl.
Cleavage takes place under vigorous conditions using concentrated acids and high temperature.
A dialkyl ether initially yields an alkyl halide and an alcohol; the alcohol may further react to formsecond
mole of alkyl halide.
CH
3
CH O CH CH
3
Br CH
3
2CH
3
CHCH
3
48% HBr
CH
3
130 140C
The initial reaction between an ether and an acid results in the formation of a protonated ether. The
cleavage then involves a nucleophilic attack by a halide ion on this protonated ether with the displacement
of the weakly basic alcohol molecule.
R O R' +HX
H
+
S
N
1
R O R' +X

or S
N
2
R X +R'OH

HX
R'X
Protonated ether
A primary alkyl group tends to undergo S
N
2 displacement and a tertiary alkyl group tends to undergo S
N
1
displacement.
CH
3
O CH
2
CH
2
CH
3
HI
HI
CH
3
I +CH
3
CH
2
CH
2
I
S
N
2
excess
CH
3
I +CH
3
CH
2
CH
2
OH
3 Methoxy propane
CH
3
O C CH
3
CH
3
CH
3
HI
S
N
1
CH
3
OH +(CH
3
)
3
CI
2 Methoxy2methyl propane
A-49, Maulana Azad Sarani, City Centre, Durgapur -16, (WB) Call-7699999929
Response @ www.iitjeeguru.in
Epoxides
Epoxides are compounds containing the three-membered ring.
C C
O
(Epoxide or oxirane ring)
Epoxides belong to a class of compounds called cyclic ethers. The three-membered ring makes epoxides
an exceedingly important class of compounds.
1, 2 Epoxybutane
CH
2
CH CH
2
CH
3
O
Epoxyethane
CH
2
CH
2
O
Preparation
Epoxides are commonly obtained by oxidation of alkenes by peroxy acids.
RCO
3
H
O
C =C
Alkene
Peroxyacid
C C
Epoxide
Silver oxide can also oxidise alkenes to epoxides. An internal S
N
2 reaction in a chlorohydrin can be used to
prepare three membered cyclic ethers.
OH
1, 2 Epoxypropane
Cl CH
2
CH CH
3
OH
O
Cl CH
2
CH CH
3
Cl
CH
2
CH CH
3
O

Reactions
Epoxides have highly strained three-membered rings that can undergo acid- or base-catalysed ring
cleavage.
1. Acid-catalysed cleavage
C C
H
O
C C
O
+
C C
Z
Z :
OH
z: =nucleophile
At first, the epoxide is protonated by an acid and the protonated epoxide can then undergo an attack by
nucleophilic reagents.
H
+
C C
O
+
C C
O
H
A-49, Maulana Azad Sarani, City Centre, Durgapur -16, (WB) Call-7699999929
Response @ www.iitjeeguru.in
+
C C
O
H
ROH
H
2
O
C C
OH
2
OH
C C
O
H
OH
R
C C
X
OH
H
+
H
+
C C
OH
OH
C C
OR
OH
1, 2, - diol
Alkoxy alcohol
Halohydrin
X

+
2. Base-catalysed cleavage
Z: + C C
O
C C
O

HZ
Z
C C
OH
Z
Under alkaline conditions, an epoxide itself undergoes nucleophilic attack.
O
C
2
H
5
O

Na
+
+CH
2
CH
2
C
2
H
5
O CH
2
CH
2
OH
2-Ethoxyethanol
O
NH
3
+CH
2
CH
2 H
2
N CH
2
CH
2
OH
2-Aminoethanol
3. Reaction with Grignard reagent
R MgX +CH
2
CH
2
+
CH
2
CH
2
OMgX

RCH
2
CH
2
OH
Primary alcohol
(Chain lengthened
by two carbon atoms)
O
R
H
+
MgBr +H
2
C CH
2
O
CH
2
CH
2
OMgBr
CH
2
CH
2
OH
H
2
O
2-Phenylethanol
Ethylene
oxide
Phenyl magnesium
bromide
A-49, Maulana Azad Sarani, City Centre, Durgapur -16, (WB) Call-7699999929
Response @ www.iitjeeguru.in
SOLVED OBJECTIVE EXAMPLES
Example 1: Phenols is less acidic than
(a) acetic acid (b) p-methoxyphenol
(c) p-nitrophenol (d) ethanol
Solution: Phenol is less acidic than carboxylic acids and more acidic than aliphatic alcohols. Moreover,
the presence of an electron-withdrawing group (eg. NO
2
) increases the acidic strength of
phenol but electron-releasing groups decrease the acidic strength. Hence, phenol is less
acidic than (a) and (c).
Example 2: Hydrogen bonding is possible in
(a) ethers (b) hydrocarbons
(c) water (d) alcohols
Solution: For hydrogen bonding, a compound should have hydrogen attached to an electronegative
atom (F, O, N). The answers are (c) and (d).
Example 3: Which of the following compounds will give a yellow precipitate with iodine and alkali ?
(a) 2Hydroxypropane (b) Acetophenone
(c) Methyl acetate (d) Acetamide
Solution: Methyl ketones and alcohols having the structure CH
3
CH(OH) give a yellow ppt. with
iodine and alkali. The answers are (a) and (b).
Example 4 : Equimolar quantities of ethanol and methanol are heated with conc. H
2
SO
4
. The product
formed is
(a) C
2
H
5
OC
2
H
5
(b) CH
3
OCH
3
(c) C
2
H
5
OCH
3
(d) all the three
Solution : 3R
1
OH +3R
2
OH
H
2
SO
4
A
R
1
O R
2
+R
2
O R
2
+R
1
O R
1
+3H
2
O
The answer is (d)
Example 5: The ether
O CH
2
when treated with HI produces
(a) CH
2
I (b) CH
2
OH
(c) I (d) OH
Solution: Phenyl group is unreactive towards substitution but an sp
3
hybridised carbon undergoes
substitution easily.
A-49, Maulana Azad Sarani, City Centre, Durgapur -16, (WB) Call-7699999929
Response @ www.iitjeeguru.in
O CH
2

