ORGANIC CHEMISTRY

VOLUME – II
(ENGLISH)

CONTENTS

• ALCOHOL & ETHER 2

• CARBONYL COMPOUND 25

• CARBOXYLIC ACID & ITS DERIVATIVES 53

• NITROGEN COMPOUNDS 88

• AROMATIC COMPOUNDS 116

• BIOMOLECULES & POLYMER 165

 ALCOHOL

1. INTRODUCTION
Their general formula is CnH2n+1OH or CnH2n+2O.
These are of following types, depending upon the no. of OH groups.
(i) Monohydric alcohol:-
Contains one –OH group only, eg.C2H5OH
(ii) Dihydric alcohol :-
Contains two –OH groups. eg. glycol
(iii) Trihydric alcohol:-
Contains three –OH groups eg. glycerol
(iv) Polyhydric alcohol :-
Contains more than three - OH groups. eg, sorbitol, manitol.

2. METHODS OF PREPARATION
2.1 From Alkyl halides:-
Alkyl halides reacts with aq. KOH/aq. AgOH or H2O and forms alcohol.
R–CH2–X + K–OH (aq.)  R–CH2OH + KX

R R
| |
R  CH  X + AgOH (aq.)  R  CH  OH + AgX

R R
| |
RC X + H–OH  R  C  OH + HX
| |
R R

2.2 From Alkenes :

2.2.1 Hydration – Alkenes are catalytically hydrated by dilute mineral acid solution.
CH2 = CH2 + H2O  dil

H SO
 CH3CH2OH
2 4

R – CH = CH2 + H2O  dil


H SO
 R  CH  CH3
2 4

|
OH

2.2.2 Oxymercuration – demercuration :

Alkenes react with mercuric acetate in the presence of water to give hydroxymercurial compounds,
which on reduction yield alcohols. (Markovnikov addition)
I I I I
>C = C< + H2O + Hg (OAc)2  C  C  Na B H4
   C  C
I I I I
OH Hg O Ac OH H
Mercuric acetate Alcohol

ALCOHOL & ETHER [2]

2.2.3 Hydroboration – Oxidation :
(Anti–Markownikov orientation)
1
>C = C< + (BH3)2  B C—C
2
H
Alkene Diborane Tri alkyl borane
H2 O 2 I I
    C  C  + B(OH)
OH I I 3
H OH

2.3 By Reduction of Carbonyl compounds :-

LiAlH / NaC H OH
R  C  H + 2H  4 25
 R–CH2OH
||
O
1º alcohol
LiAlH / NaC H OH
R  C  R + 2H  4 25
 R  CH R
|| |
O OH
2º alcohol
Note :
(i) We cannot obtain 3º alcohol from this method
(ii) If we use NaH as reductant then the process is called as 'Darzen's process'.
2.4 By Reduction of Acid & its derivatives :
R  C  OH + 4H LiAlH
 4
 RCH2OH
||
O

R  C  X + 4H LiAlH
 4
 R CH2OH + HX
||
O

R–C–OR' + 4H LiAlH
  RCH2OH + R'OH
4

||
O
RCOOCOR + 8H LiAlH  4
 2 RCH2OH + H2O
Important Note :- Acid amide does not form alcohol on reduction. It forms primary amine.
2.5 From Grignard reagent :
2.5.1 With oxygen : –
Grignard reagent forms alcohol of same no. of carbon atoms as in Grignard reagent.
2HOH
2R–Mg–X + O2 2R–O–Mg–X    2ROH + 2 Mg(X)OH

2.5.2 With ethylene oxide :

H O
 R–CH2–CH2–O–Mg–X 2 R–CH2–CH2OH+ Mg(X)OH
[Alcohol with two carbon more
than Grignard reagent ]

ALCOHOL & ETHER [3]

2.5.3 With carbonyl compounds :

H H
  | |
R  Mg  X + R 'C  H   R'C  R H
2O
 R' C  R
|| | |
O O  Mg  X OH

Note :
(i) If R' = H , Product will be 1º alcohol.
(ii) If R' = R, Product will be 2º alcohol.
(iii) If carbonyl compound is ketone, product will be 3º alcohol.
(iv) It is the best method for preparation of alcohol because we can prepare every type of alcohols.
2.6 From Primary amines :-
HCl
R–NH2 + HNO2   R–OH + N2 + H2O.
But it is not a good method for preparation of alcohol because a number of byproducts are formed in this
reaction like alkyl chloride, alkyl nitrite, alkene and ether.
Note : In this reaction if we take ethyl amine then main product will be ethanol while if we take methyl amine,
then main product will be dimethyl ether.

3. PHYSICAL PROPERTIES
(a) Alcohols are colourless with specific smell liquid. They are soluble is water due to H-bonding.
These are partially soluble in organic solvents.
(b) They are liquid in nature up to 12-carbon.
1
(c) Melting point and Boiling point  molecular mass 
No. of branches

(d) Boiling point of alcohols are higher than equivalent ethers. It is due to H-bonding.
(e) Alcohols are poisonous in nature also. Poisonous character increase with increment in molecular
weight or branching. Ethanol is exception, which is non-poisonous in nature. It is most useful
organic solvent.
(f) Methanol causes blindness.
(g) Isopropyl alcohol is called as rubbing alcohol.
(h) Cholestrol is also an example of complex alcohol which is called notorious alcohol because it
causes heart attack.
(i) Viscous nature of alcohol is directly proportional to H-bonding or number of -OH groups. That
is why we can say alcohol is less viscous than glycerol & manitol is more viscous than glycerol.
(j) Ethanol is liquid while glucose is solid. It is due to more H-bonding in glucose.

4. CHEMICAL PROPERTIES
Chemical reactions of alcohols are classified in the following three types :-
(i) Reaction of H atom of –OH group of Alcohols
(ii) Reaction of OH group of Alcohols
(iii) General reaction of Alcohols.

ALCOHOL & ETHER [4]

4.1 Reaction of H atom of –OH group of Alcohols :
These are the reactions in which alcohol shows acidic character.

4.1.1 Reaction with Na :

2R–O–H + Na –––––– 2R – O – Na + H2
The acidic order of alcohols is
MeOH > 1º > 2º > 3º
4.1.2 Esterification / Reaction with carboxylic acid:-
conc.H SO4
   2  R–C–O–R + H2O
||
O
ester
Mechanism :
H2SO4 ––––– H+ + HSO 4
.. 
RCO..
H+ H+––  
 H2O
 R  C  ROH
 R  O  C  R    R  C  OR
 H
|| || | || ||
O O H O O

Note : The above reaction is laboratory method of ester preparation.

4.1.3 Reaction with Acid derivatives :
R–O–H + X  C  R  Conc
 .H2 SO 4
 R  O  C  R + HX
|| ||
O O
Conc.H SO
2 
4
R  O  H  R  C  O  C  R   R C  O R
|| || ||
O O O
4.1.4 Reaction with Ketene :-
 
R O H + CH2 = C     CH  C  O  R
|| 3
||
O  O

4.1.5 Reaction with Isocyanic Acid :-

  
RO H +H–N= C  H – N = C  O  R  H – NH – C  O  R
|| | ||
O OH O

amino ester (urethane)

4.1.6 Reaction with ethylene oxide :
ROH
R – O- – H+ +    
H2 O

1,2-dialkoxy ethane
4.1.7 Reaction with Diazomethane :-
R–O–H + CH2 N2  R–O–CH3
(ether)

ALCOHOL & ETHER [5]

4.2 Reaction of – OH group of Alcohols :-

4.2.1 Reaction with dry HX (Grove's Process) :

R–OH + HX  R – X + H2O
4.2.2 Reaction with PCl5 :
R–OH + PCl5  R–Cl + POCl3 + HCl
4.2.3 Reaction with PCl3 :
3R–OH + PCl3  3R–Cl + H3PO3
4.2.4 Reaction with SOCl2 (Darzen reaction): –
Pyridine
R–OH +SOCl2  
 R–Cl +SO2 + HCl
4.2.5 Reaction with ammonia :
anhy.ZnCl2
R – OH+ NH3  
300  C
 RNH + H O
2 2

4.2.6 Reaction with HNO3 :

R–OH + HNO3  + H2O

(conc.) alkyl nitrate

(soluble ester)

Mechanism :-
HNO3  H+ + NO 3

R–O–H + H+  R  O  H  
H2 O
 R
|
H

R+ NO 3 

alkyl nitrate

4.2.7 Reaction with H2SO4 :-

O O
|| 20 35 º
||
(i) C2H5OH + H  O  S  OH   C2H5– O  S  OH
room temp
|| ||
O O

stable upto (80-100ºC)

..
140 º C
(ii) CH3 – CH2 – OH + H2SO4  CH3–CH2– O
..
–CH2–CH3

(excess)

ALCOHOL & ETHER [6]

 Mechanism :-
H2SO4  H+ + HSO4¯
 : + H+  CH –CH 
CH3–CH2– O  
3 2  O –H
| |
H H


CH – CH – OH
3 2
 CH3– C H 2


(protonated ether)

..
CH3  CH2  O CH2  CH3
..

(iv) CH3–CH2–OH+H2SO4   CH2= CH2

160 º C

(excess)

Mechanism :-
H2SO4  H+ + HSO4–

CH3–CH2– –H + H+  CH3–CH2–

H
 CH – CH2  
–H  
H2 O 3  CH2 = CH2

Note :-
In the above reaction excess of ethanol is present so, intermediate carbocation satisfies itself by elimination.
4.3 General reaction of Alcohols :-
4.3.1 Reduction :-
Re dP
R–O–H + 2 HI 150
 R – H
C

Reacting species of solution is HCrO4¯.

acidic KMnO 4 [o ]
    


acidic K 2Cr2O7 [o ]
    


ALCOHOL & ETHER [7]

 4.3.2 Catalytic Oxidation / Dehydrogenation :

Cu / ZnO
 
300 º

1º alcohol aldehyde

Cu / ZnO
 
300 º

secondary alcohol ketone

Cu / ZnO
 
300 º

tert. alcohol alkene

(Note : – This is dehydration process.)

4.3.3 Oxidation through Fenton's Reagent :

Higher and branched alcohols are converted into diols through Fentons reagent.
(FeSO4 + H2O2) is Fenton's reagent.
Fe+2 + H2O2  Fe+3 + O H + O H
CH3 CH3
| |
• •
CH3–C–CH2–H + OH  CH 3–C–CH 2 + H2O
| |
OH OH

CH3 CH3
| • |
•
CH3–C–CH2 + CH2–C–CH3  
| |
OH OH

2,5-dimethyl hexandiol-2,5
4.3.4 Self Condensation :
When alcohol is heated with sodium ethoxide then by self condensation they convert into higher
alcohol.

RCH2–CH2–OH + H– –CH2–OH   R–CH2–CH2– –CH2–OH

higher alcohol
Note : The above reaction is called as 'Guerbet's Reaction'.

5.1 Preparation of methanol :

Methanol is also called as carbinol or wood spirit.
5.1.1 From Water Gas :
Al2 O 3
[CO + H2] + H2 ZnO

/ CrO
 CH OH (90 %)
3 3
200  300 º

ALCOHOL & ETHER [8]

 5.1.2 From Methane : -
CH4 gives methanol on partial oxidation in Cu tube.
1
CH4 + O  Cu tube
 CH3OH (90%)
2 2 200º C
5.1.3 By Pyroligneous Acid : -
anhy. CaCl2 + CH3OH  CaCl2 • 4CH3OH
anhy. MgCl2 + CH3OH  MgCl2 • 6CH3OH
anhy. CuSO4 + CH3OH  CuSO4 • 2CH3OH
we get pure methanol on steam distillation
or
we can use oxalic acid to separate water impurities.
O=C–O–H H–O–CH3
| + 
O=C–O–H H–O–CH3
oxalic acid methyl
methanol oxalate(solid)
we get pure methanol on alkaline hydrolysis
O=C–O–CH3 H–O–Na
| +  2CH3OH +
O=C–O–CH3 H–O–Na

5.2 Preparation of Ethanol :

5.2.1 From Ethene :
By hydration with dil. H2SO4
CH2=CH2 + H - OH  dil . H2 SO 4
  CH3–CH2–OH
5.2.1 Preparation of ethanol from sugar : -
(i) Molasses : - Waste product in sugar industry is called molasses. It is a mixture of sugar
(30%) and invert sugar (32-40%).
(ii) Invert sugar : - Combine form of glucose and fructose is called as invert sugar.
yeast cell
C12H22O11 + H2O    C6H12O6 + C6H12O6
invertase enzyme

glucose fructose
C6H12O6 C2H5OH + CO2 + H2O
Note: Glucose and fructose are functional isomers.
5.2.3 Preparation of ethanol from starch :
(i) Starch solution is technically called 'Mesh'
(ii) Crushed germinated barley solution is called 'Malt'.
2(C6H10O5)n + nH2O  diastase
  nC12H22O11
starch maltose (wort)
C12H22O11 + H2O maltase
  2C6H12O6
maltase glucose
(monosaccharide)
zymase
2C6H12O6   C2H5OH + CO2 + H2O + energy

ALCOHOL & ETHER [9]

 (iii) From both of the methods conc. of ethanol achieved is 10-12% which is called 'Wash'.
(iv) Distillation of wash is done in special apparatus 'Coffee's still', which is based on counter
current method. From this distillation yield of alcohol is 90%, which is called Raw spirit.
Raw spirit Fractional
  95.5% C2H5OH + 4.5% H2O
distillation

(rectified spirit)
(v) Further purification is done in the following ways : -
95.5% C2H5OH + 4.5% H2O C6H6 + H2O + C2H5OH + Remaining C6H6
(64ºC) (78.5 ºC) + CH3CHO
(99.7%) (68ºC)
C2H5OH + Ca metal  2
 3 days
 C2H5OH + Ca(OH)2
(99.7%) (100%)
C2H5OH + anhy. CuSO4  C2H5OH + CuSO4 • 5H2O
(99.7%) white (100%)

6. DIFFERENCE BETWEEN PRIMARY,

SECONDARY & TERTIARY ALCOHOLS
6.1 By Oxidation Reaction :-
Primary alcohol gives aldehyde on oxidation, secondary alcohol gives ketone and tertiary alcohols are
resistant to oxidation.
6.2 By Catalytical Oxidation / Dehydrogenation :
Primary alcohol gives aldehyde on oxidation, secondary alcohol gives ketone and tertiary alcohol gives
alkene ( dehydration takes place in this condition to tertiary alcohols.)
6.3 Lucas Test :-
A mixture of (anhydrous ZnCl2 + Conc. H2SO4) is called as Lucas Reagent.
(i) 3º alcohol gives white ppt. with lucas reagent in 2-3 seconds only.
(ii) 2º alcohol takes 9 - 10 minutes.
(iii) 1º alcohol does not gives white ppt. at room temperature.
6.4 Victor Meyer Test : -
This test is also known as RBW ( Red, Blue, White) test.
Re d P / I AgNO 2
(a) R–CH2–OH
  R–CH2–I 
2
 R–CH2–NO2 + HNO2
 AgI

nitrate

NaOH
   red solution

nitrolic acid

AgNO 2
(b) R2–CH–OH  Re d P /I
 R2–CH–I  
2 

nitrosoderivative NaOH (blue ppt.)

Pseudonitrile
(c) R3–C–OHRe d P /I
 R3–C–I AgNO
2
  2
HNO 2
 R3–C–NO2  
 no. reaction.

ALCOHOL & ETHER [10]

6.5 Difference between Methanol and Ethanol :

Methanol Ethanol
1. When CH3OH is heated on Cu coil it gives 1. Ethanol does not give formalin like smell.
formalin like smell.

2. When CH3OH is heated with salicylic acid in 2. No such odour is given by ethanol
H2SO4 (conc.) then methyl salicylate is
formed which has odour like winter green oil
3. It does not give haloform or Iodoform test. 3. It gives haloform test.

ALCOHOL & ETHER [11]

 ALCOHOL

GMP GR
3 5HX or PX or PX
H2 O
(1)    RX
or KI +H 3PO 4 or SOCl2 or SO 2 Cl2
(1) Alkene  
aq. NaOH or aq. KOH (2) Re
d P /HI
 RH
(2) RX  
or aq. K 2 CO 3 or moist Ag2 O NH3
(3)    1º , 2º , 3º amines
dil. H SO
(3) R - O - R 2
 4
  2H S
(4) 
  R - SH Thiol
2 4dil. H SO ThO 2
(4) RCOOR   
RCOOH
(5) Na
 RONa
HNO 2
(5) 1º amine    CH MgX
(6) 3
  CH4
Exception - (Methyl amine gives
R' OR
CH3-O-CH3 or ether) ald.R'CHO
(7) 
 C Acetal
NaH dry HCl
(6) Aldehyde or ketone  
Darzon reduction H OR
(1º alc.) (2º alc.)
Na / EtOH
R-OH
(7) Acid or  
 R' OR
Bouveault Blanc reduction
Ketone R 'COR '
Acid derivative (8)     
 C Ketal
dry HCl
R MgX R' OR
(8) HCHO or Ald.or ketone  

H2 O
R 'COZ
(1º alc) (2ºalc) (3º alc.) (9)  R'COOR ester (Z = OH,Cl, OCOCH3)
 
O2
(9) RMgX 
 (10) H
2 SO 4
 ROSO2OH (Alkyl hydrogen sulphate)
H2 O

CH2  CH2
(11) HNO
 3
 RONO2 (Alkyl nitrate)

(10) CH3MgBr   

O (12) PhSO
 2 Cl
 RSO2Ph (Alkyl benzene sulphonate)

H3 O
(13)  CH

 CH
 H3C - CH (OR)2 Acetal
(11) Sugar Fermentation
 
 (14)  CH
2N2
 R - O - CH3 Ether
O

CH 2  CH 2
(15)       RO - CH2 - CH2 - OH
Alkoxyalkanol
(16)  CH
2  CO
 ROCOCH3 Ester
(17) Dehydration
 Alkene
Catalytic dehydrogenation
(18) 0
 
0
 0
Aldehyde or ketone
1 or 2 alcohol , Cu or ZnO , 300 C
Formation of EtOH by fermention - Exception - 3º alc  Alkene
Crystallization [O]
(1) Cane sugar  Molasses
  (19) Aldehyde[
1ºalc.   O]
Acid (same no. of C-atom)
Sucrose

Invertase 4 O HCrO 
  Invert sugar  zymase
 EtOH (20) 1º or 2ºalc. 
  Aldehyde or ketone + Cr+3 (green)
hydrolysis Fermentation ( orange )

4 O, HCrO 
Diastase
(21) 3º alc  
  No reaction (No. green colour)
( orange )
(2) Grain  Starch   Maltose
HOH

Maltase Zymase
  Glucose  
hydrolysis Fermentation

EtOH

ALCOHOL & ETHER [12]

 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 atom are the same, and it is
unsymmetrical if the groups are different.
CH3CH2CH2CHCH2CH3 CH3CH2OCH2CH2CH3
1-Ethoxypropane
OCH3
3-Methoxyhexane

PREPARATION :
1. Dehydration of alchols
H2SO4
2R — O — H R — O — R + H2O


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:
140°C
C2H5OC2H5 Diethyl ether
Conc.
CH3CH2OH H SO
2 4
180°C
CH2 = CH2 Ethene

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 SN1 for 2° and 3° alcohols and SN2 for 1° alcohol.
+ +
R — OH + H R — OH2 (Protonated alcohol)
–H2O ROH H
R+ R O — R H+ + R — O — R
+ SN1(3° & 2° +
R — OH2 alcohols)
H H
ROH + +
[R — O ---R----OH2] R — O — R R — O — R + H+
SN2(1° alcohols) +

2. Williamson synthesis
–
RO Na+
R – OR
RX
ArO–Na+
R – OAr
Yield from RX: CH3 > 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.

ALCOHOL & ETHER [13]

 Na
(CH3)2 CH(OH) (CH3)2CHO–Na+ + CH3CH2CH2Br CH3(CH2)2O CH(CH3)2

aq. NaOH
OH + CH3CH2Br O — CH2CH3
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.
CH3 CH3
aq.NaOH
CH — C — Br + C2H5OH CH3 — C = CH2

CH3

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
110° O
net dipole moment
R

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 form hydrogen
bonds with water molecules.
H

R — O ------ H — O

R
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

HX

R — X

Reactivity of HX : HI > HBr > HCl.

ALCOHOL & ETHER [14]

 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 form second
mole of alkyl halide.
48% HBr
CH3 — CH — O — CH — CH3 2CH3CHCH3
130 – 140°C

CH3 CH3 Br

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.

H
SN1
R — O — R+ HX R — O — R+ X– R — X + ROH
or SN2
+ HX
Protonated ether RX

A primary alkyl group tends to undergo SN2 displacement and a tertiary alkyl group tends to undergo
SN1 displacement.

HI
CH3I + CH3CH2CH2OH
SN2
CH3 — O — CH2CH2CH3
3 – Methoxy propane
HI
excess CH3I + CH3CH2CH2I

CH3
HI
CH3 — O — C — CH3 CH3OH + (CH3)3CI
SN1
CH3
2 – Methoxy–2–methyl propane

Epoxides
Epoxides are compounds containing the three-membered ring.

— C — C — (Epoxide or oxirane ring)

O
Epoxides belong to a class of compounds called cyclic ethers. The three-membered ring makes epoxides
an exceedingly important class of compounds.
CH2 — CH — CH2 — CH3 CH2 — CH2

O O
1, 2 – Epoxybutane Epoxyethane

ALCOHOL & ETHER [15]

PREPARATION
Epoxides are commonly obtained by oxidation of alkenes by peroxy acids.
O
RCO3H
C=C C — C
Peroxyacid
Alkene Epoxide

Silver oxide can also oxidise alkenes to epoxides. An internal SN2 reaction in a chlorohydrin can be used
to prepare three membered cyclic ethers.
OH– –Cl
–
Cl — CH2 — CH — CH3 Cl — CH2 — CH — CH3 CH2 — CH — CH3
OH – O
O 1, 2 – Epoxypropane

Reactions :
Epoxides have highly strained three-membered rings that can undergo acid- or base-catalysed ring
cleavage.
1. Acid-catalysed cleavage
H
O +O OH

—C—C— —C—C— —C—C—

Z: Z
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— —C—C—
O +O
H

H2 O
—C—C— —C—C— 1, 2, - diol
–H+
+ OH2 OH OH OH
—C—C— ROH
—C—C— —C—C— Alkoxy alcohol
O+ –H+
H OH OR OH
RO
H

X–
—C—C— Halohydrin

X OH

ALCOHOL & ETHER [16]

2. Base-catalysed cleavage
Z Z
Z: + — C — C — —C—C— —C—C—
HZ
O O– OH

Under alkaline conditions, an epoxide itself undergoes nucleophilic attack.

C2H5O– Na+ + CH2 — CH2 C2H5O CH2 CH2 OH

2-Ethoxyethanol
O
NH3 + CH2 — CH2 H2N — CH2 CH2 OH
2-Aminoethanol
O

3. Reaction with Grignard reagent

R — MgX + CH2 — CH2

– + H+
CH2 — CH2 — OMgX RCH2 CH2 OH
O Primary alcohol
R (Chain lengthened
by two carbon atoms)

MgBr + H2C — CH2 CH2CH2OMgBr

O H2 O
Phenyl magnesium Ethylene
bromide oxide
CH2CH2OH

2-Phenylethanol

ALCOHOL & ETHER [17]

 EXERCISE – I
Q.1 Which of the following is produced when an aqueous solution of butan-2-ol is refluxed with dilute acidic
KMnO4?
(A) butanol (B) butanoic acid
(C) potassium butanoate (D) butanone

Q.2 Which of the following has the lowest solubility in water?

CH3
(A) CH3CH2CH2CH2OH (B) CH3—CHCH2OH
(C) HOH2C — CH2OH (D) C6H5CH2CH2OH
Q.3 Chlorine reacts with ethanol to give
(A) ethylchloride (B) chloroform (C) chloral (D) acetaldehyde
Q.4 Ethanol is heated with concentrated H2SO4. The product formed is
(A) CH3 — C — O — C2H5 (B) C2H6

O
(C) C2H4 (D) C2H2

Q.5 Which of the following has the highest boiling point?

(A) CH3 — CH2 — CH — CH3 (B) CH3 — CH2 — CH2 — CH2OH

OH

CH3

(C) CH3 — CH — CH2OH (D) CH3 — C— OH

CH3 CH3

Q.6 Lucas test is used to determine the type of

(A) amines (B) alcohols (C) acids (D) phenols

Q.7 Separation of a higher phenol and an aromatic carboxylic acid can be easily carried out by
(A) NaOH (B) Na2CO3 (C) lime (D) NaHCO3

Q.8 The ether O—CH2— when treated with HI produces

(A) CH2I (B) CH2OH

(C) I (D) OH

ALCOHOL & ETHER [18]

Q.9 The reaction between sodium ethoxide and bromoethane yields
(A) methyl ethyl ether (B) dimethyl ether
(C) diethyl ether (D) propane

Q.10 The hydroboration oxidation of 2-methyl propene yields-

(A) 1º alcohol (B) 2º alcohol (C) 3º alcohol (D) None

Q.11 Action of HNO2 on CH3NH2 gives-

(A) CH3OH (B) CH3—O—CH3 (C) CH3—O—N=O (D) B and C both

Q.12 The alkaline hydrolysis of esters is known as:

(A) Hydration (B) Esterification
(C) Dehydration (D) Saponification

Q.13 Which of the following reactions of an alcohol does not involve O – H bond breaking :
(A) Reaction with alkali metals (B) Reaction with an acyl chloride
(C) Reaction with sulphonyl chloride (D) Reaction with conc. sulphuric acid.

Q.14 Replacement of -OH group in alcohol by -Cl cannot be carried out with-
(A) PCl5 (B) SO2Cl2 (C) PCl3 (D) SOCl2

Q.15 A on treatment with Na gives B and with PCl5 gives C. B and C react together to give diethyl
ether. A, B and C are in the order-
(A) C2H5OH, C2H5Cl, C2H5ONa (B) C2H5OH, C2H6, C2H5Cl
(C) C2H5OH, C2H5ONa, C2H5Cl (D) C2H5Cl, C2H6, C2H5OH

Q.16 A compound is soluble in concentrated H2SO4. It does not decolourise bromine in carbon tet-
rachloride but oxidised by chromic anhydride in aq. sulphuric acid within two seconds, turning
orange solution to blue green then opaque. The original compound is-
(A) A primary alcohol (B) A tertiary alcohol
(C) An alkene (D) An ether

Q.17 Which of the following alcohols does not give a red colour in Victor Meyer test-
(A) Isobutyl alcohol (B) Isoamyl alcohol
(C) Diethyl carbinol (D) Phenylcarbinol

Q.18 Water gas is mixture of-

(A) CO + H2 in the ratio 1 : 2 (B) CO2 + H2 in the ratio 1 : 1
(C) Steam + CO in the ratio 1 : 1 (D) CO + CO2 + Steam

Q.19 Absolute alcohol contains-

(A) 40% H2O (B) 10% H2O (C) 5% H2O (D) 100% C2H5OH

Q.20 Proof spirit contains about-

(A) 40% alcohol by weight (B) 50% alcohol by weight
(C) 25% alcohol by weight (D) 10% alcohol by weight
ALCOHOL & ETHER [19]
Q.21 Reaction of alcohol does not show cleavage of R-O linkage-
(A) ROH + PCl5 (B) ROH + SOCl2 (C) ROH + HCl (D) ROH + Na

Q.22 An organic compound dissolved in dry benzene, evolved hydrogen on treatment with sodium. It
is-
(A) A ketone (B) An aldehyde (C) A tertiary amine (D) An alcohol

Q.23 Alkyl chloride is formed when alcohol is treated with HCl in presence of anhydrous ZnCl2. The
order of reactivity with respect to alcohol is :
(A) 3º > 2º > 1º (B) 1º > 2º > 3º (C) 2º > 1º > 3º (D) 1º > 3º > 2º

Q.24 The increasing order of boiling points of 1º, 2º, 3º alcohol is -

(A) 1º > 2º > 3º (B) 3º > 2º > 1º
(C) 2º > 1º > 3º (D) None
Q.25 Hydrogen bonding is possible in-
(A) Ethers (B) Hydrocarbons (C) Alkanes (D) Alcohols

PCl5 alc.
Q.26 Consider the reaction: CH3CH2CH2OH   A 
KOH
 B . The compound ‘B’ is
(A) propane (B) propene (C) propyne (D) propanal

Q.27 The solubility of lower alcohols in water is due to -

(A) Formation of hydrogen bond between alcohol and water molecules
(B) Hydrophobic nature of alcohol
(C) Increases in boiling points
(D) None of these

Q.28 A compound ‘A’ reacts with sodium metal and also undergoes iodoform reaction. ‘A’ is
(A) phenol (B) methanol (C) n-propanol (D) iso-propanol

Q.29 Which of the following ethers is cleaved even by HCl at room temperature?
(A) C6H5OCH2CH3 (B) CH3CH2OCH2CH3
(C) (CH3)3COCH2CH3 (D) (CH3)3COC(CH3)3

Q.30 Anhydride of alcohol is-

(A) Ether (B) Aldehyde
(C) Alkanoic anhydride (D) Alkoxides

ALCOHOL & ETHER [20]

 EXERCISE–II

Q.1 W hen CH 2=CH–COOH is reduced with LiAlH4, the compound obtained will be – [AIEEE-2003]
(A) CH3–CH2–CH2OH (C) CH3–CH2–CHO
(C) CH3–CH2–COOH (D) CH2=CH–CH2OH

Q.2 Among the following compounds which can be dehydrated very easily is - [AIEEE-2004]
(A) CH3CH2CH2CH2CH2OH (B) CH3 CH2 CH2 CH3
(C) CH3CH2 CH3 (D) CH3 CH2 CH2 CH2OH

Q.3 For which of the following parameters the structural isomers C2H5OH and CH3OCH3 would be expected
to have the same values ? (Assume ideal behaviour) [AIEEE-2004]
(A) Heat of vaporization
(B) Vapour pressure at the same temperature
(C) Boiling points
(D) Gaseous densities at the same temperature and pressure

Q.4 A liquid was mixed with ethanol and a drop of concentrated H2SO4 was added. A compound with
a fruity smell was formed. The liquid was [AIEEE 2009]
(A) HCHO (B) CH3COCH3 (C) CH3COOH (D) CH3OH

Q.5 When phenol is treated with bromine water in excess, it gives

(A) m-bromophenol (B) o-and p-bromophenol
(C) 2, 4–dibromophenol (D) 2, 4, 6–tribromophenol

Q.6 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

Q.7 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

Q.8 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

Q.9 R—CH2—CH2 OH can be converted into RCH2CH2COOH. The correct sequence of reagent is
(A) P Br3, KCN, H+ (B) P Br3, KCN, H2
(C) KCN, H + (D) HCN, PBr3, H+

ALCOHOL & ETHER [21]

Q.10 The characteristic dark colour with neutral FeCl3 is given by

OH OH
(A) (B) CH3CH2 — C = CH — CH3

OH

(C) (D) CH3CH2CH2OH

CH3

Q.11 Which of the following has a higher pH?

(A) phenol (B) o-cresol (C) p-nitrophenol (D) glycerol

Q.12 Which of the following alcohols is a stronger acid?

(A) CH3OH (B) CH3 — CH2 — OH

CH3 CH3

(C) CHOH (D) CH3 — C — OH

CH3 CH3

Q.13 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

Q.14 Methyl-tert-butyl ether on heating with HI gives

(A) CH3I + (CH3)3COH (B) CH3OH + (CH3)3CCI
(C) CH3I + (CH3)3CI (D) (CH3)3CCI + CH3OH

Q.15 Which of the following compounds is resistant to nucleophilic attack by hydroxyl ions?
(A) methyl acetate (B) acetonitrile (C) dimethyl ether (D) acetamide

Q.16 Diethyl ether absorbs oxygen to form

(A) a red-coloured sweet-smelling compound (B) acetic acid
(C) ether suboxide (D) ether peroxide

Q.17 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

Q.18 Which of the following alcohols is least soluble in water ?

(A) n-Butyl alcohol (B) iso-Butyl alcohol (C) tert-Butyl alcohol (D) sec-Butyl alcohol

Q.19 2-Bromopentane is heated with potassium ethoxide in ethanol.The major product obtained is-
(A) 2-ethoxypentane (B) pentene-1 (C) cis-pentene-2 (D) trans-pentene-2

ALCOHOL & ETHER [22]

Q.20 Which of the following reactions of alkanols does not involve C – O bond breaking :
(A) CH3CH2OH + SOCl2 (B) CH3CH(OH)CH3 + PBr3
(C) CH3CH2OH + CH3COOH (D) ROH + HX
Q.21 Reactivity of alcohols with HCl is in the order of :
(A) Tert butyl alcohol > sec. butyl alcohol > primary butyl alcohol
(B) Primary butyl alcohol > sec. butyl alcohol > tert butyl alcohol
(C) Sec. butyl alcohol > tert butyl alcohol >primary butyl alcohol
(D) Sec. butyl alcohol > primary butyl alcohol > tert butyl alcohol
Q.22 Given :
Four Number of Number of
Alcohols –hydrogen –hydrogen
A 3 0
B 2 3
C 1 6
D 0 9
Which alcohol will give blue colour with Victor Meyer reagent :
(A) C (B) B (C) D (D) A
Q.23 Non–occurence of the following reaction
Br– + CH3OH  BrCH3 + OH–, is due to:
(A) Attacking nucleophile is stronger one (B) Leaving group is a strong base
(C) Alcohols are not good substrate (D) Hydroxide ions are weak bases
Q.24 Ethyl alcohol is less acidic than phenol because :
(A) The phenoxide ion is more resonance stabilized than phenol
(B) There is more hydrogen bonding in phenol than in ethyl alcohol
(C) The ethoxide ion is less resonance stabilized than ethyl alcohol
(D) Phenol has a higher b.p. than ethyl alcohol
Q.25 The compound obtained by the acidolysis of ether [dil. H2SO4] gives the following test :
(A) Yellow precipitate with NaOH and I2
(B) Smell of formaline with hot copper wire
(C) Smell of oil of winter-green with salicylic acid and H2SO4
(D) Acid obtained by oxidation decolourises KMnO4
Q.26 2-Bromoethanol reacts with magnesium to from :
(A) HOCH2CH2MgBr (B) CH3 – CH2OH
(C) CH3CH2MgBr (D) BrCH2–CH2MgBr
Q.27 Methylethylketone can be obtained by the oxidation of :
(A) 2-Butanol (B) 2-Propanol (C) 1-Butanol (D) Tert.butyl alcohol
Q.28 An alcohol (ROH) reacts with an acid to form initially :
(A) RCH2 –H2 (B) R+ (C) R–H2 (D) An alkene
Q.29 will have the minimum value of pKa when X is :
(A) F (B) Cl (C) Br (D) NO2
Q.30 The oxidation of a secondary alkanol with Cr (VI) leads to the formation of :
(A) An alkanone and Cr (II) (B) An aldehyde and Cr (III)
(C) An alkanone and Cr (III) (D) An aldehyde and Cr (II)
ALCOHOL & ETHER [23]
 ANSWER KEY

EXERCISE–I
Q.1 D Q.2 D Q.3 C Q.4 C Q.5 B Q.6 B Q.7 D
Q.8 A Q.9 C Q.10 A Q.11 D Q.12 D Q.13 D Q.14 B
Q.15 A Q.16 A Q.17 C Q.18 A Q.19 D Q.20 B Q.21 D
Q.22 D Q.23 A Q.24 A Q.25 D Q.26 B Q.27 A Q.28 D
Q.29 D Q.30 A

EXERCISE–II
Q.1 D Q.2 D Q.3 D Q.4 C Q.5 D Q.6 C Q.7 A
Q.8 A Q.9 A Q.10 A Q.11 D Q.12 A Q.13 B Q.14 C
Q.15 C Q.16 D Q.17 A Q.18 A Q.19 D Q.20 D Q.21 A
Q.22 A Q.23 B Q.24 A Q.25 A Q.26 B Q.27 A Q.28 D
Q.29 D Q.30 C

ALCOHOL & ETHER [24]

 CARBONYL COMPOUND
1. INTRODUCTION :
(a) Organic compounds in which  C  group is present are called ‘Aldehyde & Ketone’.
||
O
(b) The group  C  is called as carbonyl group so, compound are also called carbonyl
||
O
compounds. If H atom is attached with this carbonyl group then compound is called
aldehyde and if alkyl group is present on both sides then compound is called Ketone.
(c) In ketone if both alkyl group are same then they are called simple ketone, if different then
called mixed ketone.
(d) Their general formula is CnH2nO. Hybridisation state of carbon is sp2 and C = O bond
length is 1.23 Aº.
(e) The ratio of C, H & O in formaldehyde is 1 : 2 : 1 (CH2O). It is called simplest sugar.
(f) Aldehyde shows chain, position and functional isomerism.
(g) Ketone shows chain, position, functional and metamerism also. Aldehyde and ketone both
are functional isomers with each other.

2. GENERAL METHODS OF PREPARATION

2.1 From Alcohol (By Oxidation) :–

H H
| |
Cr O / Pyridine
R  C O  [O] 2 
7
  R – C  O
| |
H H aldehyde

primary alcohol

R R
| |
Cr2 O 7 / Pyridine
R  C O  [O]     R – C  O
| |
H H ketone
secondary alcohol

NOTE :–
In this reaction if we take acidic KMnO4 or K2Cr2O7 then reaction will not stop on aldehyde or ketone
because they are strong oxidising agent. They further oxidise aldehyde, ketone into acid. So, to stop the
reaction on aldehyde & ketone, we use mild oxidant Cr2O7 in pyridine solution. For better yield, we can
use CrO3 in 3º butyl alcohol. For 2º alcohol we can use aluminium tertiary butoxide [(CH3)3 CO]3 Al

R CH3 R CH3
[( CH3 )3 CO]3 Al
CH – OH + C = O   C=O+ CHOH
oppenauer oxidation
R' CH3 R' CH3

CARBONYL COMPOUND [25]

2.2 From Alcohol ( By Catalytical Oxidation ) : –
When vapours of a primary alkanol (or secondary alkanol) are passed over heated copper (or zinc
oxide) at 300º then alkanals (or alkanones) are formed.

