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CARBONYL COMPOUND

CARBOXYLIC ACID
BIOMOLECULES AND POLYMER
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THEORY AND EXERCISE BOOKLET
CONTENTS

S.NO. TOPIC PAGE NO.

CARBONYL COMPOUND
THEORY WITH SOLVED EXAMPLES ............................................................. 5 25

EXERCISE - I (JEE Main) ................................................................................ 26 37

EXERCISE - II (JEE Advanced Objective) .................................................... 38 40

EXERCISE - III (JEE Advanced) ...................................................................... 41 43

EXERCISE - IV (JEE Advanced Previous Years)................ ......................... 44 51

ANSWER KEY................................................................................................. 52 54

CARBOXYLIC ACID
THEORY WITH SOLVED EXAMPLES ............................................................ 55 81

EXERCISE - I (JEE Main) ................................................................................ 82 86

EXERCISE - II (JEE Advanced Objective) .................................................... 87 96

EXERCISE - III (JEE Advanced) ..................................................................... 97 100

EXERCISE - IV (JEE Main & JEE Advanced Previous Years) .................... 101 107

ANSWER KEY............................................................................................... 108 109

BIOMOLECULES AND POLYMER


THEORY WITH SOLVED EXAMPLES .......................................................... 110 167

EXERCISE - I (JEE Main) .............................................................................. 168 174

EXERCISE - II (JEE Advanced Objective) .................................................. 175 185

EXERCISE - III (JEE Advanced) .................................................................... 186 188

EXERCISE - IV (JEE Main & JEE Advanced Previous Years) .................... 189 196

ANSWER KEY............................................................................................... 197 200


Page # 4 Chemistry ( Booklet-1 )

JEE SYLLABUS

CARBONYL COMPOUND
.
JEE - ADVANCED
Aldehydes and Ketones oxidation, reduction, oxime and hydrazone formation; aldol condensation,
Perkin reaction; Cannizzaro reaction; haloform reaction and nucleophilic addition reactions (Grignard
addition);

CARBOXYLIC ACID
JEE - ADVANCED

formation of esters, acid chlorides and amides, ester hydrolysis; Amines: basicity of substituted
anilines and aliphatic amines, preparation from nitro compounds, reaction with nitrous acid,

BIOMOLECULES AND POLYMER


JEE - ADVANCED

Carbohydrates: Classification; mono- and di-saccharides (glucose and sucrose); Oxidation, reduction,
glycoside formation and hydrolysis of sucrose.
Amino acids and peptides: General structure (only primary structure for peptides) and physical
properties.
Properties and uses of some important polymers: Natural rubber, cellulose, nylon, teflon and PVC.
Practical organic chemistry: Detection of elements (N, S, halogens); Detection and identification
of the following functional groups: hydroxyl (alcoholic and phenolic), carbonyl (aldehyde and
ketone), carboxyl, amino and nitro; Chemical methods of separation of mono-functional organic
compounds from binary mixtures.

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CARBONYL COMPOUNDS Page # 5

CARBONYL COMPOUNDS
1. Introduction

R
These have general formula CnH2nO and contains > C O group which is present in aldehyde C=O
H
R
and C = O ketone. Thus aldehydes and ketones are collectively called as carbonyl compounds
R

5. IUPAC Nomenclature of Aldehydes and Ketones

Ketones IUPAC name

O
1. CH3 C CH3 Propanone

O
2. CH3 C CH 2 CH3 Butanone

O
3. CH3 C CH 2 CH2 CH3 Pentan-2-one

O O
4. CH3 C C CH3 Butanedione

CH 3 O CH3
5. CH3 CH C CH CH3 2, 4-Dimethyl
pentan-3-one
O
6. C CH 2 CH3 1-Phenylpropan-1-one

7. 3-Methylcyclopentanone

CH3
O

8. Cyclohex-2-en-1-one
or
2-Cyclohexenone

O OH
9. CH3 C CH 2 C CH3 4-Hydroxy-4-methyl
pentan-2-one
CH3

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Page # 6 CARBONYL COMPOUNDS

Ketones IUPAC name

O
10. CH3 C H Ethanol
O
11. CH3 CH2 C H Propanol
O
12. CH3 CH2 CH 2 C H3 Butanol

OH O
13. CH3 CH CH2 C H 3-Hydroxybutanal

14. CH3 CH2 CH = CH CHO Pent-2-en-1-el


or
Br Pen-2-enal
CH 3 O
15. 4-Bromo-3-methyl
heptanal

16. CHO Cyclohexanecarbaldehyde

CHO 2-Hydroxycyclopentane
17. -1-carbaldehyde
OH

O
18. CH3 CH2 C CH2 CHO 3-Oxopentanal

O
19. CH3 C CH2 COOH 3-Oxobutanoic acid
O
CH
20. 2-Formylbenzoic acid
COOH
O

21. 2-(3-oxobutyl)-cyclohexanone
O

22. 2-ethylhex-2-en-1-al
H

O
2,5-dimethylheptan-3-one
23.

24. CH3 CH CH CH = O 3-chloro-2-methylbutanal


Cl CH3
O
25. 3-ethycylobutanone

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CARBONYL COMPOUNDS Page # 7

8. General methods of preparation of Aldehyde and Ketones

(I) Hydration of Alkyne :


It is addition of water in the presence of heavy metal ion. acetylene on hydration gives aldehyde while
any higher alkyne gives ketone.
Hg++ /H2SO4
HC CH CH3 CH = O
H 2O
++
Hg /H2SO4
RC CH R C CH 3
H2O
O

The preparation of carbonyl compounds from alkyne depends upon R part of (A) and also presence of
inductive effect group attached to R.

(II) Hydroboration of alkyne :


It is used to get aldehyde from alkyne-1. Here reagent is (i) diborane (B2H6) (ii) H2O2(OH)
(i) B2H6
RC CH R CH2 CH = O
(ii) H2O2 /OH
In this reaction Borane (BH3) is electrophile.
BH3 H2 O2
3R C C H (R CH = CH)3B R CH = CH OH R CH2 CH = O

Higher alkyne except alkyne-1 will give ketone during hydroboration

O
(i) BH3, THF
CH3 CH2 C C CH2 CH3
CH3 CH2 C CH2 CH2 CH3
(ii) H2O2(OH )

(III) Ozonolysis of alkene :


It is used to get carbonyl compounds from alkene. The reaction is

R1 O
R3
R1 R3 C C Zn-H2O R1 R3
C=C R2 R4 C=O + C = O + ZnO
R2 R4 R2 R4
O O
Mono-ozonide
O
CH3
Ex. CHCH C ZnH2 O CH3
O3 3
CH3
CH3 CH = C CH 3 CH3 CH = O + C = O + ZnO
O O CH3
CH3

(CH3)2 S CH3
CH3 CH = O + C = O + (CH3)2 S = O
CH3

H2O CH3
CH3 CH = O + C = O + H 2O 2
CH3
H2O2

CH3 COOH

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Page # 8 CARBONYL COMPOUNDS

Note :
(I) During the cleavage of ozonide Zn is used to check further oxidation of aldehyde into acid.
(II) By this method we can locate double bond in olefin or exact structure of hydrocarbon can be
determined by knowing ozonclysis product i.e. by placing double bond at the place oftwo carbonyl
oxygen of two carbonyl compounds.

(V) Dehydrogenation of Alcohol :


Dehydrogenation means removal of hydrogen and reagent used is heated copper.
Cu/300C
1 alcohol (RCH2OH) Aldehyde (RCH = O)
H2

Cu/300C
2 alcohol (R2CHOH) Ketone (R2C = O)
H 2

Cu/300C
3 alcohol Alkene
H2

(VI) Dry distillation of Calcium salt of acid :


O
(RCOO)2Ca R C R + CaCO3
Ketone

(VII) On passing vapours of fatty acids over Magnous oxide at 300C.


O
MnO /300C
2 RCOOH R C R + CO2 + H2O
(Vap) Ketone

On passing mixture of vapours of fatty acid with formic acid we get a mixture of aldehyde, ketone and
formaldehyde.

O
MnO /300C
RCOOH + HCOOH RCR
O
A mixture
Vapour HCR of these three
O
HCH

(VIII) On aqueous alkall hydrolysis of gem-dihalides :


Terminal gemdihalides with give aldehyde while non-terminal will give ketones as follows
aq. KOH OH
R CHCl2 R CH R CH = O
H2O
OH Aldehyde
Cl
aq. KOH
R C R' R C R' R C R'
H2O
OH OH O Ketone
Cl
(IX) Wacker Process :
Alkenes can directly be oxidised to corresponding aldehydes or ketone by treating them with a solution
of PdCl2 containing a catalytic amount of CuCl2 in presence of air or O2. Except ethene any higher
alkene will give ketone.

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CARBONYL COMPOUNDS Page # 9

CuCl2
CH2 = CH2 + H2O + PdCl2 CH 3 CH = O + Pd + 2HCl
air or O2
O
CuCl2
R CH = CH2 + H 2O + PdCl2 R C CH3 + Pd + 2HCl
air or O2

Note : During the reaction PdCl2 is reduced to Pd and CuCl2 is reduced to Cu(1)

(X) Preparation of Carbonyl compounds using Grignards Reagent :


(a) Hydrogen cyanide on treating with Grignard reagent followed by double decomposition with water
gives aldehyde via imine.

H2O/H+ H2O/H+
H C = N + R MgBr H C = NMgBr H C = NH H C = O + NH3

R R R
imine Aldehyde
Alkylcyanide by using above process gives ketone via ketimine

R' C = N + R MgBr H2O/H+ H2O/H+


R' C = NMgBr R' C = NH R' C = O + NH3

R R R
Ketimine Aldehyde

(b) Alkylformate with Grignard reagent gives 2 alcohol via aldehyde, while alkyl alkanoate under
similar condition gives 3 alcohol via ketone
OMgBr
O
H 3O+ (i) RMgBr
H C OC2H5 + R MgBr H C OC2H5 R CH = O R CH OH
MgBr(OC2H5) (ii) H2O/H
+

ethyllmethanoate
R R
2 alcohol

OMgBr R
O
H3O (i) RMgBr
R' C OC2H5 + R MgBr R' C OC2H5 R' C = O R CH OH
Br (ii) H2O/H
+

ethyllmethanoate Mg
R OC2 H5 R R
3 alcohol

(A) Methode used for the preparation of Aldehydes only.


(i) Rosenmunds reaction :
Here acid chlorides are reduced to aldehyde with H2 in boiling xylene using palladium as a catalyst
supported on barium sulphate.
O
Pd-BaSO4 O
R C Cl + H2 RC + HCl
Boiling Xylene H

(ii) Stephens reduction :


SnCl2 /HCl H2O
RC=N R CH = NHHCl R CH = O + NH 4Cl

Aldimine hydrochloride

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Page # 10 CARBONYL COMPOUNDS

(iii) Oxo-process :
It is also called as carbonylation here alkene reacts with water gas at high temperature and pressure in
the presence of cobalt carbonyl catalyst to give aldehyde.

R CH = CH2 R CH CH3 + R CH2 CH2 CH = O


[CO(CO)4] 2
CH = O

(iv) Reimer-Teimann Reaction :


By this method phenolic aldehyde is prepared
OH OH
CHO
CHCl3/KOH

Phenol Salicylic aldehyde

(B) Methods used for the preparation of Ketones only


(i) Using alkanoyl chloride and Grignard reagent

O O
R C Cl + R' Mg Cl R C R' + MgCl2

(ii) Using alkanoic anhydride and Grignard reagent

O O O
Br
R C O C R + R' MgBr R C R' + Mg
OCR
O
(iii) Using alkanoylchloride and dialkyl cadmium
O O
R C Cl + R'Cd
2 R C R' + R' Cd Cl
Alkyl cadmium
chloride
O O
2R C Cl + R'Cd
2 2R C R' + CdCl2
Cadmium
chloride
(iv) By acylation or benzoylation of aromatic hydrocarbon (Friedel-Carft Reaction)

Dry
C6H6 + CH3COCl C6H5COCH3 + HCl
AlCl3
Acetophenone
Dry
C6H6 + C 6H 6COCl C6H5COC6H5 + HCl
AlCl 3
Benzophenone

(v) By Acid hydrolysis followed by heating of -Ketoester.

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CARBONYL COMPOUNDS Page # 11

Note : (i) It is -ketoacid which decarboxylate more readily as it proceeds via six membered
cyclic
H H
O O O O OH O
CH3 C C=O CH3 C C=O CH3 C = CH2 CH3 C = CH3
CO2
CH2 CH2 Acetone
Transition
state

Note : (ii) -ketoester is obtained by claisen ester condensation of two moles of ester using
sodium ethoxide as a base.

O O
C2H6ONa
e.g. 2CH3COOC2H6 CH3 C CH2 C OC2H5 + C2H5OH
Mechaniam :

CH3 COOC2H5 'B'


CH2COOC2H5+ BH

O O O H O O
BH
CH3 C OC2 H5 CH2 COOC2H5 CH3 C OC2 H5 CH3 C OC2 H5 CH 2CCH
2 COC2 H5
'B' C2H5OH
CH2 COOC2H5 CH2 COOC2H5
The product ketoester can be easily obtained by placing anion of one ester at the place of ethoxy
part of other ester as
'B'
CH3COOC2H5 CH2 COOC 2H 5

O O
CH3 C OC2H5 CH2 COOC2H5 CH3 C CH2COOC2H5
-ketoester

Note : (iii) If two ester units are same then it is inter molecular claisen ester condensation

Q. Predict the unknown (s) for the following :


+
C2H5ONa H2O/H
2CH2 CH2COOC2H5 A B C + CO2
C2H5 OH

Note : (iv) If two ester units are different then it is crossed Claisen ester condensation
O
C2H5ONa
(a) C5H5COOC2H5 + CH 3COOC2H5 C5H5 C CH2 COOC2H5
C2H 5OH

O O
C2H5ONa
(b) CH3 CH2 COOC2H5 + CH3 COOC2H5 CH3 CH2 C CH2 C OC2H5
C 2H5OH

Note : (v) If two ester units are present with in the same molecule then we get cyclic -ketoester
and the reaction is intramolecular Claisen ester condensation.
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Page # 12 CARBONYL COMPOUNDS

COOC2H5 O
C2H5ONa
(CH2)4
COOC2 H5 C2H 5OH COOC2H5

Note : (vi) Active methylene group hydrogen is too acidic that it can be replaced by alkyl of
arylakyl halide in the presence of base like sodium ethoxide.

(C) Pinacol-Pinacolone rearrangement :


Pinacole is obtained when 2 moles of acetone are heated with divalent active metal magnesium
followed by treating with water.

O O CH3 CH3 CH3 CH3


H2O
CH3 C + CH3 C CH3 CH3 C C CH3 CH3 C C CH3
CH3 O O OH OH
Mg Pinacole
Pinacole undergoes rearrangement in acidic media to give pinacolone

CH3 O
H
(CH 3)2C C(CH3) 2 CH3C CCH3
H 2O
OH OH CH3
Pinacole Pinacolone

9. Chemical Reactions of Carbonyl Compounds :


Carbonyl compounds undergo nucleophilic addition reaction and reactivity order will be :

(I) Nucleophilic Addition Reaction :

H R R
C=O > C=O > C = O (reactivity order)
H H R

(i) Reaction with alcohol :


Carbonly compounds react with alcohols in the presence of dry HCl gas to give acetal (if aldehyde) and
ketal if ketone via formation of unstable hemiacetal and hemlketal respectively.

R H R R
R'OH
C=O + R'OH C OH C OR' + H2O
H H HCl H
OR' OR'
Hemiacetal acetal
Note :
(i) Acetal is formed to protect aldehyde for a long time.
(ii) Acetal has functional groups ether.
(iii) Acetal formed can be decomposed to orignal aldehyde by dilute acid.
(iv) On treating with ethyleneglycol we get cyclic acetal or ketal (1, 3-dioxolans)
CH2OH O CH2
C=O + | C
Para toluene O CH2
CH2OH
sulphonic acid (PTS)

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CARBONYL COMPOUNDS Page # 13

Mechanism :
HO CH2 O CH2
C=O+ C
HO CH2 H 2O O CH2

(v) Acetal formation is founed to be more favourable than ketal formation.If both the carbonyl groups
are present within the molecule.

(ii) Addition of HCN :


If is base catalysed addition
'B'
C = O + HCN C OH
CN Cyanohydrin

'B'
HC N BH + CN

'B' BH
C=O CN CO C OH
:

B
CN CN

(iii) Addition of sodiumbisbulphite (NaHSO3) :


This addition is used to isolate carbonyl compounds from the mixture as we get salt.

C = O + NaHSO3 C ONa C OH

SO3H SO3Na
(salt)
Salt on acidification gives carbonyl compounds again.
H 2O
C OH C OH C=O
H2O
SO3Na OH

(II)Addition elimination reactions :


Certain compounds related to ammonia add to the carbonyl group to form derivatives that are important
chiefly for the characterization and identification of aldehydes and , Ketones the product contain a
carbon nitrogen double bond resulting from elimination of a molecule of water from the initial addition
products.

+
C + :NH2 OH H C NHOH C = NOH + H2 O
O OH

+
C + :NH2NHC6 H5 H C NHNHC6H6 C = NNHC6 H6+ H2O
O OH

+
C + :NH2NHCONH2 H C NHNHCONH2 C = NHNHCONH2 + H2O
O OH

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Page # 14 CARBONYL COMPOUNDS

:
(i) Reaction with ammonia derivatives (H2NZ) :
This reaction is nucleophilic followed by water elimination :

C = O + H3NZ C = NZ
H2O
:

C = O + H2NZ CO C OH C = NZ
H2O
HNH NH
Z Z

This reaction is carried out in slightly acidic media which will generate a nucleophilic centre for weak
base ammonia derivatives.
:

C = O: + H C=OH C OH

On using strong acidic media lone pair of electrons present at N-atom of ammonia derivatives will
accept proton forming protonated ammonia derivatives which can not act as nucleophile for carbonyl
carbon.

C = O + H2N Z >C = N Z

Z
OH Hydroxylamine Oxime

NH2 Hydrazine Hydrazone

NH C6H6 Phenylhydrazine Phenyhydrazone

NO2 2,4-dinitrophenylhydrazine 2,4-dinitrophenythdrazone


NH
(Brady's reagent) or 2,4-DNP (Solid orange precipitate)
NO2

O
NH C NH2 Semicarbozide Semicarbazone

(III) Beckmann Rearrangement in Oxime :

R' O O
H+ or
C = N OH RCNHR' + RCNHR
dry HCl (if R' is bulkier than R)
R (E + Z)

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CARBONYL COMPOUNDS Page # 15

Mechanism :

H H
R' R' O OH

:
H H2O: H
: :

C = N OH C = N OH2 RC=NR' RC=NR' RC=NR'


H2O
R R

Tautomerism
Note :
(i) Bradys reagent is used to distinguish carbonyl compounds from the mixture.
O
(ii) Oxime undergoes Beckmann rearrangement to give its isomer amide.
(iii) In this reaction the group which is anti to OH group migrates. R C NHR'
C6H5 O O
Rearrangement
C = N OH CH3 C NH C6H5 + C6H5 C NH CH 3
CH 3

C6H5 O
OH Rearrangement
C=N CH3 C NH CH3
CH3
(CH3 is anti OH)

C6H5 O
Rearrangement
C = N OH CH3 C NH C6H5
CH3
(C6H5 is anti OH)

(IV) Aldol Condensation :


It is condensation between two moles of carbonyl compounds among which at least one must have -
hydrogen atom in dilute basic media to get -unsaturated aldehyde / ketone via the formation of -
hydroxy aldehyde /ketone.

Ex.16

'B'
Mechanism : CH3 CH = O CH2 CH = O + BH

BH
CH3 CH = O + CH2 CH = O CH 3 CH CH 2 CH = O CH3 CH CH2 CH = O
:

B
Nucleophile
O OH

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Page # 16 CARBONYL COMPOUNDS

from -hydroxy aldehyde / ketone, water is eliminated on using either acidic or basic media as

:
B (basic media)
CH3CHCH2CH=O CH3CHCHCH=O
BH
:OH OH
:

(Acidic
media) H OH

CH3CHCH2CH=O CH 3CHCHCH=O CH3CH=CHCH=O


H 2O
OH2
H
Now try to get carbonyl compounds from -unsaturated carbonyl compounds as
keep H at -position and OH at -position of unsaturated carbonyl compounds to get -hydroxy
carbonyl compounds.

O O
C=CCR CCCR
OH H

Now break and carbon as shown below to get carbonyl compound.

O O
Base
C CCR C = C + H2C C R
OH H

These two carbonyl compounds can be obtained on ozonolysis of hydrocarbon C = C + CH2 if it is


R
asked.

Intramolecular aldol condensation :


O
O O O O O
:

B C
H H 2O
OH
OH CH
3

By knowing product we can get reactant as in case of intermolecular aldol condensation :

(V) Cannizzaro reaction :


Carbonyl compounds not having -hydrogen atom undergo disproportionation or redox reaction
in strong basic media.

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CARBONYL COMPOUNDS Page # 17

H O
HaOH
(i) 2HC=O H C ONa + CH3 OH
(ii) 2 C6H5CH = O HaOH C6H5COONa + C6H5CH2OH
Sodiumbenzoate Benzylalcohol

CH = O
COONa CH 2OH
(iii) 2 NaOH
+

Cl
Cl Cl

These reaction are intermolecular cannizzaro reaction :

Mechanism :

H
OH Hydride ion
HC=O
(A) H Transfer

HCO HC=O
H
OH
(I) (B)


HC=O CH3O

OH

HC=O + CH2OH

By this mechanism it clear that acid is corresponding to that carbonyl compound over which OH is
going easily as nucleophile.
Note : It is observed that hydride ion transfer from (I) to Carbonyl compound (B) is rate determining
step.

Crossed Cannizzaro reaction :


On using two types of carbonyl compounds not having -hydrogen atom, acid will be corresponding to
that aldehyde over which OH will approach without any hindrence.

H
O
OH
H C = O + C6H5 CH = O HC + C6H5CH2OH
Ex. (i)
O
(A) (B)

H
O
OH
(ii) (CH2OH)3C CH = O + H C = O (CH2OH)3C CH2OH + H C
(B) O
(A)

in case (i) OH will easily go to (A) and in case (ii) it will go to (B) hence acid will be formate ion in both
the cases.