OH +

CH
2
I
H I
The answers are (a) and (d)
Example 6: The compound that reacts fastest with Lucas reagent (conc. HCl +ZnCl
2
) at room
temperature is
(a) butan1ol (b) butan2ol
(c) 2methyl propan1ol (d) 2methyl propan2ol
Solution: Tertiary alcohols react fastest with Lucas reagent followed by 2 and 1 alcohols.
The answer is (d)
Example 7: In the following compounds,
OH
CH
3
(I)
OH
(II)
OH
(III)
NO
2
OH
(IV)
NO
2
the decreasing order of acidic strength is
(a) III >IV >I >II (b) I >IV >III >II
(c) II >I >III >IV (d) IV >III >I >II
Solution: Electron-withdrawing effect of a group increases the acidity of phenols and electron-releasing
group has the opposite effect.
In (II), there is a (+I) effect of CH
3
group. [decreases acidity]
In (III), there is a (I) effect of NO
2
group [increase acidity]
In (IV), there is (I) and (R) effect of NO
2
group. [strongly increases acidity]
The answer is (d)
Example 8: The product in the reaction
CH
3
O ?
HBr
is
(a)
CH
3
OH
Br
(b)
CH
3
(c)
CH
3
Br
OH
(d)
Br
CH
3
Solution: Acid-catalysed ring opening of epoxides involves a nucleophilic attack at a more
substituted carbon atom.
A-49, Maulana Azad Sarani, City Centre, Durgapur -16, (WB) Call-7699999929
Response @ www.iitjeeguru.in
Br
CH
3
Br

O
OH
CH
3
The answer is (c)
Example 9: Which of the following compounds is resistant to oxidation by periodic acid (HIO
4
)?
(a) HOCH
2
CO CH
2
OH (b) HO CH
2
CH
2
CH
2
OH
(c) HO CH
2
CH(OH) CH
2
OH (d) HO CH
2
CH
2
OH
Solution: For oxidation with HIO
4
, a compound should have carbonyl groups and/or hydroxyl groups
on adjacent carbon atoms. In (b), two hydroxyl groups are not adjacent to each other.
The answer is (b)
Example 10: Which of the following reagents can be used to separate a mixture of phenol and carboxylic
acid?
(a) NaOH (b) Na
2
CO
3
(c) lime water (d) NaHCO
3
Solution: Phenol is less acidic than carbonic acid whereas carboxylic acids are more acidic. Hence,
phenols are insoluble in a solution of NaHCO
3
but carboxylic acids dissolve in NaHCO
3
solution.
The answer is (d)
Example 11: The compound with the lowest boiling point, that is, the most volatile compound is
(a)
OH
NO
2
(b)
OH
NO
2
(c)
OH
NO
2
O
2
N
(d)
OH
NO
2
O
2
N
NO
2
Solution: Phenols capable of forming intermolecular hydrogen bonding have a high boiling point. But
(a) has intramolecular rather than intermolecular Hbonding and is the most volatile
compound.
O H
N
O
O
The answer is (a)
Exampl e 12: When phenol is reacted with CHCl
3
and NaOH followed by acidification,
salicylaldehyde is obtained. Which of the following species are involved in the above reaction
as intermediates?
A-49, Maulana Azad Sarani, City Centre, Durgapur -16, (WB) Call-7699999929
Response @ www.iitjeeguru.in
(a)
CCl
2
H

O
(b)
CHCl
2
OH
(c)
CHCl
H
O
OH
(d)
CHCl
2
O

Solution: This is Reimer-Tiemann reaction in which (b) and (d) are the intermediates formed.
Example 13: Phenol can be distinguished fromaliphatic alcohol with
(a) Tollens reagent (b) Schiffs base
(c) FeCl
3
(d) HCl
Solution: Phenol (all enols) can be oxidised by FeCl
3
to formcoloured complexes. Alcohols, however,
cannot get oxidised by FeCl
3
.
The answer is (c)
Example 14: When sodiumphenoxide is heated with CO
2
under pressure followed by acidification with
HCl, the product obtained is
(a) salicylic acid (b) salicyladehyde
(c) benzoic acid (d) benzaldehyde
Solution: This is Kolbe-Schmidt reaction and the product formed will be salicylic acid.
The answer is (a)
Example 15: An alcohol contains 60% carbon and 13.3% hydrogen and gives positive iodoform test.
The alcohol is
(a) 2-propanol (b) 1-propanol
(c) 2-butanol (d) 1-butanol
Solution: C : H : O =
60 13.3 26.7
: :
12 1 16
=
5 13.3 1.67
: :
1.67 1.67 1.67
=3 : 8 : 1
The formula of the compound is C
3
H
8
O.
Since the alcohol gives positive iodoformtest, it is 2-propanol.