Cu / 300 º
R – CH2OH   R – CHO + H2

R R
Cu / 300 º
CH – OH   C = O + H2
R' R'

2.3 From Alkene (Ozonolysis) : –

Desired alkanals and alkanones can be obtained by ozonolysis of appropriate alkenes.

Zn / H O
R – CH = CH – R’  O
 3  2 R – CHO + R’CHO
H2 O 2

Zn / H O

3 O
  2
H2 O 2

2.4 From Alkyne : –

Acetaldehyde is formed on passing acetylene in 40% aqueous solution of H2SO4 at 60º in the presence
of 1% HgSO4. It is called Kucherov's reaction.
rearrangement
CH  CH + HOH HgSO / dil. H SO
 CH2 =CH– OH   CH3 – CHO
4 2 4

R – C  C – H + HOH HgSO 4 / dil. H2 SO 4

   rearrangement


NOTE : Methanal cannot be formed from the above reaction.

2.5 From Grignard’s Reagent : –

Alkanal is formed by reaction of formic ester and an alkylmagnesium halide.
R R
  | |
H2 O
R  Mg X + R' C  O  R'' ——— R'C  O  R''   R'C  O
|| |
O O  Mg  X

Ketones are obtained from acetic and higher esters. Acid chlorides and amides can be taken in place of
esters. However HCOCl cannot be taken because it is unstable.
R–MgX + C2H5O–CO–R’  R–CO–R’ + C2H5O–MgX
R–MgX + Cl–CO–R’  R–CO–R’ + MgXCl
R–MgX + H2N–CO–R’  R–CO–R’ + Mg(NH2)X
NOTE : Formaldehyde cannot be formed from the above reaction.

CARBONYL COMPOUND [26]

2.6 From Nitroalkane ( Nef reaction) : –
By Nef reaction, formaldehyde can be obtained from nitromethane, acetaldehyde from nitroethane
and acetone from 2–nitropropane.

–
H O
NaOH
| H 
  R – C = N  R – C = O

H OH

H O
H
aldehyde
2.7 From Vicinal Glycol (Oxidation) :–
Carbonyl compounds are obtained on oxidation of vicinal alkanediols by periodic acid or lead
tetraacetate

R–CH–OH HIO4 or
| + [O] 
(CH3COO)4 Pb
 2R–CHO + H O
R–CH–OH 2

R
|
R–C–OH R
| HIO4 or
|
R–C–OH + [O] 
(CH3COO)4 Pb
 2R–C=O + H2O
|
R

2.8 From Calcium or Barium salt of Carboxylic acid : –

When calcium salts of alkanoic acids are subjected to dry distillation, then carbonyl compounds
are formed. The yield increases on taking barium, manganese and thorium salts of alkanoic acids.
Formaldehyde is formed on taking calcium formate (R = H) and acetone is formed on taking calcium
acetate (R = CH3).


300 º C H  C H  CaCO3

||
O


300 º C CH 3  C  CH 3  CaCO 3

||
O

Acetaldehyde can be formed by taking a mixture of calcium formate and calcium acetate.



300ºc
CH3CHO + HCHO + CH3COCH3 + CaCO3

CARBONYL COMPOUND [27]

2.9 From Carboxylic Acid : – When vapours of carboxylic acid are passed on mangnese oxide MnO
at 300ºC, then carbonyl compounds are formed.
Formaldehyde is prepared from formic acid (R = R’ = H), acetone from (R = R’ = CH3), and
acetaldehyde from a mixture of acetic acid (R’ = CH3) and formic acid (R = H).

MnO
 H  C H  CO 2  H 2 O
300º C ||
O

MnO
 CH 3  C CH 3  CO 2  H 2O
300º C ||
O

2.10 From Alkyne (Hydroboration) :–

When a dialkylborane is reacted with an alkyne, then dialkylvinylbroane adduct is formed, which
on reacting alkaline hydrogen peroxide solution forms a carbonyl compound. Alkanals are formed
from terminal alkynes, and alkanones from nonterminal alkynes.
1–Alkyne ——— Aldehyde
Other alkynes ——— Ketone

H2O2 / OH
(i) CH3—C  CHB
H
 (CH3—CH=CH—)3B 
2 6
 [CH3—CH=CHOH]
CH3–CH2–CHO
(ii) CH3—CC—CH3 B
H
 H
2 O 2 / OH
 [CH3—C=CH—CH3]
2 6

|
OH
 
2-Butanone
2.11 From Hydrolysis of oximes and acetals :-
Carbonyl compounds are formed from hydrolysis of oximes and acetals.
CH3CH=NOH H2
O
 CH3CHO + NH2OH
Acetaldoxime
(CH3)2C=NOH H
O
 (CH3)2C=O + NH2OH
2

Acetone-oxime
CH3CH(OC2H5)2 H
O
 CH3CHO + 2C2H5OH
2

Acetal
2.12 From Hydrolysis of gemdihalide :-
Carbonyl compounds are formed on heating alkylidene dihalides with aqueous caustic alkali solution.
NaOH H O 2
>CCl2   > C(OH)2   >C=O
CH3CHCl2 NaOH H2 O
    CH3–CHO
CH3CCl2CH3 NaOH H O
    (CH3)2C=O 2

CARBONYL COMPOUND [28]

3. METHODS OF PREPARATION ONLY FOR ALEDHYDES
3.1 Stephen’s Method : –
By dissolving an alkyl cyanide in ether and reacting it with stannous chloride and conc. hydrochloride,
aldimine chlorostannate salt is obtained. Alkanal is formed on hydrolysis of this salt.

SnCl2
HCl
R–CN   R–CN+HCl– 
HCl
 [R – CH  NH2 ]2 SnCl 62
Acid nitrile Al dimine chlorostannate

[R–CH=NH]2SnCl6 + 2H2O  2R – CH  O + (NH4)2SnCl6

Alkanal

Taking the example of acetonitirle (methyl cyanide) Stephen reaction can be shown expressed as follows.
SnCl2 HOH
CH3 – C  N  2H 
HCl
 CH3 – CH  NH   CH3 – CH  O
Acetonitrile Acetal dim ine Acetaldehyde

3.2 Rosenmund Reaction :

Aldehydes are formed on reduction of a carboxylic acid chloride in boiling xylene medium by
hydrogen and palladised barium sulphate.
O O
Pd
R–C–Cl + H2 
BaSO4
 R–C–H + HCl

Acetaldehyde is formed on taking acetyl chloride (R = CH3). Formaldehyde cannot be prepared by

Rosenmund reaction, because HCOCl is not a stable compound, BaSO4 acts as a catalyst poison and
decreases the catalytic efficiency of Pd catalyst, due to which further reduction of acetaldehyde formed
to primary alcohol cannot take place.
3.3 Oxo-reaction :-
When a mixture of an alkene, carbon monoxide and hydrgen is passed over cobalt catalyst at high
temperature and pressure, then alkanals are formed. Dicobalt octacarbonyl [Co2(CO)8] can be used
as a catalyst in place of cobalt. Due to addition of hydrogen and formyl group on unsaturated carbon
atoms of alkene, this reaction is called hydroformylation.
Co or
CO2 (CO)8
CH2=CH2 + CO + H2 
High
 CH2–CH2
temperature
| |
and pressure H CHO
Propanal

CHO
|
CH3–CH=CH2 + CO + H2 CH3 – CH2 – CH2 – CHO + CH3–CH–CH3
n–Butyraldehyde Isobutyraldehyde

4 METHODS OF PREPARATION ONLY FOR KETONES

4.1 From Alkyl Cyanide : –
Alkanones are formed on hydrolysis after reaction of an alkylmagnesium halide with ethyl cyanide
or its higher homologue.
R'
    |
R  C  N  R  M g  X  R  C  N  Mg X H2O  R  C  R'

||
O
In this reaction if we take HCN with G.R., product will be aldehyde but major product will be alkane
because HCN is an example of active H compound and with active hydrogen compound GR forms
alkane.

CARBONYL COMPOUND [29]

4.2 Dialkyl cadmium with acid chlorides :–
A ketone and an alkylcadmium chloride are formed on reacting a dialkylcadmium with an acid chloride.
R–Cd–R + Cl –CO–R’ R–CO–R’ + R–Cd Cl
Dialkylcadmium are obtained by the reaction of cadmium chloride with a Grignard’s reagent.
2R–Mg Cl + CdCl2 R–Cd–R + 2MgCl2

4.3 Oppenaur Oxidation : In order to prepare alkanone easily, Oppenauer oxidation of secondary alkanols
is done. In this process, a secondary alkanols is refluxed with aluminum tert–butoxide in excess amount
in acetone. Acetone is reduced to isopropyl alcohol.

3 3 [( CH ) C  O ] Al
R  C HOH  CH 3  C O    3 R  C O  CH 3  C HOH
| | | |
R CH 3 R CH 3

METHODS OF PREPARATION :
Ex.1 Choose the compound whose oxime on hydrolysis yields ethanal –
(A) HCHO (B) CH3CHO
(C) CH3CH2OH (D) CH3COCH3 (Ans.B)
Sol. Oxime of ethanal on hydrolysis gives ethanal
CH3CH = NOH H2
O
 CH3CHO + NH2OH

Ex.2 On dipping red hot coper wire in isobutyl alcohol, we get –

(A) An alkene (B) A ketone
(C) An aldehyde (D) None of the above (Ans.C)
Sol. Isobutyl alcohol contains primary alcoholic group –CH2OH which on oxidation converts to–CHO
group
Pd / BaSO
Ex.3 CH3COCl   [H ]
 A
4

The isomers of CH3COCl and A will be respectively –

(A) CH2ClCHO, oxirane (B) Chloral, vinyl alcohol
(C) -chloroethyl alcohol, epoxyethane (D) None of the above (Ans. A)
Sol. -chloroacetaldehyde and oxirane ethane are the isomers of CH3COCl and CH3CHO respec-
tively.

5. PHYSICAL PROPERTIES
(a) Aldehydes are colourless with pungent smell liquid while ketones are pleasant smell liquids
but formaldehyde is gaseous in nature.
(b) Lower carbonyl compounds are soluble in water. It is due to polarity in carbonyl group.
(c) Higher carbonyl compounds are insoluble in water due to more covalent character.
(d) Melting point & Boiling point Molecular mass
1
  
No. of branches
(e) Melting point and boiling point of carbonyl compounds are more than to corresponding
alkanes due to dipole-dipole attraction present between molecules in carbonyl compounds.

CARBONYL COMPOUND [30]

 (f) Reactivity of carbonyl compound is dependent on alkyl group which is linked with carbonyl
group.
  
H  C  H  CH3  C  H  CH3 
 C  H
|| || ||
O  O  O 

(g) 40% solution of formaldehyde is known as ‘FORMALIN’ (40% HCHO, 54-56% H2O,
4-6% methanol)

(h) Mixture of formaldehyde and lactose sugar is called ‘FORMAMINT’ which is used in
medicine of throat infection.

(i) Boiling point of carbonyl compounds are as under -

Compound Boiling Point

1. Formaldehyde – 21ºC
2. Acetaldehyde + 21ºC
3. Acetone 56ºC

6. CHEMICAL PROPERTIES :

Main reaction of carbonyl compounds are nucleophilic addition reaction.

H H H
| | H
|
E
R  C    E  – Nu  — R  C   R  C  less stable    R – C – Nu
|| | |
O  O OE OE

Rate of nucleophilic addition reaction of carbnyl compounds decreases in the following order :
HCHO > CH3CHO > CH3COCH3 > C6H5–CHO

6.1 Reaction with Hydrogen Cyanide : –

H
  

cyanohydrin

NOTE : –
(a) If R = H then product will be formaldehyde cyanohydrin.

(b) Cyanohydrin is an important compound which gives the following product on hydrolysis and
reduction.

CARBONYL COMPOUND [31]

Acetone cyanohydrin is formed on reacting acetone with HCN.

CARBONYL COMPOUND [32]

6.2 Reaction with Sodium bisulphite :
Carbonyl compound form a white crystalline addition product with sodium bisulphite called
Aldehyde / Ketone sodium bisulphite adduct.
H H H
HOH
 R – C – so3Na    R – C – OH 
NaHSO 4
 R – C = O
H2O
aldehyde
O–H OH
white crystalline solid

NOTE : –
(a) Bisulphite adduct is an important compound because it gives carbonyl compound on further
hydrolysis.
(b) The above reaction is used in purification of carbonyl compound.

6.3 Reaction with Ammonia derivatives :

Addition of nitrogenous nucleophile on carbonyl group takes place according to the following
mechanism.
H H
| | | |
 C   N – Z  – C – N – Z
|| | |
O H OH
Adduct
The end product is formed by elimination of water from the adduct under appropriate energy condition.
H
| | 
 C N  Z  C  NZ
| H O | 2
OH
In the above two steps, it appears that an unsaturated condensation product is formed by liberation of
the water molecule from carbonyl group and nitorogenous nucleohile.

 C  O  H 2 N  Z  – C  N – Z
| – H 2O |

(i) With Hydroxylamine :

(ii) With Hydrzaine :

(iii) With Phenylhydrazine :

CARBONYL COMPOUND [33]

 (iv) With 2,4–Dinitrophenylhydrazine :

(v) With Semicarbazide :

On reacting a carbonyl compound with 2,4–dinitrophenylhydrazine, a yellow precipitate of

2,4–dinitrophenylhydrazone derivative is obtained. White precipitate is obtained by the reaction with
hydroxylamine, hydrazine phenylhdrazine and semicarbazide. The pure parent carbonyl compound can
be obtained by hydrolysis of the above five derivatives.

6.4 Reaction with Alcohol : In the presence of catalyst (HgO•BF3) aldehyde form acetal with alcohol
while ketone from ketal with alcohol.
H H H
 
R– C+ + H  O  R' R – C – OR’ R – C – OR’
–
O OH OR'
hemiacetal acetal

6.5 Reaction with Alkane Thiol : Aldehyde form thio acetal with alkane thiol while ketone form thio
ketal with alkane thiol.
– S – R' Zncl2/dry HCl
H – S – R'

These are important compounds because they forms sulphonyl compounds on oxidation which are
used as hypnotic drugs.

 [
o]
 

 [
o]
 

CARBONYL COMPOUND [34]

6.6 Aldol Condensation :
In the presence of small amounts of hydroxide ions two molecules of the carbonyl compound containing
–hydrogen atoms, give a  –hydroxy carbonyl compound. This reaction is normally called Aldol
condensation. Aldol condensation of two identical carbonyl compounds is called simple aldol condenstaion.
As a source of hydroxide ions, a few drops of very dilute aqueous solution of K2CO3, Na2CO3, NaOH,
KOH, Ca(OH)2, Ba(OH)2 etc. are added.

A –unsaturated aldehyde crotonaldehyde is formed by the elimination of a water molecule on heating

acetaldol (3–hydroxybutanal)

Aldol condensation of two non identical carbonyl compounds is called mixed or crossed aldol condensation.
Theoretically four products can be formed from aldol condensation of the carbonyl compounds A and B.

CH3 – CHO CH3 – CH2 – CHO CH3–CH–CH–CHO

Actaldehyde | |
OH CH3
3–Hydroxy-2-methylbutanal

CH3 CH2 – CHO  CH3 CHO CH3CH2–CH–CH2CHO

Pr opionaldehyde
|
OH
3–Hydoxypentanal

CARBONYL COMPOUND [35]

6.7 Cannizaro Reaction : Carbonyl compound in which  – H atoms is absent, when react with strong
base like NaOH or KOH then forms sodium and pottasium salt of carboxylic acid and alcohol. It is an
example of the reaction in which one mole of the compounds is reduced. Such type of reaction is called
disproportionation reaction, also known as cannizaro reaction. In this reaction elimination of hydride ion
takes place. In this reaction oxidation number changes from 0 to +2 and 0 to –2.
Compounds showing cannizaro reaction are -

(a) 

O
||
(b) 2C6H5  C  H + KOH   C6H5COOK + C6H5CH2OH

(c) 

6.8 Tischenko Reaction :

When an aldehyde is heated with an anhydrous aluminium alkoxide in the presence of anhydrous AlCl3,
then a carboxylic acid ester having twice the number of carbon atoms is formed. All aldehydes give this
reaction.

6.9 Oxidation : Aldehyde on oxidation forms respective acid while ketone forms less carbon carboxylic
acid on oxidation according to popoff’s rule (As discussed in Alcohol theory)
acidic KMnO
4
 
 

acidic KMnO
4
 
 

NOTE :
(a) If oxidising agent is selenium oxide SeO2 then, –methylene group of carbonyl compound
oxidises into – – group and resultant dicarbonyl compound will be formed.

CARBONYL COMPOUND [36]

 H – C – H + [ O ]  SeO
 2
 NO reaction
O
 - methylene group is absent.
H – CH2 – C – H + [ O ]  SeO
 H – C – C – H
2

|| || ||
O O O
glyoxal
(dicarbonyl compound)

H – CH2 – C – CH3 + [ O ]  SeO

 2
 H – C – C – CH3
|| || ||
O O O
pyruvic aldehyde
(methyl glyoxal)

(b) If the oxidising agent is performic acid then aldehyde oxidises into respective acid while
ketone oxidises into ester. The reaction is called ‘Baeyer-villiger Oxidation’.
Other peroxy acid also give same product.
eg. CH3COOOH, C6H5COOOH, MCPBA, CF3COOOH

H
|
H – C – H + O – O – C – H  H – C – OH + HCOOH
|| | || ||
O H O O

H
|
CH3– C –H + O – O – C – H  CH3 – C – OH + HCOOH
|| | || ||
O H O O

*** MCPBA  meta chloro perbenzoic acid

H
|
CH3– C –CH3 + O– O– C –H  CH3– C –O–CH3
|| || ||
O O O

6.10 Reduction : Aldehyde on reduction form primary alcohol while ketone on reduction form secondary
alcohol.
R– C –H + 2H  R – CH2 – OH
||
O

R– C –R + 2H  R – CH – R
|| |
O OH
secondary alcohol

CARBONYL COMPOUND [37]

NOTE:
(a) In the above reaction if reducing agent is Na + C2H5OH then reaction is called ‘Bouveault
- Blanc Reaction’.
(b) If reducing agent is NaH reaction is called ‘Darzen’s Reaction’. We can also use LiAlH4
in this reaction.
(c) If reducing agent is (red P / HI) then product will be alkane.
(d) If reducing agent is Zn-Hg/conc. HCl then product will be alkane. Reaction is called
‘Clemmenson-Reduction’.
(e) If reducing agent is alkaline solution of hydrazine, product will be alkane. Reaction is called
‘ Wolf - kishner Reduction’.
(f) The percentage yield of alkane can be increased by using diethylene glycol in wolf kishner
reduction then reaction is called ‘Huang-Millan Conversion’.
(g) If reducing agent is aluminium iso propoxide (CH 3  C H  O ) 3 Al , then product will be
|
CH 3
alcohol. Reaction is called ‘Meerwein-Pondorff Verley Reduction’.

6.11 Polymerisation Reactions : Aldehyde shows addition as well as condensation polymerisation reactions
while ketone shows only condensation polymerisation reactions.

6.11.1 Addition Polymerisation reaction of Formaldehyde : –

(a) When aqueous solution of formaldehyde is heated then it converts into a white crystalline
solid called ‘Paraformaldehyde’.

n HCHO   (HCHO)n n > 6, n < 100
evaporation

paraformaldehyde
If n  50 Linear structure polymer
If n > 50 Cyclic structure polymer
(b) If formaldehyde is kept with conc. H2SO4 at room temperature then it forms a cyclic trimer
called meta formaldehyde or trioxane.
3CH2O=O (CH2–O)3

(c) If aqueous solution of formaldehyde is kept with lime water in dark room for 5-6 days then
it converts into a sweet solution called ‘FARMOSE
It is an example of linear polymer.
2 Ca( OH) / Ba OH
b g2 
6HCHO   C6H12O6
dark, 5  6 days
farmose

CARBONYL COMPOUND [38]

6.11.2 Condensation Polymerisation reaction of Formaldehyde :
(a) With Ammonia:– When formaldehyde is heated with NH3 then a white crystalline heterocyclic
compound is formed called ‘Hexamethylene tetramine’ or urotropene’ or ‘Aminoform’.

6HCHO + 4NH3   (CH2)6N4 + 6H2O

It is used in medicine or diabities or urinary infection.

(b) With Phenol : – In presence of dilute alkali formaldehyde first form o- & p- hydroxy benzyl
alcohol with phenol which on self condensation form a cross link polymer called ‘Bakelite’.

Bakelite is electric and thermal resistant. So, used in formation of electric appliances. Reaction is
called ‘Lederer-Manasse Reaction’.

6.11.3 Addition Polymerisation of Acetaldehyde :

(a) When acetaldehyde is kept with conc. H2SO4 at room temperature then it form a cyclic
trimer called paraaldehyde.
Room temp.
3CH3CHO 
Conc. H2SO4
 (CH CHO) (Paraldehyde)
3 3

Paraldehyde has nonaromatic heterocyclic structure and it is called 2,4,6–trimethyl–1,3,5–trioxan.

Paraldehyde or 2,4,6–trimethyl–1,3,5–trioxan

Paraldehyde is used as mild hypnotic.

(b) If acetaldehyde is kept with highly conc. HCl at low temperature then it forms a cyclic
tetramer called metaaldehyde.
Dry HCl gas
4CH3CHO  0º
 (CH3CHO)4

CARBONYL COMPOUND [39]

 Metaldehyde has the following nonaromatic eight–memebred heterocyclic structure.
CH3
CH3 O—CH
CH O
| |
O CH
CH—O CH3
CH3
NOTE : Metaldehyde is used as smokeless powder and Para aldehyde is used as a sedative while meta
aldehyde is used as a solid fuel.

6.11.4 Condensation Polymerisation of Acetaldehyde : –

(a) Aldol condensation – Discussed earlier.
(b) Reaction with NH3 :

 
H O

2

Acetaldimine is formed by the elimination of water molecule on heating acetaldehyde–ammonia, which

undergoes polymerisation to form a nonaromatic heterocylic addition trimer, namer 2,4,6–
trimethylhexahydro–1,3,5–triazine trihydrate as the main product.

6.11.5 Condensation Polymerisation of Acetone :

(a) If acetone is heated with conc. H2SO4 then an aromatic compound is formed called 1,3,5-
trimethyl benzene or mesitylene.
CH3
|

Conc. H2SO4
CH3COCH3  


CH3 CH3
Mesitylene

(b) If acetone would be in excess in ketal condensation or catalyst (ZnCl2 / dry HCl) is used
then three moles of acetone undergoes condensation polymerisation and form a compound
called ‘Phorone’.

2ZnCl
  
dry. HCl

[molecular wt. of phorone = 3 mole of acetone – 2 mole of H2O ]

CARBONYL COMPOUND [40]

6.12 Reaction with PCl5 :
Carbonyl compound form gemdihalide with PCl5.

  
POCl 3

gemdihalide

6.13 With RMgX :-

CH3CHO  CH
3MgBr H2 O
  

6.14 With sodium acetylide :

H2 O
CH3CHO + HCCNa  CH3 – CH  C  CH  CH3  CH  C  CH
| |
ONa OH

6.15 With primary amine :–

CH3CH=O + H2NC6H5 ——— CH3–CH=NC6H5
Schiff’s base
(CH3)2C=O + H2NC6H5 ———(CH3)2C=NC6H5

7. REACTIONS SHOWN BY ALDEHYDES ONLY

7.1 Reducing nature of Aldehyde : Aldehyde are reducing in nature, they can reduce Tollen’s reagent,
Fehling solution and mercuric chloride solution.
(a) Reaction with Tollen’s Reagent : – Ammonical silver nitrate solution is called Tollen’s
reagent. Aldehyde reduce the tollen’s reagent and form silver mirror. Aldehyde oxidises itself
into carboxylic acid.
AgNO3 + NH4OH  [ Ag(NH3)2 ]-OH
NH3–
2AgOH Ag2O
–H2O

(simplest reacting species)

 

NOTE : In the above reaction oxidation number of Ag varies from +1 to 0.

(b) Reaction with Fehling Solution : It is the mixture of two solution called Fehling solution
A and Fehling solution B.
Fehling Solution A : Aqueous solution of CuSO4 (blue)
Fehling Solution B : Alkaline solution of Roschelle salt ( sodium potassium tartarate)

(C4H4O6NaK)

CARBONYL COMPOUND [41]

 By the mixing of both solution we get a dark blue colour solution called final fehling solution. Reacting
species of this solution is cupric oxide CuO.


(red ppt.)
NOTE : Oxidation number of copper varies from +2 to +1
(c) Reaction with Mercuric Chloride solution :Aldehyde reacts with mercuric chloride so-
lution and initially form white ppt. of mercurous chloride solution, which further react with
excess of aldehyde and form black ppt. of mercury.
R – C – H + HgCl2 + H2O 
O
(white)
R – C – H + Hg2Cl2 + H2O 
O
(black)
(d) Benedict solution :
[A–CuSO4 soln,  –NaOH, Sodium citrate]
CH3CHO + 2CuO ——— Cu2O + CH3COOH
(e) Schiff’s reagent :
CH CHO
Megenta dye  SO
 2
 Colourless solution   Pink colour restored
3

8. REACTIONS SHOWN BY KETONES ONLY

(a) Reaction with NH3 : If acetone is heated with ammonia then it forms diacetone amine.




If acetone and ammonia would be in excess then product would be tri acetone amine. If
tri acetone amine is heated at high temperature then it converts into a hetrocyclic compound
by the elimination of water.
(b) Reaction with Nitrous Acid :
Oximinoacetone is formed by liberation of a water molecule on reacting acetone with nitrous
acid.


H2 O

oximino acetone
(c) Bimolecular Reduction : –
Pinacol is formed on reduction of acetone in an inert medium (like benzene) by using magnesium
amalgam and hydrogen.
H
MgHg / HCl
+2H  
dry C 6H6


H
pinacol

CARBONYL COMPOUND [42]

CHEMICAL REACTION :
Ex.4 What would be the product when carbonyl compound reacts with HCN -
(A) Cyanohydrin (B) Hydroxy acid
(C) Hydroxy amide (D)Amino alcohol (Ans.A)
H H
|
H
Sol. R–C +H CN    R – C – CN
OH

(cyanohydrin)

Ex.5 What would be the product when acetaldehyde reacts with HCN and the product is partially
hydrolysed -
(A) Lactamide (B)Methyl glyconamide
(C) Both A & B (D) None (Ans.C)

H O
CH3 OH
Sol.  2
 C
H C – NH2
O
lactamide or methyl glyconamide

Ex.6 Which carbonyl compound will be purified with sodium bisulphite -

(A) 2-Pentanone (B) 3-Hexanone
(C) 4-Heptanone (D) All above (Ans.A)
Sol. The reaction is used in purification of all types of aldehydes and methyl ketones only because the
ketones having bulky alkyl group form unstable adduct.
Ex.7 Reaction involving formation of trioxane from methanal is called :
(A) Aldol condensation (B) Addition polymerisation
(C) Condensation polymerisation (D) Cannizzaro’s reaction (Ans. B)
Sol. 3CH2O  
 [CH2O]3 trioxane [addition polymer]
dil.H2 SO 4

Ex.8 >C – CN group is called –

|
OH
(A) Hydroxy nitrile (B) Hdroxy cyanide (C) Cyanohydrin
(D) Hydroxy isocyanide
(Ans. C)
Sol. Carbonyl compound on addition with HCN gives a compound containing cyanohydrin group.
Ex.9 Butanone does not show any reaction with the reagent –
(A)  – NHNH2 (B) CH3NH2
(C) [Ag (NH3)2] + (D) NH2OH (Ans. C)
Sol. Tollen’s reagent does not react with ketone.

CARBONYL COMPOUND [43]

CARBONYL COMPOUNDS

CARBONYL COMPOUND [44]

 EXERCISE – I
Q.1 When propyne reacts with 20% H2SO4 & 1% HgSO4 , we get-
(A) Acetaldehyde (B) Propanaldehyde (C) Acetone (D) Formic acid

Q.2 The product formed by the reaction of propyne with dil. H2SO4 in the presence of Hg2+ can not be
prepared by the following reaction-
(A) Dry distillation of calcium ethanoate
(B) By passing vapours of ethanoic acid over MnO at 300ºC
(C) By ozonolysis of 2- Butene
(D) By alkaline hydrolysis of isopropylidene chloride

Q.3 Except acetylene, other alkynes react with H2O to give-

(A) Aldehyde (B) CH3CHO (C) Ketones (D) Alkanal.

Q.4 When CH3MgI reacts with CH3CN and the product is hydrolysed, we get-
(A) Propanal (B) Acetone (C) Formaldehyde (D) Acetaldehyde

Q.5 Ethylidene chloride (CH3CHCl2) on hydrolysis with NaOH gives -

(A) CH3CHO (B) CH3COCH3 (C) CH3CH(OH)2 (D) C2H5OH

Q.6 When calcium acetate is heated with calcium formate then, we get-
(A) Methanol (B) Acetic acid (C) Acetaldehyde (D) Acetone

Q.7 The reaction -

Xylene
CH3COCl + H2 Pd  CH CHO + HCl is
/BaSO 4 3
(A) Stephen's reaction (B) Rosenmund reaction
(C) Hoffmann reaction (D) Cannizzaro's reaction

Q.8 Acetone will be obtained by the ozonolysis of -

(A) 1-Butene (B) 2-Butene (C) Isobutene (D) 2-Butyne

Q.9 Which fo the following forces is correctly described about boiling point of Aldehydes & ketones -
(A) Hydrogen bond (B) Vander wall force
(C) Dipole-dipole attraction (D) None of these

Q.10 The general order of reactivity of carbonyl compounds for nucleophilic addition reactions is -
(A) H2C = O > RCHO > ArCHO > R2C = O > Ar2C =O
(B) ArCHO > Ar2C = O > RCHO > R2C = O > H2C = O
(C) Ar2C = O > R2C =O >ArCHO > RCHO > H2C = O
(D) H2C = O > R2C = O > Ar2C =O > RCHO > ArCHO

CARBONYL COMPOUNDS [45]

Q.11 Reaction of ammonia derivative with carbonyl compound is an example of -
(A) Addition and Substitution (B) Substitution and Elimination
(C) Addition and Elimination (D) Addition and intramolecular substitution

Q.12 Acetone gives test with-

(A) 2,4 Dinitro phenyl hydrazine (B) Fehling solution
(C) Schiff's reagent (D) All

Q.13 Aldol condensation between the following compounds followed by dehydration gives methyl vinyl ketone-
(A) HCHO and CH3COCH3 (B) HCHO and CH3CHO
(C) Two molecules of CH3CHO (D) Two molecules of CH3COCH3

Q.14 In Cannizzaro reaction-

(A) Aldehyde is converted into alcohol
(B) Alcohol is converted into aldehyde
(C) Primary amine is converted into isocyanide
(D) Acid is converted into amine

Q.15 Which is most difficult to oxidise-

(A) HCHO (B) CH3CHO (C) CH3COCH3 (D) CH3CH2CHO

Q.16 Acetone shows similarity with acetaldehyde in reacting to-

(A) Schiff's reagent (B) Fehling solution (C) Grignard reagent (D) Tollen's reagent

Q.17 For the reaction RCH = O + 2[H]  RCH2OH

the catalyst is-
(A) Ni only (B) Pd. only (C) Pt. only (D) Any of the above

Q.18 Which of the following combinations give t-butyl alcohol when treated with Grignard reagent-
(A) CH3MgBr + CH3COCH3 (B) C2H5 MgBr + CH3COCH3
(C) CH3MgBr + (CH3)3C. OH (D) CH3MgBr + CH3CH2CHO

Q.19 The conversion CH3CH2CHO ––––– CH3CH2CH2OH can not be affected by:
(A) NaBH4 (B) Zn/HCl (C) H2/Ni (D) Na + alcohol

Q.20 Fehling's solution –B is-

(A) NH4OH (B) Cu(OH)2 (C) CuO (D) Cu2O

Q.21 The best method for the conversion of ethanol to ethanal is-
(A) By passing ethanol vapours over Cu at 578 K
(B) By oxidation with acidic potassium dichromate
(C) By oxidation with mangenese dioxide at 300ºC
(D) By oxidation with acidic KMnO4

CARBONYL COMPOUNDS [46]

 Dry distillation
Q.22 (HCOO)2Ca + (CH3COO)2Ca      "A" - Product A is–
(A) Propanone (B) Methanal (C) Ethanal (D) One of the above

Q.23 Least reactive towards nucleophilic additon is -

(A) CH2 = O (B) CCl3  C  C2H5 (C) CH3  C  C2H5 (D) CH3  C  H
|| || ||
O O O

Q.24 Stephen reaction is the reaction involving:

(A) Reduction of alkanoyl chloride with Pd/BaSO4.
(B) Reduction of alkyl isocyanide with sodium and alcohol.
(C) Reduction of alkyl cyanide with SnCl2 and HCl and hydrolysing the intermediate aldimine.
(D) Reduction of carbonyl compound with zinc amalgam and HCl.

Q.25 HCHO with conc. alkali forms two compounds. The change in oxidation number would be-
(A) (0 to –2) in both the compounds
(B) (0 to +2) in both the compounds
(C) (0 to +2) in one compound and (0 to –2) in the second compound
(D) All are correct

Q.26 For Cannizzaro's reaction. Which is necessary-

(A) Presence of  –C (B) Absence of  –C
(C) Presence of  –H (D) Absence of  –H

Q.27 Aldehydes and ketones can be reduced to corresponding hydrocarbons by-

(A) Refluxing with strong acids (B) Passing the vapours over PbO2
(C) Refluxing with zinc amalgam (D) Refluxing with strong base

Q.28 Which of the following can be used to differentiate between ethanal and propanal-
(A) Ammonical AgNO3
(B) Ammonical AgNO3 in presence of tartrate ions
(C) I2 in presence of base
(D) Ammonical AgNO3 in presence of citrate ions

Q.29 The reaction,

2RCHO  
Al  elthoxide
 RCOOCH2 R is called-
Ester
(A) Tishenko reaction (B) Knoevangel reaction
(C) Cannizzaro reaction (D) HVZ reaction

Q.30 Which of the following does not turn schiff's reagent to pink-
(A) Formaldehyde (B) Benzaldehyde (C) Acetone (D) Acetaldehyde

CARBONYL COMPOUNDS [47]

 EXERCISE –II
Q.1 Which one of the following is reduced with zinc and hydrochloric acid to give the corresponding
hydrocarbon? [AIEEE-2004]
(A) Ethyl acetate (B) Acetic acid (C) Acetamide (D) Butan-2-one

Q.2 The best reagent to convert pent–3–en–2–ol into pent–3–en–2–one is - [AIEEE-2005]

(A) Acidic dichromate (B) Acidic permanganate
(C) Pyridinium chloro–chromate (D) Chromic anhydride in glacial acetic acid

Q.3 The increasing order of the rate of HCN addition to compounds A – D is - [AIEEE 2006]
(a) HCHO (b) CH3COCH3 (c) PhCOCH3 (d) PhCOCH3
(A) d < b < c < a (B) d < c < b < a (C) c < d < b < a (D) a < b < c < d

Q.4 Which of the folowing on heating with aqueous KOH, produces acetaldehyde ? [AIEEE 2009]
(A) CH3COCl (B) CH3CH2Cl (C) CH2ClCH2Cl (D) CH3CHCl2

Q.5 An aldehyde isomeric with allyl alcohol gives phenyl hydrazone. Pick out a ketone that too gives
a phenyl hydrazone containing the same percentage of nitrogen:
(A) Methyl ethyl ketone (B) Dimethyl ketone
(C) 2– Butanone (D) 2–Methyl propanone

Q.6 Aldehydes and ketones form hydrocarbons by:

(A) The Clemmensen reduction (B) The Cannizzaro reaction
(C) The Rosenmund reduction (D) Aldol condensation

Q.7 Acetaldehyde oxidises:

(A) Fehling's solution. (B) Ammoniacal AgNO3 solution
(C) NaOI. (D) None of these


Q.8 C6H5CHO + CH3COCH3  OH  C6H5CH(OH)CH2COCH3 –– C6H5CH = CHCOCH3 This
reaction is known as:
(A) Aldol condensation (B) Cross aldol condensation
(C) The Claisen-Schmidt reaction (D) None of these

Q.9 Acetaldehyde on warming with fehling solution gives a red precipitate of:
(A) Elemental copper (B) Cuprous oxide
(C) Cupric oxide (D) Mixture of all of the above

Q.10 Fehling solution is made by mixing two separate solutions. One of which is a solution of copper
sulphate only while the other contains:
(A) NaHCO3 (B) Na2CO3 (C) KNaC4H4O6 (D) KHCO3

CARBONYL COMPOUNDS [48]

Q.11 Dry distillation of calcium formate and subsequent treatment with dilute KOH gives the mixture of:
(A) CH3OH, HCOOK (B)CH3CHO, HCOOK
(C) HCHO, HCOOK (D) None of the above

Q.12 The conversion CH3CHO ––– OHC –– CHO can be effected by:
(A) CrO3 (B) SeO2 (C) Br2/NaOH (D) KMnO4

Q.13 Ammonia with formaldehyde gives the:

(A) Cyclic product (B) Linear product
(C) Addition product (D) Substitution product

Q.14 Match list I with list II and then select the correct answer from the codes given below the lists:
List I List II
Zn /Hg
(1) RCOR'  
HCl
 RCH R'
2 (a) Meerwein-Ponndorf Verley reduction.

N H
(2)  2 4 
C H ONa (b) Clemmensen reduction
2 5

(3) R  C  O + Aluminium (c) Tischenko reaction iso propoxide

|
R'

(4) RCHO + Al(OC2H5)3  Heat

 Ester (d) Wolff-Kishner reaction

Codes
1 2 3 4
(A) b d c a
(B) d b a c
(C) b d a c
(D) a c b d

Q.15 Match List I with list II and then select the correct answer from the codes given below the lists:
List I List II
(1) C6H5CHO (a) Mesitylene
(2) CH3COCHO (b) Paraldehyde
(3) CH3COCH3 (c) Iodoform reaction
(4) CH3CHO (d) Cannizzaro reaction
Codes
1 2 3 4
(A) d c b a
(B) d b c a
(C) a c b d
(D) d c a b

CARBONYL COMPOUNDS [49]

 
Q.16 CH 3 ––CHO  OH CH CH(OH)CH CHO In the aldol condensation of acetaldehyde

3 2
represented above, which of the following intermediate species are obtained ?
O O
|  ||
(A) CH2  C  H (B) : CH2  C  H

O O
| ||
(C) CH3  C  CH2  CH (D) All above
|
H

Q.17 Conversion of acetone into 2,3-dimethylbutane-2, 3-diol can be achieved by:

(A) Zn/Hg/HCl (B) Wolff-Kishner reduction
(C) Mg/Hg/H2O (D) The conversion is not possible.