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Page # 18 CARBONYL COMPOUNDS

(VI) Perkin reaction :


When aromatic aldehyde like benzaldehyde is treated with anhydride in the presence of sodium salt of
acid from which anhydride is derived we get -unsaturated acid.

CH = O CH = CH COOH
(CH3CO) 2O/CH3COONa
e.g. Acetic Sodium acetate
anhydride (Acts as base)
Benzaldehyde Cinnamic acid

:
B
Mechanism : CH3COOCOCH3 CH2COOCOCH3
BH

C6H5 CH = O + CH2COOCOCH3 C6H 5 CH CH 2COOCOCH3



O
+
H

+
H2O/H
C6H5CH = CH COOH C6H5CH CH2COOH C6H5 CH CH2COOCOCH3
H2O (CH3COOH)
OH OH

(VII) Reformatsky reaction :


When carbonyl compound and -halogenated ester are heated with zinc followed by treating with
water we get -hydroxyester.

C=O + Br CH COOC2H5 C CH COOC2H5


(ii) H 2O
OH R
R

This reaction can be represented as

Br CH COOC2H5 Br Zn CH COOC2H5
R R

R
H2O
C = O + Br Zn CH COOC 2H5 C CH COOC2H5 C CH COOC2H5

R OZnBr OH R

(VIII) Wittig reaction :


It is used to get alkene from carbonyl compound using phosphorus ylide via the formation of cyclic
structure betaine.

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CARBONYL COMPOUNDS Page # 19

CH = O C P(Ph)3 CO C=C + O = P(Ph)3

C P(Ph)3 Alkene

Betaine

Note : Phosphorus ylides are prepared from alkylhalide and triphenylphosphine in the presence of base
like sodium ethoxide as

Base
:

R CH2 Br + (C6H5)3P R CH2 P(C6H5)3 R CHP(Ph)3 or RCH = P(Ph)3


Br BH Phosphorus ylide

Q. Predict the product for the following :

(i) + CH2 = P(Ph)3

O
(ii) + P(Ph)3
H

CH3
(iii) C = O + CH3 CH P(Ph) 3
CH3

CH3
CH + P(Ph)3
(iv)
CH=O

+ Ph3P = CH2 CH2


Ex. [JEE-96]
O

CH3CH2
(i) KCN/H2SO4
Ex. O [JEE-96]
(ii) LiAlH4
H

Sol. CH3CH2 CH CH2 NH2


OH

(IX) Baeyer-Villiger oxidation :


It is preparaton of ester from ketone using peracid.
R
R"COOOH
C=O RCOR' + R" COOH
peracid
R'
O

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Page # 20 CARBONYL COMPOUNDS

Mechanism :

R R" C O O
H 18
: :

C = O: R C = OH R C OH
R'
R' R'

O
O O18
O O C R"
R' C OR + R" C O + H
RCOH
R'

Q. Predict product for the following

O
C6H5
C6H5 COOH
18
C=O Product
CH3

(X) Haloform reaction :


Acetaldehyde and methylalkyl ketones react rapidly with halogen (Cl2, Br2 or I2) in the presence of alkali
to give haloform and acid salt.
O O
Br2 /NaOH
R C CH3 R C ONa + CHBr3 (Bromoform)

O
In this reaction CH3 of CH3 C group is converted into haloform as it containe acidic hydrogen atom
and rest-part of alkyl methyl ketone give acid salt having carbon atom corresponding to alkyl ketone.
(a) Halogenation
(b) Alkalihydrolysis

O O
Br3
R C CH3 R C CBr3 (Halogenation)

O O
NaOH (Alkalihydrolysis)
R C CBr3 CHBr 3 + R C ONa

O
Note : This reaction is used to distinguish the presence of CH3 C group.

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CARBONYL COMPOUNDS Page # 21

(XI) Clemmensen reduction :


Used to get alkane from carbonyl compounds.

Zn Hg/HCl
C=O CH 2
3
sp
2 sp

++
H Zn Zn + 2e 2H
C=O C = O H C OH C OH
2
sp

2+
H Zn Zn + 2e
CH2 CH CH CH OH 2
H2O
2
sp

Ex. Fill in the blanks with appropriate structures of reaction products in the following transformations
SOCl2
o HOOC C6H5 CH2 C6H5 G

G anhydrous H H
Zn Hg
I [JEE-95]
AlCl3 HCl

SOCl2
Sol. o HOOC C6H4 CH2 C6H5 CH 2 + SO2 + HCl

COCl

(Z) O (H)

(XII) Wolf-Kishner reduction :


(Used to get alkane from carbonyl compounds

NH2 NH2/KOH
C=O CH 2
Using high boiling
2 solvent (ethylene glycol) 3
sp sp
:

H2O B
C = O + H 2 N NH 2 C = N NH2 C = N NH C = N NH
2
BH (A)
sp
:

BH B BH
CH2 CH CN=N C N = NH
:

N2
:

B BH B
sp2 sp2

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Page # 22 CARBONYL COMPOUNDS

(XIII) Addition of Grignard reagent over Carbonyl compound :


It gives alcohol

H2O /H
C=O + R MgBr C OMgBr C OH + MgBr OH
R R

(XIV) Reduction of Carbonyl Compounds :


(i) Reduction to alcohols

R R OH
H2/Ni or Pt or Pd
C=O C
H H H

OH
O O
C
C Ni/H2 C Ni/H2 H
H H H
e.g. H (Raney nickel) H

(90%)

O OH
(1) NaBH4
CH3CH2CH2CCH3 CH 3CH2CH 2CHCH 3
(2) H, H2O

(ii) Reduction to pinacols

CH3 CH3 CH3 CH3


(i) Mg
CH3 C + C CH3 CH3 C C CH3
(ii) H2O
O O OH OH

(XV) Reaction with PCl5 :

Carbonyl compounds give gemdihalides


Cl
>C = O + PCl5 C + POCl3
Cl

(i) CH3CH = O + PCl5 CH3 CHCl2 + POCl3

CH3 CH 3
(ii) CH3 C = O + PCl5 CH3 C Cl + POCl3
Cl

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CARBONYL COMPOUNDS Page # 23

Other reaction :

NH3
Hexamethylene
tetramine(urotropine)
Evaporated
(1) CH2 = O CH2OCH2OCH2O
to dryness Paraformaldehyde
(Formaldehyde)
O
Kept at room CH2 CH2
tempt. for a
longtime O O
CH2
Trioxane
(metaformaldehyde)

NH 2
NH3
CH3 CH OH (Acetaldehyde ammonia)

conc. H2SO4
CH3 CH = O Cyclic trimer (paraldehyde)
(2) (few drops)
(Acetaldehyde)

Dry HCl
Cyclic tetramer (Metaldehyde)

NH2 O
NH3
CH3 C CH2 C CH2
CH3 CH3
(3) CH3 CH = O Mesltylene
(Acetone)
CH3 O CH3
Dry HCl
CH 3 C = CH C CH = C CH3
(Phorone)

+ CH3 C = CH C CH 3
CH3
(Mesltyloxide)

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Page # 24 CARBONYL COMPOUNDS

O
O C CH3

OH /H2O (CH3CO)2O
(4) C6H5 CH=O C6H5 CHOCCH3 C6H5CH3
(CH3COOH) CrO2
(Benzaldehyde) O CH3
oil of bitter almond
(i) CrOC6H5Cl2/CCl4
(ii) H2O
NH3
(i) HCN + HCl /AlCl3
(ii) H2O
C6H5 CH = N CHN=CHC6H5
CO + HCl /AlCl3
C6H5
Hydrobenzamide
O
H2 /Pd BaSO4
C 6H5 C Cl
bolling xylene

C6H 5NH 2
C 6H5 CH = N C 6H5
Schiff's base or anils

Cl2
C6H5 C CH2 Cl
in absence of
catalyst O
O Phenacylchloride (Lacrymater)
(5) C6H5 C CH3
Acetophenone CH2 CH 3

Zn Hg /HCl
CH 3COCl /AlCl 3

O
(6) C6H5 C C6H5
(Benzophenone)

C6H5COCl /AlCl3 COCl2 /AlCl3

excess

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CARBONYL COMPOUNDS Page # 25

Some important reagents used for identification of aldehyde.

(i) Tollens reagent :


It is ammonical silver nitrate solution, prepared by adding ammonium hydroxide to AgNO3 solution.
During reaction, first Ag2O is formed which is dissolved in ammoniumhydroxide to give Tollens reagent.
2AgNO3 + 2NH4OH Ag2O + NH4NO3 + H2O
Ag2O + 4NH4OH 2[Ag(NH3)2]OH + 3H2O
Tollens reagent

Tollens reagent is weak oxidising agent, it gives Ag mirror test with aldehyde.

R CH = O + 2Ag(NH3)2 + 3OH RCOO + 2Ag + 2NH3 + 2H2O

(ii) Fehlings solution :


It is an alkaline solution of cupric ion complexed with sodium potassium tartarate. Two solutions are
kept by naming Fehling solution (I) (CuSO4 solution) and Fehling solution (II) (Alkaline solution of
sodium potassiumtartarate). When these two solutions are mixed we get deep blue coloured solution.
CuSO4 + 2NaOH Cu(OH)2 + Na2SO4
O CH COONa
Cu(OH)2 + HO CH COONa Cu
O CH COOK
HO CH COOK (Blue coloured compound)
Roschelle salt

Equal volume of both the solution are heated with aldehyde to give red brown precipitate of cuprous
oxide (Cu2O) which confirms the presence of aldehyde.
R CHO + 2CuO RCOOH + Cu2O (Red ppt)
Blue

RCHO 2Cu2+ + 3OH RCOO + 2Cu + 2H2 O


(Red ppt)

(iii) Banadict solution :


It is solution of CuSO4, sodium citrate and sodium carbonate. It also consists of two solution. Solution
(I) is alkaline solution of sodium citrate and solution (II) is CuSO4 solution.
CuSO4 + 2NaOH Cu(OH)2 + Na2SO4

CH2COONa CH2COONa

Cu(OH)2 + HO C COONa HO Cu O C COONa

CH 2 COONa CH2COONa
(Blue colour)
Aldehyde gives positive test with Benedict solution.
2+
RCH = O + 2Cu + 3OH RCOO + 2Cu + 2H2O
(Red ppt)

(iv) Schiffs reagent :


It is dilute solution of rossniline hydrochloride whose rad colour has been discharged by passing SO2.
Aldehyde reatores red colour when treated with schiffs reagent (Magenta solution in H2SO4).

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Page # 26 CARBONYL COMPOUNDSE

Exercise - I (Only one option is correct)


O
O

(D)
1. OH
(P) major product
H 2O O
O

Stucture of (P) is OH
-hydroxy ketone
3. (x) H 2O
OH
OH (x) cant be

(A) (B) O

O O
(A)
OH O

(C) (D)
O

O O (B) O

Sol.
O O

(C)

OH O
2. (x) dil
.NaOH

(x) is
C CH3 (D)
HCH
O
O
O
4. O dil
.KOH

(A) O ( B )

O O (P) major product

OH

O OH
(A) (B) C CH3

O
(C) O
O
OH
H3C
(C) (D) None
OHC

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CARBONYL COMPOUNDS Page # 27

Sol.
O
8. + O
Dil
.KOH

Total number of aldol condensation products


are (excluding stereoisomer)
dil.KOH
(x) (A)2 (B)3
5.
O O (C)4 (D)5
major product structure of (x) is Sol.
O O

OH CHO
(A) (B)

O
HO

CHO
COH 9. (x) + (y) dil
.NaOH



(C) (D)

(x) and (y) are


Sol. O O

(A) and
6. Aldol addition can be
(A) Acid catalysed (B) Base catalysed
(C)Acid promoted (D) A and B both
O
Sol. O

(B) and

O O
O
dil.KOH
7. (x) Structure of (x) is CH3

(C) and

O
(D) None
O
(A) (B) Sol.

OH
(C) (D)
OH
O
Sol.

10. H Ag
2O
. NH 4 OH
(p)
HO

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Page # 28 CARBONYL COMPOUNDSE

Product (P) is Reagent responsible for given conversion will


O be
(A)Ag2O,NH4OH (B)Br2,H2O
(C) Cu+2 (D)All
Sol.
(A) OH

OH
(B) 13. HCHO Conc . NaOH
(x) + (y)
HO (i) Oxidation number of carbon changes from
(A) O to +1 and 0 to 2
O
(B) 0 to +1 and 0 to 1
(C) 0 to +2 and 0 to 2
(D) None
(C) OH (ii) Given reactin is an example of
(A) oxidation (B)Reductopn
HO
(C)both (D)None
O Sol.

(D) H
14. Compound which gives cannizaro reaction?
O
(A)CD3CHO (B) C6H5CHO
Sol.
O
(C)CH3COCH3 (D)

Sol.

OH (x) O
11.
15. Compound which gives intramolecular aldol re-
Reagent (x) is action?
(A) PCC (B) CrO3,H2SO4,H2O
O
(C) Ag2O,NH4OH (D)All (A)
Sol.
O O

(B)

COOH
CHO

12. (CHOH)4 (CHOH)4 (C) (D) B and C both


O
CH2OH
CH2OH

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CARBONYL COMPOUNDS Page # 29

Sol. O O

(A) (B)

O O O

16. (
i ) Dil NaOH
Product
( ii )
(C) (D)
Degree of unsaturation in product is?
(A) 2 (B) 3
Sol.
(C) 4 (D) 5
Sol.

19. Which acid can be oxidised be Fehling solu-


tion:
O (A) Malonic acid (B) Acetic acid
(C) Oxalic acid (D) formic acid
CH3
Sol.
HO


17. heat C.Compound (C) is:
(Re tro )

OH

O
O e lodoform test
+iv
C CH3
20. C6H12 O3 iv
e Tollens test H
2O

drop of H 2SO 4
(A) (B) A

O Positive Tollens Test Compound (A) is :

O O O O OCH3

(A) CH3 C CH 2 CH 3 (B) CH3 C C CH 3


(C) (D)
OCH3
Sol.
O

(C) CH 3 C CH 2 CH OCH 3
18. This is an example of an intramolecular aldol
O OCH3

O
dil. H SO
reaction:
2 4
(A),
(D) H C CH2 CH 2 CH OCH3
O
OCH3
Product (A) is:

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Page # 30 CARBONYL COMPOUNDSE

Sol. (1) O3 / Zn
23. (A) (
2 ) conc. KOH
OH + HC O2 K

HBr (B) major


O CCl4
Product (B) is
Mel excess
21. 81% yield; Product of the
KH excess

(A) (B)
reaction is Br Br
O O
(C) (D)
(A) (B) Sol.

O
O

O
(C) (D)

24. (A) KOH




Sol.

HCHO
(B) ; Product (B) is
KOH,
O O
3 O (1mole)
22. (A) Conc
. KOH

Zn
(A) (B)
H
(B) (C) ; Product (C) is

O
O

O (C) (D)
O
(A) (B) O
O
O Sol.

O
(C) (D) OH
O
KCN
Sol. 25. (A)

; Product (B) is
H
CN

PhCH=O
(B)
KOH,

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CARBONYL COMPOUNDS Page # 31

(A) Ph CH = CH Ph 28. Ph CO2H + CH3CO2H


(B) Ph CH = CH CH = O
CaO/

(C) O O

(A) PhCPh (B) Ph C CH3


(D) Ph
O
Sol.
(C) (D) All

Sol.

Positive
26. (A) tollen

's test

29. Arrange these compounds in decreasing order


of reactivity for the nucleophilic addition reac-
tion:
PhCH=O (B) ; Product (B) is
(l) Acid chloride (ll) Aldehyde
(lll) Ketone (lV) Ester
(A) Ph CH = C CH3 Select the correct answer from the codes given
below:
O CH 3 (A) l > ll> lll > lV (B) lV > lll > ll > l
CH 3 (C) lll > ll > l > lV (D) l > lV > ll > lll
CHPh (C) Ph C Sol.
(B) =CH Ph

(D) Ph CH = CH CH = O
30. Acetal or ketal is:
Sol.
(A) Vic dialkoxy compound
(B) , -dialkoxy compound
(C) -alkoxy alcohol
(D) Gem dialkoxy compound
Sol.

27. Gem dilhalide on hydrolysis gives:


(A) Vic diol (B) Gem diol
(C) Carbonyl compound
(D) Carboxylic acid
O
Sol.

aq.Na2 CO3
31.
Product (A) is

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Page # 32 CARBONYL COMPOUNDSE

O O
O O

(C) C6H5 CH2 C CH3 and C6H5 C CH2CH3


(A) (B)

(D) HCHO and C6H5CHO


Sol.
O O

OH
(C) (D)

35. In the reaction sequence[X] is ketone:


Sol.
[X] KMnO
4 / HOOC (CH2)3CH2COOH
OH /

[X] will be:

O O
32. In the given reaction:
CH3
(A) (B)
C

Na OH / H
C6H5 OH 2 [x] , [x] will be:

(A) Only syn oxime O O

(B) Only anti oxime H3C CH 3


CH3
(C) Mixture of syn and anti oxime (C) (D)
(D) Secondary amide
Sol.
Sol.

33. Schiffs base is prepared from:


(A) Carbonyl compound and primary amine
(B) Carbonyl compound and secondary amine
(C) Carbonyl compound and tertiary amine
(D) All of these 36. In the given reaction
O
Sol.

SeO
2 [x]

[X] will be :
34. Schiffs reagent is used for the differentiation O O
between:
O
(A) HCHO and CH3CHO CHO
(A) (B)
(B) CH3COCH3 and CH3CHO

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CARBONYL COMPOUNDS Page # 33

O 40. In the reaction:


O
O O
CH 3 + O [X] will be
H/

CH 3
OH OH
O
(C) (D) OH
O
O
(A) (B)
Sol.
O O
OH
(C) (D)
O

Sol.
37. D C D 50
%
KOH
Order of the reaction is :
(A) 2 (B) 3
(C) 4 (D) 1
Sol.
41. Product of Perkin reaction is :
(A) , -unsaturated aldehyde

(B) -cyclohexyl , -unsaturated aldehyde


38. In the reaction
(C) -Aryl- , -unsaturated acid
HO
(D) All of these
NaOH
CH3 CHCH CHO Sol.
X+Y
5 C

CH 3
(X) and (Y) will respectively be:
(A) CH3CH2CHO and CH3CH2CHO
(B) CH3CHO and CH3CH2CHO
42. The product of the reaction:
(C) CH3CHO and CH3CHO

CH3 NO2 CHO+(C6H5CH2CO)2O


C6HCH
5 2 COONa/
(D) CH3CHO and CH 3CCHO
[X]
[X] will be:
CH3
(A) C6H5 CH = CH COOH
Sol.
(B) NO2 CH = CHCOOH

(C) C 6H5CH=CCOOH

39. Total number of products in the given reaction


: (excluding steroisomers)

OH NO2
C6H5CHO+CH3CHO Product will be

(D) NO2 CH=CCOOH
(A) One (B) Three
(C) Two (D) Four C 6H 5

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Page # 34 CARBONYL COMPOUNDSE

Sol. 46. Cyanohydrin of which compound on hydrolysis


will give lactic acid?
(A) C6H5CHO (B) HCHO
(C) CH3CHO (D) CH3CH2CHO
Sol.
43. Cross cannizzaro reaction is example of
(A)Redox reaction
(B) Disproportionation
(C) Both (A) and (B)
(D) Only oxidation
Sol. 47. Acetaldehyde cannot give:
(A) lodoform test (B) Lucas test
(C) Benedict test (D) Tollens test
Sol.

44. Which will give silver mirror test with Tollens


reagent:
(A)C6H5CHO (B) CH3CHO
(C) HCOOH (D) All of these OCH2CH3
Sol.
48. Compound formed by the
O CHOH

reaction of furfural O with ethanol is


O CHO

CH MgBr
(A) an aldol (B) an acetal
P2 O5
45. C NH2 W 3

X (C) a ketal (D) a hemiacetal
H 3O
Sol.
Ca ( OH ) 2 .l 2
Y
Z, Z is :
yellow ppt . y
O

(A) C CH3
O3
49. (A) Conc
(B), Product (B) is:
.KOH
Zn

(B) COOH (A) CH2OH (B) CO 2H


CH2OH CO2H
O
(C) CH2OH (D) CO 2
(C) C CO 2 CO 2
Sol.

(D)

Sol.
50. Which of the following will reacts with NaOI ?
O
O

(A) CH3 C H (B)


O

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CARBONYL COMPOUNDS Page # 35

O Sol.

(C) (D) All

Sol.
Cl

O=S=O

53. CH3O18H + (A) CH


O
3
(B) Product (B) is

O NaH,CH3 I
(P) CH3

51. O
LDA,CH3 I
(Q)
(A) CH3O S CH 3
Product (P) and (Q) respectively is:
O O O

O
(A)
18
(B) CH3 O S CH 3
O O
O

18
(B) (C) CH3 O CH3 (D)CH3OCH3
Sol.
O O

(C)
O

O O
54. A KOH

(D)
B KOH
PHCH2OH+PhC O 2 K

Sol. When A reacts with B in presence of KOH/


product C is formed product C is ?
(A)PhCH=CHCHO
O

(B) PhCH2CH2 C CH3


52. Which of the following compound not reacts O
with NaHSO3?
O O
(C) PhCH= CH C CH3
(D) None
(A) H C H (B)CH3 C H Sol.
O O

(C) (D)

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Page # 36 CARBONYL COMPOUNDSE

Sol.
55. Ph CH=O+NH2NH2
H (A). Product (A) is
known as:
(A) Aldo-Oxime (B) Hydrazone
(C) Hydrate (D) Phenyl hydrazone
Sol.
O3 KOH
58. (A)
Zn

(B)Major product (B) is:


O O

56. HOCH2CH2CH=O (
1) KCN
(A), Product (A) is:
( 2) H
( 3) H3O (A) (B)
( 4)

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

O
O Sol.
O O
(C) (D)
OH OH
Sol.
O O

59. CH3 C CH3 + H C H KOH




(A) major. Product (A) is :
O O

O O (A) (B)
2eq.KNH2
57. n
C 4 H 9 Br
(P) O HO
NH3 ( )
then H 3O

End product (P) of above reaction is: (C) (D) O


O O O O H
Sol.