CH
3
CHCH
3
OH
The answer is (a)
A-49, Maulana Azad Sarani, City Centre, Durgapur -16, (WB) Call-7699999929
Response @ www.iitjeeguru.in
Example 16: What is the product in the following reaction?
H
2
C =CH CH OH
CH
3
H
2
CrO
4
(a)
H
2
C =CH C =O
CH
3
(b)
OHC C =O
CH
3
(c) HOOC C =O
CH
3
(d) CH
3
CHO
Solution: Unlike KMnO
4
, which oxidises both a double bond and a hydroxyl group, chromic acid
(H
2
CrO
4
) does not oxidise double bond.
The answer is (a)
OBJ ECTI VE PROBLEMS
Section A
Choose the Correct Answer
1. Which of the following is produced when an aqueous solution of butan-2-ol is refluxed with dilute
acidic KMnO
4
?
(a) butanol (b) butanoic acid
(c) potassiumbutanoate (d) butanone
2. Consider the reaction: CH
3
CH
2
CH
2
OH
5
PCl alc.
KOH
A B . The compound B is
(a) propane (b) propene
(c) propyne (d) propanal
3. Which of the following has the lowest solubility in water?
(a) CH
3
CH
2
CH
2
CH
2
OH (b)
CH
3
CH
3
CHCH
2
OH
(c) HOH
2
C CH
2
OH (d) C
6
H
5
CH
2
CH
2
OH
4. Chlorine reacts with ethanol to give
(a) ethylchloride (b) chloroform
(c) chloral (d) acetaldehyde
A-49, Maulana Azad Sarani, City Centre, Durgapur -16, (WB) Call-7699999929
Response @ www.iitjeeguru.in
5. Ethanol is heated with concentrated H
2
SO
4
. The product formed is
(a)
O
CH
3
C O C
2
H
5
(b) C
2
H
6
(c) C
2
H
4
(d) C
2
H
2
6. Which of the following is also known as picric acid?
(a) phenol (b) carboxylic acids
(c) trinitrophenol (d) nitroalkane
7. Which of the following has the highest value of pK
a
?
(a) CH
3
CH
2
OH (b) Cl CH
2
CH
2
OH
(c) F
3
C CH
2
OH (d)
CH
3
CH
3
CH CH
2
OH
8. Which of the following has the highest boiling point?
(a)
OH
CH
3
CH
2
CH CH
3
(b) CH
3
CH
2
CH
2
CH
2
OH
(c)
CH
3
CH
3
CH CH
2
OH
(d)
CH
3
CH
3
C OH
CH
3
9. Wood spirit contains
(a) only methanol (b) only ethanol
(c) methanol +ethanol (d) a mixture of a number of alcohols
10. The compound which reacts faster with Lucas reagent at roomtemperature is
(a) butan1ol (b) butan2ol
(c) 2methyl propan1ol (d) 2methyl propan2ol
11. Lucas test is used to determine the type of
(a) amines (b) alcohols
(c) acids (d) phenols
12. When glycerol is heated with oxalic acid, the compound formed is
(a) allyl alcohol (b) formic acid
(c) tartaric acid (d) formic acid and allyl alochol
13. Salol is prepared from
(a) Salicylic acid and phenol (b) Salicylic acid and methanol
(c) both (a) and (b) (d) phenol and methylchloride
A-49, Maulana Azad Sarani, City Centre, Durgapur -16, (WB) Call-7699999929
Response @ www.iitjeeguru.in
14. Separation of a higher phenol and an aromatic carboxylic acid can be easily carried out by
(a) NaOH (b) Na
2
CO
3
(c) lime (d) NaHCO
3
15. A compound A reacts with sodiummetal and also undergoes iodoform reaction. A is
(a) phenol (b) methanol
(c) n-propanol (d) iso-propanol
16. Which of the following pairs gives the same compound on heating with zinc dust?
(a)
OH
CH
3
and
OH
(b)
OH
CHO
and
OH
CHO
(c) CH
3
CH
2
CH
2
OH and CH
3
CHOHCH
3
(d) 1- butanol and 2-butanol
17. Which of the following ethers is cleaved even by HCl at roomtemperature?
(a) C
6
H
5
OCH
2
CH
3
(b) CH
3
CH
2
OCH
2
CH
3
(c) (CH
3
)
3
COCH
2
CH
3
(d) (CH
3
)
3
COC(CH
3
)
3
18. The ether OCH
2
when treated with HI produces
(a)
CH
2
I
(b)
CH
2
OH
(c)
I
(d)
OH
19. The reaction between sodiumethoxide and bromoethane yields
(a) methyl ethyl ether (b) dimethyl ether
(c) diethyl ether (d) propane
20. Diethyl ether on heating with concentrated HI gives two moles of
(a) ethanol (b) iodoform
(c) ethyl iodide (d) methy liodide
Section B
Choose the Correct Answer
1. When phenol is treated with bromine water in excess, it gives
(a) m-bromophenol (b) o-and p-bromophenol
(c) 2, 4dibromophenol (d) 2, 4, 6tribromophenol
A-49, Maulana Azad Sarani, City Centre, Durgapur -16, (WB) Call-7699999929
Response @ www.iitjeeguru.in
2. The compound that does not change the orange colour of chromic acid to blue green is
(a) 2 alcohol (b) 1 alcohol
(c) 3 alcohol (d) none of the above
3. HBr reacts the fastest with
(a) 2-methyl propan-2-ol (b) propan-1-ol
(c) propan-2-ol (d) 2-methyl propan-1-ol
4. A compound X on oxidation gave B and then again on oxidation gave an acid. After the first
oxidation, it reacted with ammoniacal silver nitrate to produce a black precipitate. X is
(a) a primary alcohol (b) a tertiary alcohol
(c) acetaldehyde (d) acetone
5. RCH
2
CH
2
OH can be converted into RCH
2
CH
2
COOH. The correct sequence of reagent is
(a) P Br
3
, KCN, H
+
(b) P Br
3
, KCN, H
2
(c) KCN, H
+
(d) HCN, PBr
3
, H
+
6. Phenol forms benzene on reaction with
(a) NaHCO
3
(b) NaOH
(c) HCl (d) zinc
7. Which of the following statements is correct?
(a) phenol is acidic in nature, gives effervescence with NaHCO
3
(b) phenol is basic in nature due to the presence of OH
(c) phenol gives violet colour with neutral FeCl
3
(d) phenol as well as ethanol can be reduced to corresponding alkanes by heating with zinc dust
8. When phenol is reacted with CHCl
3
and NaOH followed by acidification, the compound
salicylaldehyde is obtained. Which of the following species is involved in the above-mentioned reaction
as an intermediate?
(a)
O
CCl
2