Q.18 Which of the following statements is wrong:

(A) All methyl ketones give a positive iodoform test.
(B) Acetaldehyde is the only aldehyde that gives iodoform test.
(C) All secondary alcohols give positive iodoform test.
(D) Any alcohol that can be oxidised to an acetyl group gives a positive iodoform test.

Q.19 Arrange [(CH3)3C]2CO (I), [(CH3)2CH]2C=O (II), (CH3)2C=O (III) and CH3CHO (IV) in order
of reactivity towards nucleophilic attack:
(A) I > II > III > IV (B) I > III > IV > II
(C) IV > III > II > I (D) II > I > III > IV

Q.20 Which of the following statements is correct:

(A) All primary alcohol give iodoform reaction.
(B) All secondary alcohols give iodoform reaction.
(C) Ethanol is the only primary alkanol that gives positive iodoform test.
(D) All aldehydes with  hydrogen atoms give positive iodoform reaction:

Q.21 Both Fehling's solution and Benedict's solution give this compound when treated with acetalde-
hyde:
(A) CuO (B) Cu2O (C) Cu(OH)2 (D) Cu(CO)4

Q.22 Aldehyde not containing -hydrogen atom reacts with aqueous alkali to form:
(A) An , unsaturated aldehyde.
(B) An , unsaturated acid.
(C) Corresponding alcohol and corresponding carboxylate anion.
(D) Corresponding carboxylic acid.

CARBONYL COMPOUNDS [50]

Q.23 Formaldehyde reacts with 50% aqueous alkali to form:
(A) A mixture of methanol and sodium acetate.
(B) A mixture of ethanol and sodium formate.
(C) A mixture of methanol and sodium formate.
(D) A resinous mass.

Q.24 CH3CH=CH-CHO may be reduced to CH3CH=CHCH2OH using:

(A) H2/Pt (B) NaBH4
(C) [(CH3)2CHO]3 Al (D) Zn-Hg/HCl

Q.25 How many aldols will be formed by CH3CHO and CH3–CH2–CHO –

(A) 2 (B) 3 (C) 4 (D) 1

Q.26 An organic compound reduces Tollens reagent and Fehling's solution. It can be –
(A) CH3CH2CHO (B) C6H5CHO (C) CH3COCH2CH3 (D) (CH3)3CCOCH3

Q.27 Methyl ethyl ketone can be reduced to

n-butane by –
(A) Meerwein-Ponndorf reduction (B) Wolff-Kishner reduction
(C) Mg-Hg, H2O (D) HI / red phosphorus at 423 K

Q.28 Ethyl cyanide is allowed to react with methylmagnesium iodide and subsequently acidified with dilute
HCl. The product formed is -
(A) propanone (B) propanal (C) butanal (D) butanone

Q.29 Which of the following alkenes is most suitable for the preparation butanone by
ozonolysis -

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

Q.30 In the reaction CH3CHO + HCN  CH3CHOHCN the product obtained is -

(A) a meso compound (B) a levorotatory compound
(C) a dextrorotatory compound (D) a recemic mixture

CARBONYL COMPOUNDS [51]

 ANSWER KEY

EXERCISE – I
Q.1 C Q.2 C Q.3 C Q.4 B Q.5 A Q.6 C Q.7 B
Q.8 C Q.9 C Q.10 A Q.11 C Q.12 A Q.13 A Q.14 A
Q.15 C Q.16 C Q.17 D Q.18 A Q.19 B Q.20 C Q.21 A
Q.22 D Q.23 C Q.24 C Q.25 C Q.26 D Q.27 C Q.28 C
Q.29 A Q.30 C

EXERCISE –II
Q.1 D Q.2 D Q.3 B Q.4 D Q.5 B Q.6 A Q.7 D
Q.8 C Q.9 B Q.10 C Q.11 A Q.12 B Q.13 A Q.14 C
Q.15 D Q.16 D Q.17 C Q.18 C Q.19 C Q.20 C Q.21 B
Q.22 C Q.23 C Q.24 C Q.25 C Q.26 A Q.27 BD Q.28 D
Q.29 A Q.30 D

CARBONYL COMPOUNDS [52]

 CARBOXYLIC ACID & IT’S DERIVATIVES

1. GENERAL INTRODUCTION
O
The organic compounds containing carboxyl (–C–OH) group are known as carboxylic acids and the
term ‘Carboxylic’ was firstly proposed by scientist ‘Bayer’.
Resonance hybrid structure of carboxylic acid group is

due to resonance, the bond length value of both the bonds [C–O & C=O] are equal, which is 1.28 Å.
1.1 Classification :
On the basis of the group to which –COOH group is attached.
O
(a) Aliphatic carboxylic acid = R– C–OH (R = H atom or alkyl group).
O
(b) Aromatic carboxylic acid = Ar– C –OH (Ar = Aryl group)

1.2 On the basic of number of –COOH groups in their molecule.

No. of –COOH group
(a) Mono carboxylic acids 1
(b) Dicarboxylic acids 2
(c) Tricarboxylic acids 3
General formula is CnH2nO2 or CnH2n+1 COOH
Saturated and unsaturated mono carboxylic acids are also called fatty acids, because higher acids like
palmitic acid, steric acid, oleic acid, etc. were obtained by hydrolysis of fats and oils.
Isomerism – Chain, positional, functional group and optical.
Hybridisation state of C in the carboxyl group in sp2

2. METHOD OF PREPARATION
2.1 By the oxidation of alcohols, aldehydes and ketones :
[O]
(a) 1º Alcohol   corresponding carboxylic acids.
O
KMnO4 or [O]
R–CH2–OH + [O] 
K 2Cr2O7
 R–CHO 
 R– C –OH
[O]
(b) Aldehyde   corresponding acids
O
Acidic K 2Cr2O7
R–CH=O + [O] 
 R– C –OH
[O]
(c) Ketones   mixture of acids of lesser no. of C atoms than the ketone.
O O
Acidic K2Cr2O7
R– C –CH2–R’ + [O]  
 R– C –OH + R’–COOH

CARBOXYLIC ACID & IT’S DERIVATIVES [53]

 O O
Acidic K2Cr2O7
Ex. CH3– C –CH3 + 3[O]  
 CH3– C –OH + HCOOH
HCOOH + [O] CO2 + H2O

2.2 By the hydrolysis of cyanides (nitriles) :

Cyanides on complete hydrolysis in the presence of dilute HCl form carboxylic acids.

2.3 From hydrolysis of acid derivatives :

O O
R– C –Z + H–OH R– C –OH + HZ
(a) From acyl halides :
O O
R– C –Cl + HOH R– C –OH + HCl
(b) From acid anhydride :

Note : Formic acid cannot be prepared by these two reactions (a & b) because it’s corresponding formyl
chloride and formic anhydride are unstable compounds.
(c) From carboxylic ester :
O O
R– C –OR’ + HOH R– C –OH + R’ –OH
(d) From acid amides :
O O
dil. HCl
R– C –NH2 + HOH   R– C –OH + NH4Cl

2.4 By alkaline hydrolysis of alkylidyne trihalides :

2.5 From carboxylation of grignard’s reagent :

By passing CO2 in ether Solution of Grignard’s reagent

Note : Formic acid can not be prepared by this method.

CARBOXYLIC ACID & IT’S DERIVATIVES [54]

2.6 Partial decarboxylation of gem dicarboxylic acids :

Note : Formic acid is prepared from oxalic acid (laboratory method) by heating at about 110º in the presence
of glycerol.
COOH Glycerol
| 
110º
 HCOOH + CO2
COOH
COOH
In absence of glycerol | 
  CO2 + CO + H2O
COOH
2.7 Carbonylation of :
(a) Sodium alkoxides or sodium hydroxide :
O
High temp. dil. HCl
H–O Na + CO 
High press
 H–COONa 
HOH
 H– C –OH
O
High temp. dil. HCl
R–ONa + CO 
High press
 R–COONa 
HOH
 R– C –OH

(b) Alcohols :
O
BF3 / HOH
R–OH + CO 
High temp. & press
 R– C –OH
O
BF3 / HOH
H–OH + CO 
High temp. & press
 H– C –OH

(c) Alkenes [Koch Reaction] :

O
H3PO4
CH2=CH2 + CO + H2O 
300– 400ºC, high press
 CH3–CH2– C –OH (Propanoic acid)

H3PO4
CH3–CH=CH2 + CO + H2O 
300– 400ºC, high press
 CH3—CH—CH3 (2–methyl Propanoic acid)
|
COOH
Note : Formic acid and acetic acid can not be prepared by this method.

2.8 Oxidation of alkenes and alkynes :

CARBOXYLIC ACID & IT’S DERIVATIVES [55]

3. PHYSICAL POPERTIES
3.1 Physical State : C1 to C3 = Colour less pungent smelling liquids.
C4 to C9 = Liquids having goat’s butter like smell.
C10 to C10+ = Colourless & odourless waxy solids.

3.2 Solubility : Up to C4 = Highly soluble in water

With the increase in molecular weight of carboxylic acid, the solubility in water decreases.
Solubility of lower members of carboxylic acids family is due to the formation of hydrogen bond between
–COOH group and water molecules.

As the alkyl group increases in size in acids, the water repelling (hydrophobic) tendency of the hydrocarbon
chain increases and it out weighs the effect of hydrogen bonding. This is why solubility decreases in
higher members.
3.3 Boiling point (B.P.) :
B.P. of acids > B.P. of alcohols
Because, A carboxylic acid molecular can enter into hydrogen bonding at two different points. This leads
to the formation of cyclic dimers in acids. This is the fact that lower acids occur as dimers in solution.

3.4 Melting point (M.P.) :

M.P. of carboxylic acids do not vary smoothly from one molecule to another
For first ten memebers M.P. of C2n > M.P. of C2n+1
(n = 1, 2, 3, 4, 5) (n = 0, 1, 2, 3, 4)
Reasons : In acids of even number of carbon atoms terminal –CH3 and –COOH group lie on the
opposite side of the carbon chain.

Provide more effective packing of the molecule in the lattice.

While in acids of odd no. of carbon atoms

Less effective packing

4. CHEMICAL PROPERTIES : Carboxylic acids give following reactions :

4.1 Due to alkyl group
4.2 Due to acidic hydrogen
4.3 Due to >C = O group
4.4 Due to – OH group
4.5 Due to – COOH group
4.6 Special reaction of alkanoic acid

CARBOXYLIC ACID & IT’S DERIVATIVES [56]

4.1 Reactions due to alkyl group :
Halogenation : Acids having  –H atom give this reaction. The  –H atoms are easily replaced by
chlorine or bromine atoms, forming halogen derivatives of acids.

Note : (i) The reaction is known as hell–volhard–Zelinisky (HVZ) reaction.

(ii) In the presence of phsophrous, monohalo product is formed as the main product.
P
R–CH2–COOH + Br2   R–CH(Br)–COOH + HBr
(iii) Formic acid does not shown HVZ reaction due to absence of alkyl group or  – H atom.

4.2 Due to acidic hydrogen :

(a) Salt Formation : Carboxylic acids form salts with metals, metal oxide, hydroxides, carbonates,
bicarbonates and compounds showing basic nature.

Note : Acids liberate CO2 with NaHCO3. This reaction is used to distinguish carboxylic acid from phenol
which does not react with NaHCO3.
(b) Reaction with Ketene :

(c) Reaction with diazomethane :

O
||
R  C OH + CH2N2  R  C OCH3  N 2
||
Methyl ester
O
Note : Diazomethane is a powerful methylating agent. So by this method methyl ester can be prepared.

CARBOXYLIC ACID & IT’S DERIVATIVES [57]

 (d) Reaction with alkene and alkyne :

4.3 Reaction due to (>C = O) group :

(a)

(b)

4.4 Reactions due to (–OH) group :

(a) With P2O5 (Dehydrations)

(b) Esterification :

Note : The reaction is proton–catalysed esterification. In the reaction OH comes from the acid and H from the
alcohol for release of H2O.
(c) Reaction with Phosphrous Chlorides :

(d) With Thionyl Chloride :

Note : In the reaction SO2 is gas so escapes out and HCl is an acid, gets absorbed by basic pyridine and pure
acyl chloride is left. So its is best method for preparing acyl chloride from acids.

CARBOXYLIC ACID & IT’S DERIVATIVES [58]

 (e) Formation of acid Amides and Alkane Nitriles :

(f) With Hydrazoic acid (Schmidt reaction) : N3H = Hydrazoic acid

The reaction is a modification of ‘‘curtius reaction’’.

H2SO4
Ex. CH3–COOH + HN3   CH3–NH2 + CO2 + N2
Mechanism :

4.5 Reaction due to (–COOH) group :

(a) Decarboxylation :

(b) Kolbe’s electrolytic synthesis :

+ 2CO2 (At Anode)

2K + 2H2O 2KOH + H2 (At Cathode)

Note : Kolbe synthesis undergoes free radical mechanism.
(c) Hundsdiecker reaction :

+ Agx 

Note : In the reaction decarboxylative halogenation of the acid takes place. The reaction is useful in stepping
down a homologus series.

CARBOXYLIC ACID & IT’S DERIVATIVES [59]

 (d) Formation of carbonyl compounds [Dry distillation of calcium salt] :

(e) With Manganous oxide :

4.6 Special reaction of alkanoic acid :

(a) Oxidation :
 By SeO2  keto acid is formed
 By H2O2 –OH group comes at  –C atom.

(b) Pyrolysis :

5. SPECIAL FEATURES OF FORMIC ACID

(a) Formic acid shows acidic character due to the presence of –COOH group as well as shown
reducing character due to the presence of –CHO group.

(b) It reduces Tollen’s reagent and forms silver mirror.

(c) It reduces mercuric chloride and forms black ppt. of mercury.

CARBOXYLIC ACID & IT’S DERIVATIVES [60]

 (d) It decolourises the pink colour of acidic KMnO4
(e) It forms brown ppt. of MnO2 with basic KMnO4
(f) It converts the orange colour of acidic K2Cr2O7 into green colour.
(g) It reduces Fehling solution.

(h) Dehydration –HCOOH 
Conc. H2SO4
 H O + CO
2 2
(i) Effect of heat :
160ºC
(a) HCOOH 

 CO2 + H2

380ºC COONa
(b) 2HCOONa 

2 | + H2
COONa
Sodium oxalate

6. DISTINCTION BETWEEN FORMIC ACID AND ACETIC ACID

7. FORMIC ACID (HCOOH)

1. Lab Reaction :
COOH Glycerol
|   HCOOH + CO2
110º
COOH
Note : BP of HCOOH is 100.5º, for removal of water from formic acid we can use PbCO3 or PbO (Litharge)
and H2S.
2HCOOH + PbCO3  (HCOO)2Pb + CO2 + H2O
100ºC
(HCOO)2Pb + H2S   2HCOOH + PbS (PPT)

2. Industrial method :
It is prepared on large scale by reaction CO with aqueous sodium hydroxide under pressure 1 atm and
473 K
473 K H2O
CO + NaOH 
1atm
 HCOONa   HCOOH + NaOH

CARBOXYLIC ACID & IT’S DERIVATIVES [61]

8. ACETIC ACID CH3COOH
Industrial methods :

(a) From ethyne :

(b) From ethyl alcohol

Cu [O]
(i) By dehydrogenation : CH3CH2OH 
300ºC
 CH3CHO 
(Magnous acetate)
 CH COOH
3
(–H2 )

(ii) By fermentation (Quick vinegar process)

Acetobector bacteria
CH3CH2OH + O2 
(Mycoderma acetail)
 CH COOH + H O
3 2

[dilute form 8 – 10% Called VINEGAR]

(iii) From CH3OH
BF3
CH3OH + CO 
or Rh
 CH3COOH

CARBOXYLIC ACID & IT’S DERIVATIVES [62]

 ACID DERIVATIVES

1. GENERAL INTRODUCTION
Replacement of –OH group of the –COOH group in a carboxylic acid by an atom or by any other
functional group give rise to certain new families of compounds. These compounds are called acid
dervatives.

Acyl chlorides are the most important acid halides. The first member of this family is acetyl chloride
because formylchloride is unstable.
Similarly acetic anhydride is the representative member of the acid anhydrides family, because formic
anhydride is unstable.
The first two members of Acid Amide family are formamide and Acetamide. Acetamide is an important
acid amide.
Esters have functional group isomerism with acids.
O
R– C –Z [where Z = –X, –NH2, –OCOR, –OR]
* Order of basic character of group Z
X– < O– COR < –OR < NH2–
* Reactivity order/Rate of hydrodysis
O O O O O
R– C –X > R– C –O– C –R > R– C –OR > R– C –NH2
* Order of stability
O O O O
R– C –NH2 > RCOOR > R– C –O– C –R > R– C –X
Derivatives regenerate the parent acid on hydrolysis.
O
2. ACETYL CHLORIDE [CH3– C –Cl]
2.1 Method of preparation :
Laboratory method :
O O
3CH3– C –OH + PCl3  3CH3– C –Cl + H3PO3
O O
CH3– C –OH + PCl5  CH3– C –Cl + POCl3 + HCl
CH3COOH + SOCl2  CH3–CO–Cl + SO2 + HCl

CARBOXYLIC ACID & IT’S DERIVATIVES [63]

 From Sodiumacetate :
CH3–COONa + PCl5  CH3–CO–Cl + POCl3 + NaCl
3CH3–COONa + PCl3  3CH3–CO–Cl + Na3PO3
2CH3–COONa + POCl3  2CH3–CO–Cl + NaPO3 + NaCl
CH3–COONa + SOCl2  CH3–CO–Cl + SO2 + NaCl
By the reaction of sulpuryl chloride on calcium ethanoate :

2.2 Physical Properties :

(i) Colourless liquid, having pungent odour.
(ii) Slowly soluble in water, soluble in organic solvents like CHCl3, CCl4, CH3–CO–CH3, etc.
(iii) Produces bilster on skin and its vapour causes irritation in eyes.
(iv) Boiling point is 51ºC.
(v) Fumes strongly in moist air.
2.3 Chemical properties :
(1) Hydrolysis :

(2) Reduction :

(i)

(ii)

(3) Curtius Reaction :

(4) Friedel Craft’s reaction :

CARBOXYLIC ACID & IT’S DERIVATIVES [64]

 (5) With Grignard’s reagent :

(6) Halogenation :

(7) With Ether :

(8) With Sodium Ethoxide :

(9) With Sodium Acetate :

(10) Acetylation of Compounds having reactive hydrogen atom :

Ex.

CARBOXYLIC ACID & IT’S DERIVATIVES [65]

 (11) With Alkene :

O O
3. ACETIC ANHYDRIDE [CH3– C –O– C –CH3]

3.1 Method of prepatation :

From Acetyl chloride :

From Acetic acid :

By passing chlorine in a mixture of SCl2 and sodium acetate :

From Ketene :

3.2 Physical Properties :

(i) It is colourless liquid having pungent vinegar like odour.
(ii) Boiling point is 138ºC.
(iii) Slowly soluble in cold water, but readily soluble in hot water

CARBOXYLIC ACID & IT’S DERIVATIVES [66]

3.3 Chemical Properties :
Hydrolysis :

With PCl5 :

With N2O5 :

With Benzene [Friedel–Craft’s Reaction] :

With Acetaldehyde :

Ethylidene diacetate
With Dry HCl gas :

Perkin’s Reaction :

(Benzaldehyde)

CARBOXYLIC ACID & IT’S DERIVATIVES [67]

 Reduction :

With Compounds having reactive H–atom :

Acetylderivative

Note : Products are similar as in case of Acetyl chloride.

O
4. ACETAMIDE [CH3– C –NH2]

4.1 Method of Preparation :

From Acetychloride :

From Acetic Acid :

From acetic Anhydride :

From Ethyl Acetate :

Partial hydrolysis of Acetonitrile :

Conc . HCl
 
H2O 2

By thermal decomposition of Ammonium acetate :

4.2 Physical properties :

(i) It is a hygroscopic white crystalline solid.
(ii) It has faint smell in pure state, but a rat like smell in impure state.
(iii) It is soluble in water and alcohol, but sparingly soluble in ether.
(iv) Melting point 82ºC and boiling point is 222ºC.

CARBOXYLIC ACID & IT’S DERIVATIVES [68]

4.3 Chemical properties :
Hydrolysis :

Dehydration :

Reduction :
Reducing Agent : Metal Catalyst + H2, Na + Ethanol, LiAlH4 etc.

With Nitrous Acid :

Amphoter character :
Acetamids forms salts on reacting with strong bases as well as strong acids. Therefore it behaves like a
weak base as well as weak acid. i.e. it shows amphoteric character.
(i) Weak acidic behaviour :

Acetamidomercuriacetate
(ii) Weak basic behaviour :

CARBOXYLIC ACID & IT’S DERIVATIVES [69]

 Hofmann Bromamide Reaction or Hypobromite Reaction :

Slightly Mechanism :
Bromination :

Dehydrobromination :

Hydrolysis :

Note : In the reaction decrease of one carbon atom takes place. Therfore it can be used in decending down a
homlogous series and it is also called Hofmann degradation.
O
5. ETHYL ACETATE AND ACETIC ESTER [CH3– C –OC2H5]

5.1 Methods of preparation :

By liquid phase Esterification :

By vapour phase Esterification :

CARBOXYLIC ACID & IT’S DERIVATIVES [70]

By Aceylation of Ethanol :

Tischenko Reaction :

Ethylation of Silver halides :

Ethanolysis of Ethanenitrile :

By addition of Acetic acid on Ethylene :

By reaction of sodium Ethoxide on Acetyl chloride :

Baeyer–Villiger Oxidation :
Ethyl acetate is formed on reacting butanone with a peracid, Methyl propionate is also formed in small
amounts.

CARBOXYLIC ACID & IT’S DERIVATIVES [71]

5.2 Physical Properties :
(i) Colourless, sweet smelling steamvolatile, inflammable liquid.
(ii) Very sparingly soluble in water, but soluble in organic solvents.
(iii) Boiling point 78º.
5.3 Chemical Properties :
Hydrolysis :

Note : In esters caustic alkalies hydrolysis is rapid and complete. Alkaline hydrolysis of esters is called
“Saponification”.
Reduction :

Ammonolysis :

With Grignard’s Reagent :

Note : The product will be tertiary alcohol when 2 mole of Grignard’s reagent are taken.
With Hydazine :

Acetyl hydrazine
With Hydroxyl Amine :

CARBOXYLIC ACID & IT’S DERIVATIVES [72]

With PCl5 :

Claisen Ester Condensation :

Pyrolysis or Thermal decomposition :

Acidolysis :

CARBOXYLIC ACID & IT’S DERIVATIVES [73]

 BENZOIC ACID

BENZOIC ACID (C6H5COOH)

Benzoic aicd was first obtained by Schiele from gum benzoin. It is also present in Peru balsam and Tolu
balsam in the form of its benzyl ester (benzyl benzoate).
C6H5COOCH2C6H5 Benzyl Benzoate
In combined form it is found as benzoylglycine in horse urine.
C6H5CONHCH2COOH Benzoylglycine
1.1 PREPARATION
(1) Oxidation of Benzyl Alcohol :
Benzoic acid is formed on permanganate oxidation of benzyl alcohol.
[O]
C6H5CH2OH (Benzyl alcohol) + [O]  C6H5CHO(Benzaldehyde)   C6H5COOH (Benzoic
acid)
(2) Oxidation of Benzaldehyde :
Oxidation of benzaldehyde takes place very readily and benzoic acid is formed.
[O]
C6H5CHO   C6H5COOH

(3) Oxidation of Aralkanes and Their Derivatives :

A side chain (alkyl group or substituent alkyl group) bonded directly to the benzene ring is converted to
a carboxyl group on oxidation. Dilute nitric acid or chromic acid or alkaline permangante can be used as
oxidant.

[O]
C6H5– C   C6H5COOH
Side chain

Benzoic acid is obtained on oxidation of many compounds like aralkanes (toluene, ethylbenzene,
n–propylbenzene, cumene, etc.) and their oxygenated derivatives (benzyl alcohol, benzaldehyde,
acetophenone, benzophenone, etc.) halogenated derivatives (benzyl chloride, benzal chloride,
benzotrichloride etc) nitrogenated derivatives (cyanobenzene benzamide, etc.)
(4) Carboxylation of Grignard’s Reagents :
Benzoic acid is formed on hydrolysis of the product obtained by passing carbon dioxide in ethereal
solution of phenylmagnesium bromide.
CO2 HOH
C6H5MgBr   C6H5COOMgBr   C6H5COOH

(5) Carboxylation of Benzene :

Benzoic acid is obtained on heating benzene and carbon dioxide in nitrobenzene medium in the presence
of anhydrous aluminium chloride.
AlCl3
C6H5H + CO2  C6H5COOH

CARBOXYLIC ACID & IT’S DERIVATIVES [74]

(6) Alkaline Hydrolysis of Benzotrichloride :
Benzoic acid is formed on hydrolysis of benzotrichloride by lime water in the presence of iron catalyst.
2Ca(OH)
C 6H5CCl3 (Benzotrichloride) 3 OH– 
Fe
 C6H5COOH + H2O + 3 Cl–

(7) Hydrolysis of Benzoyl Chloride :

Benzoic acid is obtained by hyrolysis of benzoyl chloride
C6H5COCl + HOH C6H5COOH + HCl
Benzoyl chloride is prepared by Friedel–Crafts chlororformylation of benzene, Benzoic acid is obtained
in 60% yield by the method.
AlCl3
C6H5H + Cl–CO–Cl  C6H5COCl + HCl
Phosgene

(8) Hydrolysis of Cyanobenzene :

Benzoic acid is formed on hydrolysis of cyanobenzene i.e., benzonitrile by dilute hydrochloric acid.
C6H5CN + 2HOH + HCl C6H5COOH + NH4Cl
(9) Dehydroxylation of Hydroxybenzoic Acid :
Benzoic acid is formed on dry distillation of o–, m– or p–hydroxybenzoic acid with zinc dust. The ortho
isomer is called salicylic acid.

HO–C6H4–COOH + Zn H–C6H4–COOH + ZnO

Benzoic acid

(10) Decarboxylation of Phthalic Acid :

o–Benzendicarboxylic acid is called phthalic acid. On heating its zinc of nickel or chromium salt at 200–
300º with water vapours, benzoic acid is formed by partial decarboxylation.

COOH


H O
2
 + ZnO + CO2

(11) Hydrolysis of Benzoic Acid Derivatives :

Benzoic acid is formed on hydrolysis of esters, anhydride, acid chloride and amide of benzoic acid.
C6H5CO–Z + HOH C6H5COOH + Z–H
Benzoyl chloride and benzoic anhydride very readily get hydrolysed by water, but with little bit more
diffucilty as compared to aliphatic acid chlorides. Hydrolysis by alkali takes place faster.
C6H5COCl + H2O C6H5COOH + HCl
(C6H5CO)2O + H2O 2C6H5COOH
Hydrolysis of benzoic esters takes place on heating with an alkali.
C6H5COOEt + NaOH C6H5COONa + EtOH

CARBOXYLIC ACID & IT’S DERIVATIVES [75]

 Hydrolysis of benzamide takes place on boiling with dilute acid or alkali solution.
C6H5CONH2 + H2O + HCl C6H5COOH + NH4Cl
C6H5CONH2 + NaOH C6H5COONa + NH3
Liberation of ammonia gas on heating the solution after adding sodium hydroxide solution is the test for
amides.
1.2 PHYSICAL PROPERTIES
Benzoic acid is a crystalline solid (melting point 122º) which is sparingly soluble in cold water, but readily
soluble in hot water. It is also soluble in organic solvents like alcohol ether, etc. Its acid strength is more
than that of the alkanoic acids due to weak negative inductive effect of phenyl group.
1.3 RESONANCE IN BENZOIC ACID
The COOH group present in benzoic acid is a strong electron–attracting group due to which the benzene
ring is deactivated and rate of SE reaction decreases as compared to unsubstitued benzene. Therefore,
the COOH group exerts a deactivating effect on the benzene ring.
Dimerisation in Benzoic Acid due to Hydrogen Bonding :
Benzoic acid in liquid phase (in benzene solution or in molten form) exists in the form of a dimer by
association due to intermolecular hydrogen bonding in the same fashion as in alkanoic acids. This is the
reason why the experimental value of the molecular weight of benzoic acid is twice the calculated value.
O—H O
C6H5–C C– C6H5
O H—O
Hydrogen bonded dimer of benzoic acid

1.4 REACTIONS
Benzoic acid gives the following two types of reactions.
(A) Reactions due to COOH group
(B) Reactions due to C6H5 group
(A) Reaction Due to Carboxyl Group :
1. With Bases :
Many alkaline compounds form benzoate salts on reacting with benzoic aicd.
C6H5COOH + NaOH C6H5COONa + H2O
2C6H5COOH + Na2CO3 2C6H5COONa + H2O + CO2
C6H5COOH + NaHCO3 C6H5COONa + H2O + CO2
Phenol (a weak acid) does not react with sodium bicarbonate, whereas benzoic acid gives effervescence
of CO2, although both are acidic organic compounds toward litmus. Therefore, distinction between
phenol and carboxylic acids can be done by using NaHCO3.
2C6H5COOH + Ca(OH)2 (C6H5COO)2Ca
C6H5COOH + NH3 C6H5COONH4
C6H5COOH + NH4OH C6H5COONH4 + H2O
2. With Alcohols :
An alkyl benzoate is formed by esterification on heating a mixture benzoic acid and an alkanol in the
presence of a few drops of concentrated H2SO4.
H 
C6H5COOH + HOR 

 C6H4COOR + H2O

CARBOXYLIC ACID & IT’S DERIVATIVES [76]

3. With Inorganic Chloride :
Benzoyl chloride is formed on the reaction of benzoic acid with phosphrous pentachloride or phsophrous
trichloride or thionyl chloride.
C6H5COOH + PCl5 C6H5COCl + POCl3 + HCl
3C6H5COOH + PCl3 C6H5COCl + H3PO4
C6H5COOH + SOCl2 C6H5COCl (Benzoyl chloride) + SO2 + HCl
4. With P2O5 :
Benzoic anhydride is formed on heating benzoic acid with P2O5.
P2O5
2C6H5COOH 

(C6H5CO)2O + H2O
Acetic anhydride also dehydrates two molecules of benzoic acid to give benzoic anhydride.
5. With Ammonia :
Benzamide is formed on heating benzoic acid with ammonia.

C6H5COOH + NH3 [C6H5COONH4] 
–H2O
 C H CONH
6 5 2

Benzonitrile or cyanobenzne can be obtained by heating benzamide with P2O5.

P2O5
C6H5CONH2 

C6H5CN + H2O
6. With Soda Lime :
Benzene is obtained on dry distillation of sodium salt of benzoic acid with sodalime.
C6H5COONa + NaOH  
 C6H6 + Na2CO3
7. Dry Distillation of Calcium Salt :
Benzophenone is obtained on dry distillation of calcium salt of benzoic acid.
(C6H5COO)2Ca  
 C6H5COC6H5 + CaCO3
8. Hunsdiecker Reaction :
Bromobenzene is formed on heating the silver salt of benzoic acid with bromine in carbon tetrachloride
solution
CCl4
C6H5COOAg + Br2  C6H5Br + CO2 + AgBr
9. Reduction by Lithium Aluminium Hydride :
Benzyl alcohol is formed on reduction of benzoic acid by lithium aluminium hydride (LiAlH4).
LiAlH4
C6H5COOH + 4H   C6H5CH2OH + H2O
10. Reduction by Sodium and Ethanol :
Toluene is formed on reduction of benzoic acid by sodium and ethanol.
Na
C6H5COOH + 6H 
EtOH
C6H5CH3 + 2H2O
(B) Readuction Due to Aromatic Ring :
Hydrogenation by Sodium and Amyl Alcohol :
The COOH group is not affected on reduction of benzoic acid by sodium and amyl alcohol but benzene
ring of benzoic acid is completely hydrogenated to form Cyclohexanecarboxylic acid.

COOH COOH
| |
Sodium 
+ 6H 
Amyl alcohol


Cyclohexanecarboxylic Acid

CARBOXYLIC ACID & IT’S DERIVATIVES [77]

 Aromatic Electrophilic Substitution Reaction :
Meta substitution products are formed on halogenation nitration and sulphonation of benzoic acid.

COOH COOH
| |
Cl
2 

FeCl 3
Cl
m-Chlorobenzoic acid

COOH COOH COOH

| | |
Conc. HNO
3 Fumin g HNO
3

30º

140º
NO2 O2N NO2
3,5-Dinitrobenzoic acid
m-nitrobenzoic 3,5-Dinitrobenzoic acid
COOH COOH
| |
Conc. H4 SO4
 
SO3H
m-Sulphobenzoic acid

Note : Due to the presence of a deactivating m–directing COOH group in benzoic acid, the latter does not give
Friedel–Crafts reaction.
1.5 TESTS
1. Formation of Ferric salt :
A red–brown precipitate is obtained on adding a small amount of neutral ferric chloride solution
in benzoic acid solution.
2. Esterification :
A sweet odour of ethyl benzoate is perceived on heating benzoic acid after adding a few drops
of ethyl alcohol and concentrated sulphuric acid.
3. Decarboxylation :
Inflammable vapours of benzene are liberated out on heating benzoic acid after mixing it thoroughly
with soda lime.
1.6 USES
Benzoic acid is used as follows :
1. As a germicide.
2. Benzoic acid and its salts are used in the form of medicines.
3. Sodium benzoate is used as a preservative of canned food products.
4. Benzoic acid is used in the manufacture of many synthetic dyes, like aniline blue dye.
5. Ethyl ester of benzoic acid (ethyl benzoate) is used as a flavouring agent.

CARBOXYLIC ACID & IT’S DERIVATIVES [78]

 EXERCISE -I
Q.1 In the reaction sequence :
CH MgBr (i ) CO
2  (B)
CH3–CC–H 3  CH4+ (A)   
(ii ) H 2O / H
(B) will be:
(A) CH3–CC–CH3 (B) CH3–CC–MgBr
(C) CH3–CC–COOH (D) CH3–CH=CH–COOH

Q.2 Hydrolysis of 1,1, 1-trichloro derivative (A) of alkane gives a molecule (B) on alkaline hydrolysis which
produces red coloration with aqueous FeCl3. The compound (A) is -
(A) CH3CH2CCl3 (B) CH3CCl3 (C) CHCl3 (D) None

Q.3 In the given reaction :

( i ) NaCN / HCl
CH3CHO     (A) Fenton
  (B), (B) will be :
(ii ) H 2O / H /  reagent
(A) Acetic acid (B) Oxalic acid (C) Pyruvic acid (D) Citric acid

Q.4 Which of the following is the best representation of the structure of the carboxylate ion -
– 
O O
(A) (B) R – C (C) R – C (D) None of these
O O
– 

Q.5 In the given reaction :

O
||
 CHBr3 + [X], [X] will be:
( i ) Br2 / KOH
C6 H 5  C  CH 3  

( ii ) H
(A) C6H5–CHO (B) C6H5COOH (C) C6H5–CH2OH (D) CH3COOH

Q.6 Identify Z in the sequence

( i) heat 
CH3COONH4 (  Y H
2 O(H )
Z -
ii) P O 2 5

(A) CH3CH2CONH2 (B) CH3CN (C) CH3COOH (D) (CH3CO)2O

Q.7 Sodium bicarbocate reacts with salicylic acid to form:

(A) C6H5ONa (B) (C) (D)

Q.8 Which one of the following reacts with Grignard reagent to form an addition product which can be
hydrolysed to a carboxylic acid?
(A) O2 (B) CO2 (C) SO2 (D) None

CARBOXYLIC ACID & IT’S DERIVATIVES [79]

Q.9 Which of the following will not be soluble in sodium bicarbonate solution?

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

Q.10 Consider the given reaction :

Br / 
RCOOAg 2  R–Br
which one of the following acid will give maximum yield of R–Br in the above reaction?
(A) CH  CH  COOH (B) CH3–CH2–CH2–COOH
3
|
CH 3
CH 3
|
(C) CH 3  C  COOH (D) All will give same yield
|
CH 3
Q.11 In the given reaction:

HBr
 [X], [X] will be:

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

Q.12 In the given reaction :

(i ) Br2 / red P
CH3–COOH    [X], [X] will be:
( ii ) NaCN
( iii ) H 2O / H  / 

(A) CH3COOH (B) COOH–CH2–CH2–COOH

CH 2  CO
(C) | (D) CH2
CH 2  CO

Q.13 Which of the following is a polyprotic acid -

(A) Acetic acid (B) Benzoic acid (C) Salicylic acid (D) Oxalic acid

Q.14 Reducing property of formic acid is due to the presence of :

O O
|| ||
(A) – OH (B)  C  H (C)  C  OH (D) All of these

Q.15 The Hell-Volhard Zelinsky reaction is used for preparing a/an -

(A) -Haloacid (B) -Haloacid (C) Acid halide (D) -Haloacid

CARBOXYLIC ACID & IT’S DERIVATIVES [80]

Q.16 In the given reaction:
COOC 2 H 5
+ | Pyridne
  [X], [X] will be :
COOC 2 H 5

(A) (B)

(C) (D)

Q.17 Select the compound which does not give acetic acid on hydrolysis -
(A) CH3CCl3 (B) CH3CN (C) CH3COCl (D) CH3CH2Cl

Q.18 Which of the following skeleton gives the strongest acid if COOH is attached to the free valency -
C
|
(A) C  C (B) C – C – C – (C) H – (D) C – C –

red P LiAlH
Q.19 A   CH3COOH 
4
 B. What is not true for A and B -
HI

(A) A is hydrocarbon of general formula CnH2n+2 while B belongs to alkanol

(B) A can be obtained by reducing CH3CH2Cl while B by its hydrolysis
(C) A is alkene while B is alkanal
(D) A and B both belongs to different homologous series

Heat Heat
Q.20 The product A, B, C and D in the reaction A + B   H – COOH   C + D are given by
H2 SO 4

the set -
(A) CO, H2O, CO2, H2 (B) CO2, H2O, CO, H2
(C) CO2, H2, CO, H2O (D) CO, H2, CO2, H2O

Q.21 Ozonolysis of fatty acid is carried out to ascertain -

(A) Number of –OH group (B) Number of – COOH group
(C) Position of carbonyl group (D) Position of double bond

Q.22 Dry distillation of calcium acetate gives -

(A) Acetaldehyde (B) Acetone (C) Ethane (D) Propane

CARBOXYLIC ACID & IT’S DERIVATIVES [81]

Q.23 Which of the following products is formed when adipic acid is heated -
CH2 – CH2
(A) (B) C=O
CH2 – CH2

CH2 – CH2CO
(C) O (D)
CH2 – CH2CO

Q.24 In the reaction sequence :

O
||
H 2O / H 
CH 3  C  H HCN 
  (A)   Product, Product will be:
OH 

OH OH
| |
(A) CH 3  C  COOH (B) HOOC  C  CH 3
| |
H H
OH OH
| |
(C) Mixture of CH 3  C  COOH and HOOC  C  CH 3
| |
H H
OH
|
(D) CH 3  CH  CONH 2

Q.25 Which of the following compounds gives carbondioxide with NaHCO3?