(A) (B)

O O O O O

60. CH3 C OH CaO


(A) KOH


(C) (D)

(B) D
2 O / DO
(C)
prolonged treatment

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How many hydrogen is replaced by Deuterium HO O


(A) 2 (B) 10

(C) 7 (D) 8 (C) + H
(Q)
HO
Sol.
cis-1,2-Cyclohexanediol Acetone

62. Product P is .
O OEt OEt
OEt
( i ) KCN
P (A) (B)
61. ( ii ) H O
3 OEt
H
OMe OMe
Find out the incorrect statement about the
above given reaction
OPr
(C) (D)
(A) It is a nuclephilic addition reaction OPr
(B) Obtained product is present in racemic mix- Sol.
ture
(C) If the hydrolysis of obtained product
give -hydroxy acid
(D) It is a electrophilic addition reaction
Sol.
63. Product Q is .
O
(A) (B) O

Comprehansion : (Q.62 to Q.64): O


Aldehydes and ketones react with one mol- (C) O (D)
ecule of an alcohol to form compounds called
hemiacetals, in which there is one hydroxyl Sol.
group and one ether-like group. Reaction of a
hemiacetal with a second molecule of alcohol
gives an acetal and a molecule of water. We
study this reaction
HO
OR
ROH
ROH

O

H OR H OR
The carbonyl A hemiacetal An acetal 64. Product R is .
group of an (has anOH and (has two OR
aldehyde of ketone anOr group to groups to the
same cabon)
O
the same carbon) O
O
Draw structural formulas for the hemiacetal and (A) O (B)
acetal formed from these reagents. The sto-
ichiometry of each reaction is given in the prob-
lem.

(C) (D)
O
(A) +2 CH3CH2OH
H (P)

Cyclohexanone Ethanol Sol.


O
(B) +HOCH2CH2OH H
(R)

Cyclohexanone Ethylene glycol

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Page # 38 CARBONYL COMPOUNDSE

Exercise - II (One or more than one option correct)


1. Which one of the following is mixed ketone (Ali-
5. Fehling solution gives red precipitate with:
phatic & aromatic):
O O (A) Aromatic alehyde(B) Aliphatic aldehyde
(C) Ketones (D) -hydroxy ketones
Sol.
(A) CH3 C CH3 (B) CH3 CH2 C CH3
O O

(C) Ph C CH3 (D) CH3 C6H4 C CH2Ph


Sol.
6. Silver mirror test with Tollens reagent is given
by :
(A) C6H5CHO
(B) PhCH2CHO
O
2. Two isomeric ketones, 3-pentanone and 2-
pentanone can be distinguished by:
(C) C6H5CH2 C CH2OH
(A) l2/NaOH (B) NaSO3H (D) CH3CHO
(C) NaCN/HCl (D) 2,4-DNP Sol.
Sol.

3. Stability of hydrates of carbonyl compounds


depends on:
(A) Steric hindrance
7. Which one of the following compounds will not
(B) Presence of -1 group on gemdiol carbon
give aldol:
(C) lntramolecular hydrogen bonding
(A) Acetaldehyde (B) Formaldehyde
(D) angle strain in carbonyl compound (C) Pivaldehyde (D) Crotonaldehyde
Sol. Sol.

4. Whcih of following give positive test with 2,4-


DNP?
O O
8. Schiffs reagent gives pink colour with:
(A) CH3 C H (B) CH3 C CH3 (A) Acetaldehyde (B) PhCH3
O (C) Acetic acid (D) Methyl acetate
Sol.

(C) CH3 C OH (D) CH3CH2OH


Sol.

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CARBONYL COMPOUNDS Page # 39

9. Which of the following compound will give posi- Sol.


tive Tollens test

(A) CH3CHO (B) O


OH

(C) CH3CH2CH2CH2 CH OCH3 13. Which of the reactant show geometrical isom-
OH erism when it react with hydrazine (NH2NH2)
O
OCH3 O
(D) CH3 CH
OCH3
Sol. (A) (B)

H H
O
O

(C) (D)
10. Mixture of PhCHO&HCHO is treated with NaOH
then Cannizzaro reaction involves:
(A) Oxidation of HCHO Sol.
(B) Reduction of HCHO
(C) Oxidation of PhCHO
(D) Reduction of PhCHO
Sol.

CH=O
14. PCl
5
COH
11. PhCHO + HCHO Conc.KOH

Correct statement regarding reaction will be O
(A) It is an example of redox reaction w PhMgBr
(B) H CHO is oxidised
x NH 2 NH 2
y
(C) It is cross cannizato reaction Identify final product y of the above given
reaction:
(D) PhCHO is reduced
Sol.

(A) (B)
Ph
Ph

N N
N
(C) N (D)
Paragraph for Question Nos.12 to 14 Ph Ph
Carbonyl group show characteristic reaction of nu- Sol.
cleophilic addition in which nucleophile attack in
rate determing step on carbonyl carbon.
12. Which Ph is suitable for oxime formation
(A) 45 (B) 12
(C) 810 (D) 1214

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Page # 40 CARBONYL COMPOUNDSE

15. Match list-l with list-ll and select the correct Column ll
answer using the codes give below the lists: (P) An enamine will form
List-l (Q) Schiff base will form
(R)Hydrazone will form
(A) CH2=CHCHO NaBH
4 (S) Product form willundergo Lassign test
Sol.

(B) C6H5CHO+PhNH2 H

(C)C6H5COCH3+CH3CH2NH2
H


(D) RCHO+2RCH2OH H

17. Column l
List-ll
(P) Acetal O
OH
(Q) Schiffs base
(R) Unsaturated alcohol
(A)
(S) Enamine
Sol.

O
OH

(B)

16. Match the following :


Column l OH

O (C)

(A) + H
N

H OH Cl

OH (D)

NH Ph
H

(B)
Column ll
(H2 O)

(Reagent used)
(P) Al(OCHMe2)3 or H2/Ni
O (Q)Al(OCMe2)3 or CrO3
NH2
(R) H3PO4/
(C) + (S) conc. HCl
Sol.

(D) + NH2 NH2

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CARBONYL COMPOUNDS Page # 41

Exercise - III Subjective Level-I


1. Predict the product of the reaction of propanal
with each of the following Br
(a) Lithium aluminum hydride

(b) Sodium borohydride (l) CH3CH2 CHCOOC2H5 and Zn then H2O/ H
(c) Hydrogen(nickel catalyst (Reformatsky reaction)
(d) Methylmagnesium iodide, followed by dilute acid.
(e) Sodium acetylide, followed by dilute acid
Sol.
(f) Phenyllithium, followed by dilute acid
(g) Methanol containing dissolved hydrogen chloride
(h) Ethylene glycol, p-toluenesulfonic acid, benzene
(i) Aniline (C6H5NH2)
(j) Dimethylamine, p-toluenesulfonic acid, benzene
(k) Hyderoxylamine
(l) Hydrazine
(m) Product of part(l) heated in triethylene glycol with
sodium hydroxide
(n) p- Nitrophenylhydrazine
(o) Semicarbazide
+
(p)Ethylidenetriphenylphosphorane [(C6H5)3PCHCH3]
(q) Sodium cyanide with addition of sulfuric acid
(r) Chromic acid 3. (a) Arrange the fol lwong compounds in
Sol. decreading order of Keq for hydrate formation.

C6H5COCH 3 Cl CCH 3
; ;
(1)
(2)

O O

NO2 C CH3 ; CH 3 C CH3


2. Give structure for the products of the reactio (3) (4)
when butanal is treated with each of the fol-
lowing reagents (b) Equilibrium constants for the dissociation
(Kdiss) of cyanohydrins according to equation
(a) A g(NH3) O H then HOH / H
OH
(b) O H/HOH,
O


(c) NH2OH/ H RCR' Kdiss
RCR' + HCN
(d) C6H5Li then HOH

CN
(e) C6H5CHO, O H,

Cyanohydrin Aldehyde Hydrogen
(f) CHCNa then HOH / H
or ketone cyanide

(g) CH2OH CH2OH, H have been measured for a number of cyano-
(h) SHCH2CH2CH2SH then Raney Ni/H2 hydrins. Which cyanohydrin in each of the fol-
(i) CH3MgBr then H2O
lowing pairs has the greater dissociation con-
(j) HCN
(k) NaBH4 stant?

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Page # 42 CARBONYL COMPOUNDSE

5. Suggest a reasonable mechanism for each of


OH OH the following reactions:

(i) CH3CH2 CHCN or (CH3)2 CCN O O


(CH3)3 C
C CH2 NaOCH
3 (CH ) CCCH OCH
OH OH CH3 OH 3 3 2 3

Cl (88)%

(ii) C6H5 CHCN or C6H5 CCN Sol.

CH3

Sol.

6. Predict the organic products:


O
4. Some grignard reagents react with ethyl
orthoformate followed by acidic hydrolysis to
give aldehydes. Propose mechanisms for the (a) CH3 C CH3 + HO CH2CH2NH2 H
2 / Pt

two steps in this synthesis.

OCH2CH3 OCH2CH O CH2CH2CH2NH2

HCOCH2CH 3+RMgX RCOCH2CH3


H3O
+

RCH (b) H
2 / Pt

O

OCH2CH3 H
ethyl orthoformate acetal aldehyde O

Sol.
(c) CCH3 (
i ) Cl2 / NaOH / HOH

( ii ) H

Sol.

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CARBONYL COMPOUNDS Page # 43

7. A synthesis that begins with 3,3 - demethyl-


O
2-butanone gives the epoxide shown.Suggest
reagents appropriate for each step in the syn-
thesis. C CH3
(b) (Y) NaOH /
O O

CH 3
(a) (CH3)3C C CH3 58

% (CH3)3C C CH2Br

OH
O (c) (Z) NaOH
/
O
68%
54

% (CH3)3C CCH2Br
(CH3 )3 CC CH 2

Sol.
H
(b) Overall yield of the reaction is

8. Outline resonable mechanisms for each of the


following reactions:
O O

CH2 CH2CH2CH2Br
KOC
( CH3 ) 3


benzene
10. Each of the following reactions has been re-
ported in the chemichal literature. Write the
(76%) structure of the product(s) formed in each
Sol. case.
O
Soft
C6 H 5CH 2SH
(a) H C
3
CH 2
NaOH , H 2 O

O
O
C6H5
(b) Cl CH + C6H5

KOH

ethanol

Sol.

9. Give the structure of the substance for each


of the following reaction :

(a) (x) NaOH


/

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Page # 44 CARBONYL COMPOUNDSE

EXERCISE IV PREVIOUS YEARS PROBLEMS

LEVEL I JEE MAIN


Sol.
Q.1 Which one of the following is reduced with
zi nc and hydrochl ori c aci d to gi ve the
corresponding hydrocarbon ?
[AIEEE-2004]
(A) Ethyl acetate (B) Acetic acid
(C) Acetamide (D) Butan-2-one
Sol.

Q.4 The increasing order of the rate of HCN addition


to compounds A D is -
[AIEEE 2006]
(a) HCHO (b) CH3COCH3
(c) PhCOCH3 (d) PhCOC6H5
(A) d < b < c < a (B) d < c < b < a
(C) c < d < b < a (D) a < b < c < d
Sol.

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
Sol.

Q.5 Which of the folowing on heating with aqueous


KOH, produces acetaldehyde ?
[AIEEE 2009]
(A) CH3COCl (B) CH3CH2Cl
(C) CH2ClCH2Cl (D) CH3CHCl2

Sol.

Q.3 The best reagent to convert pent3en2ol


into pent3in2one is - [AIEEE-
2005]
(A) Acidic dichromate
(B) Acidic permanganate
(C) Pyridinium chlorochromate
(D) Chromic anhydride in glacial acetic acid

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CARBONYL COMPOUNDS Page # 45

LEVEL II JEE ADVANCED


Single Choice Question : CH2OH COOH
1. Compound A (molecular formula C3 H8O) is
treated with acidified potassium dichromate to
form a product B (molecular formula C3H6O). B (C)
forms a shining silver mirror on warming with COOH CH2OH
ammonical silver nitrate. B when treated with
an aqueous solution of H2NCONHNH2. HCl and O
sodium acetate gives a product C. ldentify the O
structure of C. [JEE 2002]
(A) CH3CH2CH = NNHCONH2
(B) CH3C=NNHCONH 2 (D)
CH3 O
O
(C) CH3C=NCONHNH 2
CH3 Sol.
(D) CH3CH2CH= NCONHNH2
Sol.

3. The products of acid hydrolysis of P and Q can


be distinguished by [JEE 2003]
CHO OHC
CH3
OCOCH3
(
i ) NaOH ( excess )100 C
P=HC=
2
Q=
2. ( ii ) H / H 2 O CH3 OCOCH3
CHO OHC
(A) Lucas reagent (B) 2,4-DNP
any one of the products formed is: (C) Fehling solution (D) NaHSO3
[JEE 2003] Sol.

COOH HOOC

(A)

COOH HOOC

2
CH2OH 4. PhCC CH3 Hg
/H
A [JEE 2005]
CH2OH
O

(B) Ph Ph O

CH2OH (A) (B)


CH 2OH
CH3 CH3

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Page # 46 CARBONYL COMPOUNDSE

(C) Ph (D) Ph
OH

CH3 CH3
8. Which of the following reactats on reaction
with conc. NaOH followed by acidification gives
Sol. the following lactone as the only product?
[JEE 2006]
O

C
O

CH2
COOH
CHO
CH3COONa
5. +X
COOCH3 COOH
MeO MeO
(A) (B)
What is X ? [JEE 2005] COOH CHO
(A) CH3COOH (B) BrCH2,COOH
(C) (CH3CO)2O (D) CHOCOOH CHO COOH
Sol. (C) (D)
CHO COOH

Sol.

6. How w i l l you c onvert b utane-2-one to


propanoic acid? [JEE 2005] 9. Cyclohexene on oxonolysis followed by reac-
(A) Tollen reagent (B) Fehling solution tion with zinc duct and water gives compoundE.
(C) NaOH / I2/H+ (D) NaOH/NaI/H+ Compound E on further teratment with aque-
Sol. ous KOH yields compound F. Compound F is
[JEE 2007]

(A) CHO (B) CHO

7. The smallest ketone and its next homologue CO2H


are reacted with NH2OH to form oxime. (C) COOH (D)
CO2H
[JEE 2005]
(A) Two different oximes are formed Sol.

(B) Three different oximes are formed


(C) Two oximes are optically active
(D) All oximes are optically active
Sol.

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CARBONYL COMPOUNDS Page # 47

12. Match the compound in Column l with their


10. Statement -1 : Glucouse gives a reddish- brown characteristic test (s)/reaction(s) given in Col-
precipitate with Fehlings solution. because umn ll. lndicate your answer by darkening the
Statement -2 : Reaction of glucose with appropriate bubbles of the 4 4 matrix given in
fehlings solution gives CuO and gluconic acid. the ORS [JEE 2008]
[JEE 2007] Column l

(A) Statement -1 is True ; Statement -2 is (A) H2N N H3 Cl
True; statement-2 is a correct explanation for
statement -1
(B) Statement -1 is True; Statement -2 is NH3 I
(B) HO
True; statement-2 is NOT a corrcect expla- COOH
nation for statement -1
(C) Statement -1 is True, Statement -2 is
False.
(C) HO NH3 Cl
(D) Statement -1 is Fals, Statement -2 is True.
Sol.
(D)

O2N NH NH3 Br

NO2

Column II
(P) sodium fusion extract of the compound
gives Prussian blue colour with FeSO4
MCQ:
(Q) gives positive FeCl3 test
11. Match the compounds/ion in column l with their (R) gives white precipitate with AgNO3
properties / reaction in Cloumn ll. Indicate your
(S) reacts with aldehydes to form the corre
answer by darkening the appropriate bubbles
sponding hydrazone de rivative
of the 4 4 matrix given in the ORS.
Sol.
[JEE 2007]
Column l
(A) C6H5CHO
(B) CH3C CH
(C) CN
(D) l
Column ll Paragraph for Question No. 13 to 15
(P) give precipitate with 2,4- A tertiary acohol H upon acid catalysed dehydration
dinitrophenylhydrazine gives a product l. Ozonolysis of l leads to
(Q) gives precipitate with AgNO3 compounds J and K compound J upon reac-
(R) is a nucleophile tion with KOH gives benzyl alcohol and a com-
pound L, whereas K on reaction with KOH gives
(S) is involved in cyanohydrin formation
only M. [JEE 2008]
Sol.

O
H3C Ph
M=
Ph H

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Page # 48 CARBONYL COMPOUNDSE

Sol. 15. The st ruct ures of comp ound s J, K and


L,respectively are
(A)PhCOCH3,PhCH2COCH3 and PhCH2COOK+
(B) PhCHO,PhCH2CHO and PhCOOK+
(C) PhCOCH3, PhCH2CHO and CH3COOK+
(D) PhCHO,PhCOCH3 and PhCOOK+
13. Compound H is formed by the reaction of Sol.
O

(A) + PhMgBr
Ph CH 3
O

(B) + PhCH2MgBr
Ph CH 3
Paragraph for Question Nos. 16 to 18
O A carbonyl compound P, which gives positive
iodoform test, undergoes reaction with MeMgBr
(C) + PhCH2MgBr followed by dehydration to give an olefin Q.
Ph H Ozonolysis of Q leads to a dicarbonyl com-
pound R which undergoes intramolecular aldol
O Me reaction to give predominantly S.
[JEE 2009]
(D) +
Ph H Ph MgBr 1. O
P 1
. MeMgBr

Q
3
R 1
. OH
S
2. H , H 2 O 2. Zn,H2O 2.
Sol. 3. H 2SO 4 ,

16. The structure of the carbonyl compound P is

Me
(A) (B)
O Me
O Me
14. The structure of compound l is
O
H3C
Ph CH3 Ph
(C) (D)
(A) (B) Et
O
H Ph H Et
Ph
Sol.
Ph CH3 H 3C
CH3

(C) (D)
H CH2Ph H
Ph

Sol.

17. The structures of the products Q and R, re-


spectively are

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CARBONYL COMPOUNDS Page # 49

O O
O

Me H Me
(A) , COMe (C) (D)
Me Me
Me Me Me Me
O
Sol.

H
(B) , CHO
Me Me
Me Me

O
Paragraph of Question Nos. 19 to 21
H Two aliphatic aldehydes P and Q react in the
(C) , presence of aqueous K2CO3 to give compound
CHO
R which upon treatment with HCN provides
Me Et
Me Et compound S. On acidification and heating. S
gives the product shown below
O [JEE 2010]
Me OH
H3C
CH3
H3C
(D) , CHO O O
Me Me Et
19. The compounds P and Q respectively are -
Sol.
CH3
H3C H
CH
H C
(A) H3C C and
O
O

CH3
H H
CH
18. The structure of the product S is : H C
(B) H3C C and
O O
O

CH2 H3C H
(A) (B) H3C
H
O CH C C
Me Me Me (C) and
O O
CH3

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Page # 50 CARBONYL COMPOUNDSE

CH2 H H
O
H3C CH3
H
CH C C CH
(D) and CH
O O (D) H3 C CH H
CH3
CH
OH
Sol. H3 C

Sol.

21. The compound S is


20. The compound R is O
CH3
O
CH C
(A) H3C CH H
HC C
(A) C H H2C
H3 C CN
H 2C
OH
O

O
H3C C
(B) C H
H3C C H3C
C H H2C
(B) H C CN
3
CH
H3C OH

CH 3 CN
O
CH 3 CH CH
(C) H3 C CH OH
CH C H2C
(C) HC
3 CH H OH
CH2
OH
CN

CH
(D) H3 C OH
C
H3 C
CH 2
OH

Sol.

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CARBONYL COMPOUNDS Page # 51

CHOH
2
CHOH
2

22. Five isomeric para -disubstituted aromatic com-


HO O H H O HO
pounds A to E with molecular formula C8H8O2
were given for identification. Based on the fol- H HO H OH
lowing observations, give structure ofthe com- (A) H O H
pounds. [JEE 2002] OH H OH H
(i) Both A and B form a silver mirror with Tollens
reagent; also, B gives a positive test with FeCl3 (Q) CH2 OH
HOH2C
solution
(ii) C gives positive iodoform test. HO O H H O OH
(iii) D is readily extracted in aqueous NaHCO3 H HO OH H
solution. H O H
(B)
(i v) E on ac i d hyd rol y si s gv es 1, 4- OH H H OH
dihydroxybenzene.
Sol. (P)
Sol.

23. C6H12 HCl


C6H13Cl + (C)
O
(A) (B)
OH
( i) O NaOH
Alc.KOH ozonolysis 26. H
,
X 3 Y
(D)
(E) ( ii ) Zn / Cl 3COOH
(HCl)
ozonolysis Identify (X) and (Y) [JEE 2005]
(A) NaOH
(F) + (G) HCOONa+1alcohol
Sol.
(D) is isomer A. E gives negative test with
Fehling solution but gives iodoform test F and
G gives Tollens test but do not give iodoform
test. ldentify A to G. [JEE 2003]
Sol. 27. In the scheme given below the total number of
intramolecular aldol condensation products
formed from Y is [JEE 2010]

24. Give major product A, B,C and D in following


reaction sequence. [JEE 2004]
1
.O 3
Y 1
. NaOH ( aq )

2. Zn , H 2 O 2. heat
CH2Cl
Sol.
KCN (i) NaOEt/EtOH
(A)
DMF

(B) H3O (i) SOCl2


(C)
(ii) CH 3NH2
Sol.