H
(b)
OH
CHCl
2
(c)
O
H
CHCl
OH
(d)
O

CHCl
2
9. Reimer-Tiemann reaction is/are
(a) C
6
H
6
+CH
3
Cl
3
anhydrous
AlCl

C
6
H
5
CH
3
+HCl
(b) CH
3
COOAg +Br
2
CH
3
Br +AgBr +CO
2
(c) CH
2
=CH
2
+H
2

Ni

CH
3
CH
3
(d) C
6
H
5
OH +CHCl
3
+3KOH
C
6
H
4
OH
CHO
+3KCl +3H
2
O
A-49, Maulana Azad Sarani, City Centre, Durgapur -16, (WB) Call-7699999929
Response @ www.iitjeeguru.in
10. The characteristic dark colour with neutral FeCl
3
is given by
(a)
OH
(b)
CH
3
CH
2
C =CH CH
3
OH
(c)
OH
CH
3
(d) CH
3
CH
2
CH
2
OH
11. The following reaction
OH
+HCl +HCN
2
anhydrous
ZnCl


CHO
OH
is
(a) Perkin reaction (b) Gattermann reaction
(c) Kolbe reaction (d) Gattermann koch reaction
12. Reimer-Tiemann reaction involves
(a) carbonium-ion intermediate (b) carbene inter mediate
(c) carbanion intermediate (d) free radical intermediate
13. Which of the following has a higher pH?
(a) phenol (b) o-cresol
(c) p-nitrophenol (d) glycerol
14. A mixture of o-nitrophenol and p-nitrophenol can be separated by
(a) sublimation (b) steamdistillation
(c) fractional crystallisation (d) distillation
15. Which of the following alcohols is a stronger acid?
(a) CH
3
OH (b) CH
3
CH
2
OH
(c) CHOH
CH
3
CH
3
(d)
CH
3
C OH
CH
3
CH
3
16. The reaction of anisole with HI leads to the formation of
(a) phenol and methanol (b) phenol and methyl iodide
(c) iodobenzene and methanol (d) iodobenzene and methyl iodide
17. Methyl-tert-butyl ether on heating with HI gives
(a) CH
3
I +(CH
3
)
3
COH (b) CH
3
OH +(CH
3
)
3
CCI
(c) CH
3
I +(CH
3
)
3
CI (d) (CH
3
)
3
CCI +CH
3
OH
A-49, Maulana Azad Sarani, City Centre, Durgapur -16, (WB) Call-7699999929
Response @ www.iitjeeguru.in
18. Which of the following compounds is resistant to nucleophilic attack by hydroxyl ions?
(a) methyl acetate (b) acetonitrile
(c) dimethyl ether (d) acetamide
19. Diethyl ether absorbs oxygen to form
(a) a red-coloured sweet-smelling compound (b) acetic acid
(c) ether suboxide (d) ether peroxide
20. On boiling with concentrated HBr, phenyl ethyl ether will yield
(a) phenol and ethyl bromide (b) bromobenzene and ethanol
(c) phenol and ethane (d) bromobenzene
SOLVED SUBJECTIVE EXAMPLES
Example 1: An organic compound (A) [M.F =C
7
H
8
O] is insoluble in aqueous sodiumbicarbonate but
dissolves in aqueous sodiumhydroxide and gives characteristic colour with aqueous ferric
chloride. When treated with bromine, (A) forms a compound (B) C
7
H
5
OBr
3
. Identify (A)
and (B).
Solution: (A) must be a phenolic compound because
(i) it is soluble in aq. NaOH but not in aq. NaHCO
3
(ii) it forms coloured compounds with FeCl
3
(A) has a phenolic group and it should also have a methyl group at meta position to
OH group. [Only then (B) is formed on bromination]
Br
2
Lewis
Acid
OH
OH
CH
3
Br
CH
3
Br
Br
(A)
(B)
Example 2: A compound (A) with the molecular formula C
6
H
14
O does not react with Na, but when
heated with hot HI, it converts into a mixture of two isomeric compounds of the molecular
formula C
3
H
7
I. Identify A.
Solution: Double bond equivalent (DBE) =n
C