(A) Acetic acid (B) Hexanol (C) Phenol (D) Acetylene

Q.26 When malonic acid is heated, it gives -

(A) Formic acid (B) Oxalic acid (C) Acetic anhydride (D) Acetic acid

Q.27 Amongst the acids,

(i) CH  CCOOH (ii) CH2 = CHCOOH and (iii) CH3CH2COOH,
the acid strength follows the sequence
(A) (i) < (ii) > (iii) (B) (i) > (ii) > (iii) (C) (i) = (ii) = (iii) (D) (i) = (ii) > (iii)

Q.28 Formic acid reacts with PCl5 to form -

(A) Acetyl chloride (B) Methyl chloride
(C) Carbon monoxide and hydrogen chloride (D) formyl chloride

Q.29 Which one of the following reactions can be used for the preparation of -hydroxy ester:
(A) Perkin reaction (B) Reformatsky reaction
(C) Aldol condensation (D) Claisen condensation

Q.30 Kolbe’s electrolysis of aqueous potassium ethanoate leads to the formation of -

(A) Ethene (B) Methane (C) Ethane (D) Ethyne

CARBOXYLIC ACID & IT’S DERIVATIVES [82]

 EXERCISE -II

Q.1 End product of the following reaction is – [AIEEE-2002]

CH3CH2COOH
(A) CH3CHCOOH (B) (C) CH2=CHCOOH (D)
OH

Q.2 In the anion HCOO— the two carbon-oxygen bonds are found to be of equal length. What is the reason for
it ? [AIEEE-2003]
(A) The anion HCOO has two resonating structures
—

(B) The anion is obtained by removal of a proton from the acid molecule
(C) Electronic orbitals of carbon atom are hybridised
(D) The C=O bond is weaker than the C—O bond

Q.3 Which one of the following does not have sp2 hybridized carbon ? [AIEEE-2004]
(A) Acetone (B) Acetic acid (C) Acetonitrile (D) Acetamide

Q.4 Consider the acidity of the carboxylic acids : [AIEEE-2004]

(a) PhCOOH (b) o – NO2C6H4COOH
(c) p – NO2C6H4COOH (d) m – NO2C6H4COOH
Which of the following order is correct ?
(A) a > b > c > d (B) b > d > c > a (C) b > d > a > c (D) b > c > d > a

Q.5 The compound formed as a result of oxidation of ethyl benzene by KMnO4 is – [AIEEE-2007]
(A) benzophenone (B) acetophenone (C) benzoic acid (D) benzyl alcohol

Q.6 A liquid was mixed with ethanol and a drop of concentrated H2SO4 was added. A compound with a
fruity smell was formed. The liquid was : [AIEEE-2009]
(A) CH3OH (B) HCHO (C) CH3COCH3 (D) CH3COOH

Q.7 Acetic acid can be used for the preparation of :

(A) Ethane (B) Methane (C) Acetone (D) ethanol

red P
Q.8   [ Product ] The product of the above reaction is -


(A) -Dibromo acid (B) ,’ - Dibromo acid

(C) ,’,’’-Tribromo acid (D) No reaction takes place

CARBOXYLIC ACID & IT’S DERIVATIVES [83]

Q.9 Consider the following reaction:
O  O
|| H ||
CH 3  C  OH  CH 3  OH CH 3  C  O  CH 3  HOH

True about the above reaction is:

(A) Product is having smell like fruits
(B) Nucleophilic addition followed by elimination reaction
(C) follows AAC' mechanism
(D) it is irriversible reaction

Q.10 HVZ reaction is specific for -

(A) Replacement of  - hydrogen (B) Replacement of  - hydrogen
(C) Replacement of  - carbons (D) Replacement of  - carbons

Q.11 Which one of the following compounds will give HVZ reaction?

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

Q.12 Acetic acid vapours when passed over aluminium phosphate forms -
(A) CH3CHO (B) Ketene (C) C2H6 (D) C2H4

Q.13 Acetic anhydride is used as:

(A) Solvent (B) Dehydrating agent
(C) Acetylating agent (D) Antiseptic

Q.14 Arrange the following compounds in decreasing order of acidity -

ClCH2CH2CH2COOH CH3CHClCH2COOH CH3CH2CHClCOOH
I II III
(A) I > II > III (B) III > II > I (C) I > III > II (D) III > I > II

Q.15 Which compound will liberate CO2 from NaHCO3 solution:

(A) CH3CO NH2 (B) CH3NH2 (C) (CH3)4N+OH– (D) CH3N+H3Cl–

Q.16 Arrange OHCH2COOH ( I ), HOCH2CH2COOH (II) and CH3COOH ( III ) in order of acidity
-
(A) I > II > III (B) III > II > I (C) I > III > II (D) II > III > I

Q.17 Hofmann Bromamide degradation is given by:

(A) Imide (B) Acid chloride (C) Acid anhydride (D) Amide

Q.18 The rate of esterfication of HCOOH (I), CH3COOH (II), (CH3)2CHCOOH (III) and
(CH3)3CCOOH (IV) with ethanol follows in the order -
(A) IV > III > II > I (B) I > II > III > IV (C) II > I > IV > III (D) III > IV > I > II

CARBOXYLIC ACID & IT’S DERIVATIVES [84]

 O 18
|| HOH / H


Q.19 CH 3  C  O  CH 2  CH 3 Ethanoic acid + Ethanol

Isotopic oxygen of water will be present with
(A) Ethanoic acid
(B) Ethanol
(C) After some time it will also be present in some molecules of ester
(D) None of these

Q.20 In the electrolysis of the aqueous solution of CH3CH2COONa, anion goes to anode the possibility
of formation of following compounds takes place -
(A) CH3 – CH2 – CH2 – CH3 (B) CH2 = CH2, CH3 – CH3
(C) CH3CH2COOC2H5 (D) All the above

Q.21 Which of the following organic acid decolourises bromine water as well as forms anhydride -
(A) HOOC – COOH (B) HOOC – CH2 – COOH

(C) (D)

Q.22 The general formula of dicarboxylic acid is -

(A) (COOH)2 (B) (CH2)n(COOH)2
(C) (CH2)n–2 (COOH)2 (D) (CH2)n–1 (COOH)2

Q.23 The product A, B and C in the reaction sequence

NaOH Heat
 A   B   C are -

360º C

(A) HCHO, HCOONa, CH3OH (B) HCHO, Na2CO3, NaHCO3

(C) HCHO, HCOONa, (COONa)2 (D) HCHO, HCOONa, Na2CO3

Q.24 CH2COOH NaNO / HCl

 CH2COOH
2

| |
X Y
glycine glycollic acid
Here X and Y respectively are -
(A) OH, NH2 (B) NH2, OH (C) Cl, OH (D) None

Q.25 The carboxylic acid that does not undergo HVZ reaction is -
(A) CH3COOH (B) (CH3)2CHCOOH
(C) CH3CH2CH2CH2COOH (D) (CH3)3C COOH

Q.26 The end product ‘C’ in the following sequence of chemical reactions is
CaCO heat NH2OH
CH3COOH 3  A  B    C -
(A) Acetaldehyde oxime (B) Formaldehyde oxime
(C) Methyl nitrate (D) Acetoxime

CARBOXYLIC ACID & IT’S DERIVATIVES [85]

Q.27 Which of the following carboxylic acids undergoes decarboxylation easily?
(A) C6H5–CO–CH2–COOH (B) C6H5–CO–COOH
(C) C6H5 – CH – COOH (D) C6H5–CH–COOH
OH NH2

Cl2 Alc.KOH
Q.28 CH3CH2COOH  a   b
red P

The compound b is -
(A) CH3CH2OH (B) CH3CH2COCl (C) CH2=CHCOOH (D) CH3–CHCl–COOH

Q.29 A compound undergoes the following sequence of reactions :

Hydrolysis Cl /P
C3H5N  C3H6O2 2 C3H5O2Cl NH 3
 C3H7NO2
(a) (b) (c)
The compound C is -
(A) 1-Nitropropane (B) 2-Nitropropane
(C) 2-Aminopropanoic acid (D) 2-Hydroxypropanamide

Q.30 R – CH2 – CH2OH can be converted into RCH2CH2COOH. The correct sequence of reagent is
(A) PBr3, KCN, H+ (B) PBr3, KCN, H2
(C) KCN, H + (D) HCN, PBr3, H+

CARBOXYLIC ACID & IT’S DERIVATIVES [86]

 ANSWER KEY

EXERCISE -I
Q.1 C Q.2 B Q.3 C Q.4 B Q.5 B Q.6 C Q.7 B
Q.8 B Q.9 C Q.10 B Q.11 B Q.12 A Q.13 D Q.14 B
Q.15 D Q.16 B Q.17 D Q.18 C Q.19 C Q.20 C Q.21 D
Q.22 B Q.23 B Q.24 C Q.25 A Q.26 D Q.27 B Q.28 C
Q.29 B Q.30 C

EXERCISE -II
Q.1 C Q.2 A Q.3 C Q.4 B Q.5 C Q.6 D
Q.7 ABCD Q.8 D Q.9 AB Q.10 B Q.11 BC Q.12 B
Q.13 ABC Q.14 B Q.15 D Q.16 A Q.17 AD Q.18 B Q.19 AC
Q.20 D Q.21 C Q.22 B Q.23 C Q.24 B Q.25 D Q.26 D
Q.27 A Q.28 C Q.29 C Q.30 A

CARBOXYLIC ACID & IT’S DERIVATIVES [87]

 NITROGEN COMPOUNDS
1. GENERAL CHARACTERISTICS
(a) If a hydrogen atom of NH3 is replaced by an alkyl group then it is called primary amine
and possess –NH2(amino) group.
(b) Amines are called alkyl derivative of NH3.
(c) Aliphatic amine was discovered by ‘Wurtz’.
(d) If two hydrogen atoms of NH3 are replaced then it is called secondary amine and it posses
> NH (mino) group.
(e) If all hydrogen atoms of NH3 are replaced then it is called tert. amine and has a nitrilo N
group.
(f) N is in sp3 hybridisation and tetrahedral geometry.
(g) Bond angle increases from ammonia to 3º amines.
NH3 (107º) < RNH2 < R2NH < R3N
(h) Aliphatic and aromatic amine shows chain, position, functional and metamerism.

GENERAL CHARACTERISTICS :

Ex.1 Compound is a -

(A) 1º and 3º amine (B) Only primary amine

(C) 2º and 3º amine (D) Only secondary amine (Ans.A)
Sol. 3–Amino–N–methylpiperidine contains primary and tertiary amino groups.

Ex.2 The third member of homologous series of dimethyl amine -

(A) CH3–CH2–NH–CH2–CH3 (B) CH3–NH–CH2–CH2–CH3–
(C) CH3–NH–CH(CH3)2 (D) 2nd and 3rd are correct (Ans.D)
Sol. Compounds 2nd and 3rd contains CH3–NH– group.

Ex.3 Tertiary butyl amine is a-

(A) 1º Amine (B) 2º Amine
(C) 3º Amine (D) Quaternary salt (Ans.A)
Sol. (CH3)3C–NH2 is primary amine

Ex.4 N–atom in quaternary ammonium halide will have the form-


(A) N (B) (C) (D) (Ans.A)


Sol. Quaternary ammonium halide is an ionic compound. Hence N carries positive charge.

NITROGEN COMPOUNDS [88]

 Re duction
Ex.5 –CONH2    –CH NH
2 2
In above reaction hybridisation state of carbon changes from .....  ........
(A) sp  sp2 (B) sp  sp3
(C) sp2  sp3 (D) sp2  sp (Ans.C)
Sol. Hybridisation state of carbon changes from sp2 to sp3.

2. METHODS OF PREPARATION
2.1 From Alkylchloride :
R–Cl + H–NH2  Cu
 2O
 R–NH + HCl
2
200 º C

Note : In the above reaction Cu2O neutralises the evolved HCl in form of Cu2Cl2 + H2O otherwise
HCl forms additional salt with amines.
2.2 From Grignard reagent :
R–Mg–Cl + Cl–NH2  R–NH2 + MgCl2
2.3 From Alcohol :
300 C

 
H 2 O R–NH2 + H2O

2.4 By Aldehyde or Ketone (reaction with H2 and NH3 in presence of catalyst) :

Primary amine can be produced by passing a mixture of aldehyde or ketone and large excess of ammonia
and hydrogen under pressure (20-150 atm) over raney nickel catalyst at 40-150ºC.
Ni
R1R2C=O + NH3  R1R2CHNH2
Note: Small amount of secondary and tertiary amines are also produced in this method as by products.
2.5 By reaction of Aldehyde or Ketones (with ammonium formate or with formamide and subsequent
hydrolysis of product)
Aldehyde and ketones when react with ammonium formate or formamide or the formyl derivative of
primary amine on hydrolysis yields primary amine and formate ions.
C=O + 2HCO2NH4     CH – NHCHO + 2H2O + NH3 + CO2
(ammonium formate)

C=O + 2HCONH2   CH – NH – CHO + CO2 + NH3

2H O
CH – NH – CHO    2    CH – NH2 + HCOO
in alkaline medium

2.6 From Alkanoic acid (Schimdt Reaction) :

conc . H 2SO 4
R– C –O–H + N3H    RNH2+ N2 + CO2
||
O

Note : Alkyl isocyanate can also be produced by heating the mixture of acyl halide and sodium azide,
alkylisocyanate, once it is formed, can easily be hydrolysed into primary amine and CO2.

NITROGEN COMPOUNDS [89]

 Mechanism : –

 H2 O
R – C – OH + H     
||
O

H  N2
  

R NH H2O
H2O
|  
 R – N = C = O hydrolysis
  RNH + CO

2 2
OH  C  O
alkyl isocyanate

 OH 
R – C –Cl + NaN3    O

rearrangement
= C = N – R  RNH2 + CO2
||
O

2.7 From Acyl halide :

 R– C –N=N+ =N¯Reearrangement 
 2KOH + R–N=C=O
|| N2
O

R– NH2

Note : It is a good method for preparation of alkyl amine. Reaction is called ‘Curtius Reaction’.

2.8 From Alkanamide :

 R–NH2 + KBr + K2CO3 + H2O

Note : The reaction is called ‘Hoffmann Bromamide reaction’ discussed earlier.

2.9 By Alkyl cyanide (By reduction) :

LiAlH4
R–CN + 4H Na  R–CH –NH
Et OH 2 2
Note : When (Na + Et.OH) is used as reducing agent then reaction is called ‘Mandius Reaction’.

2.10 From Alkyl isocyanate (Alkaline Hydrolysis) :

R–N=C=O + 2KOH  R–NH2 + K2CO3

2.11 From Aldoxime (By Reduction) :

H H
| LiAlH4
| 2H
R– C =N–OH + 2H  
 R– C O R–CH –NH
– N – OH H2 2 2
| |
H H

NITROGEN COMPOUNDS [90]

2.12 From Phthalic acid :

 RI 2H O
      R–NH +
H2O HI 2

phthalic anhydride phthalimide N–alkyl phthalimide

Note : It is the best method for preparation of aliphatic amines. The reaction is called ‘Gabriel-Phthalimide
reaction’.

2.13 By reduction of Nitro compounds :

Nitro alkanes are reduced catalytically to primary amine.
(a) By LiAlH4

(b) By Metal and acid (commonly used Sn + HCl or Fe + HCl)

reduction
RNO2   RNH2 + 2H2O
4H

Note : (i) When reduction with metal is carried out in neutral solution e.g. with Zn dust & NH4Cl solution,
nitro compounds are converted into N-alkyl hydroxyl amine.
Zn 
RNO2  RNHOH + 2H2O
NH4Cl

N-alkylhydroxyl amine
(ii) When reduction of nitroalkane is carried out with SnCl2 and conc. HCl, a mixture of
N-alkyl hydroxyl amine and oxime are produced.
SnCl2 
RCH2NO2   RCH NHOH + RCH = NOH
2
conc . HCl

N-Alkyl hydroxy amine Oxime

3. PHYSICAL PROPERTIES

(a) Like ammonia, amines are polar compounds and except 3º amines can form intermoleculer H-
bonds that’s why they have higher boiling points.
(b) Unlike other organic compounds, amines are much more soluble in water. Because All amines
form a stronger H- bond with water.
(c) Solubility in water follow the order.
1º > 2º > 3º amine.
This is all due to H- Bonding.
(d) Boiling points of amines are lesser than alcohols and acids of comparable mol. weight. Because
H- bonding in amines is less pronounced in 1º and 2º than that in alcohols and carboxylic acids.
Because nitrogen is less electronegative than oxygen.
Thus every question regarding boiling point can be answered on the basis of H - bonding.
(e) Boiling points of 1º, 2º and 3º amines follow the order.
1º > 2º > 3º amine.

NITROGEN COMPOUNDS [91]

4. CHEMICAL PROPERTIES
(a) Almost all chemical properties and reactions of amines are governed by basicity of amines.
(b) A lone pair of electron on nitrogen atom in each of amines and ammonia makes them basic
in nature.
(c) Alkyl groups are electron releasing group which increases electron density on nitrogen atom
thus, we can expect the order of basicity of ammonia
1º , 2º and 3º amines to be
3º > 2º > 1º > ammonia
(d) Some other factors like steric effect, Solvation or hydration and mainly crowding on nitrogen
atom by three bulky alkyl groups, decreases the basicity of 3º amines to a great extent and
order follows -
R2NH > RNH2 > R3N > NH3
(2º) (1º) (3º) (ammonia)
(e) This can be also explained on basis of lesser capacity of 3º amine to form H- bonds with water
which stabilizes R2N+H on because it has only one H-atom

5. CHEMICAL REACTIONS
5.1 Alkylation :

LM R| OP
1
R1X R2 X R3 X
RNH2    RNHR    R – N – R    MMR  N  R PP X¯
HX 1 HX 2 HX 2

MN R| PQ
3

(quartenary amm. salts.)

5.2 Reaction with Grignard reagent : Since primary and secondary amines have active hydrogen, they
on reaction with Grignard reagent give alkanes
RNH2 + CH3MgBr   CH4 + RNH.MgBr
ether

R2NH + CH3MgBr   CH4 + R2N.Mg Br

ether

Note : Tertiary do not react because of absence of active hydrogen.

5.3 Reaction with Aldehydes and Ketone:

RNH2 +CH3CHO  RN = CHCH3 + H2O
(schiff’s base or anil’s base)

5.4 Acylation : 1º and 2º amines react with acetyl chloride or acetic anhydride to form acetyl derivatives.

R–NH2 + CH3COCl  RNHCOCH3 + HCl

R–NH2 + (CH3CO)2O  RNHCOCH3 + CH3COOH

(CH3)2NH + CH3COCl  (CH3)2N – COCH3 + HCl

Note : (a) Tertiary amines donot undergo this reaction because of absence of replacable H- atom.
(b) When Benzoyl chloride is used in place of acetyl chloride reaction is called ‘Schotten - Baumann’
reaction.

NITROGEN COMPOUNDS [92]

5.5 Oxidation : All three are oxidised in different ways depending upon conditions of oxidation.
(a) Primary Amine : Oxidised to aldehydes and ketones.
H2 O
RCH2NH2 [
O]
 R-CH =NH   R-CHO + NH3
KMnO 4

aldimine aldehyde
H2 O
R2CHNH2 [
O]
 R2C = NH   R2C = O + NH3
KMnO 4

ketimine ketone
(b) Secondary Amine :
2R2NH [
O]
 R2N-NR2
KMnO 4

(tetra-alkyl hydrazine)
R2NH  caro  R2N-OH
's acid

(dialkyl hydroxylamine)
(c) Tertiary Amine : Resistant to KMnO4 but oxidised by neutral and aqueous H2O2 in cold
to form trialkyl amine oxide.
Note: (i) NH2-NH2 is called hydrazine
(ii) NH2-OH is called Hydroxylamine

5.6 Salt formation: Amine forms salt with mineral acids

RNH2   HCl + –
 [RNH3] Cl
R2NH + HCl  [R2NH2]+ Cl¯
R3N + HCl  [R3NH]+ Cl¯
These salts may undergo dealkylation at higher temp.
For example : C2H5NH3+Cl–  
 C H Cl + NH
2 5 3

5.7 Reaction with HNO2 : This reaction distinguishes 1º, 2º and 3º alcohols.
(a) Primary Amime : Except methyl amine, reaction happens at ordinary temp. to evolve N2 Gas.
CH3CH2NH2 + HNO2CH3CH2OH + N2+ H2O
Methylamine reacts in different way:
CH3NH2 + 2HNO2 CH3-O-N = O + N2 + H2O
methyl nitrite
2CH3NH2+ 2HNO2 CH3-O-CH3 + 2N2+ 3H2O
dimethyl ether

(b) Secondary Amine : Form nitroso amines with HNO2 (No N2 gas is evolved)
R2NH + HNO2  R2 – N – N = O + H2O
(yellow)

Note : These nitroso amines formed, on warming with phenol and conc. H2SO4 give a brown or red colour
changing to blue or green on further addition of an alkali, colour changes to red . This test is called
Libermann’s nitroso test and used for identification of 2º amines.

(c) Tertiary Amine : These are inert to HNO2 but being basic in nature forms salts with it.
(CH3)3N + HNO2  (CH3)3 N - HONO

NITROGEN COMPOUNDS [93]

5.8 Reaction with water : Amine gives alkyl ammonium hydroxides which dissociate into ions-
RNH2 +H2O RNH3OH RNH3++ OH¯

5.9 Isocyanide test or Carbylamine reaction :

Primary amines when heated with chloroform and ethanolic KOH solution, alkyl isocyanides is produced
which have characteristic foul smell. This reaction is characteristic to the primary amine. This test is
known as carbyl amine test or isocyanide test.
RNH2 + CHCl3 + 3KOH RNC + 3KCl + 3H2O
The reaction proceeds via the formtion of dichloro carbene (:CCl2). In the absence of any lewis base
catalyst when HCCl3 reacts only with base, :CCl2 also produced, which is rapidly hydrolysed into CO,
HCO2¯ and Cl¯.

CHCl3 + OH  :CCl2 + H2O + Cl

(dichloro carbene)
 
RNH2 + :CCl2  R – N  C + 2HCl
(alkyl isocyanide)
OH 
:CCl2   CO + HCO  + 2Cl
H O 2 2

5.10 Reaction with Hinsberg reagent : This is a method for seperation of 1º , 2º and 3º amines Hinsberg
Reagent is
C6H5-SO2-Cl. (Benzene sulphonyl chloride)
RNH2 + Cl – SO2-C6H5  R-NH-SO2-C6H5 + HCl
(a) Primary amines form N—Alkyl benzene sulphonamide

  

(b) Secondary amines form N, N-dialkyl benzene sulphonamide



(c) Tertiary amines do not react because they do not possess a replacable Hydrogen atom.

5.11 Mustard oil reaction: A 1º amine reacts with CS2 and then with HgCl2 to form iso thiocyanate having
pungent smell of mustard oil.

HgCl
2RNH2 + S = C = S  2
 
 R – N = C = S + RNH2 + HgS +2HCl

alkyl isothiocyanate

NITROGEN COMPOUNDS [94]

5.12 Reaction with Nitrosyl chloride (TILDEN’S REAGENT) :
R–NH2 + NOCl  R-Cl + N2 + H2O

5.13 Reaction with Caro’s acid [H2SO5] :

With caro’s acid, the oxidation products of primary amine are also dependent on the nature of the alkyl
group present in the amine.
OH
RCH2NH2 O 
RCH2NHOH + RCH = NOH + R – C
by H SO 2 5 NOH
(N–alkyl (aldoxime) (hydroxamic acid)
hydroxyl amine)

O 
R2CHNH2 byH 
SO
R2C = NOH (ketoxime)
2 5

O 
R3CNH2 byH 
SO
R3CNO (nitrosoalkane)
2 5

CHEMICAL REACTION
Ex.6 The smell of mustard oil is given by the compounds -
(A) Carbylaminoalkane (B) RNCS
(C) RCNO (D) RCNS (Ans. B)
Sol. Alkyl isothiocyanate gives the smell of mustard oil.
Br2 / KOH
Ex.7 R  C  NH2   C 6H5COCl
 R–NH    R–NH – C – C6H5
2
|| ||
O O
The reactions involved in the above reaction sequence are -
(A) Stephen and Schotten Boumann (B) Hofmann and Schotten Boumann
(C) Hofmann and Cannizaro (D) Gabriel and Schotten Boumann
(Ans. B)
Ex.8 When 1-propane amine is treated with NaNO2 and HCl the products will be -
(A) 1-propanol, 2-propanol
(B) Propene
(C) 2-Chloropropane, 1-chloropropane
(D) All of these (Ans. D)
Sol. The products formed in the reaction between CH3CH2CH2NH2 and HNO2 are
1- Propanol, 2 propanol, propene,
1-Chloropropane and 2-chloropropane

6. SEPERATION OF MIXTURES OF AMINES

6.1 Hinsberg method :
This involves the treatment of the mixture with benzene sulphonyl chloride (Hinsberg Reagent) and
KOH.
(a) The primary amine forms N–alkyl benzene sulphonamide which forms a salt with KOH, which
is soluble in water.
H
 C6H5SO2 –N–R + HCl
N-alkyl benzene sulphonamide

NITROGEN COMPOUNDS [95]

 (b) The secondary amine gives N, N- dialkyl benzene sulphonamide which is insoluble in KOH
solution
(c) The tertiary amine does not react at all.

6.2 Hofmann method :

This involves the treatment of the mixture with diethyl oxalate.
(a) The primary amine forms a dialkyloxamide, which is a solid
(b) The secondary amine forms a dialkyl oxamic ester, which is an oily liquid.
(c) The tertiary amine does not react at all.

6.3 Fractional distillation :

The mixture of primary, secondary and tertiary amines, may be separated by fractional distillation
because their B.P’s. are quite different . This method is extensively used in industry.

CYANIDES, ISOCYANIDES, ALKYL NITRITES AND NITRO ALKANES

1.1 GENERAL CHARACTERISTICS :
(a) Compounds having the formula RCN are called alkyl cyanides or as nitriles of the acid which they
produce on hydrolysis.

(b) According to IUPAC system, cyanides are named as alkane nitriles, i.e., in the name of parent
hydrocarbon 'nitrile' is suffixed. In naming the hydrocarbon part, carbon of the — CN group is also
counted.
Formula As cyanide IUPAC name
CH3CN Methyl cyanide Ethane nitrile
(Acetonitrile)
C2H5CN Ethyl cyanide Propane nitrile
(Propiononitrile)
C3H7CN Propyl cyanide Butane nitrile
C4H9CN Butyl cyanide Pentane nitrile

(c) The compounds having the formula RNC are called isocyanide or isonitriles. The nomenclature of
isocyanides is similar to cyanides.
Formula As isocyanides IUPAC names
(Comman name)
CH3NC Methyl isocyanide Methylcarbylamine
(Methyl isonitrile) (Carbylamino methane)
C2H5NC Ethyl isocyanide Ethyl carbylamine
(Ethyl isonitrile) (Carbylamino ethane)
C3H7NC Propyl isocyanide Propyl carbylamine
(Propyl isonitrile) (Carbylamino propane)

(d) Isocyanides are also named as alkane isonitrile.

CH3NC Methane isonitrile
C2H5NC Ethane isonitrile
C3H7NC Propane isonitrile

NITROGEN COMPOUNDS [96]

(e) Hydrogen cyanide is known to exist as a tautomeric mixture. (Diad forms)
H—CN H— N C
Hence, it forms two types of alkyl derivatives which are known as alkyl cyanides and alkyl
isocyanides.
R — C  N R—N C
Alkyl cyanide Alkyl isocyanide

1.2 ALKYL CYANIDES

Methods of Preparation
(i) From alkyl halides : The alkyl cyanides are prepared by refluxing an alcoholic solution
of an alkyl halide with potassium cyanide. The disadvantage of this method is that a mixture
of nitrile and isonitrile is formed.
RX + KCN (or NaCN)   RCN + RNC
Alkyl halide Nitrile Isonitrile
(Major product) (Minor product)
(ii) From Grignard reagent : Grignard reagent reacts with cyanogen chloride to form alkyl
cyanides.

RMgX + ClCN    RCN +

Grignard Alkyl Cyanide

reagent

CH3MgBr + ClCN     CH3CN +

Methyl Cyanogen Methylcyanide

magnisium chloride
bromide
(iii) From acid amides : Pure nitriles are obtained by dehydration of acid amides with phosphorus
pentoxide. Amides are distilled with phosphorus pentoxide, P2O5.
P O
RCONH2 2 
5
 RCN
H2O

CH3CONH2  P2O 5 CH3CN + H2O


Acetamide Methyl cyanide
Industrially, alkyl cyanides are prepared by passing a mixture of carboxylic acid and ammonia
over alumina at 500°C.
Al O ,500C Al O
 23  
 2
3

 H2 O H2O

(iv) From primary amines : Primary amines are dehydrogenated when passed over copper
or nickel at high temperature to form alkyl cyanides. This is also a commercial method.
Cu or Ni
RCH2NH2  
500 C
RCN + 2H2
Primary amine

NITROGEN COMPOUNDS [97]

 Cu or Ni
CH3CH2NH2  
500 C
CH3CN + 2H2
Ethylamine Methyl cyanide
(v) From oximes : Aldoximes are converted into alkyl cyanides when distilled with phosphorus
pentoxide or acetic anhydride. The dehydration of aldoximes occurs.
H
| P2O 5
R  C  NOH  
H O
R — CN + H2O
2

Aldoxime Alkyl cyanide

1.3 Physical properties :
(a) Lower members containing upto 15 carbon atoms are liquids, while higher members of carbon
atoms in the molecule.
(b) Alkyl cyanides are neutral substances with pleasant odour, similar to bitter almonds.
(c) They are soluble in water. The solubility decreases with the increase in number of carbon atoms
in the molecule are solid.
(d) They are soluble in organic solvents.
(e) They are poisonous but less poisonous than HCN.
1.4 Chemical properties :
(i) Reaction with Grignard reagent : With Grignard's reagent, an alkyl cyanide forms a
ketone which further reacts to form a tertiary alcohol.
R' R'
| 2 H 2O
| OH
R—C  N + R'MgX R — C = NMgX   R — C = O + NH3 + Mg
X
R' R' R'
| | H 2O | OH
R— C = O + R" MgX  R — C — OMgX  R— C —OH + Mg
| | X
R" R"

Tertiary alcohol
(ii) Reduction : When reduced with hydrogen in presence of Pt or Ni, or LiAIH4 (Lithium aluminium
hydride) or sodium and alcohol, alkyl cyanides yield primary amines.
4H
RCN   RCH2NH2
Alkyl cyanide Primary amine
However, when a solution of alkyl cyanides in ether is reduced with stannous chloride and
hydrochloric acid and then steam distilled, an aldehyde is formed (Stephen's reaction).
SnCl2 / HCl H O
2
R — C  N    RCH = NH.HCl 
  RCHO  NH 4 Cl
2H
Imine hydrochloride Aldehyde

(iii) Hydrolysis : Alkyl cyanides are hydrolysed by both acid and alkalies. On partial hydrolysis
amides are formed while on complete hydrolysis acids are obtained.
H O 2 H O
RCN 2 RCONH2  RCOOH + NH
H  H 3
Alkyl cyanide Amide Acid
2 H O H O
CH3CN  CH CONH 2 CH COOH + NH
H 3 2 H 3 3
Methyl cyanide Acetamide Acetic acid

NITROGEN COMPOUNDS [98]

 (iv) Alcoholysis : When an alkyl cyanide is refluxed with an anhydrous alcohol in presence of dry
HCl, an imido ester is formed, which on hydrolysis with water forms ester.

  
 NH2 
 || 
H O
RCN + R'OH + HCl  R  C  OR' Cl 
2


Uses : Alkyl cyanides are important intermediates in the laboratory synthesis of a large number of
compounds like acids, amides, ester, amines, etc.

1.5 ALKYL ISOCYANIDES

Methods of Preparation
(i) From alkyl halides : The isocyanides are prepared by refluxing an alkyl halide solution in
alcohol with silver cyanide. The isonitrile is the main product but small amount of nitrile is also
formed.
R — X + AgCN  RNC + RCN
Alkyl halide Isocyanide Cyanide
(Isonitrile) (Nitrile)
Main product Minor product
CH3Cl + AgCN   CH3NC + CH3CN
Methyl chloride Methyl isocyanide
(Main product)
This method is, thus, suitable for preparing isocyanides.

(ii) From Primary Amines : (Carbylamine reaction) :Alkyl isocyanides may be prepared by
heating primary amines with chloroform and alcoholic potash.
RNH2 + CHCl3 + 3KOH  RNC + 3KCl+ 3H2O
Primary Chloroform Isocyanide
amine
(iii) From N-alkyl formamides : N-alkyl formamides when dehydrated with POCl3 in presence of
pyridine give isocyanides.
O
|| POCl
3
R — NH — C—  R — N
H   C
Pyridine
N-alkyl formamide Isocyanide
Physical properties :
(a) Alkyl isocyanides are colourless, unpleasant smelling liquids.
(b) They are insoluble in water but freely soluble in organic solvents.
(c) The boiling points of isonitiriles are lower than corresponding alkyl cyanides.
(d) Isonitriles are much more poisonous than isomeric cyanides.
Chemical properties :
(i) Hydrolysis : Alkyl isocyanides are hydrolysed by dilute mineral acids (but not by alkalies) to
form primary amines.

H
RN C + 2H2O 
 RNH2 + HCOOH
Alkyl isocyanide Primary amine Formic acid

NITROGEN COMPOUNDS [99]

 (ii) Reduction : When reduced with nascent hydrogen or hydrogen in presence of nickel, isocyanides
form secondary amines containing methyl as one of the alkyl groups.

R—N C + 4H  RNHCH3

Alkyl isocyanide Secondary amine
(iii) Action of heat : When heated for sometime at 250°C, a small amount of isonitrile changes
into isomeric nitrile.
RNC    RCN
heat

(iv) Addition reaction : Alkyl isocyanide give addition reactions due to presence of unshared
electron pair on carbon atom.
 
R : N :::C : or R — N  C
The following are some of the addition reactions shown by alkyl isocyanides.
RNC + X2 RNCX2 Alkyl iminocarbonyl halide
(Halogen)
RNC + S  RNCS Alkyl isothiocyanate
RNC + HgO  RNCO + Hg
(Alkyl isocyanate)
Distinction between Ethyl Cyanide and Ethyl Isocyanide

Et h yl C yan id e
Te s t Eth yl is o cyan id e ( C 2 H 5 NC )
(C 2 H 5 C N)

1 . Od o u r N o t u n p le a s a n t E xtre m e ly u n p le a s a n t
2 . S o lu b lity
S o lu b le In s o lu b le
in w a te r

3 . H yd ro lys is Yie ld s p ro p io n ic a cidP ro d u ce s e th yl a m in e

4 .R e d u ctio n G ive s p ro p yla m in e G ive s e th ylm e th yla m in e
(P rim a ry a m in e ) (S e co n d a ry a m in e )
5 .H e a tin g a t N o e ffe ct C h a n g e s to e th yl cya n id e
2 5 0 °C

CYNIDES AND ISOCYNIDES :

Ex.9 Alkyl halide reacts with AgCN to form –

(A) Alcohol (B) Cyanide (C) Isocyanide
(D) Both B & C
(Ans.D)
Sol. In the above reaction major product is Isocyanide and minor product is Cyanide.

Ex.10 Amide on heating with P2O5 gives –

(A) Alkane nitrile (B) Alkyl halide (C) Amine (D) None (Ans.A)
Sol. See text.

NITROGEN COMPOUNDS [100]

 SOLVED EXAMPLES
Ex.1 An example of a primary amine is -
(A) n-Propylamine (B) Isopropylamine
(C) t-Butyl amine (D) All of above (Ans.D)
Sol. All the compounds given above are examples of primary amine.

CH 3
|
CH 3  C NH 2
|
CH 3
t  butyl amine

O
||
Ex.2 For the elimination of  C group of amide following reaction is used -
(A) Hoffmann hypobromite reaction (B) Kolbe reaction
(C) Hunsdiecker reaction (D) Liebermann’s reaction (Ans.A)
Sol. For the formation of RNH2 from RCONH2, NaOH and Br2 are used as reagent. It is called Hofmann
hypobromite reaction.

Ex.3 Which of the following is hydrolysed to give secondary amine -

(A) Alkyl cyanide (B) (C) Nitro paraffins (D) Acid amide

(Ans.B)
Sol. The compound H-CO - N (CH3)2 on hydrolysis produces secondary amine .

+ H2O  

Ex.4 The structure of intermediate acetyl nitrene is -

(A) (B) (C) (D) CH3 – CO= N :

(Ans.C)
Sol. The structure of intermediate acetyl nitrene is CH3–CO–N. It is formed by the following reaction

Br
2
KOH

  
KOH
Ex.5 In hypobromite reaction of amide, carbonyl carbon atom is lost as -
(A) CO (B) CO2 (C) CO3–2 (D) None of above
(Ans.C)

NITROGEN COMPOUNDS [101]

Sol. In hypobromite reaction of amide, carbonyl carbon atom is lost as CO3–2 ion. The reaction takes
place as follows:
CH3CONH2 + Br2 + 4KOH  CH3NH2 + 2KBr + K2CO3 + H2O
K2CO3 is an ionic compound and ionizes as K+ and CO3–2 ions.