25. Which ofthe following disaccharide will not re-


duce Tollens reagent ? [JEE 2005]

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CARBONYL COMPOUNDS Page # 52

Answers
Exercise-I
1. B 2. C 3. D 4. B 5. D 6. D 7. B
8. C 9. D 10. C 11. A 12. D 13.(i)C(ii)C 14. B
15. D 16. B 17. A 18. A 19. D 20. C 21. C
22. A 23. B 24. B 25. B 26. D 27. C 28. D
29. A 30. D 31. A 32. C 33. A 34. B 35. A
36. B 37. B 38. B 39 C 40. D 41 C 42. D
43. A 44. D 45. C 46. C 47. B 48. D 49. C
50. D 51. C 52. D 53. D 54. C 55. B 56. A
57. D 58. B 59. C 60. B 61. D 62. B 63. B
64. B

Exercise-II

1. C,D 2. AB 3. A,B,CD 4. A,B 5. B,D 6. A,B,C,D 7. B,C


8. A 9. A,B,C 10. A,D 11. A,B,C,D 12. A 13. D 14. C
15. AR ; B Q ;C Q; D P 16. A P,S ; B Q, S ; C Q, S ; D S
R ,
17. A P ; B Q ; C R ; D S

Exercise-III

1. (a) CH3CH2CH2OH (b) CH3CH2CH2OH (c) CH3CH2CH2OH


OH OH OH

(d) CH3CH2 CH CH3 (e) CH3 CH2 CH CCH (f) CH3 CH2 CH Ph
O
(g) CH3CH2 CH OCH3 (h) CH3CH2CH (i) CH3CH2CH= N Ph
O
OCH3
OH

(j) CH3 CH2 CH N CH3 (k) CCC=NOH (l) CH3CH2CH=NNH2


CH3

(m) CH3CH2CH3 (p) P-Nitro phenyl hydrazone (o) semi carbazane


OH

(p) CH3CH2CH=CHCH3 (q) CH3CH2 CH CN (r) CH3CH2CO2H


O

2. (a) CCC C OH (b) CH3CH2CH2CH=CCH2CH3 (c) CCCCC=NOH


CHO

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Page # 53 CARBONYL COMPOUNDSE

OH
OH
(d) CCC CPh (e) PhCH=CCH2CH 3 (f) CCC CH CCH
O CHO
(g) CCCC (h) CCCC (i) 2 alcohol
O
OH

(j) Cyanohydrine (k) 1 alcohol (l) CH3CH2CH2 CH CHCO2H

Et

OH OH

3. (a) 3 > 2 > 1 > 4 (b) (i) (CH3)2 CCN (ii) C6H5 CCN

CH3
4. R MgX


(CH3)3C O O
O
5. C CH2 OCH3 (CH3)3C
Cl CCH2OCH3 (CH3)CCCH2OCH3
Cl
O

6. (a) CH3 CH NHCH2CH2OH (b) (c) CHCl3 + C OH


N
CH 3 |
H
7. HO /Br2; H2/Ni; NaOH

O O O

CH2CH2CH2CH2Br CH2 CH2 CH2 CH2Br




Acid Base reaction
8.
(CH3)3CO

O
O CHO

C CH 3
9. (a) (X) CH3 (Y) (b) CH2CCH3
CHO O CH 3 O

O Ph
CH =
Ph
10. (a) CH CHSCHPh
2
(b)
3 2

Cl

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Page # 54 CARBONYL COMPOUNDSE

Exercise-IV (LEVEL-1)
1. D 2. B 3. D 4. B 5. D

Exercise-IV (LEVEL-2)

1. A 2. C 3. C 4. A 5. C 6.C
7. B 8. C 9. A 10. C
11. A P,Q,S;B Q,R;C Q,R,S;D Q,R
,R
12. AR,S;BP,Q:CP,Q,R;DP,S (OR) AR; BP,Q; CP,Q,R; DP

13. B 14. A 15. D 16. B 17. A 18. B 19. B


20. A 21. D

O
CHO CHO CH2CHO COOH OCH=CH 2
CCH3

or
22. (A) (B) (C) (D) (E)

OCH3 CH2OH OH CH 3 OH
OH

CN
CH2CN
Me2 C CHMe2+Me3C CHMe
23.Me3CCH=CH2 HCl CH=C
24. (A) (B)
Cl Cl
(A) (B) (C)
CONHCH 3
COOH
CH = C
CH=C
alc. KOH
(C) (D)

Ozonolysis NaOH
(A) HCHO+Me3CCHO
(i) SOCl2
(F) (G) (D) (ii) CH3NH2
HCOONa+Me3CCH2OH(1alcohol)

25. In structure (P) both the rings are present in acetyl form therefore it will not hydrolyse in solution that
why Tollens solution connot react with this.
In structure (Q) one ring present in the form of hemiacetal. This will hydrolysed in solution it can reduce
Tollens solution.
O

26. (X) (Y) CH3 C (CH2)4CH=O

CH3
27. 1

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Carboxylic Acids & Acid Derivatives

Introduction :

Carboxylic acid

Acid halide anhydride ester amide

nitrile

Table 1 : IUPAC Nomenclature of Acid derivatives :-


Compound IUPAC Name

(1) O Methanoic acid


||
H C OH

(2) O Ethanoic acid


||
CH3 C OH

(3) 2- Cyclohexylpropanoic acid

O O 3- Oxo-2- propylbutanoic acid


|| ||
(4) CH CCH C OH
3
|
CH 2 CH 2 CH3
(5) NH2 O 4- Aminobutanoic acid
| ||
CH2 CH2 CH2 C OH
(6) PH O 3- Phenylpentanoic acid
| ||
CH3 CH2 CH CH2 C OH
(7) CH3 O 3- Methylbutanoic adic
| ||
CH3 CH CH2 C OH
(8) O Ethanoylchloride
||
CH3 C F
(9) O Propanoylchoride
||
CH3 CH2 C CI
(10) Br O 3- Bromobutanoylbromide
| ||
CH 3 CH CH 2 C Br

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(11) Cyclopentanecarbonyl chloride

(12) O O Ethanoid anyhydride


|| ||
CH3 C O C CH3
(13) O O Trifluoroethanoic anhydride
|| ||
CF3 C O C CF3
(14) 1,2- Benzenedicarboxylic anhydride

O O Ethanoic methanoic anhydride


|| ||
CH3 C O C H
O O Trifluoroethanoic propanoic
|| || anhydride
CH3 CH2 C O C CF3
Cyclopropane carbonitrile

CN 3- Cyanopentanoci acid
|
CH3 CH2 CH CH2 COOH
Ethyl o-cyanobenzoate

2- Formylcyclohexane carboxamide

OH 2- Hydroxyutane nitrile
|
CH3 CH2 CH C N

Dicarboxylic acids

If the subsituent is a second carboxyl gropu, we have a dicarboxylic acid. For example :

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Oxalic acid Malonic acid -1, 3- Succinic acid -1, 4-


Ethanedioic acid dioicacid dioic acid

Glutaric acid Adipic acid Pimelic acid


Pentane-1, 5-dioicacid Hexane-1, 6-dioicacid Heptane-1, 7- dioci acid

HOOCCH2COOH HOOCCH2CH2COOH HOOCCH2CH2CH2CH2COOH


Malonic acid Succinic acid Adipic acid
Propanedioic acid Butanedioic acid Hexanedioic acid

Physical properties of acids and acid derivatives :

1 Boiling point :
O O
|| ||
CH2 C OH CH 3 CH 2 CH 2 OH CH3CH2 CH
Acetic acid, 1-propanol Propionaldehyde
bp 1180C bp910C bp490C

The high boiling points of carboxylic acids is the result of formation of a stable hydrogen-bonded
dimer.

Hydrogen bonded acid dimer

2 Solubility :

Carboxylic acids form hydrogen bonds with water and the lower molecular weight carboxylic acids
(upto 4 carbon atoms) are miscible with water.
Acid derivatives (esters, acid chlorides, anhydride, nitriles and amides) are soluble organic solvents
such as alcohols, ethers, chlorinated alkanes and aromatic hydrocarbons.

Methods of preparation of carboxylic acids

1- Synthese of carboxylic acids by the carboxylation of grignard reagents

O O
+
dry H /H2 O
RMgX + O = C = O R C OMgX R C OH
ether Mg(OH)X

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2- Synthesis of Carboxylic acids by the hydrolysis of nitriles Mechanism :

Nitrile carboxylic acid

Chemical Reactions

1- Acidic strength %
Acidity of carboxylic acids :-

R C OH R C O H
|| ||
O O

Ex. F-CH2-COOH > Cl CH2COOH > Br CH2COOH > 1 CH2COOH

Increasing acid strength

Ex. CI CI
| |
CI C COOH CI CH COOH CI CH2COOH CH3COOH
|
CI

Increasing acid strength

Ex. HCOOH > CH3COOH > CH3-CH2-COOH

Ex.

Ex. Relative acid strength is:-


RCOOH > HOH > ROH > HC = CH > NH3 > RH

Note:- Acidity of acids is compared by compairing stability of conjugate base

2- Reaction involving removal of proton from OH group.


1 Action with blue litmus : All carboxylic acids turn blue litmus red.
2 Reaction with metals :
2 CH3 COOH + 2Na 2CH3 COONa + H2
Sodium acetate

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2CH3 COOH + Zn (CH3COO)2 Zn + H2


Zinc acetate
3 Reaction with alkalies :

CH3 COOH + NaOH CH3 COONa + H2O

4 Reaction with carbonates and bicarbonates :


2CH3COOH + Na2CO3 2CH3 COONa + CO2 + H2O
CH3COOH + NaHCO3 CH3COONa + CO2 + H2O

Reaction of carbroxylic acid with aqueous sodium carbonatge solution produces brisk
efferuescnce. However most phenols do not produce effervescence. Therefore, the reaction may
be used to distinguish between carboxylic acids and phenols.

5 Reaction with grignard reagent :

R-CH2 MgBr + RCOOH ether


R-CH3 + RCOOMgBr

Note % A stronger acid displaces a weaker acid from salt of the weaker acid.

Ex. CH3COOH (Stronger acid) + CH3ONa CH3 COONa + CH3 OH (WeakerAcid)

Ex. CH3COOH (stronger acid) + NaHCO3 CH3 COONa + H2 CO3 (Weaker acid) H2O + CO2 t
lab, test of carboxylic acide
3- Reaction involving replacement of OH group

.
O O
|| .. ||
G
R C OH
R C G OH

Strong bases so not a basicity must be

Good leaving group less then basicity of G

1 Formation of acid chlorides :

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2 Fisher Esterification

Carboxylic acid react with alcohol to form esters through a condensation reaction known as
esterification.

General Reaction :

O O
|| ||
R C OH R'OH R C OR'H2O

Specific Example:

O O
|| ||
CH3 C OH CH3 CH 2 OH CH3 C OC 2H5 H2 O

O O
|| ||
C 6H3 C OH CH3 OH C 6H3 C OCH3 H 2 O

Mechanism : Acid catalysed esterfication

If we follow the forward in this mechanism, we have the mechanism for the acid catalysed
esterification fo an acid. If however, we follow the reverse reactions, we have the meachanism
f or t h e a ci d cat al ys ed h yd rol y si s o f an est er. A ci d cat al yse d est e r h y dr ol ysi s .

O O
||
||
H2 O
R C OR'H 2 O
R C OH R'OH

3 Formation of amides :

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O O O
||
||
150 200 0 C
||
R C OH NH3 R C ONH 4 R C NH 2 H 2 O
4 Formation of acid anhydride :

4- Decarboxylation reactions:
1 Soda-lime decarboxylation :

General reaction:
O
|| NaOH aO
R C OH R H CO 2

2 Decarboxylation of - keto carboxylic acids :

O O O
|| ||
||
R C CH2 C OH R C CH3 CO 2

- keto acid

3 Kolbe electrolysis

2RCOOK + 2HOH Electrolys


is
R - R + 2CO2 + H2 + 2KOH

Mechanism R CO2K R CO2- + K+

At Anode %& R CO2- R CO2 + e- oxidation


(I)
.
R CO2 R + CO2

(II)

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R. + R. R - R
If n is the number of carbon atoms in the salt of carboxylic acid, the alkane formed 2(n-1)
carbon atoms.

Electrolysis
Ex. 2CH3 COOK + 2H2O CH3CH3 + 2CO2 + H2 + 2KOH.

4 Hunsdiecker Reaction (Brome-decarboxylation):

R-COOAg + Br2 R-Br + CO2 + AgBr

Mechanism:
O
||
Step 1: R.COOAg X 2 R C O X AgX
O
||
Step 2: R C O X RCOO X (initiation)
O
||
Step 3: R C O R CO 2

Step 4: R*. + RCOOX RX + RCOO* (Propagation)

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5. HVZ Reaction (Halogenation of aliphatic acids and Substituted acids)

CH3 COOH Cl
2 ,P
ClCH2 COOH Cl
2 ,P
Cl2CHCOOH Cl
2 ,P
Cl3 CCOOH

Na Metal 1
(1) R CH2COONa H2
2
NaOH
(2) R CH2 COONa H2O

NaHCO3
(3) R CH2 COONa CO2 H2O
CH3MgBr
(4)
R CH2 COOMgBr CH4
NaOH(CaO)
(5) R CH3 Na 2 CO 3

SOCI2
R-CH2-COOH RCH2COCOCI SO2
(6)

PCI5
(7) R CH2 COCI

NH3,
R CH2 C NH2
(8) ||
O
P2O5, R CH2 C O C CH2 R
(9) || ||
O O
ROH/H2SO4
(10) R CH2 C OR'
||
O
(i) P + X2, (ii) H2O
(11) R CH COOH
|
X
(i) SOCI2 (ii) CH2N2
(ii) Ag2O (iv) H2O R CH2 CH2 COOH
(12)
O
Ca(OH)2/ ||
Dry disstilltion R CH2 C CH2 R CaCOl 3
(13)

AgOH, Br2/
(14) R CH2 Br CO2
NaOH, electrolysis
(15) R CH2 CH2 R

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Carboxylic Acid Derivatives


Closely related to the carboxylic acids and to each other are a number of chemical families
known as functional derivatives of carboxylic acids : acid chloride, anhydrides, amide, and
esters, These derivatives are compounds in which the -OH of a carboxyl group has been
replaced byCl, -OOCR, -NR2 or OR

Acid chloride Anhydride Amide Ester

They all contain the acyl group ,

(A) Acid halides


Methods of preparations of Acyl halides

(i) RCOOH + PCl5 RCOCl + POCl3 + HCl

(ii) 3RCOOH + PCl3 3RCOCl + H3PO3

(iii) RCOOH + SOCl2 Pyridine


RCOCl + SO2 + HCl

Ex. 3CH3 COONa + PCl3 Distil


3CH3 COCl + Na3PO3
Acetyl chloride
Distil
Ex. 2C6H5COONa + POCl3
2C6H5COCl + NaCl + NaPO3
Sod. benzoate Benzoyl chloride

Chemical Reactions

1 Reaction with carboxylic acids


O O O O
|| || PY
|| ||
RCCI R' COH RCOCR' HCI
Acyl Carboxylic Acid Hydrogen
chloride acid anhydride chloride

2 Reaction with alcohols


Acyl chlorides react with alcohols to form esters. The reaction is typically carried out in the
presence of pyridine.

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Acyl Alcohol Ester Hydrogen


choride chloride

3 Hydrolysis

4 Reaction of acid halide with organometallic

(a) with Grignard reagent

(b) Reaction with Gilmann reagent

5 Reduction of acid halided

(a) Reduction LiAlH4

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(b) Reduction with H2/Pd/BaSO4 Rosenmund reduction

(B) Acid amides


Methods of preparation of acids amides

1. By reaction of esters with ammonia and amines

Ammonia is more nucleophilic than water, making it possible to carry out this reaction using
aqueous ammonia.
Ex.

2. From acid halides

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RCOCl + 2NH3 RCONH2 + NH4Cl

3. From anhydride

(RCO)2O + 2NH3 RCONH2 + RCOO NH4

4. From esters
RCOOR + NH3 RCONH2 + ROH

5. From ammonium salt of carboxylic acid


RCOONH4
RCONH2 + H2O


CH3 COONH4
CH3CONH2

6. From cyanides

Conc . HCl

R C N + H2O or R CONH2
H O NaOH
2 2
Conc . H 2SO 4
CH3C = N + H2O
CH3 - CONH2

7.

Chemical Reactions
(1) Hoffmann rearrangement

General reaction

hydrolysis

(2) Hydrolysis of amides


In acid, however, the amine is protonated, giving an ammonium ion, R2 NH2

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Summary of reaction of amide:

+
H /H2 O +
RCOOH + NH4
NaOH
RCONa + NH3
Conc. HCl
RCONH2 HCl
2Na
O
RCONHNa + H2
P2O5
R C NH 2 3RC N + 2H 3PO 4
Acid amide
SOCl2
RC N + SO2 + HCl
HONO
RCOOH + N2 + H2O
Br2 + 4KOH
RNH2 + K2CO3 + 2KBr + HO2 (Hoffmann
LiAlH4 /dry ether
RCH NH bromide reaction)
2 2
1 Amine

(C) Esters

Mathods of Preparation


H
(i) CH3 COOH + C2H5OH CH3COOC2 H5 + H2O
Acetic acid


H
C6H5COOH + CH3OH C6H5 COOCH3 + H2O

(ii) CH3 COCl + C2H5OH Pyridine


CH3COOC2H5 + HCl

Alcohols react with acyl chlorides by nucleophilic acyl substitution to yield esters. These
reactions are typically perormed in the presence of a weak base such as pyridine.

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Summary of reaction of esters :

(D) Acid anhydrides

Methods of Preparation of acid anhydrides


1- From carboxylic acids

Ex. CH3COOH + HOOCCH3 P


2O 5 ,
CH3CO.O.COCH3 + H2O
Acetic acid Acetic anhydride

Ex.

H2O

Ex.

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H2O

2. From acid and acid halide


Ex. CH3COOH + CH3COCl Pyridine
CH3 CO.O.COCH3 + HCl

Ex. CH3COCl + CH3COONa CH3CO.O.COCH3 + NaCl
Chemical Reactions
1 Reaction with aromatic compounds (Friedel crafts acylation)

2 Reaction with alcohols

Ex.

3 Reaction with ammonia and amines

4 Hydrolysis

Acid anhydrides react with to yield two carboxylic. Cycylic anhydides yield dicarboxylic acids.

5- Heating Effects :
a Heating effect on monocarboxylic acid

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b Heating effect on dicarboxylic acid

c Heating effect on Hydroxy acids

1- Hydroxy acid
2- Hyroxy acid

3- Hydroxy acid

Since 4 or 8 membered rings are less stable the refore -Hydroxy acids on heating produce ,
unsaturated carboxylic acid.

4- a-Hyroxy acid

Heating effect on esters

This reaction follows syn elimination & hoffman product is formes.

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Page # 72 Carboxylic Acids & Acid Derivatives & Amine

AMINES
1. BASIC NATURE OF AMINES

1. Aniline is less basic than ammonia. The phyenyl group exerts- I (inductive effect, i.e., it withdraw
electrons. This results to the lower availability of electrons on nitrogen for protonation.
2. Ethylamine and acetamide both contain an amino group but acetamide does not show basic
nature. This is because lone pair of electrons on nitrogen is delocalized by resonance with the carbonyl
group which makes it less available for protonation.
O O
+
H3C C NH2 H3C C = NH2

3. The compound with least s character (sp3 hydrolized) is most basic and with more s character
(sp-hydrilized) is least basic. Examples in decreasing order of basicity are :
:

(i) CH3NH2 > CH3 N = CHCH3 > CH3 C = N


3 2
(sp ) (sp ) (sp)

(ii) CH3CH2CH2NH2 > H2C =


CHCH2NH2 > HC CCH2NH2
(iii) (CH3)2NH > CH3NH2>NH3 > C6H5NH2
Electron withdrawing (C6H5) groups cause decrease in electron density on nitrogen atom and
there by decreasing basicity.
(v) CH3CH2NH2 > C6H5CONH2 > CH3CONH2

2. METHODS OF PREPARATION
1. Hafmanns bromamide reaction : Amines (only primary) can also be prepared by Hoffmann
degradation. In this method the amine will have one carbon atom less than the amide. The reaction
proceeds via formation of nitrene.
O
R C NH2 + Br2 + 4KOH RNH2 + K2CO3 + 2KBr + 2H2O

Mechanism of above reaction has been proposed as given below :


Br2 + KOH K+OBr + HBr
Mechanism
2NaOH + Br2 NaOBr + NaBr + H2O

O O

(a) R C NH2 + OBr R C N Br + OH

H
O N-bromoacetone
O

(b) R C N Br | OH R C N Br + H2O
H 2O
Rearrangment
H

H2O
R NH2 + CO2 R N = C = O (Isocyanate)

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2. Curtius, Schmidt and Lossen Rearrangment : These reaction are basically rearragment reaction
in which carbon migrates from carbon to nitrogen with the formation of an isocyanate. In these
migration i.e., 1, 2 shift, migrating group is an alkyl or aryl group and leaving group may be
Br in Hoffmann rearrangement
N2 in curtius and Schmidt rearrangement
O

Lossen rearrangement
RCO
The isocyanate formed on hydrolysis gives amine.

(a) Curtius Reaction : Acid chloride on treatment with sodium azide give acid azides which on pyrolysis
gives isocyanates on hydrolysis gives corresponding amines.
RCOCl + NaN3 RCON3 + NaCl
O O O
:

RCN=N=N RCNN N R C = N N2

R N N2 RN=C=O
C alkyl isocyanate
O
H2O

H2O
R N = C OH R N = C O
OH OH
O
R NH C OH R NH2 + CO2
CO2
(b) Schmidt Reaction : Carboxylic acid reacts with hydrozoic acid in presence of concentrated H2SO4
to give isocyanates.
O OH OH
+ NH3
RC +H RC R C OH
OH
H N N+ N

H2O

O
R C OH
H+
RN=C=O RC
isocyanate H N+ N
+
H2O N N N

R NH2 + CO2

(c) Lossen Reaction : Hydroxylamine on treatement with acid chloride gives acyl derivatives of hydroxyl
amine the acyl derivatives exist in two tautomeric form keto form called hydroxamic form and enol form
called hydroximic acid. The hydroxamic form.
OH
R COCl + NH2OH RC=N + HCl

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Page # 74 Carboxylic Acids & Acid Derivatives & Amine

O O
R C NHOH R C = N OH
Keto form the The hydroximic
hydroxamic from form (enol form)

The hydroxamic form (keto form) forms o-acyl derivatives of hydroxamic form which on heating with
bases forms isocyanates and finally amines upon hydrolysis.