1
2 2 2
N H X
n n n
+ +
where n
C
=no. of carbon atoms
n
H
=no. of Hydrogen atoms, n
X
=no. of halogen atoms
n
N
=no. of nitrogen atoms
For compound (A), DBE =6
14
2
+1 =0
(A) is a saturated compound but cannot be an alcohol, because it does not react with
Na. Hence, (A) is an ether.
A-49, Maulana Azad Sarani, City Centre, Durgapur -16, (WB) Call-7699999929
Response @ www.iitjeeguru.in
Now, C
3
H
7
I has only two possible isomers:
CH
3
CH
2
CH
2
(I)
CH
3
(B)
and CH(I)
CH
3
(C)
Hot HI cleaves (A) to (B) and (C)
Hence, (A) is CH
3
CH
2
CH
2
O CH
CH
3
CH
3
Example 3: Identify the products, giving the mechanism
(a)
CH
3
CH
2
CH CH
2
O
NaOCH
3
?
CH
3
OH, A
(b)CH
3
CH
2
CH CH
2
O
H
+
?
CH
3
OH, A
Solution: The reactions involved are the cleavage of the expoxide ring.
(a) This is a base-catalysed ring opening.
The mechanismis S
N
2 and the nucleophilic attack is on the less-crowded carbon.

CH
3
CH
2
CH CH
2
O
(Product)
OCH
3
CH
3
CH
2
CHCH
2
OCH
3
CH
3
CH
2
CHCH
2
OCH
3
OH
1-Methoxybutan-2-ol
H
+
O

(b)This is an acid-catalysed ring opening; therefore, mechanism is SN


1
and nucleophilic
attack is on the more-substituted carbon.
CH
3
CH
2
CH CH
2
O
CH
3
CH
2
CHCH
2
OH
H
+
OCH
3
(3, methoxybutanol) (Product)
CH
3
OH
Example 4: An organic compound (A) has 76.6% C and 6.38% H. Its vapour density is 47. It gives
characteristic colour with FeCl
3
solution. (A) when treated with CO
2
and NaOH at 140C
under pressure gives (B) which an acidification gives (C). (C) reacts with acetyl chloride to
give (D) which is a well-known painkiller. Identify A, B, C and D and also explain the
reactions involved.
A-49, Maulana Azad Sarani, City Centre, Durgapur -16, (WB) Call-7699999929
Response @ www.iitjeeguru.in
Solution: Molar mass of A =2 V.D =2 47 =94 g/mol
The ratio of atoms is
C : H : O =
76.6 6.38 17.02
: :
12 1 16
=6.38 : 6.38 : 1.064
=6 : 6 : 1
Hence, the empirical formula of A =C
6
H
6
O
Since empirical formula mass =94 =molar mass of A
Therefore, the formula of A is C
6
H
6
O.
Since (A) gives characteristic colour with FeCl
3
it should be phenol. The reactions involved
are
OH +CO
2
(A)
NaOH
140C, high P
OH
COO

Na
+
H
+
OH
COOH
(B)
(C)
Salicylic Acid

+
OH
(C)
O C CH
3
COOH
(D)
Aspirin (pain-killer)
COOH
CH
3
CCl
O
O
Example 5: An optically active alcohol (A), (C
6
H
10
O), absorbs two moles of hydrogen per mole of
(A) upon catalytic hydrogenation and gives a product (B). Compound (B) is resistant to
oxidation by CrO
3
and does not show any optical activity. Identify (A) and (B).
Solution: D.B.E of A =6
10
2
+1 =2
(A) must have following characteristics:
(i) is an alcohol
(ii) contains two t bonds
(iii) has an asymmetric carbon
(iv) is a tertiary alcohol being resistant to oxidation by CrO
3
A is
A-49, Maulana Azad Sarani, City Centre, Durgapur -16, (WB) Call-7699999929
Response @ www.iitjeeguru.in
OH
C
CH
2
CH
3
CH
3
C CH
3Methyl pent 1yn3ol
And, B is
OH
C
CH
2
CH
3
CH
3
C
2
H
5
Example 6: (A)
Al
2
O
3
250
. (B)
(i) HI
(ii) AgOH
(C)
Al
2
O
3
150C
(B)
(A)
(i) B
2
H
6
(ii) H
2
O
2
,

OH

(A) and (C) are isomers. (B) has a formula of C


5
H
10
which can also be obtained fromthe
product of reactions of CH
3
CH
2
MgBr and acetone. Identify (A), (B), and (C).
Solution: (B) [M.F =C
5
H
10
] can be obtained as
O
CH
3
CH
2
MgBr +CH
3
CCH
3
H
+
CH
3
CCH
3
CH
2
CH
3
OMgBr
C
2
H
5
C CH
3
CH
3
OH
A
CH
3
CH

=C(CH
3
)
2
(B)
Since (B) is formed by heating (A) with Al
2
O
3
, (A) must be an alcohol. Moreover, (A) and (C)
are isomers. Hence