Ex.6 Which one of the following will give primary amine on hydrolysis-
(A) Nitroparaffins (B) Alkyl cyanide (C) Amide (D) Alkyl isocyanide
(Ans.D)
Sol. Alkyl isocyanide on hydrolysis produces a primary amine. The reaction takes place as follows.

CH3–NC 2H2 O
  
methyl isocyanide Hydrolysis

Ex.7 The correct set of the products obtained in the following reactions-
reduction
(1) RCN   (2) RCN (
i) CH3MgBr

(ii) H2O
hydrolysis HNO 2
(3) RNC    (4) RNH2  

The answer is-

1 2 3 4
(A) 2º Amine Methyl ketone 1º Amine Alcohol
(B) 1º Amine Methyl ketone 1º Amine Alcohol
(C) 2º Amine Methyl ketone 2º Amine Acid
(D) 2º Amine Methyl ketone 2º Amine Aldehyde (Ans.B)

Sol. The products of the reaction 1, 2, 3 and 4 respectively are : 1º amine, methyl ketone, 1º amine and
alcohol.

Ex.8 The reaction of an alkyl cyanide with sodium and alcohol to form an alkyl amine is known by the
name of -
(A) Mendius reaction (B) Hofmann’s reaction
(C) Gabriel reaction (D) Ammonolysis (Ans.A)
Sol. Cyanoalkanes are reduced to primary amines in the presence of Na and ethanol. It is called
Mendius reacion
R-C  N + 4[H] Na / C 2H5 OH
  RCH2–NH2
alkyl amine

Ex.9 Formaldoxime on reaction with Na/EtOH gives –

(A) 1º Amine (B) 2º Amine (C) 3º Amine (D) All above
(Ans.A)
Sol. Formaldoxime on reaction with Na/EtOH gives
1º amine. The reaction is representated as follows :
Na / EtOH
H–CH=N–OH  
4H
 CH NH + H O
3 2 2
formaldoxime methyl amine
This method is used for the preparation of primary amines.

NITROGEN COMPOUNDS [102]

Ex.10 Which of the following compounds on reduction gives an amine -
(A) Alkyl cyanide (B) Aldoxime (C) Alkyl isocyanide (D) All above
(Ans.D)
Sol. All the given compounds like alkyl cyanide, aldoxime, alkyl isocyanide on reduction gives an amine
4H
CH3–CN   CH3 CH2NH2
Sn /HCl
acetonitrile ethyl amine
CH3–CH=NOH  4
H
 CH3–CH2–NH2 + H2
H2 O

acetaldoxime ethyl amine

4H
CH3–NC   CH3–NH–CH3
Sn /HCl

methyl isocyanide dimethyl amine

(2º amine)

Ex.11 An alkyl amine is prepared by the following reaction -

RCOOH + N3H  Conc 
. H2 SO 4
 RNH2 + CO2 + N2
Name of the above reaction is :
(A) Schmidt reaction (B) Stephan’s reaction
(C) Schotton-Baumann reaction (D) Reimer- tiemann reaction (Ans.A)
Sol. The given reaction is represented as :
RCOOH + N3H  Conc . H2 SO 4
  RNH2 + CO2 + N2
alkanoic acid hydrazoic acid alkylamine
The above reaction is known as Schmidt reaction. This is an important method of preparing primary
amines.

Ex.12 N-Ethyl pthalimide on hydrolysis gives -

(A) Methyl alcohol (B) Ethyl amine
(C) Dimethyl amine (D) Diethyl amine (Ans.B)
Sol. N- ethyl pthalimide on hydrolysis forms ethylamine. It is called Gabriel phthalimide reaction. It is
an important method of preparing primary amines.

CO COOH
C2H5NH2
N–C2H5 + 2H2O  +
ethyl amine
CO COOH

N-ethyl phthalamide phthalic acid

Ex.13 Gabriel phthalimide reaction is used to prepare -

(A) Primary amine (B) Secondry amine
(C) Tertiary amine (D) All of above (Ans.A)

NITROGEN COMPOUNDS [103]

Sol. Gabriel phthalimide reaction is used to prepare primary amine.

KOH RI 2HOH(HCl)
    
KI

phthalimide N-alkyl phthalimide

R – NH2 + 

alkyl amine (1º) phthalic acid

Ex.14 Assign number 1 for least to 4 for most to indicate the relative base strength of the following-
I II III IV
C6H5NH2 p–NO2C6H4NH2 m–NO2C6H4NH2 p–CH3OC6H4NH2

I II III IV
(A) 2 3 1 4
(B) 1 2 3 4
(C) 2 3 4 1
(D) 4 1 2 3 (Ans.A)
Sol. p–NO2C6H4NH2 is the least basic due to electron withdrawing group at the p–position (in
conjugation with NH2 group) p–CH3OC6H4NH2 is the most basic due to interaction of lone pair
of electron on oxygen atom of –OCH3 group with the benzene ring. As such lone pair of electron
on –NH2 group is more available.

Ex.15 Which compound is soluble in water-

(A) [(CH3)2NH2]+ Cl– (B) [CH3NH3]+ Cl–
(C) [(CH3)3NH]+ Cl– (D) All the above (Ans.D)
Sol. Amines salt are soluble in water.

Ex.16 Which compound will liberate CO2 from NaHCO3 solution-

(A) CH3CO NH2 (B) CH3NH2 (C) (CH3)4 N+OH– (D) CH3N+H3Cl–
(Ans.D)
Sol. + –
The compound which will liberate CO2 from NaHCO3 solution is CH3N H3Cl . The reaction
takes place as follows:
CH3N+H3Cl– + NaHCO3 CH3–NH2+ NaCl + H2O + CO2
methyl amine methyl amine
hydrogen chloride

Ex.17 Which amine will not react with nitrous acid -

(A) Methyl amine (B) Ethyl amine
(C) Dimethyl amine (D) N, N Dimethyl ethane amine (Ans.D)
Sol. Primary and secondary amines react with HNO2, while tertiary amines do not react with HNO2.
Since N, N dimethyl ethane amine

NITROGEN COMPOUNDS [104]

 N – CH2 – CH3 is a tertiary amine, hence it will not react with HNO2.

Ex.18 Which gas will be evolved out when [CH3CH2NH2 + (CH3)2CHNH2] is treated with sodium
nitrite and HCl -
(A) Chlorine (B) Ammonia (C) Nitrogen (D) NO2 (Ans.C)
Sol. Primary amine and HNO2 produces nitrogen gas.
RNH2 + HNO2  ROH + N2 + H2O

Ex.19 Which of the following compound cannot be produced if 1-propane amine is treated with NaNO2 and
HCl -
(A) Propane -1-ol (B) Propane-2-ol
(C) 2-Chloropropane (D) 2-Propaneamine (Ans.D)
Sol. In the reaction,
CH3–CH2–CH2 and CH3–CH–CH3,
carbonium ions are formed.
As such 1-propanol, 2-propanol, 2-chloro-propane, 1-chloropropane and propene are the products
while 2-propaneamine is not obtained.

Ex.20 In the following sequence of reactions the product B, will be

NaNO 2
C2H5MgBr  CINH
 2
 A   B
HCl

(A) C2H5OH (B) C2H5NO2 (C) C2H2 (D) All of the above
(Ans.A)
Sol. In the given sequence of reactions, the product B, will be ethanol. The reaction takes place as
HONO
C2H5MgBr  CINH
 2
 C2H5NH2    C H OH + N + H O
NaNO /HCl 2 5 2 2
MgBrCl 2

‘B’
Ex.21 Which set of the following compounds on reaction with an alkyl amine gives schiff’s base :
(A) HCHO, C6H5CHO, CH3CHO (B) HCHO, NH2OH, NH2 - NH2
(C) CH3CHO, NH2OH, NH2-NH2 (D) CH3COCH3, C2H5OH (Ans.A)

Sol. The aldehydes e.g. HCHO, C6H5CHO and CH3CHO on reaction with alkylamine gives schiff’s
base
C6H5CHO + H2NCH3    C6H5CH = N - CH3 + H2O
benzaldehyde methylamine schiff’s base
Ex.22 Which of the following does not give a sulphur compound with a 1º amine -
(A) Hinsberg reaction (B) Mustard oil reaction
(C) Schotton - Baumann reaction (D) Con. H2SO4 (Ans.C)
Sol. In Schotton - Baumann reaction a sulphur compound is not produced with a 1º amine
NaOH
R – NH2 + Cl – CO – C6H5    R– NHCOC6H5 + HCl
alkyl amine benzoyl chloride N-alkyl benzamide

NITROGEN COMPOUNDS [105]

Ex.23 Ethylamine on oxidation with acidified KMnO4 gives-
(A) Acetaldehyde (B) Ethylamine oxide
(C) Ethanol (D) Acetamide (Ans.A)
Sol. Oxidation of ethylamine gives acetaldehyde.

Ex.24 Mustard oil reaction is given by -

(A) Primary amine (B) Urea (C) Secondary amine (D) Acid amide
(Ans.A)
Sol. Mustard oil reaction is given by primary amine. It is known as Hoffmann’s mustard oil reaction
R – NH2 + S = C = S + HgCl2  R – N = C = S + HgS + 2HCl
alkyl isothiocyanate
This compound alkyl isothiocyanate has a smell resembling that of mustard oil.

Ex.25 Which of the following compounds has a smell of mustard oil

(A) Alkyl cyanate (B) Alkyl thiocyanate
(C) Alkyl isothiocyanate (D) alkyl isocyanate (Ans.C)
Sol. A primary amine condenses with CS2 in the presence of HgCl2 to form an alkyl isothiocyanate.
This compound has a smell resembling that of mustard oil. It is called as Hofmann’s mustard oil
reaction
R – NH2 + S = C = S + HgCl2  R – N = C = S + HgS + 2HCl
alkyl amine alkyl isothiocyanate

Ex.26 Which of the following amine does not react with Hinsberg reagent -
(A) Neopentyl amine (B) Isopropyl amine
(C) Triethyl amine (D) Ethyl methyl amine (Ans.C)
Sol. Triethyl amine is tertiary amine. It does not react with Hinsberg reagent.

Ex.27 In which of the following sequence of reaction the end product does not exhibit tautomerism-
(A) CH3CH2NH2 NOCl
 AgNO 2
   (B) (CH3)2CHNH2 
NOCl AgNO 2
  
(C) (CH3)3CNH2 
NOCl AgNO 2
    (D) CH3CH(NH2)C2H5  NOCl AgNO 2
   
(Ans.C)
Sol. rd
In the 3 reaction sequence the end product is a 3º nitro compound.
(CH3)3CNO2 It does not have -hydrogen as such tautomerism is not possible.

Ex.28 The acid used for the determination of molecular weights of amines is -
(A) H2PtCl6 (B) Picric acid (C) HAuCl4 (D) H2SO4 (Ans.A)
Sol. The acid used is H2PtCl6. It is a solution of platinic chloride, Pt Cl4 in con.HCl
2R-NH2 + H2 [PtCl6]  [R NH3]2+ [PtCl6]–2
alkylamine platinichloride
Chloroplatinates on ignition leave a residue of metallic Pt. This reaction is employed in determining
molecular weight of amines.

NITROGEN COMPOUNDS [106]

Ex.29 Methyl amine on reaction with chlorine in the presence of NaOH gives-
(A) Chloroform
(B) Methyl chloride
(C) N-Methyl chloramine
(D) Chloramine (Ans.C)
Sol. Methyl amine reacts with Cl2 in the presence of NaOH undergoes a substitution of a H-atom of
amino group by a Cl group and N-methyl chloramine is formed.
NaOH
CH3NH2 + Cl2    CH3–NHCl
NaCl, H2 O

N-methyl chloramine

NITROGEN COMPOUNDS [107]

 EXERCISE–I
Q.1 Amide on heating with P2O5 gives –
(A) Alkane nitrile (B) Alkyl halide (C) Amine (D) None

Q.2 Mendius reaction involves the reduction of -

(A) Cyanoalkanes (B) Alkyl isocyanides (C) Oximes (D) Nitroalkanes

H2O
Q.3 CH3CONH2 PCl
 5
 A  B
(partial)

 reduction
C
The functional groups of B and C respectively are -
(A) – C –NH2, –NH2 (B) – C –NH2, –COOH
|| ||
O O

(C) –CN, –NH– (D) – C –OH, – N –

|| |
O

Q.4 KOH
  A CH
3Br
 B HOH
 C + D , C and D in the sequence are -

H

(A) Benzoic acid + aniline (B) Phthalic acid + ethylamine

(C) Phthalic acid + aniline (D) Benzoic acid + ethylamine

Q.5 Which of the following would undergo Hoffmann bromide reaction to form primary amine-
(A) RCONHCH3 (B) RCOONH4 (C) RCONH2 (D) RCONHOH

Q.6 A reaction used in descending a homologous series would be -

(A) RCONH2 + Br2 + KOH (B) RCH2Cl + KCN
(C) RNH2 + CHCl3 + KOH (D) None of the above

Q.7 In Hofmann degradation of amide the correct order of reagent is-

(A) Br2, KOH, H2O (B) KOH, Br2, H2O
(C) H2O, KOH, Br2 (D) None of the these

Q.8 Alkyl halide reacts with AgCN to form –

(A) Alcohol (B) Cyanide (C) Isocyanide (D) Both B & C

Q.9 In the reaction sequence identify the functional group present in A, B, C

Sn / HCl HNO2 C2H5OH
A   B 
o
 C   C6H6 -
0 C

(A) NO2, NH2, N=N (B) NO2, NH2, OH (C) –OH -NH2, -NO2 (D) –NH2, -NO2, –N=N

NITROGEN COMPOUNDS [108]

 NaOH
Q.10 CH3CH2CONH2 
Br2
 A

Aqueous solution of A :
(A) Turns blue litmus to red (B) Turns red litmus to blue
(C) Does not effect the litmus’ (D) Decolourise the litmus
Q.11 Amines are basic in nature because-
(A) They produce OH¯ ions when treated with water
(B) They have replaceable H atoms on N atoms
(C) They have lone pair of electron on N atom
(D) None of these

Q.12 Minimum boiling point would be of :

(A) Ethylmethyl amine (B) Ethyl.amine (C) n-Propyl amine (D) Trimethylamine

Q.13 A mixture of 1º, 2º and 3º amine is formed in the reaction-

(A) 1º Amide + caustic potash + bromine (B) Methyl halide and ammonia
(C) Cyclic imide + H3O + (D) Alkyl isocyanide + H2

Q.14 The presence of primary amines can be confirmed by-

(A) Reaction with HNO2 (B) Reaction with CHCl3 and alc. KOH
(C) Reaction with Grignard reagent (D) Reaction with acetyl chloride

Q.15 C2H5NH2 cannot be prepared by the reduction of-

(A) C2H5NO2 (B) CH3CH=NOH (C) C2H5NC (D) CH3CN

Q.16 Tilden’s reagent is-

(A) C6H5SO2Cl (B) NOCl (C) CINH2 (D) (C2H5)2 Zn

Q.17 Acetonitrile has the structure :

(A) C2H5NC (B) C2H5CN (C) CH3NC (D) CH3CN

Q.18 The compound obtained by the reaction between primary amine and aldehyde is-
(A) An amide (B) Imine (C) Nitrite (D) Nitro

R
Q.19 R´–N is a-
R’’
(A) Mixed 3º amine (B) Unsymmetrical amine
(C) Both 1st and 2nd (D) Quartenary salt

Q.20 The alkanenitriles are isomeric with-

(A) Primary alkanamines (B) Secondary alkanamines
(C) Alkyl isocyanides (D) Nitroalkanes

NITROGEN COMPOUNDS [109]

Q.21 Which of the following is obtained by reducing methyl cyanide with Na + C2H5OH -
(A) Methyl alcohol (B) Acetic acid (C) Ethyl amine (D) Methane

Q.22 Which of the following is optically active amine-

(A) CH3NH2 (B) CH3NHCH3
(C) (D) Secondary butylamine

Q.23 Ethyl iodide on reaction with potassium nitrite gives –

(A) Ethyl nitrite (B) Nitro ethane (C) Amine (D) Acid

Q.24 Ethylamine can be prepared by the all except -

(A) Curtius reaction (B) Hoffmann reaction
(C) Mendius reaction (D) Reduction of formaldoxime

Q.25 Fast heating of urea yields :

(A) Cyanuric acid (B) Carbamic acid (C) Parabanic acid (D) Barbituric acid

Q.26 The basic character of amines can be explained-

(A) In terms of Lewis and Arrhenius concept
(B) In terms of Lowry and Bronsted concept
(C) In terms of Lewis and Lowry Bronsted concept
(D) Only by Lewis concept

Q.27 Which of the following diazonium salt is relatively stable of 0-5ºC -

(A) CH3–NN} Cl¯ (B) CH3–C(CH3)–NN} Cl¯
(C) C6H5–NN} Cl¯ (D) (CH3)3C–NN} Cl¯

Q.28 Lowest boiling point will be of the compound-

(A) Ethylamine (B) Ethylmethylamine
(C) 1-Propaneamine (D) N,N-Dimethylmethanamine

Q.29 Which of the following compound gives the smell of mustard oil-
(A) Alkyl isocyanate (B) Alkyl isothiocyanate
(C) Alkyl isocyanide (D) Alkyl isonitrile

Q.30 The odour of alkyl cyanides is similar to –

(A) Bitter almonds (B) Acid (C) Fruity smell (D) None

NITROGEN COMPOUNDS [110]

 EXERCISE–II
Q.1 Reaction :
Primary amine + CHCl3 + KOH  product, here product will be - [AIEEE-2002]
(A) Cyanide (B) Isocyanide (C) Amine (D) Alcohol

Q.2 The compound formed in the positive test for nitrogen with the Lassaigne solution of an organic compound
is - [AIEEE-2004]
(A) Fe4[Fe(CN)6]3 (B) Na3[Fe(CN)6] (C) Fe(CN)3 (D) Na4[Fe(CN)5NOS]

Q.3 Which one of the following methods is neither meant for the synthesis nor for separation of amines ?
[AIEEE-2005]
(A) Hofmann method (B) Hinsberg method (C) Curtius reaction (D) Wurtz reaction

Q.4 Reaction of cyclohexanone with dimethylamine in the presence of catalytic amount of an acid forms a
compound if water during the reaction is continuously removed. The compound formed is generally
known as – [AIEEE-2005]
(A) an enamine (B) a Schiff's base (C) an amine (D)an imine

Q.5 In the chemical reaction, CH3CH2NH2 + CHCl3 + 3KOH  (A) + (B) + 3H2O, the compounds (A)
and (B) are respectively – [AIEEE-2007]
(A) C2H5CN and 3KCl (B) CH3CH2CONH2 and 3KCl
(C) C2H5NC and K2CO3 (D) C2H5NC and 3KCl

Q.6 The reaction

CH3Br + NH3(excess) heat  CH3NH2+HBr
is an example of a–
(A) bimolecular electrophilic substitution reaction
(B) unimolecular nucleophilic substitution reaction
(C) bimolecular nucleophilic substituion reaction
(D) bimolecular free radical substitution reaction

Q.7 A secondary amine is a compound which possesses–

(A) two–NH2 groups
(B) one–NH2 group attached to a secondary carbon
(C) one–NH–group bonded to two alkyl or aryl groups
(D) one–NH2 group attached to the second carbon of the main carbon chain

Q.8 The IUPAC name of the compound

N
is–

(A) N,3-dimethyl-N-propyl-3-propanamine (B) N-methyl-N-propyl-2-butanamine

(C) s-butylmethyl-n-propylamine (D) N, 1-dimethyl-N-propyl-propanamine

NITROGEN COMPOUNDS [111]

Q.9 How many molecules of methyl bromide should react with ethylamine successively to convert the latter
into a quaternary ammonium salt ?
(A) One (B) Two (C) Three (D) Four

Q.10 Which of the following compounds on hydrolysis yields a carboxylic acid and a secondary amine ?
(A) CH3CH2NC (B) CH3CONHCH3 (C) PhNHCOCH3 (D) Ph C ONPh
|
CH 3

Q.11 The end product (B) formed in the reaction

AgCN
CH3CH2Br   A 1
. NaOH , prolonged heat
   B is–

H 3O

(A) CH3CH2NHCH3 (B) CH3CH2CH2NH2 (C) CH3CH2NH2 (D) CH3CH2NHCOH

Q.12 Which of the following compounds possesses a chiral nitrogen atom ?

(A) CH 3CH 2 C HCH 3 (B) CH3CH2NHCH2CH3

|
NH 2

(C) CH 3CH 2CH 2 N CH 2CH 3 (D) CH 3CH 2 N CH 2 CH 3

| |
NH 2 CH 3
Q.13 An amine (X) on being heated with an excess of methyl bromide produces diethyldimethylammonium
bromide. The amine (X) is–
(A) C2H5NH2 (B) (C2H5)2NH (C) C2H5NHCH3 (D) C2H5N(CH3)2

Q.14 Which one of the following compounds will produce a water-insoluble yellow oily liquid of nitrosamine
on reaction with NaNO2 and dilute HCl at 0ºC ?
(A) Ethylamine (B) Methylamine (C) Diethylamine (D) Triethylamine

Q.15 Which of the following compounds will liberate CO2 from NaHCO3 ?
(A) CH3CONH2 (B) CH3CH2NH2 (C) CH3NH3+Cl– (D) (CH3)4N+OH–

Q.16 The reaction of RCONH2 with a mixture of Br2 and aqueous KOH gives RNH2 as the main product.
The intermediate(s) involved in this reaction is(are)–
–
(A) RCONHBr (B) RCO N BrK+ (C) R–N=C=O (D) All of these

Q.17 The end product (B) formed in the reaction

1. Br2 CCl 4
CH2=CH2     A 1 . LiAIH 4
   B
2. KCN ( excess) 
2. H 3O

(A) CH2=CHCH2NH2 (B) H2N(CH2)4NH2

(C) CH3NH(CH2)2NHCH3 (D) NC(CH2)2CN

Q.18 In which of the following compounds are intermolecular hydrogen bonds not formed among its
molecules ?
(A) (C2H5)2NH (B) C2H5OH (C) C2H5COOH (D) (C2H5)3N

NITROGEN COMPOUNDS [112]

Q.19 Among the following compounds which one will produce a Schiff base on reaction with cyclohexanone?

NHCH3 NH2 N(CH3)2

(A) N (B) (C) (D)
H

Q.20 Which of the following reactions does not yield an amine ?

Na
(A) RX + NH3  (B) RCH=NOH  
C H OH 2 5

H 
1. LiAlH 4
(C) RCN + H2O 
 (D) RCONH2 2. 
H O


2

Q.21 The product (A) and (B) of the reaction

CH3CH2NH2 + CH3MgBr  A + B
are–
(A) CH3CH2CH3 and NH2MgBr (B) CH3CH2NHCH3 and MgBr2
(C) CH3CH2N(CH3)2 and MgBr2 (D) CH3CH2NHMgBr and CH4

Q.22 Which nitrogen is protonated readily in guanidine ?

2
NH
1
HN=C 3 2
NH 2
(A) 1 (B) 2 (C) 3 (D) All of these

Q.23 Which of the following statements is not correct regarding ethylamine and aniline ?
(A) Each has a –NH2 group
(B) Both dissolve in HCl
(C) Each reacts with a mixture of CHCl3 and KOH to form a bad smelling compound
(D) Each reacts with HNO2 to give a hydroxy compound

Q.24 Which of the following is most basic ?

NH2
(A) (B) (C) (D) N
N NH2 H

Q.25 A compound (X) having the molecular formula C3H9N reacts with benzenesulphonyl chloride to form
a solid that is insoluble in alkalis. The compound (X) is–
(A) CH3CH2CH2NH2 (B) (CH3)2CHNH2
(C) CH3CH2NHCH3 (D) (CH3)3N

Q.26 Which of the following may be prepared by Gabriel phthalimide synthesis ?

(A) Aliphatic amines (B) Aromatic amines (C) Aliphatic amides (D) Aromatic amides

NITROGEN COMPOUNDS [113]

Q.27 When an organic compound was treated with sodium nitrite and HCl in the ice-cold condition, nitrogen
gas was evolved. The compound is :
(A) a nitro compound (B) a primary amine (C) a secondary amine(D) a tertiary amine

Q.28 Primary amines on being heated with CS2 in the presence of HgCl2 form alkyl/aryl isothiocyanates.
The reaction is known as–
(A) Hofmann hypobromite reaction (B) Hofmann elimination reaction
(C) Hofmann-Martius reaction (D) Hofmann mustard oil reaction

Q.29 -amino acids on heating with Ba(OH)2 gives:

(A) Ba salt of acid (B) Amine (C) -hydroxy acids (D) None of these

Q.30 R–Cl + NH3 (excess)  (X) (major product), the major product (X) is a :
(A) 1° amine (B) 2° amine (C) 3° amine (D) 4° ammonium salt

NITROGEN COMPOUNDS [114]

 ANSWER KEY

EXERCISE–I
Q.1 A Q.2 A Q.3 A Q.4  Q.5 C Q.6 A Q.7 A
Q.8 D Q.9 A Q.10 B Q.11 C Q.12 D Q.13 B Q.14 B
Q.15 C Q.16 B Q.17 D Q.18 B Q.19 C Q.20 C Q.21 C
Q.22 C Q.23 A Q.24 A Q.25 A Q.26 C Q.27 A Q.28 A
Q.29 B Q.30 A

EXERCISE–II
Q.1 B Q.2 A Q.3 D Q.4 A Q.5 D Q.6 C Q.7 C
Q.8 B Q.9 C Q.10 D Q.11 C Q.12 C Q.13 D Q.14 C
Q.15 C Q.16 D Q.17 B Q.18 D Q.19 C Q.20 C Q.21 D
Q.22 A Q.23 C Q.24 C Q.25 C Q.26 C Q.27 D Q.28 D
Q.29  Q.30 A

NITROGEN COMPOUNDS [115]

 AROMATIC COMPOUNDS
Benzene
[i] Aromatic compounds contain high percentage of carbon. They burn with smoky flame,
[ii] Aromatic compounds have the cyclic system and contain (4n + 2) electrons [Huckel rule].
Where n = 0, 1, 2, 3, .............
Dipropylcyclopropenium n=0 2–electron
perchlorate
Benzene, pyridine, pyrrole, n=1 6–electron
Furan, thiophen etc.
Napthalene n=2 10–electron
Anthracene n=3 14–electron

Aromatic Compounds : Main Source

Bituminous coal when subjected to destructive distillation in the absence of air [1000º–1200ºC] the
chief constituent obtained is coal tar.
Fractional distillation of coal tar : Different fractions are :

Fraction Temperature Main constituents

(a) Light oil 80 – 170ºC Benzene, toluene, xylene etc.

(b) Middle oil 170º – 230ºC Naphthalene,
(carbolic oil) Phenol etc.
(c) Heavy oil 230º 270ºC Cresols, naphthalene
(d) Green oil 270º – 360ºC Anthracene

Benzene
[i] Discoverer : Michael Faraday [ii] C–hybridisation : sp2
[iii] Geometry – Hexagonal [iv] Bond angle : 120º
[v] C–C Bond length : 1.39Å [vi] C–H Bond length : 1.09 Å

Methods of Preparation of Benzene :

[1] Isolation From ‘Light Oil Fraction – Industrial method :
[2] Decarboxylation of Sodium Benzoate – Laboratory Method :
Benzene is formed on dry distillation of sodium benzoate with soda lime.
Dry distillation
C6H5COONa + NaOH   C6H6 + Na2CO3
Dry distillation
[3] Reduction of Phenol : C6H5OH + Zn   C6H6 + ZnO

[4] Hydrolysis of Benzene sulphonic Acid : C6H5SO3H + H2O (steam)  
dil.H Cl
 C6H6 + H2SO4
[5] Reduction of Benzenediazonium Chloride :
C6H5N2Cl + C2H5OH C6H6 + CH3CHO + N2 + HCl
Hypophoshorus acid (H3PO2) or sodium stannite (SnCl2 + NaOH) or formic acid can also be used for
reduction in place of ethanol.
C6H5N2Cl + H3PO2 + H2O C6H6 + H3PO3 + N2 + HCl

AROMATIC COMPOUNDS [116]

 SnCl2
C6H5N2Cl + 2H 
NaOH
 C6H6 + N2 + HCl

C6H5N2Cl + HCOOH C6H6 + CO2 + N2 + HCl

[6] Hydrolysis of Phenylmagnesium bromide :

C6H5MgBr + H2O C6H6 + Mg(OH)Br

[7] Reduction of Chlorobenzene :

Ni / Al
C6H5Cl + NaOH + 2H   C6H6 + NaCl + H2O

[8] Trimerisation of Acetylene :

Ni(CO)4 (C6H5 )3 P
3C2H2   C6H6
In benzene

[9] Hydroforming of n–Hexane :

CH3(CH2)4CH3 
Heavy metal oxides
 C6H6 + 4H2
500º

Physical Properties :
Benzene is a colourless liquid (boiling point, 80º), having a characteristic smell. It forms a colourless
crystaline solid (melting point, 5.4º) on cooling. It burns with smoky or sooty flame. It is lighter than
water (relative density, 0.8790) and is immiscible with water. Being nonpolar in nature. It is miscible with
many organic solvents, like alcohol ether, acetone, acetic acid, carbon tetrachloride, carbon disulphide,
etc.
Reaction :
Benzene is a compound having very low reactivity, because it remains unaffected by many common
reagents, like HCl, KOH, NaOH, KMnO4, K2Cr2O7, etc.
Benzene shows the following types of reactions :
[a] Addition
[b] Electrophilic substitution
[c] Oxidation

Addition Reaction :
1. Halogenation :

hv
+ 3Cl2  

Benzene hexachloride is also known by many other names e.g., B.H.C., gammaxene, gammane,
lindane 666 (triple six) and 1,2,3,4,5,6–hexachlorocyclohexane. It was found that the  isomer is a
very strong insecticide and pesticide, hence the names gammaxene and gammane.

AROMATIC COMPOUNDS [117]

2. Hydrogenation

2 3H

Ni / Pt / Pd

3. Ozonolysis :

+ 3O3 3 + 3H2O2

3H2O2 + 3Zn 3ZnO + 3H2O

Electrophilic Substitution :
A continuous  cloud is spread above and below the benzene ring. Due to this, an electrophile is attracted
towards the benzene ring. This electrophile removes proton (the weaker electrophile) and take its place
in order to gain greater stability and forms an electrophilic substitution product or SE product. This
process is called aromatic electrophilic substitution.

Nonaromatic intermediate carbocation formed in an aromatic electrophilic substitution reaction is known

as Wheland intermediate.
Mechanism of Aromatic SE reaction :
H
H E
H H H + H
+
+E
Slow
H H H H
H H
Cyclic Secondary carbocation

Cyclic secondary carboncation formed is established by resonance.

H E H E H E
H + H H H H + H

H H H + H H H
H H H
E
H E
H + H +
—H
Fast
H H
H

This is called as SE2 mechanism i.e.; substitution electrophilic bimolecular reaction.

AROMATIC COMPOUNDS [118]

4. Nitration :
NO2 NO2 NO2
| | |
  
NO2 NO2 NO2
<60º >60º Fummg H2SO4
 
–H Nitrobenzene –H O2N 100º O2N NO2
m-Dinitrobenzene  1,2,3-Trinitrobenzene (TNB)
–H

5. Halogenation :

Cl–Cl + AlCl3

6. Sulphonation :
H2SO4 SO3 + H2O
(Conc.)

– 
H SO3 + H SO3H
| | |
+ SO3

80º

Benzenesulphonic acid

7. Friedel–Crafts Reaction :
Friedel–Crafts reaction involves replacement of hydrogen atom of an aromatic ring by a carbocation
species obtained from a compound in the presence of anhydrous aluminium chloride. Fridel–Crafts
reaction is always carried out in nitrobenzene (boiling point. 211º) medium and in the presence of anhydrous
AlCl3.

[i] Friedel-Crafts Alkylation :

Anhyd. AlCl
3  C H – CH  HCl
C6H6  CH3 – Cl  6 5 3
Methyl chloride Toluene

Anhyd. AlCl
3  C H – C H  HCl
C6H6  C2H5 – Cl  6 5 2 5
Ethylbenzene

Anhyd. AlCl3
C6H6  CH3CH2CH2 – Cl   C6H5 – CH(CH3 )2  C6H6 – CH2 CH2CH3
nPr opyl chloride Cumene (67%) n Pr opylbenzene (33%)

Note : A mixture of cumene and n–propylbenzene is also obtained on taking propylene in place of n–propyl
chloride in the above reaction. because intermediate 1º carbocation rearrange to give 2º carbocation
Anhyd.
2C6H6 + CH2Cl2   C6H5 – CH2 – C6H5  2HCl
AlCl3
Diphenylmethane

Anhyd.
3C6H6 + CHCl3 
AlCl3
 (C6H5 )3 CH + 3HCl
Triphenylmethane
[ii] Friedel–Crafts Acylation : (reaction with acyl chloride)

AROMATIC COMPOUNDS [119]

[a] Acetylation :
C6H6 + ClCOCH3 Anhyd.AlCl3
  C6H5 COCH3 + HCl
Acetyl chloride Acetophenone

Anhyd.AlCl3
C6H6 + (CH3 CO)2 O   C6H5 COCH3 + CH3COOH
Acetic anhydride Acetophenone

[b] Benzoylation :
Anhyd.AlCl3
C6H6 + ClCOC6H5   C6H5 COC6H5 + HCl
Benzoyl chloride benzophenone

Anhyd.AlCl3
2C6H6 + ClCOCl   C6H5 COC6H5 + 2HCl
Benzene Phosgene Benzophenone
(Excess)

The above conversions can be carried out by taking many other compounds in place of anhydrous
AlCl3, e.g., FeCl3, FeBr3, SnCl2, ZnCl2, BF3, etc.

8. Mercuration :
Benzene on heating with mercuric acetate forms Acetoxymercuribenzene.
CH3COO
Hg + H–C6H5 CH3COOH +
CH3COO CH3COOHg–C6H5
Phenylmercuric acetate
(Acetoxymercuribenzene)

Oxidation :
9. Catalytic Air Oxidation :
Oxidation of benzene by air in the presence of vanadium pentaoxide can be carried out as follows :
[i] At 300º – Phenol is obtained as the major product
H OH
| |
VO
2 5
+ [O] 
300º
Phenol

[ii] At 450º – Maleic anhydride is obtained as the major product.

O

VO
2 5
+ 9[O]  O + 2CO2 + 2H2O
450º

O
Maleic anhydride

10. Silver Oxide Oxidation :

Mainly p-benzoquinone is formed when oxidation of benzene is carried out by silver oxide and HNO3.
O
||
Ag O
2 
+ 3[O]  + H2O
HNO3
||
O
p-Benzoquinone

11. Combustion :
2C6H6  15O2 12CO2  6H2 O

AROMATIC COMPOUNDS [120]

Catalytic Pyrolysis :
When the vapours of benzene are passed through red-hot copper or iron tube at 600º biphenyl is
formed.
C6H5–H + H–C6H5 C6H5–C6H5 + H2

Uses of Benzene :
[1] As an industrial solvent. [2] In dry cleaning.
[3] As a constituent of power alcohol. [4] In the manufacture of an insecticide and pesticide.
[5] In the manufacture of an explosive. [6] In the manufacture of dyes.
[7] In the manufacture of medicines. [8] In the manufacture of perfumes.
[9] In the synthesis of many aromatic compounds. [10] As a fuel.

TOLUENE
Toluene, C6H5CH3

INTRODUCTION

(a) When a methyl group is directly attached with benzene ring, the compound is called Toluene.
(b) Toluene is a higher homologue of benzene.
(c) It can be obtained by the light oil obtained from distillation of 'Coal-tar'.
(d) Toluene is the compound, which is more reactive than benzene in chemical reactions.

Methods of Preparation
1. From ‘Light Oil’ Fraction – Industrial Method :
Toluene fraction can be collected by distillation at 110º after separation of benzene from 90% benzol.
2. By Hydroforming of n–Heptane :

Heavy metal CH3

CH3(CH2)5CH3 oxides + 4H2

500º

3. By Dehydroxylation of Cresols :
Dry distillation
CH3 – C6H4 – OH  Zn   CH3–C6H5 + ZnO
Cresol (o, m or p)

4. By Friedel–Crafts Methylation of Benzene :

AlCl3
C6H5–H + Cl–CH3   C6H5–CH3 + H–Cl

5. From Wurtz–Fitting reaction :–

A mixture of aryl & alkyl halide reacts in ether solution with sodium and forms toluene.

AROMATIC COMPOUNDS [121]

 anhy. ehter
   

6. By Decarboxylation of Toluic Acids :

CaO
CH 3 – C6H4 – COONa  NaOH   CH –C H + Na CO
Dry distillation 3 6 5 2 3
Sodium toluate
(o, m or p)

7 From Grignard's reagent :–

Phenyl magnesium iodide reacts with pure methyl iodide and forms toluene.

CH3 + Mg I2

8. By Hydrolysis of Toluene Sulphonic Acids :


CH3 – C6H4 – SO3H  HOH  CH –C H + H SO
Toluene sulphonic acids
Conc. acid 3 6 5 2 4
(o, m or p)

9. By Reduction of Benzyl Chloride :

C6H5–CH2Cl + 2H C6H5–CH3 + HCl

10. By Reduction of Toluenediazonium Chlorides :

CH3 – C6H4 – N2Cl  2H C6H5–CH3 + N2 + HCl

Toluenediazonium chlorides
(o, m or p)

Ethanol, hypophoshorous acid (H3PO2), sodium stannite (SnCl2 + NaOH) or formic acid can be used
as the reducing agents.
6.2 Physical Properties :
Toluene is a colourless liquid (boiling point 111º). It has benzene–like smell. It is lighter than water and
immiscible with water. It is miscible with organic solvents, like alcohol, ether, benzene, etc. It also burns
like benzene with smoky and sooty flame.