H O H O
R C N OH + R C Cl RCNOCR

:
O
H2O
RHN2 RN=C=O RCNOCR

:
O

3. By reduction of nitrothane :
Sn + HCl
C2H5NO2 + 6[H] C2H5NH2 + 2H2O
Nitroethane Ethylamine

4. By reduction of methyl cyanide :

Na + C2H5OH
CH3CN + 4[H] CH3CH 2NH2
Methyl Ethylamine
cyanide

5. By reduction of acetamide : Ethylamine is obtained by reduction of acetamide with sodium and


absolute alcohol or LiAlH4 in ether or hydrogen in presence of nickel catalyst.
Na + C2H5OH
CH 3CONH2 + 4[H] CH3CH2NH2 + H2O
Methyl cyanide Ethylamine

6. By reduction of aldoxime : Aldoxime on reduction with hydrogen and nickel catalyst or sodium
and absolute alcohol or LiAlH4 in ether yields ethylamine.
CH3CH = NOH + 4[H] CH3CH2 NH2 + H2O
Acetaloxime Ethylamine

7. By the hydrolysis of ethyl isocyanate : Ethyl isocyanate on heating with caustic potash solution
undergoes hydrolysis forming ethylamine.
C2H5NCO + 2KOH C2H5NH2 + K2CO3
Ethyl
isocyanate Ethylamine

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8. By the acid hydrolysis of ethyl isocyanide : Ethyl isocyanide undergoes hydrolysis with a
mineral acid and forms ethylamine.
C2H5NC + 2H2O C2H5NH2 + HCOOH
Ethyl
isocyanate Ethylamine Formic acid

9. By Schmidt reaction :
C2H5COOH + N3H C2H5NH2 + N2 + CO2
Propionic acid Hydrazoic
acid Ethylamine

In this reaction the acyl azide (RCON)2 and alkyl isocyanate (R NCO) are formed as an intermediate.

10. By the action of chloramine on Grignard reagent : When chloramine reacts with ethyl magnesium
iodide, the formation of ethylmine occurs.

C2H5MgI + ClNH2 C2H5NH 2 +Mg


Ethyl magnesium Chloramine
Iodide Ethylamine Cl

11. By Gabriels phthalimide reaction :

CO KOH CO
NH NK
CO H2O CO

C2H5l

COOH 2H2O CO
C2H5NH2 + NC 2H5
COOH HCl CO
Ethylamine

Phthalic acid N-Ethyl Phthalimide

12. Laboratory preparation of ethylamine : Ethylamine is prepared in the laboratory by Hofmanns


bromide reaction. Proprionamides is heate with bromine and pottassium hydroxide solution.
C2H5CONH2 + Br2 + 4KOH C2H5NH2 + 2KBr + K2CO3 + 2H2O

Propionamide Ethylamine

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Page # 76 Carboxylic Acids & Acid Derivatives & Amine

3. PHYSICAL PROPERTIES
(a) It is a colourless inflammable liquid. Its boiling point is 19C.
(b) It has fishy ammonical odour.
(c) It is highly soluble in water. Its aqueous solution is basic in nature and turns red limus blue.
The solubility in water is due to hydrogen bonding with water moelcules.

4. CHEMICAL PROPERTIES
(i) Basic nature : It is more basic than ammonia. Following reactions prove its basic nature
(a) It forms ethyl ammonium hydroxide when dissolved in water.
C2H5NH2 + H2O C2H5NH3OH

Ethyl ammonium
hydroxide

Ethyl ammonium hydroxide ionises to give OH ions

C2H5NH3OH C2H5 +
NH3 + OH

(b) It reacts with acids to form salts.


C2H5NH2 + HCl C2H5NH3Cl or C2H5NH2.HCl
Ethyl ammonium chloride
or
Ethylamine hydrochloride
C2H5NH2 + H2SO4 (C2H5NH3)2 SO4
Ethyl ammonium sulphate
(c) Its aqueous solution behaves like ammonium hdyroxide. The aqueous solution of ethylamine
precipitates iron, chlromium and aluminium as hydroxides when salts are treated with it.
3C2H 5NH3OH + FeCl 3 Fe(OH)3 + 3C2H5NH3Cl
Ethyl ammonium Ferric Ferric Ethyl ammonium
hydroxide chloride hydroxide chloride

(d) Its hydrochloride, like ammonium chloride, forms double salts with PtCl4 and AuCl3
2C2H5NH3Cl + PtCl4 (C2H5NH3)2 PtCl6
Ethylamine
Chloroplatinate

C2H5NH3Cl + AuCl3 C2H5NH3AuCl4


Ethylamine auric
Chloroplatinate
These double salts decomposes on heating to pure metal and this method is used to determine
the molecular mass of amines.
(ii) Reaction with alkyl halides (Alkylation) :
Ethylamine reacts with alkyl halides and form secondary, tertiary amines and quaternary ammonium salt.

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C2H5NH2 + C2H5I (C2H5)2NH . HI


Diethyl ammonium
iodide

(C2H5)2 NH + C2H5I (C2H5)3 NHI


Triethyl ammonium
iodide
(C2H5)2 N + C2H 5 I (C2H5)2NI
Tetraethyl ammonium
iodide

(iii) Reaction with acetyl chloride or acetic anhydride : Acetylation takes place when ethylamine
combines with acetyl chloride or acetic anhydride.
C2H5NH + ClOCCH3 C2H5NHOCCH3 + HCl
Acetyl Acetyl ethylamine
chloride or
N-Ethyl acetamide

C2H5NH2 + (CH 3CO) 2O C2H5NHOCCH3 + CH3COOH


Ethylamine Acetic anhydride N-Ethyl ethylamide

(iv) Carbylamine Reaction


RNH2 + CHCl3 + 3KOH RN
+
C : 3KCl + H 2O
an isocyanide
(foul smelling)

Nucleophilic RNH2 attacks electrophilic intermediater [:CCl2] dichlorocarbene.


This reaction is used for the detection of primary amines.
Mechanism

Cl
:

R NH2 + : CCl2 R HN C
Cl

H
HCl

+
RN C R N = Cl Cl

(v) Reaction with sodium : Hydrogen is evolved when ethylmine is heated with sodium.
2C2H5NH2 + 2Na 2C2H5NHNa + H2
Sodium derivative
of ethylamine

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Page # 78 Carboxylic Acids & Acid Derivatives & Amine

(vi) Reaction with Grignard reagents : Ethylamine reacts with Gragnard reagents to form alkanes.

2C2H5 NH2 + RMgX R H + C2H5NHMgX


Grignard Alkane
reagent

2C2H5NH2 + CH3MgI CH4 + C2H5NHMgI


Methyl Methane
Magnesium iodie

(vii) Hofmanns mustard oil reaction : Carbon disulphide reacts with ethylamine in presence HgCl2 to
form ethyl isothiocyanate which has a mustard oil like smell.
C2H5NH2 + CS2 + HgCl2 C2H5N = C = S + 2HCl
Ethyl isothiocyanate
(viii) Reaction with aldehydes : Ethylamine reacts additively with aldehydes to form -hydroxyl
amines which are changed to Schiff bases with the elimination of water molecule.

H
C2H5NH2 + O = C CH3 C2H5 N C CH3
Ethylamine Acetaldehyde
H2O

C2H5N = CH CH 3
Ethylidene ethylamine
(Schiff's base)

DISTINCTION BETWEEN PRIMARY, SECONDARY AND TERTIARY AMINES


Test Primary amine Secondary amine Tertiary amine

1. Action Test CHCl3 and Bad smelling carbyl-amine No action. No action.


alcoholic KOH. (Isocyanide is formed)

2. Action of CS2 and Alkyl isothiocyanate is No action. No action.


HgCl 2. (Mustard Oil formed which has pungest
test smell like mustard oil.

3. Action of Nitrous acid. Alcohol is formed with Forms nitrosoamine which Forms nitrite in cold which
evolution of nitrogen. gives green colour with on hearing gives nitrosoamine
phenol and conc. H2SO4 which responds to
(Liebermann's test.) Liebermann's test.

4. Action of acetyl Acetyl derivative is Acetyl derivative is No action.


chloride. formed formed

5. Action of Hinsberg's Monoalkyl sulphon-amide Dialkyl sulphonamide is No action.


reagent is formed which is soluble formed which is insoluble
in KOH. in KOH.

6. Action of methyl 3 molecules (moles) of 2 moles of CH3I to form One mole of CH3I to form
iodide. CH3I to form quaternary quaternary salt with one quaternary salt with one
salt with one mole of of mole of secondary amine. mole of tertiary amine.
primary amine.

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Carboxylic Acids & Acid Derivatives & Amine Page # 79

5. GENERAL CHEMICAL PROPERTIES OF AROMATIC AMINES

5.1 REACTION WITH NITROUS ACID


1. Primary Amines : Primary amines react with nitrous acid to produce diazonium ion as follows.
ArNH2 + HNO2 Ar N N:
R NH2 + HNO2 R N N
But the diazonium ions of aliphatic amines are very unstable and produces carbocation
immediately, which can produce different products.
N2
R N N R+ (Carbocation)

+
+ H (Hydride shaft)
N Cl N3 + Cl + H3C CH2 H3C CH2
H3C N
+
H
Cl

OH Cl
H3C H3C H3C CH2 CH3 CH3
prop-1-ene
propan-1-ol 1-chloropropane H3C H3C

OH Cl
propan-2-ol
2-chloropropane

H3PO 2
Al H

KI
Ar I

CuCl(CuBr)
ArCl/(A,Br) (Sandmeyer reaction)

Ar N N
Ar F

+
H2O/H
Ar OH
CuCN
Ar CN (Sandmeyer reaction)

ROH
Ar OR

6. RING REACTIONS OF AROMATIC AMINES


NH2 NHR and NR2 strongly activate the benene ring toward electrophilic substitution
1. Haogenation : For monohalogenation, NH2 is first acetylated, because
H3C C N
O H

is only moderately activating and is o and p-director in nature

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Page # 80 Carboxylic Acids & Acid Derivatives & Amine

NH2 NH2 NHCOCH3 NHCOCH3 NH 2


Br Br
Br 2 Ac2O Br2 H2O
H2O OH
Br Br Br
2. Sulfonation :

NH2 NH3 +HSO4 NHSO3H NH3

H2SO4 180C 180C


H2O 3 hours

Anilinium Sulfate Sulfamic acid SO3


Sulfanilic acid
(a dipolar ion)

The dipolar ion structure of sulfanilic acid account for its (a) high melting point, (b) insolubility in H2O
and organic solvents, (c) solubility in aqueous NaOH, (d) insolubility in aqeous HCl.

H2N CO2H

will not exists as a dipolar ino since, COOH is too weakly acidic to transfer an H+ to the weakly basic
NH2 attached to the electron withdrawing benzene ring. When attached to an aliphatic C, the NH2 is
sufficiently basic to accept H from COOH.

O O

NH2 HN CH 3 HN CH3 HN2

CH 2CO)2O HNO3.H2SO4 OH
heat

aniline N-phenylacetamide N-(4-nitrophenyl)acetamide NO2


4-nitroaniline

H X
N NH2 NH2
X
and

(i) The Hinsberg Test


Ths test can be used to demonstrate whether an amine is primary, secondary or tertiary. Primary
amines react with benzenesulfonyl chloride to form N-substituted benzenesulfonamides. These, in
turn, undergo acid-base reactions with the excess potassium hydroxide to form water - soluble potassium
salt. Acidification of this solution will, cause the water-soluble in the next stage, cause the water-
insoluble N-substituted sulfonamide to precipitate.

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Carboxylic Acids & Acid Derivatives & Amine Page # 81

Acidic hydrogen

H O H O
OH
RN: + Cl S :N S
(HCl)
H R
O O
1 amine

KOH

+
O K O
H HCl
:N S :N S
R O R O

Water insoluble salt Water soluble salt


(precipitate) (clear solution)

Secondary amies react with benzenesulfonyl chloride in aqueous potassium hydryoxide to form insoluble,
N - N-disubtituted sulfonamides that precipitate after the first stage. N3N
Disubstituted sulfonamides do not dissolved in aqueous potassium hydroxide.

R'

O R' O
OH
R H + Cl S :N S
(HCl)
O R O

Water insoluble salt


(precipitate)

If the amine is a tertiary amine and if it is water insoluble, no apprated change will take place in the
mixture as we shake it with benzenesulfonyl choride and aqueous KOH. When we acidify the mixture,
the tertiary amine dissolves because it forms a water soluble salt.

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Page # 82 Carboxylic Acids & Acid Derivatives & Amine

EXERCISE I OBJECTIVE PROBLEMS (JEE MAIN)


1. Which of the following acids has the smallest 4. In the following ester there are three carbon
dissociation constant ? oxygen bonds denoted by x, y and z
(A) CH3 CH COOH O
x
NO2 Their lengths are in order
(B) O2NCH2CH2COOH CH 3COCH 3
y z
(C) ClCH2CH2COOH (A) x = y = z (B) x < y < z
(D) NCCH2CH2COOH (C) x < y = z (D) z < y < x
Sol. Sol.

2. Which compound should have zero dipole mo-


A O C O
ment ?
5. H C H C
O O B
O H D O
C C (C O) bond lengths designated by A,B,C are
(A)
OC2H5 OC2H5 in order :
(A) A = C < B = D (B) A < B < C = D
O O (C) A < C = D < B (D) All equal
C C Sol.
(B)
OH OH

(C) CN CN

O
(D) N C N

O CH2F
1.Mg diethyl ether
Sol. +
6. 2.CO2, 3.H3O

Br

CH2 COOH COOH

(A) (B)
COOH COOH
3. When picric acid is treated with aqueous so-
14

dium bicarbonate (NaH C O3) a gas is liberated COOH CH2COOH


with effervessence. The gas evolved would
be : (C) (D)
(A) H2 (B) CO2
CH 2F Br
(C) 14CO2 (D) NO2
Sol. Sol.

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Carboxylic Acids & Acid Derivatives & Amine Page # 83

10. The final product of the following reaction se-


CH2CN
quence is
+
H2O/H
7. Me3C Cl CH3CH2CH2Cl KMnO4/OH
AlCl3 AlCl3
Cl

CH 2 COOH COOH COOH


COOH

(A) (B)
(A) (B)
Cl Cl
COOH
CH3 COOCH3
CMe3
COOH
(C) (D)
Cl Cl (C) (D)
Sol.
COOH COOH
Sol.

8. The acid D obtained through the following sequence of


reactions is -

C2H5Br Alc Br

2 KCN
11. In the reaction sequence X & Y are
. KOH
A CCl4 B (excess)
CH 3 KMnO4
C H3O D NaOH X
(A) Malonic acid (B) Succinic acid Et CH2Cl Mg CO2
(C) Maleic acid (D) Oxalic acid ether Y
Sol. H H

(A) Homologs (B) Identical


(C) Structural isomers (D) Enantiomers
Sol.

9. Identify X in the reaction sequence COOH


CH
X Br2 KCN H3O HOOCCH2 CH2COOH COOH
CCl4 KMnO4
(A) CH3 CH3 (B) CH2 = CH2 12. X
Y
(C) H C C H (D) CH3 CH = CH CH3
Sol.
In the above reaction sequence X & Y are.
(A) Identical (B) Homologs
(C) Structural isomers (D) Stereisomers
Sol.

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Page # 84 Carboxylic Acids & Acid Derivatives & Amine

13. A racemic mixture of carboxylic acid having COOH


one chiral centre is treated with enantiomerically (i) NaOH Br2 KCN(excess)
pure amine. the products formed are : 16. (P) (ii) Electrolysis CCl4 H3O
(A) disatereomers (both optically active) COOH
(B) diasteremoers (only one is optically In the above reaction Q is
active)
(C) Racemic mixture COOH COOH
(D) two optically inactive ammonium salts of
acid. (A) (B)
Sol.
COOH COOH

COOH COOH

(C) (D)
COOH

Sol.

14. The product of the following reaction is


14
LiAlH4 SOCl2 KCN H3O
CH3COOH P
14

(A) CH3COOH (B) CH3CH2 C OOH


14 14

(C) CH3 C OOH (D) CH3 C H2COOH


Sol.

17. End product of this reaction is


O
+
NaBH4 H /
CH3CCH2CH2CH 2COOH
15. For the following conversion CH3
O
CH3 CH3
(A) O (B) O
CH3 C CH2 COOH CH3 C COOH CH3 O
CH3 CH3 O
Br2 / hv Mg (i) CO
NaOH / CaO 2 O O
(A)

(C) (D)
ether (ii) H
O
O
NaOH / CaO Br2 / hv KCN HO
(B) 3 Sol.
ether
NaOH / CaO Br / hv KCN (i) O KMnO 4/OH
(C) 2

2

ether (ii) H 2O

NaOH / CaO Br / hv H2O/Acetone KMnO 4/OH


(D) 2
(ii) H2O
Sol.

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Carboxylic Acids & Acid Derivatives & Amine Page # 85

18. For the following conversion the correct se- Sol.


quence of reacgent is

CH3 CH CH2 C C COOH O


OH O
+
H2/Ni H
(A)
+
Na/LiqNH3 H
(B)
+
H2/Pd/BaSO4 H
(C) 21. In the reaction sequence CH3CH2COOH
Br2/PBr3 x Br2 y H2O
+
H H2/Pd/BaSO4
(D) O
Sol. (A) x is CH 3 CH2 C Br

O
(B) y is CH 3 CH C Br
Br
O
CO2H
(i) P/Br2 (C) z is CH3 CH C OH
19. (ii) H 2O X, X is :
Br
* COOH (D) All are correct
CO2Br Sol.
(A) (B) *

Br
* Br Br
(C) * (D) CO2H
CO2H
Sol.
CH2 CH2COO
22. Ca A, A is :
CH2 CH2COO
O
O
(A) (B)

O O
O
20. In the given reaction (C) (D)
(i) Br2/P O
CH3COOH (ii) NaCN [x], [x] will be
Sol.
(iii) H2O/H/
(A) CH3COOH
(B) HOOCCH2CH2COOH
O O
CH 2 C C
O CH 2 O
(C) CH 2 C (D) C
O O

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Conc.HI (i) 2CO2 C2H5 C2H5


23. O 2Mg/Ether +
H3O
Excess (ii) 2H
25. CH3 CH COOH + CH 3 CH OH
Ca(OH)2 (d) (d+l)
P the product P is :
x + y the organic products x and y are :
O (A) Enantiomers (B) Diasteremoers
O (C) Metamers (D) Achiral molecules
(A) O (B) Sol.

O O
(C) (D)
O
Sol.

26. For the following acids the rate of decarboxy-


lation on heating would be :
O O
I. C6H5CCH2COOH II. C6H5CCOOH
III. NO2CH2COOH IV. HOOCCH2COOH
24. The correct sequence of reagent for the fol- (A) III > I > IV > II (B) I > III > IV > II
lowing conversion. (C) III > IV > I > II (D) I > IV > III > II
Sol.
COOH
O is
COOH
(A) LiAlH4 SOCl2 (i) KCN Ca(OH) 2
+
(ii) H3O

LiAlH4 HI Mg/ether Ca(OH) 2 NaOH


(B)
CaO/
(ii) H3O

(C) LiAlH4 PCl 3 (i) KCN KOH/CaO


+
(ii) H3O

(D) LiAlH4 HCl (i) KCN CaO


ZnCl2 (ii) H3O
+

Sol.

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Carboxylic Acids & Acid Derivatives & Amine Page # 87

EXERCISE II OBJECTIVE PROBLEMS (JEE ADVANCED)


1. Nucleophilic substitution at acyl carbon of a
carboxylic acid derivative generally proceeds O
by.
(A) Addition-elimination mechanism (B) C6H5 C O C6H5
(B) Elimination-addition mechanism O
(C) SN1 mechanism
(D) SN2 mechanism (C) C6H5 C NH C6H 5
Sol. O
(D) C6H5 C O C6H5
Sol.

2. The correct order of decreasing reactivity of


the given compound towards hydrolysis under
identical condition is:
(A) CH3COCl>CH3CONH2>(CH3CO)2O> CH3COOCH3
(B)CH3COCl>(CH3CO)2O>CH3COOCH3> CH3CONH2
O
(C) CH3COOCH3>CH3COCl>(CH3CO)2O> CH3CONH2
(D)(CH3CO)2O>CH3COCl>CH3COOCH3> CH3CONH2 5. H2NNH2+Ph C Cl (excess) NaOH X, X is
Sol.
O O
(A) H C NHPh (B) Ph C NHOH
O O O
(C) Ph C NH2 (D) Ph C NHNH C Ph
Sol.

3. Which of the following proposed reactions


would take place most quickly under mild con-
ditions ?
(A) CH3CONH2 + NaCl CH3COCl + NaNH2
O
(B) C6H5CO Cl + CH3NH2 C6H5 C NH CH3
(C) CH3COCl+CH3NH2 CH3CONHCH3 6. Phosgene(COCl2) + 1 mol C2H5OH NH3
(D) CH3COOC2H5+HOH NaOH CH3COONa + C2H5OH X, X is
Sol.
(A) NH2 C NH2 (B) NH = C = O
O
(C) NH2 C Cl (D) EtO C NH2
O O
Sol.

4. In the given reaction sequene :


H2O/H/ SOCl2 C6H5/AlCl3
C6H5CN A B C, (C) is
O O O
Pyridine
7. CH3O CCl + CCH
(A) C6H5 C C6H5
OH
X, X is
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Page # 88 Carboxylic Acids & Acid Derivatives & Amine

Ph CH3
CH2CH2CH2CH3
CH2CHCH 3
(A) Ph O C O CH C H
O N O
O CH3 O O N O

Ph (C) (D)
O
Br S Br
(B) Ph O C O CH C H Br S Br
CH3 O
Sol.
O
(C) CH O C O CH C Ph
3

Ph O
O
(D) Ph O C O CH C Ph
CH 3 O NH2 O
Sol.
9. + Cl C Cl X, X is
CO2H

O
NH C Cl
(A

O O COOH

ClC CCl N OH
8. + CH3CH2CH2CH2NH2 140C C
O
Br S Br (B) CH
X, X is OH

CH 3 NH
CH3CHCH2CH3 O
CH3CCH 3
C=O
O N O
O N O (C) CH

(A) (B) OH

Br Br NH O
S
Br S Br C

(D) C O

O
Sol.