(A) is CH
3
CH CHCH
3
CH
3
OH
(B) is CH
3
CH =C CH
3
CH
3
(C) is CH
3
C CH
2
CH
3
OH
CH
3
;
;
Example 7: Compound (A), C
10
H
12
O gives off hydrogen on treatment with sodiummetal and decolourises
Br
2
in CCl
4
to give (B), C
10
H
12
OBr
2
. (A) on treatment with I
2
in NaOH gives iodoform
and an acid (C) after acidification. Give the structures of (A) to (C) and also of all geometrical
and optical isomers of (A).
Solution: D.B.E. of (A) =10
12
2
+1 =5
Since (A) decolouries bromine water and adds only a molecule of bromine, (A) should
have a double bond.
A-49, Maulana Azad Sarani, City Centre, Durgapur -16, (WB) Call-7699999929
Response @ www.iitjeeguru.in
D.B.E. of A =5; it should also have a benzene ring.
(A) gives positive iodoform test and should have structure of the type
R CHCH
3
OH
(R =alkyl/aryl group)
Hence (A) =
CH =CHCHCH
3
OH
Br
2
CCl
4
CHBrCHBrCH(OH)CH
3
(B)
CH =CHCHCH
3
OH NaOH
(C)
I
2
CHI
3
+
Iodoform
CH =CHCOOH
(A)
(A) has a chiral carbon and exists in two enantiomeric forms:
CH =CHC
6
H
5
OH H
CH
3
CH =CHC
6
H
5
H HO
CH
3
(A) has two geometrical isomers:
C =C
CH(OH)CH
3
C
6
H
5
H
H
C =C
CH(OH)CH
3
H
C
6
H
5
H
(trans)
(cis)
Example 8: Two different Grignard reagents (X) and (Y) produce C
6
H
5
CH
2
C(CH
3
)
2
OH on reaction
with (P) and (Q) respectively. Give the structures of (X), (Y), (P), and (Q).
Solution: The compound
CH
3
C
6
H
5
CH
2
C CH
3
OH
can be synthesised as
C
6
H
5
CH
2
CCH
3
O
(P)
+ CH
3
MgX
(X)
CH
3
C CH
3
O
(Q)
+ C
6
H
5
CH
2
MgX
(Y)
C
6
H
5
CH
2
C CH
3
OH
CH
3
A-49, Maulana Azad Sarani, City Centre, Durgapur -16, (WB) Call-7699999929
Response @ www.iitjeeguru.in
Example 9: A phenolic compound (A), C
7
H
8
O
2
on mild oxidation gives a highly volatile oil (B). (A)
forms (C) on reaction with dimethyl sulphate in alkali. The oxidation of (C) with hot KMnO
4
gives (D) which then reacts with bromine water to give (E), containing about 72% bromine.
Identify (A) to (E) with proper reasoning.
Solution: D.B.E. of [A] =7 4 +1 =4
D.B.E. =4 indicates that [A] might contain a benzene ring.
[A] should contain a benzene ring as well as a phenolic group.
The molecular formula will be C
6
H
5
OH CH
2
O.
Since (A) undergoes mild oxidation, the ring should contain a CH
2
OH group and since on
oxidation a hightly volatile oil is obtained, this group should be at ortho-position.
(highly volatile due to
intra-molecular H-bonding)
mil
OH
CH
2
OH
[A]
oxidation
OH
CHO
OCH
3
CH
2
OH
[C]
hot
KMnO
4
OCH
3
COOH
[D]
Bromine
Water
OCH
3
Br
[E]
Br
Br
Etherfication
(CH
3
)
2
SO
4
/OH

Percentage of Br in [E] =69.56 % (~ 72)


Example 10: An organic compound (A) on treatment with CHCl
3
and KOH gives (B) and (C), both of
which, in turn, give the same compound (D) when distilled with Zn dust. The oxidation of
(D) yields (E) of formula C
7
H
6
O
2
. Sodiumsalt of (E) on heating with soda-lime gives (F)
which can also be obtained by distilling (A) with zinc dust. Identify (A) to (F).
Solution: The summary of reactions is
[A]
CHCl
3
KOH
[B] + [C]
Zn-dust
[F]
(i) NaOH
(ii) soda -lime
[E]
[O]
[D]
Zn-dust
C
7
H
6
O
2
D.B.E. of E(C
7
H
6
O
2
) =7
6
2
+1 =5
[E] should contain a benzene ring and it undergoes decarboxylation with soda-lime.
A-49, Maulana Azad Sarani, City Centre, Durgapur -16, (WB) Call-7699999929
Response @ www.iitjeeguru.in
[E] can be benzoic acid

COOH
[F] can be benzene (C
6
H
6
)
[A] is undergoing Reimer-Tiemann reaction; thus, [A] is phenol.
The reactions involved are
OH
(A)
CHCl
3
KOH
OH
CHO
(B)
+
OHC OH
(C)
COOH
(i) NaOH
(ii) Soda-sime
CHO
[O]
[F]
[E]
[D]
Zn-Dust
Zn-Dust
Example 11: Compound (A) gives positive Lucas test in 5 minutes. When 6.0 g of (A) is treated with
sodium metal, 1120 ml of hydrogen is evolved at STP. Assuming (A) to contain one atom
of oxygen per molecule, write the structural formula of (A).
Compound (A) when treated with PBr
3
gives compound (B) which when treated with
benzene in the presence of anhydrous AlCl
3
gives compound (C). Write the structural
formula of (B) and (C).
Solution: Let the molecular formula of (A) be ROH.
[given that (A) contains one oxygen atom/molecule]
(A)
ROH +Na
RO