Chemical Propertes :
Toluene mainly gives four type of reactions :–
1. Addition reactions
2. Ring substitution reactions
3. Side chain substitution reaction
4. Oxidation reactions

AROMATIC COMPOUNDS [122]

Addition reaction (Reactions Due to Benzene Nucleus ):
1. Catalytic Hydrogenation :
Ni / Pt CH3
CH3 + 3H2  

Methylecyclohexane

2. Sulphonation :

CH3 CH3 CH3

| | SO2OH |
Conc.
H2SO4
 +
o-Toluene sulphonic |
acid SO2OH
p-Toluene sulphonic
acid

3. Nitration :

CH3 CH3 CH3

CH3 | | CH3 |
| NO2 | O2N NO2
NO2
H SO
2 4 2 H SO
4 2 H SO
4

HNO3 + 
HNO3

HNO3
o–Nitrotoluene
NO2 NO2
NO2
p–Nitrotoluene 2,4,6–Trinitro toluene (TNT)
2,4–Dinitrotoluene

4. Alkylation :
CH3 CH3 CH3
| | |
CH3
3FeBr


+
|
o-Xylene CH3
p-Xylene

5. Free Radical Nuclear Additive Chlorination :

hv
C6H5CH3 + 3Cl2   C6H5 CH3 Cl6
Toluene hexachloride
6. Nuclear Electrophilic Substitutive Chlorination :
CH3 CH3 CH3
| | |
Cl
3FeBr

Cl2 +
o-Chlorotoluene |
Cl
p-Chlorotoluene

Reactions Due to Methyl Side Chain :

7. Free Radical Side Chain Substitutive Chlorination :
Cl2 Cl2 Cl2
C6H5–CH3 
110º
C6H5 – CH2 Cl  C6H5 – CHCl2  C6H5 – CCl3
110º 110º
Benzyl chloride Benzal chloride Benzotrichloride

8. Oxidation :
Benzoic acid is obtained on oxidation of toluene by alkaline permanganate or acidified dichromate
or dilute nitric acid.
C6H5–CH3 _ 3[O] C6H5–COOH + H2O

AROMATIC COMPOUNDS [123]

 If more than one side chain is present, then the same number of COOH groups will be formed for
example, phthalic acid is formed from o-xylene.

CH3 COOH
3[O]
 
–H2O
CH3 COOH
o-Xylene Phthalic acid

Reaction due to Whole Molecule :

9. Combustion :
C6H5–CH3 + 9O2 7CO2 + 4H2O

Uses :
[1] As a constituent of aviation gasoline.
[2] As a solvent.
[3] In the manufacutre of explosive.
[4] In the manufacture of dyes.
[5] In the manufacture of medicines.
[6] In the manufacture of perfumes.
[7] In the synthesis of many aromatic compounds.

AROMATIC COMPOUNDS [124]

 PHENOL (C6H5OH)
Phenol is also known as carbolic acid or Benzenol or hydroxy benzene.
In phenol –OH group is attached to sp2 – hybridised carbon
It was discovered by Runge in the middle oil fraction of coaltar distillation and named it carbolic acid
(carbo = coal; oleum = oil)
It is also present in traces in human urine.

Methods of preparation :

[1] From Benzene sulphonic acid :

When sodium salt of benzene sulphonic acid is fused with NaOH phenol is obtained.
C6H5SO3Na + NaOH  C6H5OH + Na2SO3

[2] From benzene diazonium chloride :

When benzene diazonium chloride solution is warmed phenol is obtained with evolution of nitrogen.
N = N — Cl OH
| |
H2O


 + N2 + HCl

[3] By distilling a phenolic acid : with sodalime (decarboxylation) :

OH
| OH
COOH |
NaOH  CaO
  + Na2CO3
Salicylic acid

[4] From Gignard reagent : The grignard reagent on reaction with oxygen and subsequent hydrolysis by
acid yields phenol
[O] H2O
C6H5MgBr   C6H5OMgBr   C6H5OH + MgBrOH

[5] From bezene :

OH
|
V2O5
+ [O] 
300ºC


[6] Industrial preparation of phenol : Phenol can be prepared commercially by :

[a] Middle oil fraction of coaltar distillation [b] Raschig process
[c] Dow’s process [d] Cumene

AROMATIC COMPOUNDS [125]

[a] Middle oil fraction of coaltar :
Fractional
Coaltar 
distillation
Middle oil (172–230º C)

(Phenol, cresols, Naphthalene)

Cool

Naphthalene liquid
(Solid crystals seperate out) NaOH
C6H5ONa
CO2/H2O

C6H5OH + Na2CO3

[b] From cumene : (Isopropyl benzene ) : Curmene is oxidised with oxygen in to cumene hydro peroxide
in presence of a catalyst. This is decomposed by dil. H2SO4 in to phenol and acetone.

O–OH
CH3 CH3 |
CH C(CH3)2 OH
| | |
O2 H2O

Catalyst
   + CH3– C –CH3
H ||
O

[c] Dow process : This process involves alkaline hydrolysis of chloro benzene
OH
|
Cu–Fe
C6H5Cl + NaOH 
300ºC
 + NaCl

2. Physical Properties :
• Phenol is a colourless, hydroscopic crystalline solid.
• It attains pink colour on exposure to air and light.

C6H5OH ------------- O = =O-------HOC6H5

Phenoquinone (Pink colour)

• It is poisonous in nature but acts as antiseptic and disinectant.

• Phenol is silghtly soluble in water, readily soluble in organic solvents.
• Solubility of phenol in water is much lower than alcohols because of larger hydrcarbon part in the
molecule.
• Due to intermolecular H–Bonding, phenol has relatively high B.P. than the corresponding hydrocarbons,
aryl halides etc.
3. Chemical properties :Chemical properties of phenol are classifi ed in the following four categories.
1 Reactions of —H atom of —OH group.
2 Reactions of —OH group of phenol.
3 Reactions of Benzene ring.
4 Other Reactions.

AROMATIC COMPOUNDS [126]

1. Reactions of —H atom of —OH group
2. Acidic Nature : Phenol is a weak acid. The acidic nature of phenol due to formation of stable phenoxide
ion in solution.
C6H5OH + H2O C6H5O– + H+3O
The phenoxide ion is stable due to resonance.
• The negative charge is spread through out the benzene ring which is stabilising factor in the phenoxide
ion.
• Electron with drawing groups (–NO2, –Cl) increase the acidity of phenol while electron releasing
groups (–CH3 etc.) decrease the acidity of phenol.
• Phenol is stronger acid than alcohols but weaker than the carboxylic acids and even carbonic acid.
The acidic nature of phenol is observed in the following :
[i] Phenol changes blue litmus to red.
[ii] Highly electron positive metals react with phenol.
2C6H5OH + 2Na  2C6H5ONa + H2
[iii] Phenol reacts with strong alkalies to form phenoxides
C6H5OH + NaOH  C6H5ONa + H2O
[vi] However phenol does not decompose Na2CO3 or NaHCO3 because phenol is weaker acid than carbonic
acid.
C6H5OH + Na2CO3 or NaHCO3  No reaction
Reaction due to –OH group :
[1] Reaction with PCl5 : Phenol reacts with PCl5 to form chloro benzene. The yield of chlorobenzene is
poor and mainly triphenyl phosphate is formed.
C6H5OH + PCl5  C6H5Cl + POCl3 + HCl
3C6H5OH + POCl3  (C6H5)3PO4 2HCl

[2] Reaction with Zn dust : When phenol is distilled with zinc dust benzene is obtained.
C6H5OH + Zn  C6H6 + ZnO

[3] Reaction with NH3 : Phenol reacts with NH3 in presence of anhydrous ZnCl2 to form aniline.
ZnCl2
C6H5OH + NH3   C H NH + H O

6 5 2 2

[4] Reaction with FeCl3 : Phenol gives violet colouration with FeCl3 solution (netural) due to formation of
a complex.
C6H5OH + FeCl3  Voilet colour
* This reaction is used to differentiate phenol from alcohols.
[5] Acetylation : Phenol reacts with acid chlorides or acid anhydrides in alkali solution to form phenyl
esters.
NaOH
C6H5OH + ClCOCH3   C6H5OC–CH3
O

AROMATIC COMPOUNDS [127]

 * C6H5OH + Cl– C –C6H5  C6H5O– C C6H5
O O
This reaction is called Schotten–Baumann reaction.

[6] Ether Formation : Phenol reacts with alkyl halides in alkali solution to form phenyl ethers.
RX
C6H5OH + NaOH C6H5ONa 
–NaX
C6H5OR
* C6H5OH + CH2N2 C6H5OCH3 + N2

[7] Reaction with P2S5 :

5C6H5OH + P2S5 5C6H5SH + P2O5

Reaction of Benzne Ring : The –OH group is ortho and para directing. It activates the benzene nucleus.
[1] Halogenation : Phenol reacts with bromine in CCl4 to form mixture of o–and p–bromo phenol.

*Phenol reacts with bromine water to from a white ppt. of 2, 4, 6 tribromo phenol.

[2] Nitration :
[a] Phenol reacts with dil. HNO3 at 5–10ºC to form o– and p– nitro phenols.

[b] When phenol is treated wtih conc. HNO3 in presence of conc. H2SO4 2,4,6–trinitro phenol (picric
acid) is formed.

[3] Sulphonation : Phenol reacts with conc. H2SO4 to form mixture of o– and p– hydroxy benzene sulphonic
acid.

AROMATIC COMPOUNDS [128]

[4] Friedel–Craft’s reaction : Phenol when treated with methyl chloride in presence of anhydrous AlCl3
p–cresol is main product.

[5] Gattermann aldehyde synthesis : When phenol is treated with liquid HCN and HCl gas in presence
of anhydrous AlCl3 yields mainly p–hydroxy benzaldehyde.
AlCl3
HCl + HCN   HN = CHCl

[6] Reimer–Tiemann reaction : Phenol on refluxing with chloroform and NaOH (aqueous) followed by
acid hydrolysis yields o–hydroxy benzaldehyde. When CCl4 is used salicylic acid is formed.

[7] Kolbe’s Schmidt reaction : This involves the reaction of C6H5ONa with CO2 at 140ºC followed by
acid hydrolysis salicylic acid is formed.

[8] Hydrogenation : Phenol when hydrogenated in presence of Ni at 150–200º C forms cyclohexanol.

AROMATIC COMPOUNDS [129]

[9] Fries rearrangement reaction :
When phenyl ester is heated in nitrobenzene solution, in the presence of anhy. AlCl3 then rearrangement
takes place in which acyl group is transferred at o - & p-positions of phenolic group. Up to 60ºC, para
product is obtained mainly and above 160ºC ortho products are obtained as major product.

[10] Coupling reactions :

[a] Phenol couples with benzene diazonium chloride in presence of an alkaline solution to form a dye(p–
hydroxy azobenzene)

[b] Phenol couples with phthalic anhydride in presence of conc. H2SO4 to form a dye (phenolphthalien)

[11] Condensation with formaldehyde : Phenol condenses with HCHO (excess) in presence of NaOH to
form a polymer known as bakelite.

AROMATIC COMPOUNDS [130]

[12] Liberman’s nitroso reaction : When phenol is reacted with NaNO2 and conc. H2SO4 it gives a deep
green or blue colour which changes to red on dilution with water. When made alkaline with NaOH
original green or blue colour is restored.
The reaction is used as a test of phenol.
2NaNO2 + H2SO4 2HNO2 + Na2SO4

[13] Reaction with acetone :

[14] Oxidation :

[1] In presence of air :

[2] KMnO4 :

Test of Phenol :
[1] Phenol turns blue litmus to red.
[2] Aqueous solution of phenol gives a violet colour with a drop of ferric chloride.
[3] Phenol gives Lieber mann’s nitroso test.
NaNO2 NaOH excess
Phenol in conc. H2SO4 
excess of water
 Red colour   Blue colour

[4] Aqueous solution of phenol gives a white ppt. of 2,4,6 tribromophenol with bromine water.
[5] Phenol combines with phthalic anhydride in presence of conc. H2SO4 to form phenolphthalein which
gives pink colour with alkali.
[6] With ammonia and sodium hypochlorite, phenol gives blue colour.

AROMATIC COMPOUNDS [131]

Differences between phenol and alcohol (C2H5OH) :
[1] Phenol is more acidic than aliphatic alcohol due to resonance in phenoxide ion.
[2] Phenol gives violet colour with FeCl3 while aliphatic alcohol does not give.
[3] Phenol gives triphenyl phosphate with PCl5 while aliphatic alcohol gives alkyl chloride.
[4] Phenol has phenolic odour whereas alcohol has pleasent odour.
[5] Phenol on oxidation gives quinone while alcohol gives aldehyde or ketone and acids.

Uses of Phenol :
Phenol is used :
[1] As an antiseptic in soaps and lotions.
[2] In manufacutre of azodyes, phenolphthalein, picirc acid (explosive), cyclohexanol (Solvent for rubber),
plastic (bakelite) etc.
[3] In manufacture of drugs like aspirin salol, phenacetin etc.
[4] As preservation for ink.

AROMATIC COMPOUNDS [132]

 BENZALDEHYDE

Benzaldehyde, C6H5CHO, Oil of bitter Almonds

Benzaldehyde is present in the form of glucoside called amygdalin in bitter almonds. One molecule of
amygdalin is composed of one molecule of benzaldehyde, two molecules of glucose and one cyano
groups bonded to one another. Banzaldehyde is obtained on hydrolysis of amygdalin by dilute acid or by
an enzyme emulase.

Method of Preparation
[1] By Oxidation of Benzyl Alcohol : Benzaldehyde is obtained on oxidation of benzyl aclohol by dilutre
nitric acid
C 6H5CH2OH + [O] 
Dil. HNO3
 C6H5CHO + H2O

[2] By Catalytic Dehydrogenation of Benzyl Alcohol : Benzaldehyde is obtained on passing benzyl

alcohol vapour over copper catalyst or zinc oxide heated to 300º.
Cu or ZnO
C6H5CH2OH 
300º
 C6H5CHO + H2

[3] By Alkaline Hydrolysis of Benzal Chloride : Benzaldehyde is obtained by hydrolysis of benzal

chloride, i.e., benzylidine chloride using dilute alkali.
C6H5CHCl2 + 2KOH [C6H5 CH(OH)2 ] + 2KCl
Unstable

[C6H5CH(OH)2] C6H5CHO + H2O

[4] By Ozonolysis of Styrene : A mixture of benzaldehyde and formaldehyde is obtained on ozonolysis of

styrene.

O
H O
2 
C6H5CH=CH2 + O3 C6H5–CH CH2 
Zn
C6H5CH=O + CH2=O

O O
Styrene ozonide

[5] By Dry Distillation of Calcium Salts of Acids : Benzaldehyde can be obtained by dry distillation of
a mixture of calcium benzoate and calcium formate taken in equimolar ratio.
(C6H5COO)2Ca + (HCOO)2Ca 2C6H5CHO + 2CaCO3
Barium salts can also be used in place of calcium salts of carboxylic acids.

[6] By Grignard’s Reagent : Banzaldehyde is formed by the reaction of phenylmagnesium bromide with
ethyl formate :
C6H5–MgBr + EtO– C–H C6H5– C–H + EtO–MgBr
O O

AROMATIC COMPOUNDS [133]

[7] By Rosenmund’s Reaction : Benzaldehyde is formed by the reduction of benzoyl chloride in the
presence of palladised barium sulphate.
Pd
C6H5– C–Cl + H2 
BaSO4
 C H – C–H + HCl
6 5
O O

[8] By Stephen’s Reaction : Benzaldehyde is obtained on reduction of benzaldimine, which is formed on

reduction of benzonitrile (cyanobenzene) by stannous chloride and conc. HCl in ethereal solution.
C6H5–CN + 2H C6H5 – CH  NH C6H5–CH=O
Benzaldimine

[9] By Oxidation of Benzyl Chloride : Slow oxidation of benzyl chloride takes place on passing a stream
of carbon dioxide through the aqueous solution of copper nitrate or lead nitrate and benzaldehyde is
formed.
2  H O 3 2  Cu(NO )
C6H5CH2Cl 
CO2 C6H5CH2OH 
or Pb(NO3 )2 C6H5CHO

[10] By Sommelet Reaction of Benzyl Chloride : Benzyl chloride is refluxed with urotropine in aqueous
alcoholic solution, when a product is formed. This product is subjected to hydrolysis by steam–distillation
after adding small amount of an acid, when benzaldehyde is obtained.
H2O 
C 6 H 5 CH 2 Cl + (CH 2 ) 6 N 4 
EtOH
{C6 H 5 CH 2 (CH 2 ) 6 N 4 } + Cl – 
H
 [C 6 H 5 CH 2 –
N=CH2]
H3O 
C6H5CH=N–CH3(N–Methylbenzaldimine) 
Distillation
 C6H5CH=O

[11] By Gattermann Aldehyde Synthesis : Benzaldehyde can also be obtained by heating benzene, HCN
and HCl in the presence of anhydrous AlCl3.
C6H5H + [HCN + HCl] C6H5CH=NH + HCl
H2O
C6H5CH=NH   C6H5CH=O

Physical Properties
Benzaldehyde is a colourless, volatile oily liquid (boiling point 179°) having characteristic odour of bitter
almonds. It is miscible with organic liquids, like alcohol, ether, etc., and immiscible with water. Its solu-
bility in water is very low. It is poisonous and volatile in steam.

Reaction : Benzaldehyde gives the following two types of reactions.

[A] Reactions due to aldehyde group
[B] Reactions due to benzene ring
[A] Necleophilic Addition on Aldehyde group :
Nucleophilic addition on -CHO group in benzaldehyde takes place as follows.
Nu Nu
 – | |
C6H5–CH=O + E – Nu C6H5 – CH – O–  E C6H5 – CH – OE
Oxide ion Adduct

AROMATIC COMPOUNDS [134]

[B] Electrophilic Substitution Reactions Due to Benzene Ring :
Aldehyde group bonded to the benzene ring is deactivating and meta-directing group due to strong
negative mesomeric effect (-M effect). Therefore, the attack of an electrophile on aromatic ring of
benzaldehyde takes Place at slower rate as compared to unsubstituted benzene. and m- SE substitution
product is formed under strong conditions, i.e., not easily.

[A] Reaction Due to Aldehyde Group :

[1] Reduction : Benzyl alcohol is formed on reuction of benzaldehyde by sodium amalgam + HCl or Zn +
HCl.
C6H5CHO + 2H C6H5CH2OH
[2] Oxidation : Benzoic acid is formed by slow auto-oxidation of benzaldehyde in the presence of air and
light. Other oxidants bring about oxidation very fast.
C6H5CHO + [O] C6H5COOH

Due to its easy oxidation, benzaldehyde behaves a s reducing agent. However. It is weaker reducing
agent as compared to aliphatic aldehydes. It restores pink colour of Schiff’s reagent, gives white precipitate
turning grey with mercuric chloride solution, and it reduces silver ions of Tollen reagent, i.e., ammoniacal
silver nitrate solution to metallic silver. But it does not give red precipitate of cuprous oxide with Fehling’s
solution and Benedict’s solution due to strong steric hindrance of benzene ring.
[3] With Sodium Bisulphite : The reaction of sodium bisulphite with benzaldehyde gives benzaldehyde-
sodium bisulphite adduct, which is a white crystalline solid.
C6H5CHO + NaHSO3 C6H5CH(OH)SO3Na
[4] With Hydrogen Cyanide : Mandelic acid is obtained on hydrolysis of mandelonitrile i.e., benzaldehyde
cyanohydrin, formed by addition of hydrogen cyanide on benzaldehyde.
H H H
H2O
C6 H5 — C + HCN C6H5 — C — CN C6H5 — C — COOH

O OH OH
Mandelonitrile Mandelic acid

[5] With Alcohols : An aromatic acetal is obtained on heating a mixture of benzaldehyde and alcohol in the
presence of dry HCl gas.
C6H5CHO + 2HOC2H5 
Dry HCl gas
 C6H5CH(OC2H5)2 + H2O
The above aromatic acetal obtained from benzaldehyde and ethanol is called phenytal.

[6] With Thiols : Aromatic thioacetals are formed by reacting benzaldehyde and thioalcohols in the presence
of dry HCl gas.
C6H5CHO + 2HSC2H5 
Dry HCl gas
 C6H5CH(SC2H5)2 + H2O

[7] With Ammonia : On heating benzaldehyde with ammonia a complex compound called hydrobenzamide
is formed.

AROMATIC COMPOUNDS [135]

[8] With Primary Amines : Schifff’s bases are formed on heating benzaldehyde with primary amines. The
reaction of benzaldehyde and aniline gives a Schiff’s base, named benzlideneaniline or benzalaniline of
N–phenylbenzaldimine.

C6H5–CH=O + H2N –C6H5   C6H5 – CH  N – C6H5 + H2O
benzylideneaniline

[9] With Hydroxylamine : Benzaldoxime is formed by the reaction of benzaldehyde and NH2OH.

C6H5–CH=O + H2N–OH C6H5 – CH  N – OH + H2O

Benzaldoxime

[10] With Hydrazine : Benzladehydehydrazone is formed by the reaction of benaldehyde and NH2NH2.

C6H5–CH=O + H2N–NH2 C6H5 – CH  N – NH2 + H2O

Benzaldehydehydrazone

[11] With Phenylhydrazine : The reaction of benzladehyde and C 6 H 5 NHNH 2 gives

benzaldehydephenylhydrazone.

C6H5CH=O + H2N–NHC6H5 C6H5 CH  N – NHC6H5 + H2O

benzaldehydephenylhydrazone

[12] With Semicarbazide : The reaction of benzaldehyde and semicarbazide gives benzaldehyde
semicarbazone.

C6H5–CH=O + H2N–NH–CO–NH2 C6H5 – CH  N – NH – CO – NH2 + H2O

Benaldehyde semicarbzaone

[13] With Phosphorus Pentachloride : Benzaldehyde reacts with PCl5 to form benzal chloride, which is
also called benzylidene dichloride.
C6H5–CH=O + PCl5 C6H5–CHCl2 + POCl3
[14] With Phenol :

p.p’–Dihydroxytriphenylmethane
The above product is a triphenylmethan dye :

AROMATIC COMPOUNDS [136]

[15] With N,N–Dimethylaniline : If the reaction of benzldehyde and N,N–dimethylaniline is carried out in
the presence of a few drops of conc. H2SO4 or anhydrous ZnCl2, then a green coloured triphenylmethyl
dye, called Malachite green is obtained.

Malachite green
(p.p’–Bis–[dimethylamino]triphenylmethane)

[16] Cannizzaro’s Reaction : Due to absece of  hydrogen atom in benzaldehyde, oxidation of one molecule
to benzoate ion and reduction of the second molecule to benzyl alcohol takes place on adding strong
solution of caustic alkali at room temperature
2C6H5CHO + OH– C6H5COO– + C6H5CH2OH

[17] Tischenko Reaction : When benzaldehyde is heated in the presence of an aluminium alkoxide (ethoxide,
isopropoxide, etc.) taken in an inert solvent (CCl4, xylene, etc.), benzyl benzoate is formed by bimolecular
addition.

[18] Benzoin Condensation : When benzaldehyde is heated with aqueous alcoholic KCN solution, a ketonic
secondary alcohol, benzoin is formed by bimolecular condensation.
KCN
C6H5CHO + C6H5CHO   C H COCH(OH)C H
H 2O, EtOH,  6 5 6 5

On Oxidation of benzoin with conc. nitric acid, the secondary alcohol group is converted to a ketone
group and a diketone, called benzil is formed.
C6H5COCHOHC6H5 + [O] 
Conc.HNO3
 C6H5COCOC6H5 (Benzil) + H2O

[19] Claisen Reaction : An –unsaturated aldehyde (or ketone) is formed on the condensation of
benzaldehyde with an aldehyde (or a ketone) having at least two  hydrogen atoms, in the presence of
dilute alkali cinnamaldehyde is obtained on the condensation of benzaldehyde with acetaldehyde.
C6H5CH=O + H2CH–CHO C6H5 CH  CH – CHO + H2O
Cinnamaldehyde

AROMATIC COMPOUNDS [137]

 Benzalacetone, i.e. benzlideneacetone is obtained on condensation of benzaldehyde with acetone.
C6H5CH=O + H2CHCOCH3 
Dil. alkali
 C6H5 CH  CHCOCH3 + H2O
Benzalacetone

[20] Perkin’s Reaction : When benzaldehyde is heated at 180º with an anhydride and the sodium salt of a
carboxylic acid, then an unsaturated carboxylic acid is formed. For example, Cinnamic acid is obtained
on the reaction of acetic anhydride and sodium acetate on benzaldehyde.

[21] Knoevenagel Reaction : When benzaldehyde is heated with malonic ester in the presence of pyridine.
then cinnamic acid is formed in the following steps.

Malonic ester contains one reactive methylene group. whose two reactive hydrogen atoms take away
the oxygen atom from benzaldehyde to form a water molecule. A reactive methylene group is present
between two strongly electronattracting groups (like CO. CN. etc.), due to which the hydrogen atoms
of methylene group acquire a tendency of getting released in the form of protons.
[22] Reformatsky Reaction : When benzaldehyde is reacted with bromoacetic ester in the presence of
zinc in dry ether. then cinnamic acid is obtained in the following steps.

[B] Reactions Due to Benzene Ring :

Benzaldehyde gives the following SE reactions.
[23] Halogenation : m–Chlorobenzaldehyde (or m–Bromobenzaldehyde) is formed on heating benzaldehyde
with chlorine (or bromine) in the presence of AlCl3.

CHO CHO
| |
Cl
2 

AlCl3

Cl

AROMATIC COMPOUNDS [138]

[24] Nitration :
m–Nitrobenzaldehyde is formed on nitration of benzaldehyde by fuming nitric acid.
CHO CHO
| |
Fumin g


HNO3

NO2

[25] Sulphonation : Benzaldehyde undergoes sulphonation on heating with conc. sulphuric acid to form m–
formylbenzensulphonic acid.
CHO CHO
| |
Conc.


H2SO4

SO2OH

[26] Friedel–Crafts Reaction : It should be noted that due to strong deactivation of benzene ring in
benzaldehyde. Friedel–Crafts reaction does not take place.

USES : Benzaldehyde is used

[1] As a deodorant.
[2] In the manufacture of synthetic dyes, and
[3] In the synthesis of many aromatic compounds.
Some Important Point :
Uses :
S.No. Formaldehyde Acetaldehyde Acetone

Disinfectant and preservative for In the preparation of dyes polish,

1 Solvent for cellulose,
biological specimens. (formalin) varnishes

In the manufacture of ethanol, In the preparation of sulphonals

2 Urotropine, a urinary antiseptic
acetic acid, synthetic rubber etc. (hypotic)

Formamint, for throat treatment For the preparation of In the preparation of chlororform,
3
(formalin + lactose) metaldehyde (a solid fuel) iodoform

Distinction between Aldehydes and Ketones :

Test Aldehyde Ketone

Schiff's reagent Pink colour X
Tollen's reagent Silver mirror X
Fehling Solution Red ppt. X
NaOH solution Brown resin X
Mercuric chloride Black ppt. X

AROMATIC COMPOUNDS [139]

 NITRO BENZENE
1 Introduction :
[a] Aromatic nitro compounds are obtained when hydrogen atom or atoms are of aromatic compound
replaced by –NO2 (nitro) group.
[b] Aromatic nitro compound are of two types.
[i] Those compounds in which nitro group is attached directly to the benzene ring eg. nitrobenzene.
[ii] Those compounds, in which nitro group is attached to a side chain which is directly attached to the
benzne ring.

[c] Nitrobenzene is also called as ‘oil of mirbane’ or ‘artifical oil of bitter almond’s.
[d] If has a smell similar to benzaldehyde.
2. Methods of Preparation :
From Benzene (Nitration) :

Note :
[i] The reaction species is +NO2 (nitronium ion)
[ii] The above reaction is lab method of nitrobenzene preparation.

3. Physical Properties :
[a] It is yellowish, oily liquid, insoluble in water and soluble in organic solvents.
[b] It has odour like bitter almonds.
[c] It is steam volatile and poisonous in nature.
[d] Its boiling point is 211ºC.

4. Resonance in nitrobenzene :
[a] The groups which can attract the electron from benzene ring or deactivate the benzene ring or make
electron dificient to the benzene ring or shows –I effect or shows –M effect or –R effect are called as
meta directing groups. They do not show Friedel Craft reaction.

eg.

AROMATIC COMPOUNDS [140]

 [b] The group which can donate the electron to the benzene ring or activate the benzene ring or make
electron efficient to the benzene ring or shows + I effect of + M or +R effect are always ortho and para
directing groups.

eg. etc.

[c] Resonating structures of nitrobenzene.

It is evident from the above structures that ortho and para positions are electron deficient and attacking
electrophilie is also electron deficient, so it does not attack on ortho and para positions but attacks at
meta position.

5. Chemical Reactions : Chemical reaction of nitrobenzene are classified in three groups as follows :
1. Reaction of –NO2 group
2. Reaction of Benzene ring
3. Other reactions
1 Reaction of –NO2 group :
Readuction :
[a] Acidic medium :
Reagents : Sn/HCl or SnCl2/HCl or Zn/CH3COOH etc.
6H
C6H5NO2   C6H5NH2 + 2H2O
aniline
Propbale intermediate steps :
2H 2H 2H
C6H5–NO2 
–H2O
 C6H5NO   C6H5NHOH 
–H2O
 C6H5NH2

nitrosobenzene phenyl aniline

hydroxylamine
[b] Neutral Medium : Reagents : Zn/NH4Cl or Zn/CaCl2 or Al–Hg/NH4Cl etc.
4H
C6H5NO2   C6H5NHOH + H2O
Phenyl
hydroxylamine

AROMATIC COMPOUNDS [141]

 [c] Alkaline Medium : Reagents : Zn/NaOH or SnCl2/NaOH, or Glucose/NaOH etc.

[d] Electrolytic reduction : [Medium : conc, H2SO4]

Reaction with AlCl3 : Nitrobenzene behaves as weak base and makes a complex compound with
aluminium chloride.

2. Reaction of Benzene ring :

Halogenation :

Nitration :

Sulphonation :

AROMATIC COMPOUNDS [142]

3. Other Reactions : Nitrobenzene shows nucleophilic substitution reaction also. It is accomplishes in the
following way. Mechanism of nucleophilic substitution reaction – In nitrobenzene nucleophile attackes
at o– & p– positions as these are the electron deficient centres.

Reaction with Solid KOH :

Reaction with Sodamide :

Reaction with Ethanol :

o– and p–nitro phenetole

Test for Nitrobenzene :

[Mulliken and Barker’s method]
The alcoholic solution of nitrobenzene is heated with zinc powder and calcium chloride. This hot mixture
on filtration in Tollen’s reagent gives a black precipitate.

C6H5NO2 (alcoholic) + Zn + CaCl2   [C6H5NHOH] filter in AgNO3 + NH4OH 2Ag 
Black precipitate

AROMATIC COMPOUNDS [143]

 ANILINE
1 Introduction :
[a] Aniline is called phenyl derivative of ammonia.
[b] It was initially obtained by the scientist ‘Unverdorben’.
[c] Aniline is also called amino derivative of benzene because when a hydrogen atom is replaced by NH2
group, aniline is obtained.

2. Method of Preparation :
From Nitrobenzene (Reduction in acidic medium) :
[a] Lab method :
O
Sn / HCl
C6H5—N + 6H   C6H5NH2
O
[b] Industrial method :
O
Fe  HCl
C6H5—N + 6H   C6H5NH2
O
From Benzamide :
C6H5– C –NH2 + Br2 + KOH (alc.) C6H5NH2 + K2CO3 + KBr + H2O
O

Note : The above reaction is called as ‘Hofmann hypobromite reaction’.

From Chlorobenzene :
[a] With NH3 :
Cu2O
C6H5 —Cl + H— NH2 
200ºC
 C6H5 NH2 + HCl

Note : We use Cu2O to neutralize the formed HCl otherwise HCl forms additional salt with aniline.
Cu2O + 2HCl Cu2Cl2 + H2O
[b] With sodamide :

C6H5 —Cl + Na— NH2 
200ºC
 C6H5NH2 + NaCl

From Phenol :
anhy. ZnCl2
C6H5 —OH + H— NH2 
300ºC
 C6H5–NH2 + H2O


From Grignard reagent :

C6H5 —MgCl + Cl— NH2 C6H5NH2 + MgCl2
chloramine

AROMATIC COMPOUNDS [144]

 From phenyl isocyanate (By alkaline hydrolysis) :

Note : The above method is called as ‘wurtz method’.

From Benzoic acid (Schimdt reaction) :

By reudction of azo and hydrazo compounds with sodium dithionite :

By curtius reaction :

By Gabriel Phthalimide reaction :

3. Physical properties :
[a] Aniline is soluble in organic solvents as well as in water.
[b] Solubility in water is due to hydrogen bonding.
[c] It is colourless and poisonous liquid.

4. Resonance in Aniline :
Aniline is less basic than ammonia and primary amine because it possess resonance

AROMATIC COMPOUNDS [145]

 It is evident from the above sturcutres that I.p. on N atom is delocalised and aniline behaves as a weak
base. In these resonating structure, its ortho and para positions are electron richer (due to presence of
negative charge) so electrophile attacks on these positions only. That’s why we can say it is ortho & para
directing.

5. Chemical Reaction :
Chemical reactions of aniline are broadly classified in the following two ways :
5.1 Reaction of –NH2 group
5.2 Reactions of benzene ring
5.3 Other reactions

5.1 Reactions of –NH2 group :

Alkylation :

quaternary salt
Acetylation :

N-phenyl acetamide Or acetanilide

Note : The product formed is important because it is used in preservation of –NH2 group in aniline.

Schotten–baumann reaction :

N–phenyl benzamide or benzanilide

Reaction with Hinsberg reagent :

AROMATIC COMPOUNDS [146]

Hoffmann Carbylamine reaction (Isocyanide test) :

There isocyanides has very offensive smell. Reaction is used for testing of primary amines.

Reaction with Phosgene :

Reaction with Carbondisulphide :

[a] When aniline is in excess :

[b] When aniline is in lesser quantity :

Note : There isothiocyanate has odour like mustard oil so reaction is called ‘Hoffmann–mustard oil
reaction.

Reaction with Grignard reagent :

Reaction with Sodium metal :

AROMATIC COMPOUNDS [147]

 Reaction with HNO2 and HCl (Diazotisation) :

Note : It is an important compound because we can obtain a number of aromatic compounds from
benzene diazonium chloride like.

Salt formation :

Note : By the help of this salt we can calculate the mol. wt. of primary amine.

AROMATIC COMPOUNDS [148]

 Reaction with Benzaldehyde :
C6H5NH2 + C6H5CHO C6H5–CH=N–C6H5
(schiff base or anil)
5.2 Reaction of benzene ring :
Halogenation :
Aniline does not show halogenation or nitration directly due to presence of active hydrogen on –NH2
group so for nitration, halogenations first we preserve –NH2 group with acetyl chloride or by the formation
of acetanilide.

Note :
[i] Para product always yield more :
[ii] If reaction occurs in the presence of polar medium like bromine water, then product will be white ppt.
of 2, 4, 6 tribromo aniline.
[iii] Aniline on iodination gives para–iodo product only.

Nitration :

Note : [i] Meta products is formed because intermediate anilinium ion is formed which is meta directing.
[ii] If nitration occurs with conc. HNO3 then product will be yellow ppt. of 2, 4, 6–trinitroaniline.

Sulponation :

Note : Sulphanilic acid is used as hypnotic drug.

AROMATIC COMPOUNDS [149]

 Reduction :

Reaction with benzene diazonium chloride :

5.3 Other reactions :

Oxidation : Aniline forms different compounds on oxidation as follows :

Test for Aniline :

N=N–
|
NaNO2 10% NaOH OH
[a] Aniline 
HCl(0–5º)
 C H N Cl 
6 5 2   – naphthol


-phenyl azo –naphthol (orange–red dye)

light
[b] Aniline + NaOCl  p–Aminophenol   Purple–colour

CHCl3
[c] Aniline 
KOH
 Phenyl isocyanide
(most unpleasant smell)

AROMATIC COMPOUNDS [150]

 SOLVED EXAMPLE

Ex.1 Which of the following is not correctly matched-

(A) Hydrolysis of phenyl magnesium iodide – benzene
(B) –Isomer of BHC– lindane
(C) (2n + 4)  Rule– aromaticity
(D) Trimerisation of propyne– mesitylene Ans.(C)
Sol. The Huckel rule to account for aromaticity is closed ring of (4n + 2)  electrons.

Ex.2 Benzene can be directly obtained from-

(A) Acetylene (B) Ethene and butadiene
(C) Chlorobenzene (D) All the above Ans.(A)
Sol. See Text.

Ex.3 Ozonolysis of benzene yields -

(A) Glyoxal (B) Glycerine (C) Glycol (D) Glycerol (Ans.A)
Sol. Ozonolysis of benzene yields glyoxal. Benzene adds three molecules of ozone and forms benzene
triozonide which on decomposition with water gives three molecules of glyoxal
C6H6 + 3O3  C6H6 O9
benzene ozone benzene triozonide

H 2O H–C=O
C6H6 O9  3 |
H–C=O

benzene triozonide glyoxal

Ex.4 An aromatic compound contains ....  electrons

(A) 4n (B) 4n + 1 (C) 4n + 2 (D) 4n + 3 (Ans.C)
Sol. An aromatic compound contains (4n + 2)  electrons. It is according to Huckel's rule, which
represents the aromaticity of the molecules. Aromatic compounds possess a sweet smell which is
characteristic and different from other fragments.
The term aromatic compounds is now used for benzene and the compounds structurally related to
benzene, even if they do not possess a sweet smell.

Ex.5 Which of the following will show aromatic character -

I II III IV
(A) I, II and III (B) II and III (C) II and IV (D) All the four
(Ans.C)

AROMATIC COMPOUNDS [151]

Sol. Benzene has 6 electrons (2 from each double bond) present in cyclic continous form.

benzene furan
Furan also has 6 electrons present in continous cyclic cloud, note that one of the pair of electrons
present in sp2 orbital does not involve in overlapping of the sextet; while the unused pair of
electrons present in p orbital is involved in overlapping forming sextet.

Ex.6 Which of the following is not a friedel craft's reaction –

(A) C6 H5 – OH + Cl – COCH3  C6H5OCOCH3
(B) C6 H6 + ClCOCH3   C6H5–COCH3
AlCl 3

(C) C6 H6 + CH3Cl   C6 H5 – CH3

AlCl3

(D) C6 H6 + C2H5Cl   C6H5 – C2H5

AlCl 3 [Ans. A]
Sol. Friedel craft reaction occurs in the presence of lewis acid. Note that carbon directly links with
benzene ring in friedel crafts reaction.