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Carboxylic Acids & Acid Derivatives & Amine Page # 89

O O
10. (CH3)3C C Cl+LiAlH4 (excess) H3O (D) CH3 CH C S Ph
X, X is
CH3
O Sol.
(A) (CH3)3C C H
CH 3
(B) CH 3 C CH2 OH
CH 3

CH 3CHCH2CH2OH
(C)
CH 3
(D) CH3CH2CH2CH2CH2OH
13. List the following esters in order of decreasing
Sol.
reactivity in the second step of a nucleophilic
acyl substitution reaction.
O
(I)
CH3 C O C6H 5

11. For the given reaction (II) CH3 C O

O
O
CH 3 (CH 2)4 C Cl + (A)
(III) CH3 C O CH3
O
O
CH3 (CH 2)4 C CH = CH 2, (A) is
(IV) CH3 C O Cl
(A) CH2 = CH OCH3 (B) CH2=CHOH
(C) (CH2=CH)2CuLi (D) (CH2=CH2)2Cl
Select the correct answer from the codes given
Sol.
below:
(A) IV > I > III > II (B) IV > III > I > II
(C) III > IV > I > II (D) II > I > III > IV
Sol.

O
12. PhCH2 C Cl + CH3CH2SH X, X is
O
(A) Ph C S CH CH3 14. Which one of the following is least reactive for
hydrolysis reaction ?
CH3
O
O
(A) C6H5 C O NO2
(B) Ph CH2 C S CH2CH3
O O
(C) CH3CH2 CH2 C S Ph (B) C6H5 C O CHO

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O O
O
(C) O2N CO NO2 (III) is more reactive than
O O
O Of these the correct statements are
(A) I and II (B) I, II and III
(D) O2N CO CHO (C) II and III (D) I and III
Sol.
Sol.

15. Which one of the following esters is most re-


active for saponification ? 17. Ease of esterification of following acids with
O CH3OH
(A) (I) HCOOH (II) CH3 COOH
CH 3COCH3 (III) CH3 CH2 COOH
O (IV) CH3 CH COOH, is
CH3
CH3COCHCH3
(B) (A) I = II = III = IV (B) I > II > III > IV
CH 3 (C) I < II < III < IV (D) I > IV > III > II
Sol.
O CH3

(C) CH 3COCCH3
CH3

O
(D) CH3CO

Sol. H3C CH3


ethanol, H2SO4
18. C C X, X is
H CO2H
C2H5 H
(A) C C
C2H5 COOH
16. Consider the following statements for hydrolysis
reaction : H C2H5
(B) C C
(I) NO2 COOC2H5 is more reactive C2H5 COOH

CH3 CH 3
than C6H5COOC2H5
C C
O H C OCH2CH3
(C)
(II) NO2 OCCH3 is more reactive O

O CH3 CH3
C C
than CH3O OCCH3 C
(D) CH 3 CH2 OH
O

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Carboxylic Acids & Acid Derivatives & Amine Page # 91

Sol. 21. In the given reaction


O
C 2H 5 O C O C 2H 5+ H O C H 2 C H 2 O H

H [X], [X] is

O
19. In the given reaction
(A) C2H5O C OCH2CH2 OH
OC2H5
O
OCH3 H/H 2O
(B) HOCH2CH2O C OCH2CH2 OH
COOC2H 5
O
[P], [P] will be :
C
O
OC2H5 (C) O O
OH
(A) (B) CH 2 CH2
COOC2H5 COOH
(D) No reaction is possible
OCH 3 Sol.
O
OH
(C) (D)
COOH COOH
Sol.

O
O
22.
OCH 3 X, X is
CH 3OH
20. In the given reaction
O
CH2COOC2H5
(A) H3CO C (CH2)5OH
H [X], [X] is
CH2OH O
(B) H3CO C CH CH2 CH2 CH2 OH
CH 2COOH CH 2COOH
CH3
(A) (B) O
CH2
(C) H3CO C CH2 CH CH2 CH2 OH
O O
CH3
CH2C CH2C O
(C) (D) (D) H3CO C CH2 CH2 CH CH2 OH
CH2 O CH2 C O CH3
Sol. Sol.

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Page # 92 Carboxylic Acids & Acid Derivatives & Amine

O (A) HOOC O

23. EtO
EtOH COOH
O
HO COOEt (B) HOOC O
(A) X =
COOH
HO COOEt HOOC
(B) X = (C) O
HOOC

COOEt COOH
HO HOOC
(C) X = (D) HOOC O

COOH
COOEt Sol.

HO
(D) X =

Sol.

O
C
CH3 CH3OH/H/
26. 1.eq.
x, x is
24. Ease of esterification of following alcohol with C OH
HCOOH is
O
(I) CH3CH2OH (II) (CH3)2CHOH
(III) (CH3)3COH
O
(A) III > II > I (B) I > II > III HO OCH 3
(C) II > I > III (D) II > III > I
Sol. CH 3
CH3
(A) (B) OCH 3
COOH O

HO OCH3 CH3O CH3

CH 3 O
(C) OCH 3 (D)
25. The product x in the above reaction is O O
O Sol.
O
C OC2H5
OC2H5 C
H3O
O
OC2H5 C
O C OC2H5
O

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Carboxylic Acids & Acid Derivatives & Amine Page # 93

O Sol.
CH3NH2
27. C OCH3 X, X is
heat

O
(A) NH C CH3

(B) NH CH2 CHO


O
O (1) LiAlH4
29. N (2) H2O X, X is
(C) C NH CH3 H
OH
O
(A) NH (B)
(D) C CH2 NH 2 NH

Sol.
(C) NOH (D) NH
HO
Sol.

30. Consider the following compounds :


O
KMnO4/OH NH3 (I) CH 3 C NH
28.

x in the above reaction is O NO2


O O (II) CH3 C NH
C ONH2 C NH2
O
(A) (B)
C ONH2 C NH2
(III) CH3 C NH NO2
O O

O
O O
(IV) CH3 C NH
NH
NH The decreasing order of reactivity towards
(C) (D) NH
hydrolysis by aqueous NaOH is :
O O (A) I > II > III > IV (B) III > II > IV > I
(C) IV > I > II > III (D) I > IV > II > III

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Page # 94 Carboxylic Acids & Acid Derivatives & Amine

Sol. CH3 O
Br2, NaOH
33. PhCH2 CH CH2 C NH 2 X, X
is
CH3
(A) CH3 CH CH2 NH Ph

CH3

O (B) Ph CH 2 CH CH NH2
H
N OH
31. NaOH/ X, X is
H2O
CH3
(C) Ph CH 2 CH CH 2 NH2
O O
ONa NH2 CH3 CH 3

(A) NH2 (B) ONa (D) Ph CH CH C NH2


O
Sol.
O O

ONa ONa

(C) (D)
NH 2 NH2
Sol.
O O
15
34. C NH 2 + CH2 C NH2
OH, Br2, heat

X+Y
Product X & Y are :
15
NH2 CH2NH2

(A) &

NH3/ KOBr HNO2


32. X B (CH3)3C
15
OH, X is : CH2NH2 CH2NH2
(A) (CH3)3C COOH (B) (CH3)3C CH2O
(C) (CH3)3C CONH2 (D) none is true (B) &
Sol.

15
CH2NH2 NH2

(C) &

15
NH2 NH2

(D) &

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Sol. 37. Following will not yield a cyclic compound on


heating :
COOH
CH2 COOH
(A) CH2 (B)
CH2 COOH
COOH
COOH
CH2COOH
(C) CH2 (D)
35. Urea (H2 NCONH2) + hot dilute NaOH X + CH2COOH
NH3, X is COOH
Sol.
(A) NaNH C NH.Na (B) NH2 C NHNa
O O
(C) Na2CO3 (D) H C NH2
O
Sol.

36. In the given reaction sequence



NH2 38. In the following reaction X Y. X is the
C2H5 COOH O=C lowest molecular weight optically active
SOCl2 NH2 dicarboxylic acid. What is the structure of Y.
C (A) (B)
C2H5 C2H5ONa
COOH O
CH3
(A) and (B) respectively are : O
(A) CH 3 CH COOH(B)
O
O
C 2H 5 COCl C 2H 5 C NH
(A) C and C C O O O
C 2H 5 COOH C 2H 5 COOH
NH2
O O
C 2H 5 COCl C 2H 5 CO NH (C) (D)
(B) C and C C O O O
C 2H 5 COCl C 2H 5 CO NH
Sol.
C 2H5 COCl C 2H 5 CO NH
(C) C and C C O
C 2H5 COOH C 2H 5 CO NH

C 2H5 CO C 2H 5 CO NH
(D) C and C C O
C 2H5 CO C 2H 5 CO NH
Sol.

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Page # 96 Carboxylic Acids & Acid Derivatives & Amine

Sol.
O NH 2
39. O + X, X is

O
NH
(A) OH
O

O
N
(B) O
OH C
O
41.
O + CH OH X, X is ;
3
NH O C
O
(C) O Phthalic anhydride

O O

COOCH3 C O CH3
O NH
(A) (B)
(D) O COOCH3 C OH

O O

Sol. COOH COOCH3


(C) (D)
COOH COOH
Sol.

LiAlH4 PCC
40. O A B

O
NH2NH2
C, Product (C) is
O
NH
N
(A) NH (B)
N
O

OH
NH2
N
(C) N (D)
NH2
OH

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Carboxylic Acids & Acid Derivatives & Amine Page # 97

EXERCISE III OBJECTIVE PROBLEMS (JEE ADVANCED)


1. The increasing order of basicity of RCN, RCN = 6. Which of the following reagents can convert
NR and RHN2 is benzene diazonium chloride into benzene ?
(A) RCN<RCH=NR<RH2N (A) Water
(B) RNH2<RCH<RCH=NR (B) Acid
(C) RCN=NR<RNH2<RCN (C) Hypophosphorous acid
(D) RH2N<RCH=NR<RCN. (D) HCl
Sol. Sol.

2. How many isomeric amines with that formula


C7H9N contains a benzene ring ? 7. The bromination of aniline produces
(A) two (B) three (C) four (D) five (A) 2-bromoaniline (B) 4-bromoaniline
Sol. (C) 2,4,6-tribromoaniline (D) 2,6-dibromoaniline
Sol.

3. Isopropylamine can be obtained by


(A) (CH ) CHO+NH OH? LiAlH4
3 2 2

(B) (CH3)2CHO+NH3 ? H2/Ni


H3C 8. The compound, which on reaction with aqueous
(C) CHOH+NH3 (D) All of these nitrous acid at low temperature produced an
H3C only nitrosoamine is
Sol. (A) Methyl amine (B) Ethylamine
(C) Diethylamine (D) Triethylamine
Sol.

4. Reaction of RCONH2 with a mixture of Br2 and


KOH gives RNH2 as the main product. The 9. Carbylamine test is performed in alcoholic KOH
intermediate involved in the reaction is by heating a mixture of
O (A) Chloroform and silver powder
(B) Trihalogenated methane and a primary amine
(A) RCNHBr (B) RNHBr (C) An alkyl halie and a primary amine
O (D) An alkyl cyanide and a primary amine
Br Sol.
(C) RCN (D) RC=N=O
Br
Sol.

10. Activation of benzene ring by NH2 in aniline


5. Amines are highly soluble in: can be reduced by treating with
(A) Alcohol (B) Diethyl ether (A) Dilute HCl (B) Ethyl alcohol
(C) benzene (D) Water (C) Acetic acid (D) Acetyl chloride
Sol. Sol.

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Page # 98 Carboxylic Acids & Acid Derivatives & Amine

11. Dipolar ion structure for amino acid is Sol.


(A) H2NCHCOOH (B) H2NCHCOO +
R R
+
(C) H3NCHCOO (D) None of these
R
Sol.

16. Which of the following amine form N-nitrose


derivative when treated with NaNO2 and HCl ?

12. NH2 group shows acidic nature while reacts (A) H3C NH 2 (B) NH 2
with reagent.
(A) Na (B) CS2
(C) Br2+NaOH (D) Water.
Sol. (C) N(CH3)2 (D) NH(CH 3)

Sol.

13. Which of the following does not give ethylamine


on reduction
(A) methyl cyanide (B) Ethyl nitrile
(C) Nitro ethane (D) Acetamide
Sol.

17. The strongest base among the following is


H2N H2N
C NH 2 C NH 2
(A) (B)
H2N H2N
14. In the reaction,
CH3NH2 excess CH Cl (X) Ag
3
2 O
(Y) (Z) the H2N H2N
moist C O CHOH
final product (Z) is (C) (D)
(A) (CH3)3N (B) (CH3)4N+Cl H2N H2N
+
(C) (CH3)4N OH (D) (CH3)2NH Sol.
Sol.

15. The product not obtained in the following


reaction,
CH3NO2+Cl2+NaOH is
(A) ClCH2NO (B) Cl2CHNO2
(C) Cl3CNO2 (D) CH3NH2

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18. Identfiy compound (A) in the following oxidation 20. Acetamide is treated with the following
reaction. reagents. Which one of these would give
methylamine ?
K2Cr 2O7,H2SO4 (A) PCl5 (B) NaOH+Br2
(a) O O
(C) soda lima (D) Hot conc. HSO4
Sol.

NH2 OH

(A) (B)

NH2 NH2

OH

21. Treatment of ammonia with excess of ethyl


(C) (D) All of these chloride will yield
OH (A) diethyl amine
Sol. (B) dethane
(C) tetraethylammonium
(D) methyl amine
Sol.

19. pCl C 6 H 4 NH 2 and PhNH 3 + Cl can b e


distinguished by
(A) Ag(OH) (B) NaOH
(C) AgNO3 (D) None of these
Sol.

22. C6H5C N and C6H5N = C exhibit which type


of isomerism ?
(A) Position
(B) Functional
(C) Dextroisomerism
(D) Positional isomerism
Sol.

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Page # 100 Carboxylic Acids & Acid Derivatives & Amine

23. The correct reagent sequence for the follow- Sol.


ing conversion
CH 3 CH3
CH 3 C Br CH 3 C COOH, is
CH 3 CH3

(A) KCN H3O

(B) Mg/ether CO 2 H

(C) Mg/ether ClCOOH

HCOCl KMnO4 /OH


(D) Mg/ether
1.eq. 1.eq.
Sol.
25. The correct order/s for the given pair of iso-
mers is /are
CH 3 CH3 CH3 H
(A) C C > C C
H H H CH3
(Melting point)
H H
(B) C C >
HOOC COOH
H COOH
C C (Dipole moment)
HOOC H

H Cl Cl Cl
24. Correct water solubility order/is amongst the (C) C C > C C
following pairs is/are. Cl H H H

CH 3 (Boiling point)
(A) CH3CH2CH2CH2OH > CH3 C CH 3
H3C H H 3C COOH
CH 3
(D) C C > C C
COOH H COOH H H
COOH (Water solubility)
OH Sol.
(B) <

OH

Cl
Cl
Cl
(C) <

Cl

H3C H H 3C COOH
(D) C C > C C
H COOH H H

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Carboxylic Acids & Acid Derivatives & Amine Page # 101

EXERCISE IV PREVIOUS YEARS PROBLEMS

LEVEL I JEE MAIN


Q.1 End product of the following reaction is proton from the acid molecule

[AIEEE-2002] (C) Electronic orbitals of carbon atom are


hybridised
Cl 2
CH3CH2COOH red


P Alcoholic
KOH
(D) The C=O bond is weaker than the CO
CH 3CHCOOH CH2CH2COOH bond
(A) (B) Sol.
OH OH
CH2CHCOOH
(C) CH2 = CHCOOH (D)
Cl OH
Sol.

Q.4 When CH2 = CHCOOH is reduced with LiAlH4,


the compound obtained is :
[AIEEE-2003]
Q.2 Picric acid is [AIEEE-2002]
(A) CH3CH2CH2OH (B) CH3CH2CHO
COOH
COOH (C) CH3CH2COOH (D) CH2=CHCH2OH
(A) (B) Sol.
OH
NO2
OH
NO2 NO2 COOH

(C) (D)
NO2 NH2

Sol.

Q.5 The general formula CnH2nO2 could be for open


chain : [AIEEE-2003]
(A) Diols (B) Dialdehydes
(C) Diketones (D) Carboxylic acid
Sol.

Q.3 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

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Page # 102 Carboxylic Acids & Acid Derivatives & Amine

Q.6 Which one of the following does not have sp2 Q.9 Consider the acidity of the carboxylic acids :
(1) PhCOOH (2) 0-NO2C6H4COOH
hybridized carbon ? [AIEEE-2004] (3) p-NO2C6H4COOH (4) m-NO2C6H4COOH
(A) Acetone (B) Acetic acid Which of the following order is correct ?
(C) Acetonitrile (D) Acetamide [AIEEE-2004]
Sol. (A) 2 > 3 > 4 > 1 (B) 2 > 4 > 3 > 1
(C) 2 > 4 > 1 > 3 (D) 1 > 2 > 3 > 4
Sol.

Q.7 Consider the acidity of the carboxylic acids :


[AIEEE-2004] Q.10 On mixing ethyl acetate with aqueous sodium
(a) PhCOOH chloride, the composition of the resultant
(b) o NO2C6H4COOH solution is : [AIEEE-2004]
(A) CH3Cl + C2H5COONa
(c) p NO2C6H4COOH
(B) CH3COONa + C2H5OH
(d) m NO2C6H4COOH
(C) CH3COCl + C2H5OH + NaOH
Which of the following order is correct ? (D) CH3COOC2H5 + NaCl
(A) a > b > c > d (B) b > d > c > a Sol.
(C) b > d > a > c (D) b > c > d > a
Sol.

Q.11 Which one of the following is reduced with


zi nc and hydrochl ori c aci d to gi ve the
corresponding hydrocarbon :[AIEEE-2004]
Q.8 Rate of the reaction : (A) Butan-2-one (B) Acetic acid
O O (C) Acetamide (D) Ethyl acetate
Sol.
RC + Nu R C + Z
Z Nu
is fastest when Z is : [AIEEE-2004]
(A) OCOCH3 (B) NH2
(C) OC2H5 (D) Cl
Sol.

Q.12 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

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Carboxylic Acids & Acid Derivatives & Amine Page # 103

Sol. Q.16 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
Sol.

Q.13 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
Sol.
Q.17 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 Schiffs base
(C) an amine (D)an imine
Sol.
Q.14 Reaction
Primary amine + CHCl3 + KOH product,
here product will be - [AIEEE-2002]
(A) Cyanide (B) Isocyanide
(C) Amine (D) Alcohol
Sol.

Q.18 In the chemical reaction, CH3CH2NH2 + CHCl3


+ 3KOH (A) + (B) + 3H2O, the compounds
(A) and (B) are respectively - [AIEEE-2007]
(A) C2H5CN and 3KCl
Q.15 The compound formed in the positive test for (B) CH3CH2CONH2 and 3KCl
nitrogen with the Lassaigne solution of an (C) C2H5NC and K2CO3
organic compound is - [AIEEE-2004] (D) C2H5NC and 3KCl
(A) Fe4[Fe(CN)6]3 Sol.
(B) Na3[Fe(CN)6]
(C) Fe(CN)3
(D) Na4[Fe(CN)5NOS]
Sol.

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Page # 104 Carboxylic Acids & Acid Derivatives & Amine

LEVEL II JEE ADVANCED


Sol.
O
||
Q.1 The reaction of R C NH 2 with a mixture of
Br2 and KOH gives RNH2 as a product. The
intermediates involved in this reaction are:
[IIT 1992]
O
||
(A) R C NHBr (B) RN=C=O
Q.4 When propionic acid is treated with aqueous
O NaHCO3, CO2 is liberated. The 'C' of CO2 comes
|| from [IIT 1999]
(C) RNHBr (D) R C N (A) Methyl group
(B) Carboxylic acid group
Sol.
(C) methylene group
(D) bicarbonate
Sol.

Q.2 Which of the following carboxylic acids undergo


decarboxylation easily:[IIT 1995]
(A) C6H5COCH2COOH
(B) C6H5COCOOH
Q.5 Benzoyl chloride is prepared from benzoic acid
(C) C 6 H 5CH 2 COOH by: [IIT 2000]
| (A) Cl2, hv (B) SO2Cl2
OH (C) SOCl2 (D) Cl2, H2O
Sol.
(D) C 6 H5CH 2 COOH
|
NH 2
Sol.

Q.6 Which of the following acids has the smallest


dissociation constant? [IIT 2002]
(A) CH3CHFCOOH (B) FCH2CH2COOH
(C) BrCH2CH2COOH (D) CH3CHBrCOOH
Sol.
Q.3 The molecular weight of benzoic acid in
benzene as determined by depression in
freezing point method corresponds to :
[IIT 1996]
(A) Ionization of benzoic acid
(B) Dimerisation of benzoic acid
(C) Trimerisation of benzoic acid
(D) Solvation of benzoic acid

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Q.7 When benzamid is treated with POCl3, the Sol.


product is: [IIT 2004]
(A) Benzonitrile (B) Aniline
(C) Chlorobenzene (D) Benzylamine
Sol.

Q.10 Match the compounds in Column I with their


characteristic test(s)/reaction(s) given in
Column II. Indicate your answer by darkening
Q.8 The correct IUPAC name of C6H5COCl is the appropriate bubbles of the 4 4 matrix
given in the ORS. [IIT 2008]
[IIT 2006]
(A) Benzoyl chloride
Column I
(B) Benzene chloro ketone
(C) Benzene carbonyl chloride + -
(A) H2N NH3Cl
(D) Chloro phenyl ketone

+ -
Sol. NH3I
(B) HO
COOH

+ -
(C) HO NH3Cl

Q.9 Which of the following reactants on reaction + -


with conc. NaOH followed by acidification gives (D) O2N NH NH3Br
the following lactone as the only product?
[IIT 2006] Column II NO2
(P) sodium fusion extract of the compound
gives Prussian blue colour with FeSO4
(Q) gives positive FeCl3 test
(R) gives white precipitate with AgNO3
(S) reacts wi th aldehydes to form the
corresponding hydrazone derivative
Sol.