Na
+
+
6g
1120 ml at STP
1
2
H
2
1 mole of (A) gives =11200 ml at STP
So, the molar mass of (A) =60 gm (6 gm of A gives 1120 ml of H
2
at STP)
Weight of alkyl group (R) =molar mass of A (mass of O +mass of H)
in one mole of (A)
=60 16 1 =43
Let R =C
n
H
2n +1
12n +2n +1 =43 n =3
Thus, the molecular formula of A is C
3
H
7
OH
Since (A) gives positive Lucas test in 5 minutes, it is a secondary alcohol.
A-49, Maulana Azad Sarani, City Centre, Durgapur -16, (WB) Call-7699999929
Response @ www.iitjeeguru.in
(A) =CH
3
CHCH
3
OH
The reactions involved are
(A)
(B)
(C)
(CH
3
)
2
CHOH
PBr
3
(CH
3
)
2
CHBr
C
6
H
6
AlCl
3
CH
CH
3
CH
3
SUBJECTIVE PROBLEMS (BASIC LEVEL)
1. An ether was cleaved with excess of concentrated HI, giving two isomers of an alkyl iodide that
contained 74.69% iodine. Identify the ether.
2. Compound (A), C
7
H
8
O is insoluble in aqueous NaHCO
3
and aqueous NaOH. When treated with
bromine water, (A) rapidly forms compound (B), C
7
H
5
OBr
3
. Identify (A) and (B).
3. An optically active alcohol A (C
6
H
10
O) 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 structures of A and B.
4. Compound X (molecular formula =C
5
H
8
O) 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 CH
4
at S.T.P. Treatment of X with H
2
in the presence of Pt catalyst
followed by boiling with excess of HI gives n-pentene. Suggest the structure for X and write the
equations involved.
5. Write mechanismfor the following reaction:
(a)
H
+
CH
2
OH
6. Complete the following reactions:
(a)
(CH
3
)
2
CHOCH
3
HI(excess)
A
Two products
(b)
CH
3
CHO
[A]
dil. H
2
SO
4
Hg
2+
(CH
3
CO)
2
O
[B]
(c)
OH
?
OH
CHO
(d)
CH
3
MgBr
H
3
C CHO ?
OH
?
H
3
C C CH
3
H
A-49, Maulana Azad Sarani, City Centre, Durgapur -16, (WB) Call-7699999929
Response @ www.iitjeeguru.in
(e)
moist
C
2
H
5
I
Ag
2
O
(A)
H
2
SO
4
(B)
C
2
H
5
OH
140C
(C)
(f)
OH
NO
2
(C
2
H
5
)
2
SO
4
OH