Ex.7 Toluene may be prepared by :–

(A) Toluic acid (B) Cresol
(C) Toluene sulphonic acid (D) All the above [Ans. D]
Sol. Toluene may be prepared by all the above compounds described earlier.

Ex.8 The chlorination of toluene in presence of ferric chloride gives predominantly–

(A) Benzyl chloride (B) m–Chlorotoluene
(C) Benzal chloride (D) o– and p– Chlorotoluene [Ans. D]

CH3 CH3 CH3

Cl2 Cl
+
Sol. FeCl3
Cl

In presence of halogen carrier, substitution occurs in benzene nucleus.

Ex.9 Chlorination of toluene in the presence of light and heat followed by treatment with aqueous NaOH
gives –
(A) o – Cresol (B) p – Cresol
(C) 2,4–Dihydroxytoluene (D) Benzyl alcohol [Ans. D]
light , heat aq.NaOH
Sol. C6H5CH3 + Cl2    C6H5CH2Cl    C6H5CH2OH

AROMATIC COMPOUNDS [152]

 CrO Cl
2 2 H O
Ex.10 –CH3    A   B
2

[Where  = C6H5]
The functional group present in B and name of the reaction would be –
(A) –CHO, Gattermann aldehyde synthesis (B) –CHO, Etard reaction
(C) –COCH3, Friedel Crafts reaction (D) –CHO, Oxo reaction [Ans. B]
Sol. The compound ' B ' is benzaldehyde and the reaction is called Etard reaction.

Ex.11 The correct order of reactivity towards electrophilic substitution is -

(A) Phenol > Benzene > Chlorobenzene > Benzoic acid
(B) Benzoic acid > Chlorobenzene > Benzene > Phenol
(C) Phenol > Chlorobenzene > Benzene > Benzoic acid
(D) Benzoic acid > Phenol > Benzene > Chlorobenzene (Ans.A)
Sol. Presence of o-, p- directing groups in benzene nucleus activates ring for SE reaction. Presence
of m-directing group deactivates ring for SE reactions. Also halogens are deactivating gp. due to
— IE. inspite of o-and p-directing nature.

Ex.12 Which among the following is the strongest o-, p-directing group in benzene is -
(A) –OH (B) –Cl (C) –OCH3 (D) –CH3 (Ans.A)
Sol. –OH gp. posses the maximum tendency to throw electron pair towards benzene nucleus.

Ex.13 The compound represented by the molecular formula C7H8O are -

(A) Only alcohol (B) Only ether
(C) Only phenolic compound (D) All the three types of compounds (Ans.D)
Sol. Benzyl alcohol, anisole and o —, m—, p— cresols can be written by the molecular formula
C7H8O.

Ex.14 Indenify A, B, and C in the following reactions–

A
(a)   (b)  Zn
 B (c) C  C
H l
2 5

 

(A) Sodalime, benzene, potassium phenoxide

(B) Zn, benzene, sodium ethoxide
(C) Zn, cyclohexanone, sodium ethoxide
(D) None of the above (Ans.A)
Sol. Sodalime, benzene, potassium phenoxide are the A, B and C compounds respectively.

Ex.15 Rate of substitution reaction in phenol is -

(A) Slower than the rate of benzene (B) Faster than the rate of benzene
(C) Equal to the rate of benzene (D) None (Ans.B)
Sol. – OH group is activating group towards electrophilic substitution reactions.

AROMATIC COMPOUNDS [153]

Ex.16 Which is least soluble in water -
(A) Phenol (B) Ethanol (C) Benzoic acid (D) Benzene (Ans.D)
Sol. Benzene can not form H-bonding thus, it is least soluble.

Ex.17 Which of the following reagen (s) cannot be used to distinguish between phenol and benzyl alcohol-
(A) NaOH (B) NaHCO3 (C) Br2/CCl4 (D) FeCl3 (Ans.C)
Sol. Only phenol reacts with NaOH, NaHCO3 and FeCl3 none of the two compounds react with
Br2/CCl4.

Ex.18 Phenol condenses with formaldehyde to form-

(A) Bakelite (B) Asbestos (C) Polyacrylaldehyde (D) Polyester (Ans.A)
Sol. When phenol and formaldehyde react in presence of dilute alkali, p-hydroxybenzyl alcohol is
obtained as a major product on further heating for some time, a cross-linked polymer, called
phenol- formaldehyde resin or bakelite is formed.

Ex.19 + CHCl3 + NaOH  

The above reaction is called -

(A) Gattermann Kosch aldehyde synthesis
(B) Gattermann aldehyde synthesis
(C) Reimer Tiemann reaction
(D) Ledrer Mannase reaction (Ans.C)
Sol. The above reaction is Reimer Tiemann reaction.

Ex.20 In Etard’s reaction toluene is oxidised to benzaldehyde using –

(A) H2O2 (B) Cl2
(C) Chromium trioxide or CrO2Cl2 (D) KMnO4 (Ans. C)
Sol. CrO3 or CrO2Cl2 and a mixture of K2Cr2O7 + H2SO4 + NaCl can also be used.

Ex.21 In Perkin reaction –

(A) Benzaldehyde reacts with acetic anhydride in the presence of sodium acetate forming cinnamic
acid.
(B) Benzaldehyde reacts with acetaldehyde in the presence of sodium hydroxide to give
cinnamaldehyde.
(C) Calcium salt of benzoic acid on dry distillation gives benzophenone.
(D) None of these (Ans.A)
Sol. Perkin reaction can be shown as –
C6H5CHO + (CH3CO)2O  CH3 COONa
  C6H5CH = CH – COOH + CH3COOH

Ex.22 Benzaldehyde and formaldehyde differ from acetaldehyde in their reaction with –
(A) NaOH (B) HCN
(C) 2,4-Dinitrophenyl hydrazine (D) Semi carbazide (Ans.A)

AROMATIC COMPOUNDS [154]

Sol. Benzaldehyde (C6H5 – CHO) and formaldehyde do not have -hydrogen atoms so they give
disproportionation reaction with NaOH but CH3CHO does not give it.

Ex.23 When an aldehyde was heated with alkali, part of it was converted into an alcohol and part of it
into an acid. The aldehyde is –
(A) An aliphatic aldehyde other than formaldehyde
(B) An aliphatic aldehyde or salicylaldehyde
(C) An aromatic aldehyde other than salicylaldehyde
(D) An aromatic aldehyde or formaldehyde (Ans.D)
Sol. The aldehydes which do not have -hydrogen atoms show disproportionation reaction. These
aldehyde may be aliphatic aldehyde (formaldehyde) or aromatic aldehyde.

Ex.24 Product obtained on the addition of an aqueous alkali to benzaldehyde followed by acid hydrolysis
is –
(A) Benzoic acid (B) Benzyl alcohol (C) Benzyl benzoate (D) All of the above
(Ans.D)
Ex.25 Benzaldehyde reacts with acetaldehyde in the presence of a base to give –
(A) Crotonaldehyde (B) Cinnamaldehyde (C) Crotonic acid (D) Cinnamic acid
(Ans.B)
Sol. Benzaldehyde reacts with acetaldehyde in the presence of a base to give cinnamaldehyde. It is
called crossed Aldol condensation or Claisen's condensation
CHO CH=CH.CHO
| |
OH 
+ CH3CHO 
H2O

benzaldehyde acetaldehyde cinnamaldehyde

Ex.26 In the reaction between benzaldehyde and formaldehyde, point out the wrong statement
(A) Benzaldehyde is reduced to benzyl alcohol
(B) Formaldehyde is oxidised to formic acid
(C) Benzyl formate is formed
(D) The reaction is known as crossed aldol condensation
(Ans.D)
Sol. In the reaction between benzaldehyde and formaldehyde the wrong statement is that the reaction
is known as crossed aldol condensation. Actually the reaction is called Crossed Cannizaro's reaction.

(1)OH
C6H5CHO + HCHO  
( 2 )HCl

benzaldehyde formaldehyde
C6H5CH2OH + HCOOH
benzylalcohol formic acid

AROMATIC COMPOUNDS [155]

Ex.27 Which of the following will undergo aldol condensation –
Acetaldehyde Propanaldehyde
(1) (2)
Benzaldehyde rideuterosacetaldehyde
(3) (4)
(A) 1 (B) 1, 4 (C) 1, 2, 4 (D) All of them (Ans.C)
Sol. CH3CHO CH3CH2CHO
(1) (2)

C6H5CHO CD3CHO
(3) (4)
Benzaldehyde has no -hydrogen atom, remember that CH3CHO and CD3CHO both behave
similarly in chemical properties.

AROMATIC COMPOUNDS [156]

 EXERCISE I
Q.1 Solvent used in the, Friedel Craft’s reaction is :
(A) Nitrosobenzene (B) Nitrobenzene (C) Benzene (D) Toluene

Q.2 Which of the following is not an aromatic compound:

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

Q.3 Benzene is obtained when phenol is distilled with -

(A) Copper turnings (B) Aluminium dust (C) Zinc dust (D) Pumice stone

Q.4 Which one of the following is the most basic compound :

(A) C6H5–NH2 (B) C6H5–NHCH3 (C) C6H5–N(CH3)2 (D) C6H5N(C2H5)2

Q.5 Friedel–Crafts' reaction does not occur in case of –

(A) Toluene (B) Benzene (C) Naphthalene (D) Pyridine

Q.6 Toluene may be prepared by -

(A) Friedel craft's reaction (B) Wurtz–fitting reaction
(C) Grignard reagent (D) All of the above

Q.7 The main product of the reduction of benzaldehyde with Zn-Hg/conc. HCl is -
(A) Benzyl alcohol (B) Cyclohexyl methanol
(C) Toluene (D) None of these

CH COCl
Zn  Hg
Q.8 C6H6 3 A    B
AlCl3 HCl

The end product in the above sequence is:

(A) Toluene (B) Ethyl benzene (C) Both the above (D) None

Q.9 Which of the following will undergo sulphonation at fastest rate ?

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

Q.10 Ozonolysis of toluene gives -

(A) Two molecule of glyoxale
(B) Three molecule of glyoxale
(C) Two molecule of glyoxale and one molecule of methyl glyoxale
(D) Two molecule of methyl glyoxale and one molecule of glyoxale

AROMATIC COMPOUND [157]

Q.11 m-Bromotoluene is prepared by:
(A) Bromination of toluene
(B) Friedel Craft's reaction of bromobenzene with CH3Cl
(C) Bromination of nitrobenzene and subsequent replacement of –NO2 group with methyl group
(D) Bromination of aceto-p-toluidine followed by hydrolysis and deamination

Q.12 Phenol reacts with conc. HNO3 in the presence of conc. H2SO4 to give –
(A) Meta nitrophenol (B) Ortho nitrophenol
(C) Ortho and para nitrophenol (D) Picric acid

Q.13 In the Liebermann’s nitroso reaction changes in the colour of phenol occurs as:
(A) Brown or red-greenish red-deep blue (B) red-deep blue-green
(C) red-green-white (D) white-red-green

Q.14 Reimer Tiemann reaction involves -

(A) Carbanion intermediate (B) A carbene intermediate
(C) Carbonium ion intermediate (D) Free redical intermediate

Q.15 Methyl group attached to benzene can be oxidised to carboxyl group by reacting with:
(A) Fe2O3 (B) AgNO3 (C) KMnO4 (D) CrO3

Q.16 The formylating agent in ‘Gattermann Koch’ synthesis is -

(A) CO + HCl (B) CO + H2 (C) HCl + HCN (D) CHCI3 + alc.KOH

Br KMnO
Q.17 A 2 4  B
 

Compound A and B respectively are:

(A) o-Bromostyrene, benzoic acid (B) p-Bromostyrene, benzaldehyde
(C) m-Bromostyrene, benzaldehyde (D) Styrene dibromide, benzoic acid

Q.18 Benzaldehyde is oxidised and reduced simultaneously in the presence of –

(A) NaHCO3 (B) NaOH (C) Na2CO3 (D) HCl

Q.19 Benzaldehyde can be converted to benzyl alcohol by –

(A) HCl (B) NaOH (C) LiAlH4 (D) B and C are correct

Q.20 Benzaldehyde condenses with acetic anhydride to give cinnamic acid in presence of –
(A) Sodium acetate (B) Sodium chloride (C) Sodium benzoate (D) Sodium metal

Q.21 HCHO and C6H5CHO can be distinguished by –

(A) Fehling solution (B) Tollen’s reagent (C) KMnO4 (D) All of these

Q.22 Nitrobenzene has a smell similar to that of :

(A) Benzaldehyde (B) Formaldehyde (C) Acetaldehyde (D) Salisylaldehyde

AROMATIC COMPOUND [158]

Q.23 How many  electron are there in the following species :

(A) 2 (B) 4 (C) 6 (D) 8

Q.24 Benzene is a resonance hybrid mainly of two Kekule structures. Hence:

(A) Half of the molecules correspond to one structure, and half of the second structure
(B) At low temperatures benzene can be separated into two structures
(C) Two structures make equal contribution to resonance hybrid
(D) An individual benzene molecule changes back and forth between two structures

Q.25 Which of the following group is divalent:

(A) Benzoyl (B) Benzyl (C) Benzal (D) p-Tolyl

Q.26 Which of the following is not the property of benzene:

(A) Characteristic smell (B) Inflammable
(C) Addition reactions (D) Colourless

Q.27 The intermediate formed in the reaction of benzene with an electrophile is –

(A) Wheland intermediate (B) – complex
(C) Benzenium cation (D) All the above

Q.28 Anhydrous AlCl3 is used in the Friedel – Craft's reaction because it is -

(A) Electron rich
(B) Soluble in ether
(C) Ionisable to chloride and aluminium ions
(D) Electron deficient

Q.29 Acetylene on polymerisation gives -

(A) Mesitylene (B) Benzene (C) Ethyl benzene (D) Propyle benzene

Q.30 Nitration of toluene takes place at -

(A) o – Position (B) m –Position
(C) p – Position (D) Both o– and p – positions

AROMATIC COMPOUND [159]

 EXERCISE–II
Q.1 Bottles containing C6H5I and C6H5CH2I lost their original labels. They were labelled A and B for
testing. A and B were separately taken in test tubes and boiled with NaOH solution. The end solution
in each tube was made acidic with dilute HNO3 and then some AgNO3 solution was added.
Substance B gave a yellow precipitate. Which one of the following statements is true for this experiment?
(A) B was C6H5I (B) Addition of HNO3 was unnecessary
(C) A was C6H5I (D) A was C6H5CH2I [AIEEE-2003]

Q.2 Which one of the following undergoes reaction with 50% sodium hydroxide solution to give the
corresponding alcohol and acid ? [AIEEE-2004]
(A) Phenol (B) Benzaldehyde (C) Butanal (D) Benzoic acid

Q.3 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 - [AIEEE-2005]

(A) (B)

(C) (D)

Q.4 Fluorobenzene (C6H5F) can be synthesized in the laboratory - [AIEEE 2006]

(A) from aniline by diazotisation followed by heating the diazonium salt with HBF4
(B) by direct fluorination of benzene with F2 gas
(C) by reacting bromobenzene with NaF solution
(D) by heating phenol with HF and KF

Q.5 Phenyl magnesium bromide reacts with methanol to give - [AIEEE 2006]
(A) a mixture of benzene and Mg(OMe) Br (B) a mixture of toluene and Mg(OH)Br
(C) a mixture of phenol and Mg(Me)Br (D) a mixture of anisole and Mg(OH) Br

OH O–Na+
Q.6 + CHCl3 + NaOH .
CHO
The electrophile involved in the above reaction is - [AIEEE 2006]
È
(A) dichlorocarbene ( :CCl2) (B) trichloromethyl anion ( CCl3)
 
(C) formyl cation (CHO) (D) dichloromethyl cation (CHCl2)

AROMATIC COMPOUND [160]

Q.7 The structure of the compound that gives a tribromo derivative on treatment with bromine water is -
[AIEEE 2006]

CH2OH CH3 CH3 CH3

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

Q.8 The reaction of toluene with Cl2 in presence of FeCl3 gives predominantly- [AIEEE 2007]
(A) benzoyl chloride (B) benzyl chloride
(C) o-and p-chlorotoluene (D) m-chlorotoluene

Q.9 Phenol, when it first reacts with concentrated sulphuric acid and then with concentrated nitric acid,
gives- [AIEEE 2008]

(A) o-nitrophenol (B) p-nitrophenol (C) nitrobenzene (D) 2,4,6-trinitrobenzene

Q.10 Toluene is nitrated and the resulting product is reduced with tin and hydrochloric acid. The product so
obtained is diazotised and then heated with cuprous bromide. The reaction mixture so formed contains-
[AIEEE 2008]
(A) mixture of o– and p-dibromobenzenes (B) mixture of o- and p-bromoanilines
(C) mixture of o- and m-bromotoluenes (D) mixture of o- and p-bromotoluenes

Q.11 The major product obtained on interaction of phenol with sodium hydroxide and carbon
dioxide is - [AIEEE 2009]
(A) salicylaldehyde (B) salicyclic acid (C) phthalic acid (D) benzoic acid

Q.12 Which of the following are classified as aromatic?

(A) 1, 2, 3-Triphenylcyclopropenium cation (B) Cyclooctatetraenyl dianion
(C) Azulene (D) Annulene

SnCl2 / HCl 2 NaNO / HCl

Q.13 C6H5NO2   A 
o
 B  Benzene, In the above sequence B  Benzene is suitably
0
obtained by using :
(A) Ethanol (B) H3PO2 (C) Both the above (D) Methanol

Q.14 Which of the following reactions of benzene proves the presence of three carbon–carbon double bonds
in it:
(A) Formation of a triozonide with ozone
(B) Hydrogenation of benzene to cyclohexane
(C) Formation of C6H6Cl6 by addition of chlorine
(D) Formation of nitrobenzene on heating benzene with a mixture of concentrated nitric acid and sulphuric
acid

AROMATIC COMPOUND [161]

Q.15 Which of the following can be used in Friedel Crafts reaction to generate electrophile?

(A) (B) CH2=CH–Cl (C) CH3CH2Cl (D) CH2=CH–CH2–Cl

Q.16 Aniline is purified by :

(A) Azeotropic distillation (B) Steam distillation
(C) distillation in presence of magnesium (D) Fractional crystallisation

Q.17 The replacement of a hydrogen atom in benzene by alkyl group can be brought about with the following
reagents:
(A) Alkyl chloride and AlCl3 (B) Alkene and AlCl3
(C) Alkanol and alkali (D) Alkanol and acid

Q.18 C6H5NH2, CHCl3 and KOH give the main product :

(A) Phenyl cyanide (B) Benzyl cyanide (C) Benzyl carbylamine (D) Phenyl isonitrile

Q.19 Benzene reacts with n-propyl chloride in the presence of anhydrous AlCl3 to give predominantly:
(A) n-Propylbenzene (B) Isopropylbenzene
(C) 3-Propyl-1-chlorobenzene (D) Cumene

Q.20 Aniline on direct nitration produces :

(A) o-Nitroaniline (B) m-Nitroaniline (C) p-Nitroaniline (D) 1 & 3 are correct

Q.21 Which of the following does not gives Friedel-Crafts reaction?

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

Q.22 Which one of the following is not an azo compound :-

(A) Methyl orange (B) Benzenediazonium chloride
(C) Phenolphthalein (D) p-hydroxyazobenzene

Q.23 The good method for converting benzene into propyl benzene is:
(A) C6H6 + CH3CH2CH2Cl + Anhyd. AlCl3
(B) C6H6 + CH3CH2COCl + Anhyd. AlCl3 and then treatment with Zn/Hg/HCl
(C) C6H6 + CH3CH2COCl + Anhyd. AlCl3 and then treatment with H2 Ni
(D)C6H6 + Anhyd. AlCl3 + cyclopropane

Q.24 Which of the following statements is incorrect for electrophilic substitution.

(A) Ortho-and para-directing groups increase electron density at ortho-and para-positions
(B) Meta-directing groups increase electron density at meta-position
(C) Meta-directing groups decrease electron density at meta-position
(D) Ortho-and para-directing groups decrease electron density at meta-position

AROMATIC COMPOUND [162]

Q.25 Nitration of aniline is carried out after acylation, because :
(A) Oxidation can be avoided
(B) Reaction becomes manageable
(C) o and p-nitroanilines are obtained in good amount
(D) All the above .

Q.26 Which of the following statements is/are not true?

(A) All ortho-para directing groups activates the ring
(B) All ortho-para directing groups except halogens activate the ring
(C) All meta-directing groups have -bond on the atom directly attached to the ring
(D) All meta directing groups are deactivating.

Q.27 Nitration of aniline comes under :

   
(A) N u-addition (B) N u-substitution (C) E -addition (D) E -substitution

Q.28 False statement is / are :

(A) Although benzene contains three double bonds, normally it does not undergo addition reaction.
(B) m-chlorobromobenzene is an isomer of m-bromochlorobenzene.
(C) In benzene, carbon uses all the three p orbitals for hybridization.
(D) An electron donating substitutent in benzene orients the incoming electrophilic group to the meta
position.

Q.29 Urethanes are esters of –

(A) Carbamic acid (B) Citric acid (C) Malonic acid (D) Succinic acid

Q.30 Amongst the following, the moderately activating group is

R
||
(A) —NHR (B) —NHCOCH3 (C) – O – C – R (D) —CH3

AROMATIC COMPOUND [163]

 ANSWER KEY

EXERCISE I
Q.1 B Q.2 B Q.3 C Q.4 D Q.5 D Q.6 D Q.7 C
Q.8 B Q.9 B Q.10 C Q.11 D Q.12 D Q.13 A Q.14 B
Q.15 C Q.16 A Q.17 D Q.18 B Q.19 D Q.20 A Q.21 A
Q.22 A Q.23 C Q.24 C Q.25 C Q.26 C Q.27 D Q.28 D
Q.29 B Q.30 D

EXERCISE–II
Q.1 C Q.2 B Q.3 A Q.4 A Q.5 A Q.6 A Q.7 D
Q.8 C Q.9 A Q.10 D Q.11 B Q.12 ABC Q.13 C Q.14 ABC
Q.15 CD Q.16 B Q.17 ABD Q.18 D Q.19 BD Q.20 B Q.21 BCD
Q.22 C Q.23 BD Q.24 BCD Q.25 A Q.26 ABC Q.27 D Q.28 BCD
Q.29 A Q.30 BC

AROMATIC COMPOUND [164]

 BIOMOLECULES
I. Introduction :
(a) All common activities of a living organism (bioactivity) involve reactions of certain organic
compounds (mostly organic). Such compounds are called ‘biomolecule’
(b) The synthesis of a biomolecules inside the body is known as anabolism while its degradation to
simple products is known as ‘catabolism’ and two process collectively are called metabolism.
(c) Nowadays, carbohydrates are defined as the optically active polyhydroxy aldehydes or ketones
or Substances which yield these on hydrolysis.

II. Carbohydrates :
(a) In these compounds H : O = 2 : 1 (same as water).
(b) Animal cell – Glucose, Glycogen. (forms of carbohydrates).
(c) Plant cell – cellulose, starch form (In plant cells carbohydrates are stored in form of starch).
(d) It’s formula is : Cn(H2O)m.
(e) These are called hydrates of carbon.

Classification
Carbohyrates
 Are of 3 types
  
Monosaccharides Oligosaccharides Polysaccharides

1. Monosoccharides :
(a) In it n = m
(b) There naming is of following type –
S.No. Formula Group Aldolase Ketose

1 C 3H 6O 3 Triosase Gylceraldehyde Dihydroxy acetone

2 C 4H 8O 4 T etrosase Eryithrose Erythrulose

3 C5H10O5 Pentosase Ribose Ribulose
4 C6H12O6 Hexosase Glucose Fructose.

Because in monosaccharides - CHO (Aldehyde) group is present so it keep reducing nature. They are
reduced by Fehling (Cu2O), Benedict solution.
(c) In aldolase aldehyde group is present and all central molecules are asymmetrical (chiral).
(d) In ketose ketone group is present and except 2nd carbon all molecules are asymmetrical.
(e) These are found in two isomeric forms L–form and D–form
(f) Simplest sugar  Glyceraldehyde
(g) Monosaccharides are of two types

 
Cyclic Non–cyclic

Biomolecules & Polymer [165]

 (h) Cyclic compound are of 2 types :

¯ ¯
Pyranosase Furanosase
¯ ¯
Ring made up of 6 members Ring made up of 5 members

(i) Pyranosase and furanosase name was Coined by Howorth on basis of thermodynamics.
(j) Body sugar is called as glucose.
(k) Fructose, Mannose and galactose are hexoses.
(l) Water hydrolysis of monosaccharides cannot take place.
(m) Main isomeric form in it is –isomers, ,  isomers  Anomeres.

(i) Derivatives of Monosaccharides : Following are derivatives of monosaccharrides.

(a) Deoxy suger : If 1 hydrogen occupies the position of one – OH or one – OH is replaced by one -H
than deoxy sugar is formed.

H–C=O H–C=O
| |
H–C–H H – C – OH
| |
H – C – OH H – C – OH
| |
H – C – OH H – C – OH
| |
H – C – OH H – C – OH
| |
OH OH
Deoxyribose Ribose

(b) Amino sugar : –OH group of Aldolase is replaced by –NH2 group than it is called as amino sugar.
Eg. D–glucosamine, D–galactosamine

(ii) Structure of Glucose & Fructose Glucose is adohexose it is a monomer of larger carbohydrate.
structure:

FRUCTOSE (LAEVULOSE), C6H12O6

Fructose is a ketohexose. It is obtained along with glucose by the hydrolysis of sucrose..

Biomolecules & Polymer [166]

Structure of Fructose
Fructose has the molecular formula C6H12O6 and on the basis of its reactions it was found to contain a
ketonic functional group at C—2 and six carbon atoms in straight chain as in case of glucose.
It belongs to D-series and is a laevorotatory compound. Therefore, fructose is correctly named as
D-(–)-fructose. Its open chain structure may be written as:

Fructose also exists in two cyclic forms which are obtained by the addition of –OH at C–5 to the
( = O) group. The ring thus formed is a five membered ring and is named as furanose with analogy
to the compound furan.

The cyclic structures of two anomers of fructose are represented by Haworth structures as given

2 Oligo saccharides :
It is formed by combination of 2 to 9 mono saccharide units.
(i) Disaccharides :
(a) The disaccharides are sugars composed of two molecule of same or different monosaccharides.
(b) Generally one molecule of water is reduced in forming disaccharides.
(c) Reaction is called as dehydrogenation
(d) General Formula = Cn(H2O)n–1
(e) Monosaccharides attach called as monomers.
(f) Bond present in between them is called as glycosidic bond.

Biomolecules & Polymer [167]

 Some Important Disaccharides :

(i) Maltose  Glucos e  Glucos e  Maltose

(ii) Lactose  Galactose  Glucos e  Lactose

 5% in milk (only mammals)

(iii) Sucrose  Glucos e  Fructose  Sucrose

 It is a commercial or kitchen sugar.

 It is called invert sugar or (cane sugar)
 Hydrolysis of sugar is called as inversion of sucrose
 Equimolar mixture of glucose and fructose called as invert sugar.
(iv) Trehalose
 It is the major sugar of insect haemolymph. Among plants,.it is found in fungi and yeasts.
(ii) Trisaccharides : (Three monomers)
(a) Manotriose = 2 Galactose + 1 Glucose
(b) Raffinose = 1 Glucose + 1 Galactose + 1 Fructose
 It is found in cotton seed.
(c) Melanoxylose = 1 Fructose + 2 Glucose
(iii) Tetrasaccharides (Four monomers)
 Stachyose = 1 Glucose + 1 Fructose + 2 galactose
3 Polysaccharides
(a) Polysaccharides yield more than 9 molecules of monosaccharides on hydrolysis.
(b) General Formula = (C6H10O5)n.
(c) These are linear polymers and also highly branched
(d) These are not called as sugar. because are not sweet in taste.
Excep. - Inulin is sweet.
(e) Glycosidic bond is present between monomers
(f) Suffix - ‘an’ is present in last part of there names.
Polysaccharides
 two types
 
Homopolysaccharide Heteropolysaccharides

(i) Homopolysaccharides :
(a) There monomers are of one type of monosaccharides.
(b) These are simple type polysaccharides.
(c) Physiologically important homopolysaccharides.

(A) Starch

Biomolecules & Polymer [168]

  Stored food of plant
 It is most improtant food source
 It is found in normal amount in all types of food source It is insoluble in water.
 It gives blue colour with iodine
 Its monomer is a –D glucose.
 It is mixture of two compounds.

 
Amylose Amylopectin

(a) Amylose :
 They give blue colour with I2.
 It is 15% to 20% in starch.
(b) Amylopectin :
 Branch of 24–30 glucose monomers.
 Give Purple colour with I2.
 It is 80–85%.
(B) Glycogen :
 Stored food of animals.
 Called as animal starch.
 Give red colour with I2.
(C) Cellulose ;

 It is mainly found in plant cells.

 It is main constituent of cell wall.

Preparation of Glucose
1. By Hydrolysis of Cane-sugar
In laboratory glucose can be prepared by hydrolysis of cane-sugar in the prsence of alcohol using dilute
hydrochloric acid. Glucose and fructose are formed in equal amounts. Glucose, being less soluble in
ethyl alcohol than fructose, crystallizes out.
H
C12H22O11 + H2O   C H O +C H O
6 12 6 6 12 6
Sucrose Glucose Fructose
2. By Hydrolysis of Starch
Glucose is obtained, on commercial scale, by hydrolysis of starch by boiling it with dilute sulphuric acid
at 393 K under a pressure of 2–3 bar.

H
(C6H10O5)n + nH2O    nC H O
393 K ,2  3bar 6 12 6

Starch Glucose

Evidences that support the linear structure of Glucose

1. Reduction
Ni
HOH2C . (CHOH)4 . CHO + H2  HOCH2.(CHOH)4 . CH2OH
Sorbitol

Biomolecules & Polymer [169]

2. Reaction with Hydrogen Iodide
HI
HOCH2 – (CHOH)4 – CHO  H3C – CH2 – CH2 – CH2 – CH2 – CH3
n-Hexane
3. Oxidation
Br / H O
HOH2C . (CHOH)4 . CHO + [O]    HOCH2 .(CHOH)4 . COOH
2 2

Gluconic acid
IV PROTEINS
(a) Proteins are polymers of amino acids.
(b) Protein is 3/4 part of dry weight of tissues.
(c) Protein forms structure of body.
(d) C, H, O, N are necessary present in proteins.
(e) In some proteins P, S, Fe, Cu, I, also may be present. They are called trace elements.
(f) 70 types of Amino acids are known. But in proteins about 20 types of amino acids are used.
other amino acids are called non-proteinious amino acid for e.g. citruline, ornithine
1 Chemical Structure :
(a) Amino acids can be given by the general formula.
R R
H2N–C–C–OH or H2N–C–COOH
H O H
R = Alkyl group.
(b) If 'R' Changes amino acids formed also changes.
e.g. If R = H  Glycine (Simplest A. Acid)
If R = CH3  Alanine
If R = CH2OH  Serine.
'R' group attach with the carbon than that carbon is called  - carbon.
H
NH2–C–COOH or NH2–CH2–COOH
H
Glycine
CH2OH CH3
NH2–C–COOH NH2–C–COOH
H H
Serine Alanine
(c) Amino acids have also NH2 group. Which is basic and also COOH group. Which is acidic. So
Nature of Aminoacid is Acidic + Basic
(d) Amino Acids are amphoteric in nature. So for it a special term is coined called Zwitter ion.
(e) They have following structure in solution
R
+
H 3N–C–COO –

H
[Zwitter Ion]
[Net charge on it is zero]

Biomolecules & Polymer [170]

2 Classification of Amino Acids :
(A) According to synthesis amino acid is of two types-
(i) Essential amino Acids :
 These are taken by food. Not synthesized in the body.
 These are as follows
(1) Leucine (2) Isoleucine
(3) Lysine (4) Methionine
(5) Phyenyl alanine (6) Threonine
(7) Tryptophan (8) Valine
Arginine and Histidine are semiessential amino acids ie. they are bartly synthesized in tissues.
(ii) Non - Essential Amino Acid :
(a) These are synthesized in body.
(b) These are not required in food.
(c) These are as follows
(1) Alanine (2) Aspargine
(3) Aspartic acid (4) Cistine
(5) Glutamic acid (6) Glutamine
(7) Hydroxy proline (8) Glycine
(9) Proline (10) Serine
(11) Tyrosine
(d) Except glycine all Amino Acid has 2 optical image (1 and 2)
(e) Optical isomerism are those which has a simmilar common formula but there images opposes
to each other.
(f) For it chiral carbon atom is necessary. Chiral carbon atom is that carbon atom whose four
valency are not satisfied by same group or atoms.
(g) In Glycine chiral carbon atom is absent. It is optically inactive.
(h) L-form synthesize protein.

3 Peptide bond :
(a) Two or more than two amino acid linked and form a peptide.
(b) The bond present in between peptides is called peptide bond.
It is of 3 types

Dipeptide Tripeptide Polypeptide

(nAA = 2) (nAA = 3) (nAA > 3)

(c) A peptide bond is bond between -NH3 of one Amino acid and -COOH of another amino acid.
R R R R
| | H2O
| |
H– N – C – C – O  H  H – N – C – C – OH  
 H– N – C – C–N –C – C –OH
| | || | | || | | || | | ||
H H O H H O H H O H H O

Amino Acid Amino Acid Peptide Bond

Formation of Peptide Bond

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4 Configuration of proteins :
(a) Biological nature or function of protein was confirmed by its conformation.
(b) This conformation is of 4 types

Primary Secondary Tertiary Quaternary

(A) Primary Structure :

 This type of structure was given by Friedrich Sanger in 1953 in Insulin (of one chain)
 Primary structure is conformed by a single polypeptide chain in a linear manner.
 All amino acid are attached in a straight chain by peptide bond.
 No biological importance & soon changed to other forms.

(B) Secondary Structure :

 In it structure of straight chain from irregular changes to form coils.
 H-bond + peptide bond present in secondary. structure.
 This H bond is present between hydrogen of Amino group and oxygen atom carboxylic
acid group.
 This structure is of two types

-helix - pleated sheet

C
O N N N
C RCH RCH RCH
C
54 pm

O C C C O
HO H N O O
C H H N H N
N HCR
O C HCR HCR
N
H O C C C
C O N H O O H
H
C N N H N
O RCH RCH RCH
N O
H H C C C O
H O O
N N H N H N
HCR HCR
H N HCR
C C C
N

(i)  - helix
 Chain is spiral
 3.7 atoms in one coiling
 Right handed circular.
Eg.  Myosin, Keratin etc.
(ii)  -pleated sheet
 Structure of protein is not arranged in a sequence.
 Polypeptide chain are parallel to each other
 H - bond form by near chains Eg. Silk fibres.

Biomolecules & Polymer [172]

(C) Tertiary structure :
 In this structure of protein atoms are highly coiled and form a spherical form
Ex. Albumin
 This structure is formed by 4 regular hydrogen bonds which makes a regularity in it
(i) Hydrogen bond :
|
C = O........H — N —
| |
H
Hydrogen bond

 They are formed between oxygen of acidic amino acid and H of basic amino acid.
(ii) Hydrophobic bond -
 Non - polar side chains of neutral amino acid tends to be closely associated with one another in
proteins.
 Present in between the amino Acid.
 These are not true bonds.
(iii) lonic bond :
– COO–.....H3+N –
Ionic bond

 These are salt bonds formed between oppositely charged groups in side chains of Amino acids
Eg. Aspartic acid
Glutamic acid
(iv) Disulphide bonds :

| ------ S - S ---- |

 Relatively stable bond and thus is not broken readily under usual conditions of denaturation.
 Formed between the -SH group of Amino acid Ex. Cystine and Methionine.

(D) Quaternary structure :

 When 2 or more polypeptide chains united by forces other than covalent bonds (i.e. not peptide
and disulphide bonds) are called Quaternary structure.
 It is most stable structure.
Ex. Haemoglobin

5 Types of proteins
 Classification of protein is based upon three general properties shape, Solubility and Chemical
composition.
Proteins


                              
Simple Conjugated Derived

Biomolecules & Polymer [173]

(i) Simple proteins
 It is formed of only Amino Acids
 Types

       
Fibrous Globular

(A) Fibrous :
 It is insoluble
 It is of elongated shape.
 It is highly resistant to digestion by proteolytic enzymes.
 Their main function - Protection.
Ex. Collagen, Keratin etc

(B) Globular :
 These are spherical and oval in shape. Chains are highly coiled
 These are soluble.
Ex. Albumin

(ii) Conjugated Proteins

 These are complex proteins in which protein molecule is combined with characteristic non-
amino acid substance.
 Non-amino acid or Non - Protein part is called as prosthetic group
Ex. Nucleoproteins
(Protein + Nucleic acid),
Phosphoproteins (Protein + (PO3)2–)
Eg.  Casein of milk., Vitelline of egg - yolk

(iii) Derived proteins :

(a) These are obtained as a result of partial hydrolysis of natural proteins.
Eg.  Proteose, Metaproteins, Peptones

(b) Denaturation of Proteins

When a protein in its native form, is subjected to a physical change like change in temperature, or a
chemical change like change in pH, the native conformation of the molecule is disrupted and proteins so
formed are called denaturated proteins.
The denaturation may be reversible or irreversible. The coagulation of egg on boiling is an example of
irreversible protein denaturation.
However, it has been shown now that in some cases, the process is actually reversible. The reverse
process is called renaturation.

6 Test of Protein :
(a) With conc. HNO3 on heating give yellow ppt. Which on more heating give solution On adding
NH4OH Red colour appears. It is Xanthoprotic test.
(b) (NH4OH) + dil. CuSO4 protein give Blue violet colour. It is a biurete test.

Biomolecules & Polymer [174]

7 Biological Importance of protein :
(a) Component of plasma membrane.
(b) All enzymes are protein.
(c) Many hormones are protien.
(d) Antigen and antibody are protein.
(e) Actin and myosin protein are important in muscle contraction.
(f) Proteins are important in growth, regeneration and repairing.
(g) Calorific value 4.0 kcal.