(A) (B)

(C) (D)

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Page # 106 Carboxylic Acids & Acid Derivatives & Amine

Q.11 Match each of the compound in Column I with


its characteristic reaction(s) in Column II. OH
(B) (Q) Elimination
[IIT 2009]
Column I
(A) CH3CH2CH2CN CHO
(B) CH3CH2OCOCH3
(C) CH3 CH = CH CH2OH (C) (R) Nucleophilic
(D) CH3CH2CH2CH2NH2 OH addition

Br
Column II
(P)Reduction with PdC / H2 (D) (S) Esterification with
NO2 acetic anhydride
(Q) Reduction with SnCl2 / HCl
(R) Development of foul smell on treatment
with chloroform and alcoholic KOH (T) Dehydrogenation

(S) Reduction with diisobutylaluminium hydride Sol.


(DIBAL H)
(T) Alkaline hydrolysis
Sol.

Q.13 The major product of the following reaction is

[IIT 2011]

O
C
(i) KOH
NH
C (ii) Br CH2Cl

Q.12 Match each of the compounds given in Column O


I with the reaction(s), that they can undergo,
C
given in Column II. [IIT 2009] (A) N CH2 Br
C
Column I Column I O

Br
O
(A) (P) Nucleophilic C
O substitution (B) N CH2Cl
C
O

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Carboxylic Acids & Acid Derivatives & Amine Page # 107
Sol.

O
C
(C) N
C
O CH2 Br

O
C
(D) N
C
O CH2Cl

Sol. Q.16 The compound that undergoes decarboxylation


most readily under mild condition in
[IIT 2012]

COOH COOH
CH2COOH O
(A) (B)

COOH CH 2COOH
Q.14 Among the following compounds, the most
COOH O
acidic is [IIT 2011] (C) (D)
(A) p-nitrophenol
(B) p-hydroxybenzoic acid
Sol.
(C) o-hydroxybenzoic acid
(D) p-toluic acid
Sol.

Q.15 The carboxy functional group (COOH) is


present in [IIT 2012]
(A) picric acid
(B) barbituric acid
(C) ascorbic acid
(D) aspirin

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Carboxylic Acids & Acid Derivatives & Amine Page # 108

Answers
Answer ExI OBJECTIVE PROBLEMS (JEE MAIN)

1. C 2. C 3. C 4. B 5. C

6. D 7. A 8. B 9. B 10. D

11. A 12. B 13. A 14. B 15. C

16. B 17. A 18. C 19. D 20. A

21. D 22. A 23. B 24. A 25. B

26. D

Answer ExII OBJECTIVE PROBLEMS (JEE ADVANCED)

1. A 2. B 3. C 4. A 5. D

6. D 7. C 8. C 9. D 10. B

11. C 12. B 13. A 14. B 15. A

16. A 17. B 18. C 19. D 20. C

21. C 22. A 23. B 24. B 25. A

26. D 27. C 28. C 29. A 30. B

31. A 32. A 33. C 34. A 35. C

36. B 37. A 38. C 39. A 40. B

41. B

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Page # 109 Carboxylic Acids & Acid Derivatives & Amine

Answer ExIII SUBJECTIVE PROBLEMS (JEE ADVANCED)

1. A 2. B 3. A 4. A 5. D

6. C 7. C 8. C 9. B 10. B

11. C 12. C 13. B 14. C 15. D

16. D 17. A 18. D 19. C 20. B

21. C 22. B 23 B,D 24. ACD 25. BD

Answer ExIV PREVIOUS YEARS PROBLEMS

LEVEL I JEE MAIN

1. C 2. C 3. A 4. D 5. D

6. C 7. D 8. D 9. A 10. D

11. A 12. C 13. D 14. B 15. A

16. D 17. A 18. A

LEVEL II JEE ADVANCED

1. A,B 2. A 3. B 4. D 5. C
6. C 7. A 8. C 9. C
10. (A) R,S ;(B) P,Q; (C) P,Q,R ;(D) P,S

11. (A) P,Q,S,T (B) P,S,T (C) P (D) R 12. (A) P,Q,T (B) P,S,T (C) R,S (D) P

13. A 14. C 15. D 16. B

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Page # 110 BIOMOLECULES,POLYMER & POC

CARBOHYDRATES
1. Introduction:
Carbohydrates received their name becasue of their general formula Cx(H2O)y, according to which
they appear to be hydrates of carbon.
Sunlight,chlorphyll
xCO2 + yH2O C x (H2O)y + xO2
carbohydrate
Photosynthesis

Sunlight,chlorphyll
6CO2 + 6H2O + 18 ATP C6H12O6 + 6O2
Cellular Respiration

Enzymes
C6H12O6 + 6O2 6CO2 + 6H2O + 38 ATP (36 ATP net gain)
2. Classification and structure of Carbohydrates:
Carbohydrats are polyhydroxy aldehydes and ketones and substances which hydrolyse to polyhydroxy
aldehydes and ketones.
The simplest carbohydrates are called sugars or saccharides, (Latin: Saccharum, sugar). Carbohydrates
can be classified as monosaccharides, oligosaccharides and polysacchaides.

3. General Characteristic of Monosaccharides:


The important characteristics of monosaccharides as follows:
(i) All monosaccahrides are water soluble due to the presence of hydrogen bonding between the
different OH groups and surrounding water molecules.
(ii) Monosaccharides have sweet taste and upon heating they get charred and give the smell of
burning sugar.
(iii) Monosaccharides are optically active in nature due to the presence of chiral carbon atoms.
(iv) The chemical characteristics of monosaccharides are due to OH groups and carbonyl group
which may be either aldehydic or ketonic group.
Glyceraldehyde contains one asymmetric carbon atom (marked by an astrisk) and can thus exist in two
optically active forms, called the D-form and the L-form. Clearly, the two forms are mirror images that
cannot be superimposed, that is they are enantiomers.
CHO CHO

H C OH OH C H

H2C OH H2C OH
D-Glyceraldehyde L-Glyceraldehyde

D Means on
HC O the right HC O
1 1

H C OH OH C H L Means on
2 2
the left
H2C OH H2C OH
3 3

D-Glyceraldehyde L-Glyceraldehyde

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BIOMOLECULES,POLYMER & POC Page # 111

All four isomers have been prepared synthetically. The D-and L-erythrose are mirror images, that is,
they are enantiomers. They have exactly the same degree of rotation but in opposite directions. Equal
amounts of the two would constitute a racemic mixture, that is a mixture that would allow a plane-
polarised light to pass through the solution unchanged.

C C C C C CHO

OH OH OH OH OH
Supplying hydrogen atoms to the five carbon atoms to satisfy their tetravalency, following structure
(open chain) may be assigned to glucose: (* indicates assymetric carbon atom).

H H H H H

H C C C C C CHO

OH OH OH OH OH

6. Configuration* of Glucose:
Since the above structure possesses four asymmetric carbon atoms (shown by asterisks), it an exist in
24 = 16 optically active forms, i.e., eight pairs of enantiomers. All these are known and correspond to
the D- and L-forms of glucose, mannose, galactose, allose, glucose, idose and talose.
The naturally occuring dextrorotatory glucose (+)-glucose is only one of the 16-stereoisomers.
CHO
1
|
H C OH
2
|
HO3C H CHO
| |
H4 C OH H C OH
| |
H5 C OH H2C OH
6|
H2C OH
D(+)Gucose (+)-Glyceradehyde
Notations D- and L- for denoting configuration were given by Rosanof; according to this convention
any compound whose bottom asymmetric carbon atoms has the configuration similar to the configuration
of dextrorotatory glyceraldehyde (drawn above, i.e. the bottom carbon atom has OH to the left and
H to the right is given L-configuration. Remember that the symbols D-and L- have no relation with the
specific rotation value, i.e., with (+) or () value. For example, the natural () fructose belongs to D-
series, i.e., it is D()-fructose)
7. Objections to open-chain structure of glucose:
Even through open chain structure of (+) glucose exaplains most of its reactions, it fails to explain the
following facts about it.
i) Glucose does not restore Schiffs reagent colour.
ii) Glucose does not form a bisulphite and aldehyde-ammonia compound.
iii) Glucose forms two isomeric penta-acetates neither of which reacts with carbonyl reagents.
iv) The existence of the two isomeric glucoses and the change in specific rotation (mutarotation) is not
explained by an open-chain formula.
v) Glucose reacts with methanol in presence of dry HCl gas to form two isomeric glucosides.
Since glucose is less soluble in ethanol, it separates out on cooling the reaction mixture. Commercially,
it is obtained by the hydrolysis of starch which is available from relatively inexpensive source such as
maize, potatoes and rice.

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Constitution of Glucose:
1. Molecular Formula: By the usual analytical methods, the molecular formula glucose is found to be
C6H12O6.
2. Straight Chain of six carbon atoms:
i) Reduction of glucose with conc. HI and phosphorus gives 2-iodohexane and n-hexane. This indicates
that six carbon atoms in glucose are present in a straigth chain

HI/P
C6H12O6 Prolonged
CH3 (CH2)4 CH3
heating

Glucose n-hexane

ii) Glucose when oxidized with bromine water gives gluconic acid which when reduced with excesss of HI
gives n-hexanoic acid, CH3.(CH2)4.COOH confirming the presence of a straigth chain of six carbon
atoms in glucose.
3. Presence of five hydroxyl groups: When treates with acetic anhydride, glucose forms penta-acetate
indicating the presence of 5 OH groups and since glucose is a stable compound, the five OH groups
must be attached to 5 different carbon atoms.
C6H5NHNH2
C6H12O6 C6H5N
CHO
Glucose |
(CHOCOCH3)4
|
CH2OCOCH3
Glucose pentaacetate

4. Presence of an aldehydic groups:


i) Glucose forms a cyanohdrin with hydrogen cyaide and a mono-oxime with hydroxylamine suggesting
the presence of a carbonyl group.

HCN
C6H12O6 CN
Glucose |
(CHOH)5
|
CH2OH
Glucose cyanohydrin

ii) Glucose reduces Fehling solution and Tollens reagent indicating that the carbonyl group is aldehydic in
nature.
iii) The presence of aldehydic gruop in glucose is confirmed by its oxidation to gluconic acid having the
same number of carbon atoms.

Br2
C 5H 11 . CHO + (O) C 5H11O5 . COOH
Glucose Gluconic acid

Now since aldehydic group is monovalent, it must be present on the end of the chain.
5. Open chain structure: On the basis of the abov points, glucose may be assigned following prt
structure orientation shown in the anomer has the OH trans to the CH2OH group and the anomer
has the OH cis to the CH2OH group.

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STRUCTURE FORMULAS FOR MONOSACCHARIDES:


Although many of the properties of D(+)-glucose can be explained in terms of an open-chain strcuture
(1, 2, or 3), a considerable body of evidence indicates that the open-chain strcuture exists, primarily,
in equilibrium with two cyclic forms. These can be represented by structures 4 and 5 or 6 and 7. The
cyclic forms of D(+)-glucose are hemiacetals formed by an intramolecular reaction of the OH group at
C5 with the aldehyde grup. Cycliation creates a new stereogenic centre at C1, and this stereogenic
centre explains how two cyclic forms are possible. These two cyclic forms are diastereomers that
different only in the configuration of C1. In carbohydrate cheistry diastereomers of this type of called
anomers, and the hemiacetal carbn atom is called the anomeric carbon atom.

Structures 4 and 5 for the glucose anomers are called Haworth formulas and, although they do not give
an accuate picture of the shap of the six-membered ring, they have many practical uses. Demonstrates
how the representation of each stereogenic centre of the open-chain form can be correlated with its
representation in the Haworth formula.
Each glucose anomer is designated as an anomer or a anomer depending on the location of the OH
gruop of Cl. When we draw the cyclic forms of a D sugar in the

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MUTAROTATION:
Ordinary D(+)-glucose has a melting point of 146C. However, when D(+)-glucose is crystallized by
evaporating an aqueous solution kept above 98C, a second form of D(+)-glucose with a melting point
of 150C can be obtained. When the optical rotations of these two forms are measured, they are found
to be significantly differnt, but when an aqueous solutin of either form is allowed to stand, its rotation
changes. The specific rotation of one form decreases and the rotation of the other increases, until
both solutions.
show the same value. A solution of original D-(+)glucose (mp 146C) has an initial specific rotaiton of
+112, but, ultimately, the speciic rotation of this solution falls to +52.7. A solution of second form of
D(+) glucose (mp 150C) has an initial specific rotation of +18.7, but slowly, the specific rotation of
this solution rises to +52.7. This change in rotation towards an equilibrium value is called mutarotation.

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The explanation for this mutarotation lies in th existence of an equilibrium between the open-chain
form of D(+) gucose an the and forms of the cyclic hemiacetals.

CONVERSION TO ESTERS:
Treating a monosaccharide with excess acetic anhydride and a weak base (such as pyridine or sodium
acetate) converts all of the hydroxyl groups, including the anomeric hydroxyl, to ester groups. If the
reaction is carried out at a low temperature (e.g., 0C), the reaction occurs stereospecifically; the
anomer gives the -acetate and the anomer gives the -acetate. Acetate esters are common
protecting groups for carbohydrate hydroxyls.

BENEDICTS OR TOLLENS REAGENTS: REDUCING SUGARS


Benedicts reagent (A alkaline solution containing a cupric citrate complex ion) and Tollens solution
[Ag+(NH3)2OH] oxidize and thus give positive tests with aldoses and ketoses. The tests are positive
even though aldoses and ketoses exist primarily as cyclic hemiacetals.

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Sugars that give positive tests with Tollens or Benedicts solutions are known as readucing sugars, and
all carbohydrates that contain a hemiacetal group given positive tests. In aqueous solution these
hemiacetals exist in equilibrium with relatively small, but not insignificant, concentratiosn of noncyclic
aldehydes or -hydroxy ketones. It is the latter two that undergoes the oxidation until one reactant is
exhausted.
Carbohydrates that contain only acetal groups do not given positive tests with Benedicts or Tollens
solutions, and they are called non-reducing sugars. Acetals do not exist in equilibrium with aldehydes
or -hydroxy ketones in the basic aqueous media of the test reagents.

BROMINE WATER : THE SYNTHESIS OF ALDONIC ACID


Monosaccharides do not undergo isomerization and fragmentation reactions in mildly acids solution.
Thus, a useful oxidizing reagent for preparative purposes is bromine in water (pH 6.0). Bromine water is
a general reagent that selectively oxidizes the CHO group to a CO2H group. It converts an aldose to
an aldonic acid.

Experiments with aldopyranoses have shown that the actual course of the reaction is somewhat more
complex than we have indicated above. Bromine water specifically oxidizes the anomer, and the initial
product that forms is a -aldonolactone. This compound may then hydrolyze to an aldonic acid, and
the aldonic acid may undergo a subsequent rign closure to form a -aldonolactone:

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NITRIC ACID OXIDATION: ALDARIC ACID


Dilute nitric acid a stronger oxidizing agent than bromine watre oxidizes the both CHO group and
the terminal CH2OH group of an aldose to CO2H groups. These dicarboxylic acids are known as aldaric
acids:

O H O CH
O C
CH
HC OH O
H OH HC OH
HC OH O
HO H H2O
or CH2
CH
H OH HC OH
HC OH
H OH C
C
CH2 OH OH O
O
This aldaric acid obtained from D-glucose is called D-glucoaric acid.
PERIODATE OXIDATIOSN: OXIDATIVE CLEAVAGE OF POLYHYDROXY COMPOUNDS
Compounds that have hydroxyl groups on adjacent atoms undergo oxidative cleavage when they are
treated with aqueous periodic acid (HIO4). The reaction breaks carbon-carbon bonds and produces
carbonyl compounds (aldehydes, ketones, or acids).

H C OH
O
+ HIO4 2 C + HIO3 + H2O

C OH

Since the reaction usually takes place in quantitative yield, valuable information can often be gained
by measuring the nubmer of molar equivalents of periodic acid that is consumed in the reaction as well
as by identifying the carbonyl products.
Periodate oxidations are though to take place through a cyclic intermediate:

Before we discuss the use of periodic acid in carbohydrate chemistry, we should illustrate the course of
the reaction with several simple examples. Notice in these periodate oxidations that for every C C
bond broken, a C O bond is formed at each carbon.
1. When three or more CHOH groups are continuous, the internal ones are obtained as formic acid.
Periodate oxidation of glycerol, for example, gives two molar equivalents of formuladehyde and one
molar equivalent of formic acid;

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2. Oxidative cleavage also take place when an OH group is adjacent to the carbonyl group of an
aldehyde or ketone (but not that of an acid or an ester). Glyceradehyde yields two molar equivalents
of formic acid and one molar equivalent of formaldehyde, while dihydroxyacetone gives two molar
equivalents of formaldehyde and one molar equivalent of carbon dioxide.

Periodic acid does not cleave compound in which th hydroxyl gruops are separated by an intervening
CH2 group, nor those in which a hydroxyl group is adjacent to an ether or acetal.

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REDUCTION OF MONOSACCHARIDES: ALDITOLS


Aldoses (and ketoses) can be reduced with sodium borohydride to compounds called alditols:

Reduction of D-glucose, for example, yields D-glucitol.

REACTIONS OF MONOSACCHARDIES WITH PHENYLHYDRAZINE: OSAZONES


The aldehyde group of an aldose reacts with such carbonyl reagents as hydroxylamine and
phenylhydrazine. With hydroxylamine, the product is the expected oxime. With enought phenylhydrazine,
however, three molar equivalents of phenylhydrazine are consumed and a second phenylhydrazeone
group is introduced at C2. The product is called a phenylosazone. Phenylosazones crystallize readily
(unlike sugars) and are useful derivatives for identifying sugars.

The mechanism for osazone formation probably depends on a series of reaction in which C N

C O in giving a nitrogen version of an enol.


behaves very much like

A Mechanism for the Reaction


Phenylosazone Formation

H A H H
tautomerization HC N N C6H5
HC N NHC6H5

A: C O H
H C OH
:A

Formed from the aldose


HC NH C NHHC6H5
(C H NH )
6 5 2
(+2 C6H5NHNH2)
C O C NHHC6H5 + NH3 + H2O

Osazone formation result in a loss of the stereogenic centre at C2 but does not affect other stereogenic
carbons; D-glucose and D-mannose, for example, yield the same phenylosazone:

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CHO CH NHHC6H5 CHO


H OH C NHHC6H5 HO H
HO H HO H HO H
C 6H 5NHNH 2 C6H 5NHNH 2
H OH H OH H OH

H OH H OH H OH

CH2 OH CH2 OH CH2 OH


D-Glucose Same Phenylosazone D-Mannose
This experiment, first done by Emil Fischer, established that D-glucose and D-mannose have the same
configuration about C3, C4 and C5. Diastereomeric aldoses that differ in configuration at only one
carbon (such as D-glucose and D-mannose) are called epimers. In genral, any pair of diastereomers
that differ in configuration at only a single tetrahedral stereogenic carbon can be called epimers.

Epimers:
Many common sugars are closely related, differing only by the stereochemistry at a single carbon
atom. For example, glucose and mannose differ only at C2, the first asymetric carbon atom. Sugars
that differs only by the stereochemistry at a single carbon are called epimers. and the carbon atom
where they differ is generally stated. If the number of a carbon atom is not specified, it is assumed to
be C2. Therefore, glucose and mannose are C2 epimers or simply epimers. The C4 epimer of glucose
is galactose and the C2 epimer of erythrose is threose.

Cyclic structure of Fructose:


Like glucose, fructose also has a cyclic structure. Since fructose contains a keto group, it forms an
intramolecular hemiketal. In the hemiketal formation, C5OH of the fructose combins with C2-keto
group. As a result, C2 becomes chiral and thus has two possible arrangements of CH2OH and OH group
around it. Thus,

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D-fructose exists in two stereoisomeric forms, i.e., -fructopyranose and -D fructopyranose. However
in the combined state (such as sucrose), fructose exists in furanose form as shown below:
Hydroylsis of Sucrose:
6
CH2OH
5
H O H
H 1
4
OH H
-link
2
OH 3
O Glycosidic
H OH linkage
(Glucose unit)
CH2OH O
-link

H OH

H CH2OH
OH H
(Fructose unit) Sucrose

(Invert Sugar or Invertose). Hydrolysis of sucrose with hot dilute acid yields D-glucose and D-fructose.
+

C12H 22O 11 + H2O H C6H 12O 6 + C6H 12O 6


Sucrose D(+)-glucose D()-Fructose
[]D = +66.5 []D = +53 []D = 92
Invert Sugar
[]D = (+53) (92) = 39
Surose is dextrorotatory, its specific rotation being +66.5%, D-glucose is also dextrorortatory, []D =
+53, but D-fructose has a large negative rotation, []D = 92. Since D-fructose has a greater
specific rotation than D-glucose, the resulting mixture is laevorotatory. Because of this the hydrolysis
of sucrose is known as the inversion of sucrose, and the equimolecular mixture of glucose and fructose
is known as invert sugar or invertose.

POLYSACCHARIDES
Polysacchardies are the polymers of monosacchardies. The natural polysacchardies generally contain
about 100-3000 monosacchardie units. The three most abundant natural polysaccharides-cellulose,
starch and glycogen are derived from the same monomer, i.e., glucose.
Starch: It is a polymer of glucose. Its molecular formular is (C6H10O5)n where the value of n(200
1000) varies from source to source. It is the chief food reserve material or storage polysacchardie of
plants and is found mainly in seeds, roots, tubers, etc. Wheat, rice, potatoes, corn, bannans etc., are
rich source of starch.
Starch is not a single compound but is a mixture of two components a water soluble component
called amylose (20%) and a water insoluble component called amylopectin (80%). Both amylose and
amylopectin are polymers of -D glucose.
Amylose is a linear polymer of -D glucose. It contains about 200 glucose units which are linked to one
another through -linkage involving C1 of one gluose unit with C4 of the other.