[A]
Zn, HCl
[B]
NaNO
2
, HCl
5C
[C]
[D]
C
6
H
5
OH
(g)
OH
H
+
?
7. An organic compound [A] of formula C
2
H
6
O on treatment with concentrated H
2
SO
4
gives
a neutral compound [B] (C
4
H
10
O). The later on treatment with PCl
5
gives a product which
on subsequent treatment with KCN yields [C] (C
3
H
5
N). Compound (C) on hydrolysis gives
an acid, C
3
H
6
O
2
and on reduction with sodium amalgam gives base C
3
H
9
N. Identify
[A], [B], and [C].
8. An organic liquid [X] has a sweet smell and boiling point of 78C. It contains C, H and O and on
heating with concentrated H
2
SO
4
forms a gaseous product (Y) of empirical formula CH
2
. (Y)
decolorises bromine water and adds one mole of H
2
in the presence of Ni. Identify (X) and (Y).
9. An organic compound (X) containing C, H and O reacts with sodiumwith the release of hydrogen.
Controlled oxidation of (X) gives (Y) which forms a precipitate with sodiumbisulphite but does not
give Ag mirror test. A solution of 7.41 g of (X) in 100 g of water freezes at 1.86 C. Identify (X) and
(Y). [K
f
for water =1.86C/molal].
SUBJECTIVE PROBLEMS (ADVANCED LEVEL)
1. An organic compound containing C, H, and O exists in two isomeric forms (A) and (B). An amount
of 0.108 g of one of the isomers gives on combustion 0.308 g of CO
2
and 0.072 g of H
2
O. (A) is
insoluble in NaOH and NaHCO
3
whereas (B) is soluble in NaOH. (A) reacts with concentrated HI
to give compounds (C) and (D). (C) can be separated from(D) by the ethanolic AgNO
3
solution and
(D) is soluble in NaOH. (B) reacts readily with bromine water to give compound (E) of molecular
formula, C
7
H
5
OBr
3
. Identify (A), (B), (C), (D), and (E).
2. An organic compound (A) containing 60% C and 13.3 % H gave the following results
(i) 0.2 gm of the compound displaced 74.66 ml. of air at N.T.P.
(ii) On treatment with PCl
5
, (A) gave another compound (B) which contained 45.2% chlorine
(iii) On dehydration, (A) produced a hydrocarbon (C) containing 85.7% C and 14.7% H.
(iv) On successive treatment with HI and moist silver oxide, (C) gave a compound (D), isomeric with
(A).
Identify (A), (B), (C), and (D).
3. An organic compound (A), (C
7
H
8
O) yields two isomeric mono-nitro derivatives (B) and (C) on
nitration. Treatment of (A) with acetyl chloride produces (D), which on oxidation with chromyl
chloride gives (E) whose oxidation with neutral KMnO
4
followed by hydrolysis gives (F).
Compound (F) on heating with soda-lime gives phenol. (A) on treatment with benzene sulfonyl
chloride produces (G) which on oxidation with KMnO
4
gives (H). Hydrolysis of (H) also gives (F).
Identify (A) to (H).
A-49, Maulana Azad Sarani, City Centre, Durgapur -16, (WB) Call-7699999929
Response @ www.iitjeeguru.in
4. An organic compound (A), C
7
H
8
O
2
on mild oxidation gives a highly volatile oil (B) which forms
(C) on reaction with dimethyl sulphate in alkali. Oxidation of (C) with KMnO
4
gives (D) which then
reacts with bromine water to give (E) containing about 72% bromine. Identify (A) to (E).
5. A 0.450 g of an aromatic compound (A) on ignition gives 0.905 g of CO
2
and 0.185 g of
H
2
O. 0.350 g of (A) on boiling with HNO
3
and adding AgNO
3
solution gives 0.574 g of AgCl. The
vapour density of (A) is 87.5. (A) on hydrolysis with Ca(OH)
2
yields (B) which on mild reduction
gives an optically active compound (C). On heating (C) with I
2
and NaOH, iodoform is produced
alongwith (D). With HCl, (D) gives a solid which is markedly more soluble in hot water than in cold.
Identify (A) to (D) with proper justification.
6. An organic compound (A) containing 78.69% of C, 8.19 % of H, and 13.11 % of O does not react
with metallic sodium. (A) yields two compounds (B) and (C) on treatment with HI. (B) reacts with
sodiumto liberate hydrogen and also forms a salt with sodium hydroxide. (B) can be brominated and
the product contains two bromine atoms. Compound (C) containing iodine on treatment with Mg in
ether followed by the addition of CO
2
followed by acidification with dilute acid gives acetic acid.
Identify (A), (B), and (C).
7. An organic compound (A) is treated with moderately concentrated NaOH solution and after
sometime produces (B) and (C). The percentage of carbon, hydrogen, and oxygen in compound (B)
is 77.8, 7.4, and 14.8 respectively. Oxidation of (B) yields (C) which on acidification with a mineral
acid and further treatment with lithiumaluminiumhydride gives (B). Identify (A), (B), and (C).
A-49, Maulana Azad Sarani, City Centre, Durgapur -16, (WB) Call-7699999929
Response @ www.iitjeeguru.in
ANSWERS
OBJECTIVES PROBLEMS
SECTION A
1. d 2. b 3. d 4. c 5. c
6. c 7. d 8. b 9. a 10. d
11. b 12. d 13. a 14. d 15. d
16. b 17. d 18. a, d 19. c 20. c
SECTION B
1. d 2. c 3. a 4. a 5. a
6. d 7. c 8. a, b 9. d 10. a, b
11. b 12. b 13. d 14. b 15. a
16. b 17. c 18. c 19. d 20. a
SUBJECTIVE PROBLEMS (BASIC LEVEL)
1.
CH
3
CH
2
CH
2
OCH
CH
3
CH
3
2. (A) =
OCH
3
, (B) =Br OCH
3
Br
Br
3.
CH
3
(A) =CH C C OH
C
2
H
5
,
CH
3
(B) =CH
3
CH
2
C OH
CH
2
CH
3
4. (X) =HC C CH
2
CH
2
CH
2
OH
The reactions involved are
(i) HC CCH
2
CH
2
CH
2
OH
AgNo
3
NH
4
OH
AgC CCH
2
CH
2
CH
2
OH
(ii) HC C CH
2
CH
2
CH
2
OH
2CH
3
MgBr
MgBrC C CH
2
CH
2
CH
2
OMgBr +2CH
4
(iii) HC CCH
2
CH
2
CH
2
OH
H
2
/Pt
CH
3
CH
2
CH
2
CH
2
CH
2
OH
HI
CH
3
CH
2
CH
2
CH=CH
2
A-49, Maulana Azad Sarani, City Centre, Durgapur -16, (WB) Call-7699999929
Response @ www.iitjeeguru.in
5.
H
+
CH
2
OH
CH
2
OH
2
+
H
2
O
CH
2
+
+
H
H
H
6. (a) (CH
3
)
2
CHI +CH
3
I
(b) CH CH[A], CH
3
CH(OCOCH
3
)
2
[B]
(c) CO
2
, 125C, 3 5 atm. or CHCl
3
+NaOH
(d)
CH
3
C
H
OMgBr
CH
3
, H
2
O
(e)C
2
H
5
OH, C
2
H
5
HSO
4
, C
2
H
5
OC
2
H
5
(f) [B] : [A] :
NO
2
OC
2
H
5
NH
2
OC
2
H
5
[C] :
N
2
Cl
OC
2
H
5
+

[D] :
HO N =N OC
2
H
5
(g)
CH
3
O
7. [A] : C
2
H
5
OH [B] : C
2
H
5
OC
2
H
5
[C] : C
2
H
5
CN
8. (X) : C
2
H
5
OH, (Y) : CH
2
=CH
2
9. (X) : CH
3
CH
2
CHOH
CH
3
(Y) :
CH
3
CH
2
C
CH
3
O
A-49, Maulana Azad Sarani, City Centre, Durgapur -16, (WB) Call-7699999929
Response @ www.iitjeeguru.in
, [E] and [F] :
COOH
[D] :
Br
Br
COOH
Br
,
Br
CH
2
COOH
Br
7. [A] : HCOOCH (CH
3
)
2
, [B] : CH
3
CH(OH)CH
3
8. , [B] :
CH
3
[A] :
COOH
COOH
,
Br
COOH
C
2
H
5
[C] :
COOH
9. [X] : CH
3
CH
2
COOCH
2
CH
2
CH
3
, [Y] : CH
3
CH
2
COOH
[Z] : CH
3
CH
2
CH
2
OH
10.
, [B] :
CH =CHCH
3
[A] :
CH
2
CH =CH
2
Cl
,
CH
2
CH
2
CH
3
Cl
[C] :
Cl
OC
2
H
5
OC
2
H
5
OC
2
H
5
11. [A] :
CO
CO
O, [B] :
C
6
H
5
COOH
O
, [C] :
O
O
C
6
H
5
[D] :
N
N
C
6
H
5

You might also like