8 Nucleic Acid :
(a) These are special type of acids which are present in nucleus & cytoplasm.
(b) Control help in metabolic activity of cell
(c) They are also found in Mitochondria, centriole and chloroplast.
DNA (Deoxy Ribo Nucleic acid)
Types  These are of 2 types
RNA (Ribo Nucleic acid)

(d) It is discovery by First of all in pus cells of WBC iri 1869 by Friedrich Meischer.
(e) Fischer discovered Nitrogen bases in 1888
Nitrogen Base

 
Purine Pyrimidine
(f) Levan found sugar
 2 types
 
Ribose (RNA) Deoxyribose (RNA)
(g) Altman coined the term “nucleic acid”

9 DEOXY RIBONUCLIC ACID (D.N.A.) :

(a) It is found in Nucleus
(b) Double helical structure of DNA was given by Watson Crick. (a)
(c) Chargaff told that ratio of A or T and G or C = 1
(d) DNA made up of 3 units

  
Nitrogen base Deoxyribose sugar Phosphoric acid (H3PO4)

 
Pyrimidine Purine
[i] Thymine [i] Adenine
[ii] Cytosine [ii] Guanine

Biomolecules & Polymer [175]

 (e) Nucleoside
When nitrogen base combined with deoxyribose sugar it constitute a nucleoside.

Deoxyadenosine  It is a part of Nucleotide.

(f) Nucleotide
(g) Nitrogen base + Sugar + Phosphate  Nucleotide
(h) It is a unit of DNA
(i) All nucleotides combined and form a chain called polynucleotides by which RNA and DNA
formed.
(A) Function of DNA :
(i) Self–Replication or self–Duplication
(ii) Protein Synthesis
(iii) Mutation 

(B) Replication of DNA :

(a) The synthesis of new DNA molecules from preexisting DNA is called replication.
(b) It occurs in mitosis and meiosis I in S phase of interphase.
(c) DNA replication is semiconservative proposed by Watson and Crick.

(C) Significance of DNA :

Chromosomes are mainly composed of DNA, RNA and histone protein.
Among these molecules, DNA is the main hereditary material.

10. Ribonuclic Acid (RNA) :

Found in cytoplasm as well as in nucleus.
Cytoplasm  In the ribosome (heigher amount)
Occourence
Nucelus  Nucleus
(A) Types of RNA and their Functions :
There are 3 main types of RNA molecules
(i) Messenger RNA (mRNA)
(ii) Transfer RNA (tRNA)
(iii) Ribosomal RNA (rRNA)

(i) Messenger RNA (mRNA)

Discovered by Astrachan, Huxley.

Biomolecules & Polymer [176]

11. Enzymes :
Proteins which are used as a catalyst in biochemical reaction is known as biocatalysts.
(A) Structure of enzyme
(a) They are globular proteins.
(b) With having tertiary structure it can be collected as crystals.
(c) In the presence of enzymes biochemical reactions is completed with body temperature, normal
pressure and normal pH 7 in the body.

(B) Specific cheracteristics :

Enzymes have following two specific cheracter as :
(i) Specificity (ii) Efficiency

(C) Specificity of enzymes

(a) Generaly one enzyme can catalyze only one biochemical reaction.
(b) It can increases rate of reaction upto 1020 times.
(c) In some cases one enzyme can catalyzes more than one reaction and one reaction can be catalyzes
more than one enzyme also.
eg. Enzyme present in Yeast (Zymase) can fermant both glucose and fructose into .alcohol and also
cane-sugar can be hydrolyses by invertase and sucrase enzymes.
(D) Efficiency of enzymes
(a) One molecule of enzyme can convert millions of substrate molecules into product per second.
eg. Carbonic anhydrase enzyme present in red blood carpcells can convert 6 lac molecules of
carbonic acid into carbondioxide and water per second.
(b) With having tertiary structure it can be collected as crystals.
(c) Enzyme can be stored at low temperature.

(E) Importance of enzymes

In the thousands of enzymes presents in body if even a single enzyme would be absent or damaged than
complex disease in results.
eg. Scacity of Phenylalaine hydroxylase enzyme in human body is result in phenylketonuria disease.

11. VITAMINS
It has been observed that certain organic compounds are required in small amounts in our diet but their
deficiency causes specific diseases. These compounds are called vitamins.
Classification of Vitamins
Vitamins are classified into two groups depending upon their solubility in water or fat.

(i) Fat soluble vitamins:

Vitamins which are soluble in fat and oils. But insoluble in water are kept in this group. These are vitamins
A, D, E and K. They are stored in liver and adipose (fat storing) tissues.

(ii) Water soluble vitamins:

B group vitamins and vitamin C are soluble in water so they are grouped together. Water soluble vitamins
must be supplied regularly in diet because they are readily excreted in urine and can not be stored
(except vitamin B12) in our body.
Some important vitamins, their sources and diseases caused by their deficiency are listed in table.

Biomolecules & Polymer [177]

S.N. Name of Vitamins Source D eficiency Diseases

1 Vitamin A (Retinol) Fish liver oil, carrots, butter Xerophthalmia

and milk (hardening of cornea of eye)
N ight blindness
2 Vitamin B 1 (Thiamine) Yeast, milk, Green Beri beri (loss of appetite,
vegetables and cereals and retarded growth)
grams
3 Vitamin B 2 (Riboflavin) Milk, eggwhite, liver, Kidney C heilosis (fissuring at corners of mouth and
lips), digestive disorders and burning
sensation of the skin
4 Vitamin B 6 (Pyridoxine) Yeast, milk, egg yolk, cereals C onvulsions
and grams
5 Vitamin B 12 (Cyanocobal- Meat, fish, egg and curd Pernicious anaemia (RBC deficient in
amine) haemoglobin)

6 Vitamin C (Ascorbic acid) Citrus fruits, amla and green scurvy (bleeding gums)
leafy vegetables
7 Vitamin D (Calciferol) Exposure to sunlight, fish and R ickets (bone deformities in children) and
egg yolk osteo-malacia (soft bones and joint pain in
adults)
8 Vitamin E (Tocoferol) Vegetable oils like wheat Increased fragility of RBCs and muscular
germ weakness
oil, sunflower oil, etc
9 Vitamin K (phyllo-quinone) Green leafy vegetables Increased blood clotting time

Biomolecules & Polymer [178]

 POLYMERS

1. INTRODUCTION :
A polymer is a compound of high molecular mass formed by the combination of large number of small
molecules and process is called polymerisation. The small molecules which constitute the repeating units
in a polymer are called monomer units. These large molecule have relative molecular masses in the range
104 - 106.
eg.
nCH2 =CH2 [–CH2 – CH2–]n.
ethene polythene.
5
Where n is as high as 10 . The number of monomers units in a polymer is called the degree of
polymerisation.
2. CLASSIFICATION OF POLYMERS
Polymers are classified on the following basis -
2.1 Classification based on monomers :
(a) Homopolymer : The polymer formed from one kind of monomer is called homopolymer.
eg. Polyethylene
(b) Copolymer or mixed polymer : Polymer formed from more than one kind of monomer
units is called copolymer.
eg. Buna - S
2.2 Classification based upon origin or source :
There are of two types based on source
(a) Natural polymers whose source is animal and plants are called natural polymers
eg. starch,cellulose, protein etc.

(b) Synthetic polymers :- These are man made polymers synthesised in the laboratory from
low molecular weight compounds.
eg. Nylon, dacron, bakelite, synthetic rubber, polystyrene etc.
2.3 Classification bassed on structure :
These are of three types based on structure –
(i) Linear polymers
(ii) Branched chain polymers
(iii) Cross linked polymers
(i) Linear polymers : In which monomer units are linked together to form long straight chains. The
polymeric chains are stacked over one another to give a well packed structure. Such polymers have
high densities, high tensile strength and high melting points.
eg. : Polythene, Nylon and polyesters
(ii) Branched chain polymers : In this type of polymers, the monomeric units are linked to constitute long
chains (called main chain). There are side chains of different lengths which constitute branches. Branched
chain polymers are irregularly packed and they have lower tensile strength and lower melting points as
compared to linear polymers.
eg. : Amylopectin (Component of starch)

Biomolecules & Polymer [179]

(iii) Cross linked polymers : The monomeric units are linked together to constitute a three dimensional
network. Cross linked polymers are hard , rigid and brittle because of their network structure.
eg. : Bakelite, Formaldehyde resin etc.
2.4 Classification based on synthesis :
These are of two types based on synthesis -
(a) Condensation polymerisation: In this the monomer (same or different) units link with each other by
the elimination of a small molecule (e.g. water, methyl alcohol) as a by-product. The polymer formed is
known as condensation polymer. Nylon and terylene are the most common examples.
Since the condensation polymerisation proceeds by a stepwise intermolecular condensation, it is also
known as step polymersation and the polymer formed is known as step growth polymer.

(b) Addition polymerisation : This involves the self addition of several unsaturated molecules of one or
two monomers without loss of any small mulecule to form a single giant molecule. The polymer formed
is known as addition polymer. Polythene is the most common example.

Differences between Addition and Condensation Polymers

S.N. Addition polymers Condensation polymers
1. Formed by addition reaction. Formed by condensation process with
elimination of small molecules like H2O.
2. Molecular mass is a whole number multiple Molecular mass is not whole number multiple
of the monomer. of the monomer units.
3. Generally involve one monomer unit. Generally involve more than one monomer
unit.
4. Monomers are unsaturated molecules. Monomer units must have two active
functional groups.
5. They are generally chain growth polymers. They are generally step growth polymers.

2.5 Classification based on intermolecular forces :

(a) Elastomers : These are the polymers having elastic character. The polymer chains in such type of
polymers are held together by weakest intermolecular forces. These forces permit the polymer to be
stretched under stress but they regain their former shape when the stress is relieved. The elasticity of
such polymers can be further modified by introducing few cross links between the chains.
eg. : Natural rubber
(b) Fibres : These are the polymers which have quite strong interparticle forces such as H-bonds.
eg. : Nylon , Dacron etc.
(c) Thermoplastics : These are the polymers which can be easily moulded into desired shapes by heating
and subsequent cooling to room temperature. The intermolecular forces in thermoplastic polymers are
intermediate to those of elastomers and fibres. Thermoplastic polymers soften on heating and become
fluids but on cooling they become hard.
eg. : Polyethene, Polystyrene
(d) Thermosetting polymers : These are the polymers which become hard and infusible on heating.
Heating results in excessive cross linking between the chains forming three dimensional network of bonds.
eg. : Bakelite, Melamine

Biomolecules & Polymer [180]

3. METHOD OF POLYMERISATION
(a) Addition Polymers :
(i) A polymer formed by direct addition of repeated monomer’s without the elimination of any
byproduct molecules.
(ii) In this type, the monomers are unsaturated compounds and are generally derivative of ethene.
(iii) The addition polymers have same empirical formula as their monomers.
Ex. Nylon 6, 6, Terylene, bakelite etc.
Chain growth polymerization :
(i) There is a series of reaction each of which consume a reactive particle and produce another,
similar particle, each individual reaction thus depend upon the previous one.
(ii) The reactive particle can be free radical, cations or anions.
(iii) The polymerization start when a molecule of monomers react with an initiator to form an active
intermediate.
(iv) This active intermediate is added to another monomer forming another intermediate. In this way
chain propagation continue and ultimately a polymer is formed.
(a) Peroxide  Rad• Chain initiating step
(b) CH2  Rad – CH2 – CH2
Chain Propagating step
(c) Rad – CH2 – Rad –CH2 – CH2 – CH2 – CH2
Chain Propagating step
(d) Rad – CH2 – CH2 – CH2– CH2• 
[–CH2 – CH2–]n + Rad• 
Chain terminating step
Example :
Polyethylene, Polypropylene, PVC, teflon, etc.
Monomer Polymer Uses

Polythene Bags, toys etc.

Polypropylene Beakers, mill cartons etc.

Polyvinyl chloride (PVC) Rain Coats, pipes, tiles etc.

Carpets etc.

Biomolecules & Polymer [181]

 Polystyrene Thermocole, insulating, material etc.

Plexiglass Transparent objects lenses etc.

Teflon (PTFE)

4 NATURAL RUBBER
(a) It is cis Polyisoprene

H3C H H3C H H3C H H 3C H H 3C H H 3C H

1,4-addition
C–C + C–C + C–C C=C C=C C=C
2 3 2 3 2 3
H2C CH2 H2C CH2 H2C CH2 CH2 CH2 CH2
1 4 1 4 1 4 H2C H2C H2C

Isoprene cis -polyisoprene (natural rubber)

(b) Gutta percha:

H3C CH2 H2C H H3C CH2 H3C CH2 H2C H H3C CH2
C–C + C–C + C–C C=C C=C C=C
H CH2 H H CH2 H
H2C H3C H2C H2C H3C H2C

trans - polyisoprene (gutta percha)

5. SYNTHETIC RUBBER

(i) Buna S : It is copolymer of 1, 3 butadiene and styrene. It is obtained by the polymerisation of butadiene
and styrene in the ratio of 3 : 1 in the presence of sodium
CH=CH2

nCH2=CH–CH=CH2 + n Heat,Na
  (–CH2–CH=CH–CH2–CH–CH2–)n

Buna-S
Butadiene styrene
Uses : Buna - S is also vulcanised and used in making tyres for the vehicles. It is also used as rubber
soles and in making water proof shoes.

Biomolecules & Polymer [182]

(ii) Buna-N :
CN
| CN
nCH2=CH–CH=CH2 + nCH2 = CH Copolymeri zation |
 
–(CH2 – CH  CH – CH2 – CH2 – CH)–n
Buna-N
1,3-Butadiene Acrylonitrile
 It is used in making oil seals, tank lining, etc.

(iii) Neoprene
nCH2= C –CH=CH2 K2S 2O
 8  (–CH – C =CH–CH –)
2 2 n
pot.per sulphate
Cl Cl

Chloroprene Neoprene

Vulcanisation :
In vulcanisation rubber is heated (3 hrs) it with sulphur (3-10%) at a temperature of 125-1400C.
Rubber hydrocarbon combines with the sulphur atoms to form the sulphur bridges. The resulting
product is tough, non-elastic and resistance to heat. It becomes non-abrasive and not affected by
chemicals.

S
S
–CH2–C(CH3)–CH–CH2
–CH2–C(CH3)=CH–CH2– +S S
–CH2–C(CH3)=CH–CH2– Vulcanisation
S
–CH2–C(CH3)–CH–CH2–
S
S

6. STEP GROWTH POLYMERISATION

(i) This type of polymerization involve a series of reaction each of which is essentially independent
of the proceeding one.
(ii) A polymer is formed simply because the monomer happen to undergo reaction at more than
one functional group.
(iii) In the case of polyester, a diol for example, react with a dicarboxylic acid to form an ester
but each moiety of the simple ester contain a group that can react to generate another ester
linkage and hence a large molecule, which itself can react further, and so on

  O  CH 2  CH 2  O  C C 
HOCH2CH2OH + HOOC – COOH  —
 || || —

 O O 
 n

C H 2  OH   O  CH 2  CH 2  O  C C 
| + HO  C (CH 2 ) 4  C O  H H —
 || || 
—
CH 2  OH || ||  O O 
O  n
O

Biomolecules & Polymer [183]

6.1 Condensation polymers :
(i) A polymer formed by the condensation of two or more than two monomers with the elimination
of simple molecule like -
H2O / NH3 etc..
(ii) In this type, each monomer generally contain two functional group. Ex.Nylon 6, 6, Terylene,
bakeliteete
O
(a) Polysters : These are the polymers having ester linkage ( – C –O–)
Example : Terylene :
O O
nHO–CH2–CH2–OH + nHO–C– – C–O–H

Ethylene Glycol terephathalic acid

–nH2O
O O
(–O–CH2–CH2–O–C – – C–)n

terylene

O
(b) Polyamides : Such polymers have amide linkage (–C–N–) in the chain
H

O O
nH2N–(CH2)6–NH2 + nHO–C–(CH2)4–C–OH
Hexa methylene diamine Adipic acid

H H O
(i) Nylon -66 [–N–(CH2)6–N–C–(CH2)4–C–]n + nH2O Heat
O
(nylon 66)
Uses : Nylon 66 have high tensile strength so it is used in the manufacture of carpets, textile fibres and
bristles for brushes. It is used in making elastic hoisery.

(ii) Nylon-6
O NOH

Oxidation NH2OH
–H2O

Oxime

H2SO4
Backmann rearrangement

Carpolactum
H2O H2N — (CH2)5 — COOH
Heat

O
||
Heat
(— NH — (CH2)5 — C —)n

(Nylon–6)

Biomolecules & Polymer [184]

(c) Phenol-formaldehyde resins( Bakelite)

OH
Base
+ HCHO

Bakelite
Because bakelite is hard and is a good electrical insulator, it is extensively used on making electrical
switches, fuse holders, etc.
(d) Glyptal or (alkyd resin) : The most simple glyptal (polyethylene phthalate) formed from the
polycondensation of glycol and phthalic acid.

O O
HOOC COOH
——O–CH2–CH2–O–C C—— + nH2O

n[HO–CH2–CH2OH] + n

Uses : It is used in the manufacture of paints

(e) Melamine formaldehyde resin : Melamine formaldehyde resin is formed by the co-polymerisation of
melamine and formaldehyde.
NH2 N NH2 NH2 N NHCH2OH –HN N NH2–CH2–
HCHO
N N   N N Polymerization
   
 N N
NH2 NH2 NH
n
Melamine intermediate

Uses : It is used for making non breakable plastic crockery i.e cup plates etc.

7. MOLECULAR WEIGHT OF POLYMERS

There are two types of average molecular weight in case of polymers.
(a) Mn = Number average molecular weight.
(b) Mw = Weight average molecular weight.

Biomolecules & Polymer [185]

(a) Number average molecular weight ( Mn )
Total weight of the molecules
( Mn ) = Total number of molecules

If: n1 molecules of mol. wt. M1.

n2 molecules of mol. wt. M2.
n3 molecules of mol. wt. M3. Then
n1M1  n2M2  n3M3    
Mn 
n1  n2  n3    

ni Mi
Mn 
 ni

(b) Weight average molecular weight Mw

w1M1  w 2M2  w 3M3    
Mw 
w1  w 2  w 3    

[Weight = no. of molecules × molecular weight]

Where : w1 = weight of the molecules of mol. wt. M1
w2 = weight of the molecules of mol. wt. M2
w3 = weight of the molecules of mol. wt. M3
NOTE :– Polydispersity index (PDI) is the ratio of weight average mol mass to no. average mol
mass PDI = M w / M n
For natural polymers PDI = 1 i.e. Mw  Mn
For Synthetic polymers PDI > 1 i.e. Mw  Mn

POLYMER THEORY
Ex.1 The product of addition polymerization reaction is-
(A) PVC (B) Nylon (C) Terylene (D) Polyamide (Ans. A)
Sol. PVC (polyvinyl chloride) is an addition polymer while nylon, terylene and polyamides are condensation
polymers.
Ex.2 A raw material used in making nylon-6,6 is-
(A) Adipic acid (B) Butadiene
(C) Ethylene (D) Methyl methacrylate (Ans.A)
Sol. Nylon-6,6 is a copolymer of adipic acid [COOH(CH2)4COOH] and hexamethylene diamine.

Ex.3 Polymerisation of chloroethylene gives rise to the polymer -

(A) Polyethene (B) PVC (C) Teflon (D) Nylon (Ans.B)
Sol. Chloroethylene is CH2 = CHCl (vinyl chloride) whose polymer will be PVC (polyvinyl chloride).

Ex.4 Rubber is heated with sulphur and the process is known-

(A) Galvanization (B) Vulcanization (C) Bessmerization (D) Sulphonation (Ans.B)
Sol. It is used for making tyres.

Ex.5 Monomer of orlon is:

(A) vinyl chloride (B) styrene (C) propylene (D) acrylonitrile (Ans.D)
Sol. Acrylonitrile is CH2= CHCN

Biomolecules & Polymer [186]

 SOLVED EXAMPLES
BIOMOLECULES
Ex.1 Which of the following is not a reducing sugar-
(A) Glucose (B) Sucrose (C) Mannose (D) Fructose Ans. (B)
Sol. Sucrose is not a reducing sugar because it does not reduce fehling’s solution.

Ex.2 Which one of the following is the reagent used to identify glucose-
(A) Neutral ferric chloride (B) Chloroform and alcoholic KOH
(C) Ammonical silver nitrate (D) Sodium ethoxide Ans. (C)
Sol. Ammonical silver nitrate (Tollen’s reagent) oxidises glucose to gluconic acid and itself reduced to metallic
silver.

Ex.3 Following is/are the oligosaccharides-

(A) Glucose (B) Sucrose (C) Lactose (D) Cellulose Ans. (B,C)
Sol. Oligosaccharides are the compounds which give 2 to 10 monosaccharides on hydrolysis. For example
- sucrose, lactose, maltose etc

Ex.4 N  C  group is characteristic of-

| ||
H O

(A) Cellulose (B) Nucleic acid (C) Proteins (D) Phospholipids Ans. (C)
 N  C 
Sol. Peptide bond  | ||  is characteristic of proteins.
 H O 
 

Ex.5 The pH value of a solution in which a polar amino acid does not migrate under the influence of electric
field is called-
(A) Isoelectronic point (B) Isoelectric point
(C) Neutralisation point (D) None Ans. (B)
Sol. Isoelectric point is the pH at which structure of amino acid has no charge.

Ex.6 The simplest amino acid is-

(A) Glycine (B) Alanine (C) Guanine (D) All the above Ans. (A)
Sol. Simplest amino acid is glycine (amino acetic acid H2 N– CH2 – COOH).

Ex.7 The main structural feature of protein is–

(A) Ester linkage (B) Ether linkage (C) Peptide linkage (D) All of these Ans. (C)
Sol. The main structural feature of proteins is the presence of peptide linkage.

Ex.8 The primary structure of a polypeptide is determined by-

(A) The numer of disulphite bonds in the polypeptide
(B) The number of amino acids in the polypeptide
(C) The order of amino acids in the polypeptide
(D) The length of the polypeptide Ans. (C)
Sol. The primary structure of a polypeptide is the information of order of different amino acids in that
polypeptide.

Biomolecules & Polymer [187]

Ex.9 DNA molecule consists of units of-
(A) Base–sugar (B) Base – sugar– phosphate
(C) Base – phosphate (D) None of these Ans. (B)
Sol. DNA has nucleotide unit, i.e., Sugar + base + H3 PO4 .

Ex.10 The process of formation of RNA from DNA is known as-

(A) Translation (B) Transcription (C) Replication (D) Mutation Ans. (B)
Sol. The process of formation of RNA from DNA is called transcription.

Ex.11 The organic compound which will answer Fehling’s solution test is-
(A) Ethanol (B) Acetone (C) Maltose (D) Benzaldehyde Ans. (C)
Sol. Maltose, being reducing sugar, reduces Fehling solution.

Q.12 The main point of difference between DNA and RNA is-
(A) Presence of thymine in DNA and RNA
(B) Presence of deoxyribose and thymine in DNA, ribose and uracil in RNA
(C) Presence of ribose and thymine in DNA, deoxybribose and uracil in RNA
(D) Presence of deoxyribose in DNA and ribose in RNA Ans. (B)
Sol. DNA has deoxyribose sugar, RNA has ribose sugar with three bases common as adenine, guanine and
cytosine. DNA has fourth base thymine ; RNA has uracil.

POLYMER

Ex.13 Which one is used as a heterogeneous catalyst in the polymerization of ethylene into polyethene-
(A) Walker catalyst (B) Ziegler-Natta catalyst
(C) Wilkinson’s catalyst (D) Ruthenium catalyst (Ans.B)
Sol. In the polymerisation of ethylene into polyethylene Zeigler–Natta catalyst (Triethyl aliminium + Titanium
tetrachloride) is used as heterogeneous catalyst.

Ex.14 Natural polymer is-

(A) Polyester (B) Glyptal (C) Starch (D) Nylon-6 (Ans.C)
Sol. Starch is natural polymer of D glucose.

Ex.15 Which is a synthetic rubber-

(A) Buna-S (B) Neoprene (C) Both the above (D) None (Ans.C)
Sol. Buna – S and neoprene are synthetic rubber.

Ex.16 Thermosetts are-

(A) Cross - linked polymers
(B) Do not melt (or soften) on heating
(C) Cross-linking is usually developed at the time of moulding where they harden irreversibly
(D) All (Ans.D)
Sol. Ex of thermosetts is bakelite

Biomolecules & Polymer [188]

Ex.17 Di–n–butyl phthalate is-
(A) Plastisizer (B) Thermoplastic
(C) Polymer (D) Thermosetting plastic (Ans.A)
Sol. Di–n–butylphthalate is plastisizer added to PVC to make it soft.

Ex.18 Natural rubber is-

(A) Trans polyisoprene (B) Cis polyisoprene
(C) Cis and trans isoprene (D) None of these (Ans.B)
Sol. Natural rubber is a homopolymer of cis-isoprene.

Ex.19 The structual formula of monomer of poly methymethacrylate (PMMA) is-

CH3
|
(A) CH2 = CHCOOCH3 (B) CH2  C  COOCH3

(C) CH3COOCH=CH2 (D) CH3 COOC  CH2 (Ans.B)

|
CH3

Sol. Formula 2nd is of methyl methacrylate, the monomer of PMMA. or Plexiglass.

Ex.20 Which one of the following compounds is polyester-

(A) Bakelite (B) Nylon 6,6 (C) Terylene (D) Rubber (Ans.C)
Sol. Terylene is a polyester fibre made up of by the polymerisation of ethylene glycol and pterephthalic acid.

Ex.21 Nylon is classified as a condensation polymer because-

(A) In its preparation a solid is formed from liquid monomers
(B) Its structure contains the peptide linkage, –CONH–
(C) It can be prepared from aqueous solutions of its monomers
(D) A small molecule is eliminated in its formation from its monomers (Ans. D)
Sol. Nylon is a condensation polymer because in the reaction of adipic acid with hexamethylene
diamine, small molecule H2O is eliminated in its formation.

Ex.22 The primary structure of a polypeptide is determined by-

(A) The number of disulphide bonds in the polypeptide
(B) The number of amino acids in the polypeptide
(C) The order of amino acids in the polypeptide
(D) The length of the polypeptide (Ans. C)
Sol. The primary structure of a polypeptide is the information of order of different amino acids in that
polypeptide.

Biomolecules & Polymer [189]

 EXERCISE – I
BIOMOLECULES
Q.1 Which of the following bonds determines the secondary structure of proteins ?
(A) Electrovalent bond (B) Covalent bond (C) Hydrogen bond (D) Coordinate bond

Q.2 Which of the following is called the power house of the living cell ?
(A) Golgi bodies (B) Nucleus (C) Mitochondria (D) Lysosome

Q.3 Which of the following part of the cell is the centre of protein synthesis?
(A) Plasma membrane (B) Golgi bodies (C) Ribosome (D) Lysosome

Q.4 Which of the following bonds is responsible for the coiled structure of proteins ?
(A) Dipeptide bond (B) Peptide bond (C) Hydrogen bond (D) Ionic bond

Q.5 Which of the following diseases is due to the deficiency of vitamin A ?

(A) Scurvy (B) Nightblindness (C) Beri-beri (D) Anemia

Q.6 Which of the following compounds is not the component of a balanced diet ?
(A) Vitamin (B) Hormone (C) Carbohydrate (D) Fat

Q.7 Insulin belongs to which of the following families ?

(A) Antiseptic (B) Vitamin (C) Hormone (D) Enzyme

Q.8 Which of the following acts as a biocatalyst ?

(A) Enzyme (B) Amino acid (C) Nitrogen molecule (D) Carbohydrate

Q.9 Which of the following enzymes convert starch to maltose ?

(A) Invertase (B) Zymase (C) Maltase (D) Diastase

Q.10 Which of the following is an example of an aldohexose ?

(A) Fructose (B) Glucose (C) Sucrose (D) Ribose

Q.11 Glucose and fructose are ................................... of each other

(A) homologues (B) functional group isomers
(C) mirror image isomers (D) nonisomers

Q.12 Which of the following disaccharides is found in the milk?

(A) Sucrose (B) Galactose (C) Lactose (D) Maltose

Q.13 Which of the following is invert sugar ?

(A) Mixture of glucose and galactose (B) Mixture of glucose and fructose in equimolar ratio
(C) A type of cane sugar (D) Optically inactive form of sugar

Q.14 Which of the following factors is not a denaturant of enzymes ?

(A) Heat (B) Mechanical energy
(C) High salt concentration (D) pH 7

Q.15 Which of the following is an example of a pentose sugar?

(A) Fructose (B) Arabinose (C) Glucose (D) Galactose

Biomolecules & Polymer [190]

 POLYMER
Q.16 Which of the following is not a copolymer-
(A) Plexiglass (B) Buna-S (C) Nylon-66 (D) Dacron

Q.17 Polymerisation in which two or more chemically different monomers take part is called-
(A) Addition polymerisation (B) Copolymerisation
(C) Chain polymerisation (D) Homopolymerisation

Q.18 Chemical name of melamine is-

(A) 2,4-Diamino-1,3,5-triazine (B) 2-Amino-1,3,5-triazine
(C) 2,4,6 -Triamino-1,3,5-triazine (D) 1,3,5-Triamino-2,4,6-triazine

Q.19 Carprolactum is used to prepare which of the polymer-

(A) Nylon – 66 (B) Melamine (C) Nylon–6 (D) PMMA

Q.20 The fibre obtained by the condensation of hexamethylene diamine and adipic acid is-
(A) Dacron (B) Nylon 66 (C) Rayon (D) Teflon

Q.21 Of the following which is a step growth polymer-

(A) Bakelite (B) Polyethylene (C) Teflon (D) PVC

Q.22 Bekelite is:

(A) Addition polymer (B) Elastomer (C) Thermoplastic (D) Thermosett

Q.23 Perlon is:

(A) Rubber (B) Nylon (C) Terylene (D) Orlon

Q.24 Nylon-6, 6 is made by the polycondensation of:

(A) Adipic acid + Hexamethylene diamine (B) Phthalic acid + Glycerol
(C) Phenol + Formaldehyde (D) Urea + Formaldehyde

Q.25 An example of a natural biopolymer is-

(A) Teflon (B) Neoprene (C) Nylon-66 (D) DNA

Q.26 Natural silk is a-

(A) Polypeptide (B) Polyacrylate (C) Polyester (D) Polysaccharide

Q.27 Peptide bond is a key feature in-

(A) Polysaccharide (B) Proteins (C) Nucleotide (D) Vitamins

Q.28 Neoprene rubber is obtained by the polymerization of :

(A) 1, 3-Butadiene (B) 2- Methyl -1, 3-butadiene
(C) 2- Chloro -1, 3 butadiene (D) Styrene and butadiene

Q.29 Which of the following is not a natural polymer

(A) Starch (B) Cellulose (C) Glyptal (D) Glycogen

Q.30 Which of the following is natural polymer:

(A) Polyisoprene (B) Polybutadiene
(C) Polyethylene terephthalate (D) Polyethylene

Biomolecules & Polymer [191]

 EXERCISE–II
BIOMOLECULES
Q.1 RNA contains - [AIEEE-2002]
(A) Urasil, Ribose (B) Thiamine, Ribose
(C) Cytocine, Deoxyribose (D) Adenine, Deoxyribose
Q.2 Complete hydrolysis of cellulose gives – [AIEEE-2003]
(A) D-glucose (B) L-glucose (C) D-fructose (D) D-ribose
Q.3 The reason for double helical structure of DNA is operation of – [AIEEE-2003]
(A) Hydrogen bonding (B) Electrostatic attractions
(C) vander Waal’s forces (D) Dipole-dipole interaction
Q.4 Coordination compounds have great importance in biological systems, In this context which of the following
statements is incorrect ? [AIEEE-2004]
(A) Chlorophylls are green pigments in plants and contain calcium
(B) haemoglobin is the red pigment of blood and contains iron
(C) Cyanocobalamin is B12 and contains cobalt
(D) Carboxypeptidase–A is an enzyme and contains zinc
Q.5 Which base is present in RNA but not in DNA ? [AIEEE-2004]
(A) Uracil (B) Cytosine (C) Guanine (D) Thymine
Q.6 Insulin production and its action in human body are responsible for the level of diabetes. This compound
belongs to which of the following categories ? [AIEEE-2004]
(A) A co-enzyme (B) A hormone (C) An enzyme (D) An antibiotic
Q.7 Identify the correct statement regarding enzymes : [AIEEE-2004]
(A) Enzymes are specific biological catalysts that can normally function at very high temperatures
(T~ 1000 K)
(B) Enzymes are normally heterogeneous catalysts that are very specific in their action
(C) Enzymes are specific biological catalysts that cannot be poisoned
(D) Enzymes are specific biological catalysts that possess well-defined active sites
Q.8 In both DNA and RNA, heterocylic base and phosphate ester linkages are at – [AIEEE-2005]
(A) C2' and C5' respectively of the sugar molecule
(B) C5' and C2' respectively of the sugar molecule
(C) C5' and C1' respectively of the sugar molecule
(D) C1' and C5' respectively of the sugar molecule
Q.9 The pyrimidine bases present in DNA are – [AIEEE 2006]
(A) cytosine and guanine (B) cytosine and thymine
(C) cytosine and uracil (D) cytosine and adenine
Q.10 The term anomers of glucose refers to – [AIEEE 2006]
(A) a mixture of (D)-glucose and (L)-glucose
(B) enantiomers of glucose
(C) isomers of glucose that differ in configuration at carbon one (C-1)
(D) isomers of glucose that differ in configurations at carbons one and four (C-1 and C-4)

Biomolecules & Polymer [192]

Q.11 The secondary structure of a protein refers to – [AIEEE 2007]
(A) -helical backbone
(B) hydrophobic interactions
(C) sequence of -amino acids
(D) fixed configuration of the polypeptide backbone
Q.12 -D-(+)-glucose and -D-(+)-glucose are [AIEEE 2008]
(A) epimers (B) anomers (C) enantiomers (D) conformers
Q.13 The two functional groups present in a typical carbohydrate are : [AIEEE 2009]
(A) – OH and –COOH (B) – CHO and –COOH
(C) > C = O and –OH (D) – OH and –CHO

POLYMER
Q.14 Monomers are converted to polymer by – [AIEEE-2003]
(A) Hydrolysis of monomers
(B) Condensation reaction between monomers
(C) Protonation of monomers
(D) None is correct
Q.15 Nylon threads are made of – [AIEEE-2003]
(A) Polyamide polymer (B) Polyethylene polymer
(C) Polyvinyl polymer (D) Polyster polymer
Q.16 Which of the following is a polyamide ? [AIEEE-2005]
(A) Nylon-66 (B) Teflon (C) Bakelite (D) Terylene
Q.17 Which of the following is fully fluorinated polymer- [AIEEE-2005]
(A) Teflon (B) Neoprene (C) PVC (D) Thiokol
Q.18 Bakelite is obtained from phenol by reacting with [AIEEE 2008]
(A) CH3CHO (B) CH3COCH3 (C) HCHO (D) (CH2OH)2
Q.19 Buna-N synthetic rubber is a copolymer of - [AIEEE 2009]
Cl
|
(A) H2C  CH  C  CH 2 and H2 C  CH  CH  CH 2

(B) H2 C  CH  CH  CH 2 and H5 C 6  CH  CH 2

(C) H2C = CH – CN and H2C = CH – CH = CH2

(D) H 2 C  CH  CN and H 2 C  CH  C  CH 2
|
CH 3

Biomolecules & Polymer [193]

Q.20 The disaccharide present in milk is :
(A) Maltose (B) Lactose (C) Sucrose (D) Cellobiose
Q.21 Insulin is :
(A) An amino acid (B) Protein (C) A carbohydrate (D) A lipid
Q.22 Glucose when heated with CH3OH in presence of dry HCl gas gives  and –methyl glucosides because
it contains :
(A) An aldehyde group (B) A–CH2OH group (C) A ring structure (D) Five hydroxyl groups
Q.23 The commonest disaccharide has the molecular formula :
(A) C10H18O9 (B) C10H20O10 (C) C18H22O11 (D) C22H22O11
Q.24 It is best to carry out reactions with sugars in neutral or acid medium and not in alkaline medium. This is
because in alkaline medium sugars undergo one of the following changes :
(A) Racemisation (B) Decomposition (C) Inversion (D) None of these
Q.25 The fibre obtained by the condensation of hexamethylene diamine and adipic acid is :
(A) Dacron (B) Nylon ’66’ (C) Rayon (D) Teflon
Q.26 Natural rubber is basically a polymer of or the monomer of natural polymer rubber is :
(A) Neoprene (B) Isoprene (C) Chloroprene (D) Butadiene
Q.27 Rayon yarns are obtained from :
(A) Polymethylene (B) Polyesters (C) Cellulose (D) Styrene
Q.28 Polymerisation in which two or more chemically different monomers take part is called :
(A) Addition polymerisation (B) Copolymerisation
(C) Chain polymerisation (D) Homopolymerisation
Q.29 Which of the following polymers contains nitrogen :
(A) Nylon (B) Polythene (C) PVC (D) Terylene
Q.30 Which of the following is teflon :

H H H CH3 F F H F
| | | | | | | |
(A) –C–C– (B) –C–C– –C–C–
(C) | | –C–C–
(D) | |
| | | |
H H n H H n F F n
F Cl n

Biomolecules & Polymer [194]

 ANSWER KEY
EXERCISE – I
Q.1 C Q.2 C Q.3 C Q.4 C Q.5 B Q.6 B Q.7 C
Q.8 A Q.9 D Q.10 B Q.11 B Q.12 C Q.13 B Q.14 D
Q.15 B Q.16 A Q.17 B Q.18 C Q.19 C Q.20 B Q.21 A
Q.22 D Q.23 B Q.24 A Q.25 D Q.26 A Q.27 B Q.28 C
Q.29 C Q.30 A

EXERCISE – II
Q.1 A Q.2 A Q.3 A Q.4 A Q.5 A Q.6 B Q.7 D
Q.8 D Q.9 B Q.10 C Q.11 A Q.12 B Q.13 C Q.14 B
Q.15 A Q.16 A Q.17 A Q.18 C Q.19 B Q.20 B Q.21 B
Q.22 C Q.23 D Q.24 C Q.25 B Q.26 B Q.27 C Q.28 B
Q.29 A Q.30 C

Biomolecules & Polymer [195]