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Amlopectin, on the other hand, is a highly branched polymer. It consists of a large number (several
branches) of short chains each containnig 20-25 glucose units which are joined together through -
linkages involving C1 of one glucose unit with C4 of the other. The C1 of terminal glucose unit in each
chain is further linked to C6 of the other glucose.
unit in the next chain through C1-C6 -linkage. This gives amylopectine a highly branched structure as
shown below:

C1 C4 -linkage

Glucose Glucose Glucose

Glucose Glucose Glucose

Glucose Glucose Glucose

Hydrolysis:
Hydrolysis of starch with hot dilute acids or by enzmyes give dextrins of varying complexity, maltose
and finally D-glucose. Starch does not reduce Tollens reagent and Fehlings solution.
Uses:
It is used as a food. It is encountered daily in the form of potatoes, bread, cakes, rice etc. It is used
in coating and sizing paper to improve the writing qualities. Strch is used to treat textile fibres before
they are woven into cloth so that they can be woven without breaking. It is used in manufacture of
dextrins, glucose and ethyl alcohol. Starch is also used in manufacture of starch nitrate, which is used
as an explosive.
Cellulose:
Cellulose is the chief component of wood and plane fibres; cotton, for instance, is nearly pure cellulose.
It is insoluble in watre and tasteless; it is a non-reducing carbohdrate. These properties, in part at
least, are due to extremely high molecular weight.
OH H
H H HO OH
O HO
O O O
HO O HO
O O

H OHH
H OH
HO
H
Cellulose
Cellulose has the formula (C6H10 O5 )n. Complete hydrolysis by acid yields D(+)-glucose as the
monosaccharide. Hydrolysis of completely methylated cellulose gives a high yield of 2, 3, 6-tri-O-
methyl-D-glucose. Like starch, therefore, cellulose is made up of chains of D-glucose units, each unit
joined by a glycoside linkage of C-4 of the next.
Cellulose differs from starch, however, in the configuration of the glycoside linkage. Upon treatment
with acetic anhydride and sulfuric acid, cellulose yields octa-O-acetylecllobiose, there is evidence that
all glycoside linkages in cellulose, like the one in (+) cellobiose, are beta linkages.

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Physical methods give molecular weights for cellulose ranging from 250000 to 1000000 or more; it
seems likely that there are at least 1500 glucose units per molecule. End group analysis by both
methylation and periodic acid oxidation gives a chain legnth of 1000 glucose units or more. X-ray
analysis and electron microscopy indicate that these long chains lie side by side in bundles, undoubtedly
held together by hydrogen bonds between the numerous neighbouring OH groups. These bundles are
twisted togethr to form.
Rope like structure which themselvs are grouped to from the fibers we can see. In wood these cellulose
ropes are embedded in lignin to give a structure that has been likened to reinforced concrete.
Properties of Cellulose:
We have seen that the glycoside linkages of cellulose are broken by the action of acid, each cellulose
molecule yielding many molecules of D(+)-glucose. Now let us look briefly at reactions of cellulose in
which the chain remains essentially intact. EAch glucose unit in cellulose contains three free OH
groups; these are the positions at which reactions occurs.
These reactions of cellulose, carried out to odify the properties of a cheap, available ready-made
polymer, are of tremendous industrial importance.
Like any alcohol, cellulose forms esters. Treatment with a mixture of nitric and sulfuric acid converts
cellulose into cellulose nitrate. The properties and uses of the product depend upon the extent of
nitration. Guncotton, which is used in making smokeless powder, is very nearly completely nitrated
cellulose, and is often called cellulose trinitrate (three nitrate groups per glucose unit). Pyroxylin is less
highly nitrated material containing between two and three nitrate groups per glucose unit. It is used in
the manufacture of plastics like celluloid and collodion, in photographic film, and in lacquers. It has the
disadvantage of being flammable, and forms hihgly toxic nitrogen oxides upon burning.
Industrially, cellulose is alkylated to ethers by the action of alkyl chlorides (cheaper than sulfates) in
the presence of alkali. Considerable degradation of the long chain is unavoidable in these reactions.
Methyl, ethyl, and benzyl others of cellulose are important in the production of textiles, films, and
various plastic objects.
AMINO ACIDS
1. Intorudction:
Amino acids are the compounds which contain both an amino group and a carboxy group in their
molecules. They constitute a particularly imortant class of difunctional compounds as they are the
building blocks of proteins.
While several hundred different amino acids are known to occur naturally, 20 of them deserve special
mention as they ae preesent in proteins. These amino acids are listed in Table. As given in this table,
for amino acids trivial names are common. The convention to use a three letter code, as an abbreviation,
for each amino acid is also given in the table. These abbreviations are particularly useful in designating
the sequence of amino acids in peptides and proteins which your will study.

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Nature
of OH
amino E/N.E R Name Abbreviation
acid
NH2

Neutral H2N
amino NE
OH Glycine Gly
acid

Neutral OH
amino Alanine Ala
NE H3C
acid
NH2

Neutral H3C
amino E Valine Val
NH2
acid
HO

Neutral CH3 Leucine


HO Leu
amino
E
acid
NH2 CH3

Neutral O
amino
E NH2 Isoleucine Ile
acid
CH3
CH3

Acidic
OH Aspartic Acid Asp
amino NE
HO
acid
NH2 O

2
Acidic
amino HO OH Glutamic Acid Glu
NE
acid

Basic 2 2
amino E Lysine Lys
acid

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NH NH2
Basic
amino NE O Arginin Arg
acid NH2 NH
OH

Basic
N Histidine His
amino OH
acid
NE
NH2

Neutral
amino S Methionine Met
E HO CH 3
acid
NH2

Neutral
amino N O Proline Pro
acid NE

Neutral
O
amino E Phenylalanine Phe
acid
H 2N OH

Neutral
OH
amino Tryptophan Trp
acid E
NH2
N

Neutral OH Serine Ser


NE
amino
H2 N
acid

H 3C
Neutral
amino NH2 Threonine Thr
E
acid HO
O
threonine
Neutral
amino OH Cysteine Cys
acid NE
H2N

2
Neutral
amino Tyrosine Tyr
NE
acid O OH

E = essential amino acid NE = Non essential amino acid

AMINO ACID AS DIPOLAR IONS:


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Amino Acids contain both a basic group (NH2) and an acidic group (COOH). In the dry solid state,
amino acids exist as dipolar ions, a form in which the carboxyl group is present as a carboxylate ion,
CO2, and the amino group is present as an aminium ion, NH3+ (Dipolar ions are also called zwitterions.)
In aqueous solution, an equilibrium exists between the dipolar ion and the anionic and cationic forms of
an amino acids.

+ OH +
H3 N CHCO2H +
H3 N CHCO2 H2NCHCO2
H3O

R R R

Cationic form (Predominant in strongly Dipolar ion Anionic form (Predominant in strongly
acidic solutions, e.g., At pH 0) basic solutions, e.g., At pH 14)

If alanine is dissolved in a strongly acidic solution (e.g. pH 0), it is present in mainly a net cationic form.
In this state the amine group is protonoted (bears a formal +1 charge) and the carboxylic acid group is
neutral (has no formal charge). As is typical of -amino acids, the pKa for the carboxylic acid hydrogen
of alanine is considerably lower (2.3) than the pKa of an ordinary carboxylic acid (e.g., propanoic acid,
pKa 4.89):

The reason for this enhanced acidity of the carboxyl group in an -amino acid is the inductive effect of
the neighboring aminium cation, which helps to stablize the carboxylate anion formed when it loses a
proton. Loss of proton from the carboxyl group in a cationic -amino acid leaves the molecule electrically
neutral (in the form of a dipolar ion). This equilibrium is shown in the red-shaded portion of the equation
below.
The protonated amine group of an -amino acid is also acidic, but less so that the carboxylic acid
group. The pKa of the animium group in alanine is 9.7. The equilibrium for loss of an aminium proton is
shown in the blue-shaded portion of the equation below. The carboxylic acid proton is always lost
before a proton from the aminium group in an -amino acid.

The state of an -amino acid at any given pH is governed by a combination of two euilibrium, as shown
in the above equation for alanine. The isoelectric point (pI) of an amino acid such as alanine is the
average of pKa1 and pKa2;
pI = (2.3 + 9.7) = 6.0 (isoelectric point of alanine)
When a base is added to a solution of the net cationic form of alanine (initially at pH 0, for example),
the first proton removed is the carboxylic acid proton, as we have said. In the case of alanine, when a
pH of 2.3 is reached, the acid proton will have been removed from half of the molecules. This pH
represents the pKa of the alanine carboxylic acid proton, as can be demonstrated using the Henderson-
Hasselbalch equation. The Henderson - Hasselbalch equation shows that for an acid (HA) and its
conjugate base (A),

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HA
pKa = pH + log
[A ]
When the acid is half neutralized,
b) Co-polymers are another tye of polymer. These contains more than one sub-unit (or monomer).
Example:
In the above example styrene and maleic anhydride monomers laternate. Co-polymer can be a block
co-polymer.
Example:
Co-polymers can be random as well.
B A A B A B B A B A B B A
A and B are monomers.
6. There are many polymers in nature.
Example: Cellulose, starch, pepsin, insulin, egg albumin, rubber, DNA (Deoxyribonucleic acid) etc.
These are called Biopolymers.
Man made polymers are, Nylon, Terylene, Polythene, Polystyrene, PVC (Polyvinyl chloride), Bakelite,
Perspex, Polysiloxane etc.
7. The propertis of a polymer solution are strikingly different from those of a true solution. For example,
when polyvinyl alcohol is added to water, it swells.
a) Its shape gets distorted and after a long time it dissolves.
b) When more of polymer is added to a given solvent, saturation point is not reached. The mixture of
polymer and solvent assumes a soft dough-like consistency.
8. Addition polymers and condensation polymers are two important types of polymers.
9. Polymer can be described as linear, branched and network.

POLYMERS AND POLYMERIZATION:


Macromolecules, both natural and man-made, own their great size to the fact they are polymers
(Greek: many parts); that is, each one is made up of a graet many simpler unit - identical to each
other or at least chemically similar - joined together in a regular way. Theyare formed by a process we
touched on earlier: polymerizatioin, the joining together of many small molecules to form very large
molecules. The simple compounds from which polymers are made are called monomers.
PETIDES AND PROTEINS:
In the last section, you studied the polymers of monosaccharides which act as structural components
in plants and serve as energy storage in animals. In this section, you will study another kind of natural
polymers called peptides and proteins.
Peptides are biologically important polymers in which 2-amino acids are joined by the amide linkages,
formed by the reaction of the carbxy group of one amino acid with the amino group of another amino
acid. These amide linkages are also called peptide bonds. The general structure of a peptide is shown
below:

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Peptides can be classified as dipeptides, tripeptides and tetrapeptides, depending on whether the
number of amino acids, two, three or four, respectively. Peptides containing upto 50 amino acids are
called polypeptides. Bradykinin is an important naturally occurring nonapeptide which is present in
blood plasma and is involved in the regulation of blood pressure.
ArgPro Pro Gly Phe Ser Pro Phe Arg
Bradykinin

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 Quatemany

Primary Structure :
This type of structure was given by FriedrichSanger 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.

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 O
C O N H 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 HCR
N C C C
N

(i) -helix
Chain is spiral
3.7 atoms in one coiling
Right handed circular.
Eg. Myosin, Keratin etc.

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(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.
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 :

N
C = O .. H
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 .
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
Types of proteins
Classification of protein is based upon three general properties shape, Solubility and Chemical
composition.

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Proteins

Simple Conjugated Derived

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

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

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.

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.

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(c) Millon reaction. Proteins on adding Millons reagent (a solution of mercuric and mercurous nitrates in
nitric acid containing a little nitrous acid) followed by heating the solution give red precipitate or
colour.
(d) Ninhydrin reaction. Proteins, peptides and a-amino acids give a characteristic blue colour on treatment
with ninhydrin.

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.

SOLVED SUBJECTIVE PROBLEMS

Problem 1: Write the hemiacetal formation for glucose.


Solution:

Problem 2: The pKa of the carboxyl group in an amino acid valine, (CH3)2CHCH(NH2)(COOH) is 2.31
and the pKa for the amino group of the same amino acid is 9.69. compute the Isolectric point
(pI) for valine and draw the structure of this amino acid when the pH of the solution equals
top1. Also draw the structures of valine that predominate at pH =2 and pOH =2.
Solution: The isoelectric point (p1) is the pH at which the amino acid exists only as a dipolar ion with net
charge zero.

At isoelectric point, for a neutral amino acid,

The dissociation of cationic form of valine can be represented as

The species with zero net charge exists between species with (+1) and (I) net charges.

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When the p1-I of the solution equals to p1, the structwe of valine is

When the pH of the solution is two, the structure of valine is

When the pH of the solution is 12, the structure of valine is

Problem 3: Sucrose on hydrolysis yields a mixture which is


(a) Optically inactive (b) Dextrorotatory (c) Laevorotatory (d) Racemic

Solution: (c) Sucrose on hydrolysis yields equimolar mixture of D-()-fructose and D-(+)glycose. Since
specific rotation of ()-fructose is greater than (+)-glucose D the mixture is laevorotatory.

Problem 4: A high molecular weight molecule which does not contain repeating structural units is called a
(a) Polymer (b) Macromolecule (c) Both (a) and (b) (d) None of these
Solution: (b) A polymer has always repeating structural units derived from monomer. For example proteins
and nucleic acid are regarded as macromolecules, but not polymers because their molecules do not
contain repeating structural units. All polymers are macromolecules, but all macromolecules are not
polymers.

Problem 5: The force of attraction between the neighbouring peptide chains is


(a) van der Waals force (b) Covalent bond (c) Hydrogen bond (d) Peptide linkage
Solution: (c) Nei ghbouri ng pepti de chai ns are hel d by hydrogen bonds between CO and
NH.

Problem 6: Peptides on hydrolysis give


(a) Ammonia (b) Amines (c) Amino acids (d) Hydroxy acids
Solution: (c) Peptides are formed by condensation of -amino acids. Therefore, on hydrolysis they yield -
amino acids.

Problem 7: An example of a condensation polymer is


(a) PVC (b) terylene (c) polypropylene (d) polystyrene
Solution: (b) In condensation polymerization, a series of condensation reactions between the (generally
two) monomers containing atleast two functinal groups each occur with the loss of a small molecule
such as H2O, CH3OH or HX (X = halogen). Terylene is a condensation polymer of ethylene glycol and
terephthalic acid.

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Problem 8: Suggest a mechanism for the process. Is polymerisaton of the chain reaction or step
reaction type ?

Problem 9: Although both polymers are prepared by free radical processes, poly (vinyl chloride) is
amorphous and poly (vinylidene chloride) (saran) is highly crystalline. How do you account for
the different ? (vinylidene chloride is 1,1-dichloroethene).
Solution: As poly (vinyl chloride) is able to show stereoisomerism and further it is formed by a free radical
process, it is atactic (chlorine atoms (distributed randomly), the molecules fit together poorly.
Poly (vinylidene chloride) has two identical substitutents on each carbon and the chains fit together
well.

Problem 10: Compound A C5H10O4, is oxidized by Br2 H2O to the acid, C5H10O5. (A) Forms a triacetate
(Ac2O) and is reduced by HI to n-pentane. Oxidation of (A) with HIO4 gives, among other product,
1 molecule of CH2O and 1 molecule of HCO2H. What are the possible strcutures of (A) and how
could you distinguish between them ?

Solution: (A) is an aldehyde, contains three hydroxyl groups and the carbon skeleton consists of five
carbon atoms in a straight chain. Also, the formula C5H10O4 therefore suggests that (A) is a deoxy-
sugar. If we now try to work out the possibilities based directly on the periodic oxidation of (A), we
shall find it.

Problem 11: Convert

Solution:

Problem 12: i) Sulphanilic acid although has acidic as well as basic group, it is soluble in alkali but
insoluble in mineral acid.
ii) Sulphanilic acid is not solube in organic solvents.
Solution: i) Sulphanic acid exist as Zwitterion

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The weakly acidic NH3+ transfers H+ to OH to form a soluble salt, PNH2C6H4SO3Na+ on the other
hand SO3 is too weakly basic to accept H+ from strong acids.
iii) Due to its ionic character it is insoluble in organic solvents.
Problem 13: Compound (A) C5H10O5, give a tetra-acetate with Ac2O and oxidation of (A) with Br2
H2O gives an acid, C5H10O6. Reduction of (A) with HI and red phosphorous gives 3-methylbutane.
What is structure of (A) ?
Solution: The formation of tetracetate indicates of 4OH group and oxidation with bromine water indicates
presence of CHO group. Reduction with red phosphorous and HI indicates presence of one carbon in
the side chain. Thus, the structure of (A) would be

Problem 14: What is the structure of nylon-6, made by alkaline polymerisation of caprolactum ?

Solution: The configuration of these carbons which are unchanged in the reactions, must be identical in
order to get the same osazone.
a) Nylon-6: Another polymer of this class is nylon-6. It is a monomer of caprolactum which is obtained
from cyclohexane.

It used for making tyre cords, fabrics and ropes.


b) Nylon-6, 10: A polymer of hexamethylene diamine (six carbon atoms) and sebacic acid (ten carbon
atoms).

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These polymers are formed by the condensation of two or more monomers with the elimination of
simple molecules like H2O, NH3, ROH etc.
Problem 15: Supply structures for H through K. Given :

An Aldohexose H I J K.
(b) Explain the last step (c). What is net structural change (d) Name this overall method. (c)
Discuss the possibility of epimer formation.
Solution: a) H is an oxime HOCH2 (CHOH)4CH = NOH; 1 s the completely acetylated oxime, AcOCH2(CHOH)4CH
= NoAc that loses 1 mole of HOAc to form J, AcOCH2(CHOAc)4 C N; K is an aldopentose,
HOCH2(CHOH)3CHO.
b) The acetates undergo transesterification to give methyl acetate freeing all the sugar OHs. This is
followed by reversal of HCN addition.
c) There is loss of one C from the carbon chain.
d) Wohl Degradation
e) The -CHOH becomes the CH = O without any configurational changes of the other chiral carbons.
Thus no epimers are formed.

Problem 16: Glycine exists as (H3N + CH2COO) while anthranilic acid (P NH2 C6H4 COOH) does not exist
as dipolar ion.
Solution: COOH is too weakly acidic to transfer H+ to the weakly basic NH2 attached to the electron
withdrawing bezene ring. When attached to an aliphatic carbon, the NH2 is sufficiently basic to
accept H+ from COOH group.
Problem 17: Why should isoelectric oint for Aspartic acid (2.98) be so much lower than that of leucine ?
Solution: This may be explained by considering following ion equilibrium

It is apparent that ions (A) and (B) are neutral, while (C) is a cation and (D) is dianion. In species (D),
the anion is derived from the second COOH group present in aspartic acid and is not possible in leucine.
At neutral pH a significant concentration of (D), will be present in aqueous solution. It will therefore, be
necessary to decrease the pH of such a solution if the formation of (D) is to be suppressed to a stage
where anions and cations are present in equal concentration (the isoelectric point).

Problem 18: (a) Show how an aldohexose can be used to synthesize 2-ketohexose.
(b) Since glucose is converted to fructose by this method, what can you say about the configuration
of C3, C4 and C5 in the sugars.

CHO
Solution: (CH2OH)4 + 3C6H5NH.NH2
C6H5NH2
CH2OH H2O
NH3

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Here aldohexose reacts with one molecule of phenylhydrazine which condenses with the aldehyde
group to give phenylhydrazone. When warmed with excess of phenyl hydrazine, the secondary alcoholic
group adjacent to the aldehyde group is oxidised by another molecule of phenylhydrazine, to a ketonic
group. With this ketonic group, the third molecule of phenylhydrazine condenses to given osazone. The
pheynlhydrazinyl group is transferred from osazone to C6H5CHO giving C6H5CH = N.NHC6H5 and a dicarbonyl
compound called an osone. The more reactive aldehyde group of the osone is reduced, not the less
reactive keto group and it give the 2-ketohexose.

Problem 19: Starch is polymer of


(a) Fructose (b) Glucose (c) Lactose (d) None
Solution: (b) Starch is homopolysaccharide of glucose having 24 30 ghcose units.

Problem 20: The commonest disaccharide has the molecular formula


(a) C10H18O9 (b) C10H20O10 (c) C11H22O11 (d) C12H22O11
Solution: (d ) The most c om mon di sacc hari de i s sucros e, w hose m ol ec ul ar formul a i s
C11H22O11.

Problem 21: The structure ofglyclne (amino acid) is H3N+CH2 COO (Zwitter Ion.)
Select the correct statement of the following.
(a) Glycine, as well as other amino acids are amphoteric.
(b) The acidic functional group in amino acids is NH3+
(c) The basic functional group in amino acids is CO2
(d) All the statements are correct
Solution: (d) Glycinc and all other amino acids are amphoteric because of the presence of NH2 and CO2H
group both. The amino acid exists and Zwitter ion and acidic group is NH3+ while basic group is CO2

Problem 22: Sugars are characterised by the preparation of osazone derivatives. Which sugar have identical
osazones.
(a) Glucose and lactose (b) Glucose and fructose
(c) Glucose and arabinose (d) Glucose and maltose

Solution: (b) The reaction with phenyl hydrazone gives same osazone because glucose and fructose differ
only on carbon atoms 1 and 2 which are involved in osazone formation.

Problem 23: Cane sugar on hydrolysis yields


(a) Glucose and maltose (b) Glucose and lactose
(c) Glucose and fructose (d) Only glucose

HOH
Solution : (c) C12H22O11
H
C6H12O6 + C6H12O6

Glucose Fructose
The process is known as inversion of cane sugar.

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LIPIDS
(a) Lipids words is derived from greek word lipos which means fat.
(b) Lipids are heterogeneous group of substances which have common property of being relatively insoluble
in water and soluble in non-polar solvents such as ether, Chloroform etc.
(c) Form 3-5% part of protoplasm.
(d) H2O 2 : 1 (different from water)
(e) Ratio of oxygen is less.
(f) Specific gravity < 1
Three types

Simple Compound Derived

Simple lipid :
Simple lipid
two types

Natural fats or Wax


Triglycerides

Triglycerides
(a) These are esters of fatty acids with glycerol.
Ester bond is present
(b) Synthesis is of following type-

H H H H
H C OH HOOCR HCOOCR
H C OH + HOOCR HCOOCR
3H2O
H C OH HOOCR HCOOCR
H H H H
Glycerol Fatty Acid Fats

(c) Fatty acids which occur in natural fats usually contain an even number of carbon atoms(4 to 30) in
straight chains.
(d) Simplest fatty acid HCOOH.
(e) More complex fatty acid are formed by successive addition of CH2 groups.
Fatty acids are of 2 types

Saturated Unsaturated
(i) Saturated :
Only single bond is present in them.
First member is CH3COOH.
Other examples :
Palmitic acid - C15H31COOH
CH3(CH2)14 COOH
Stearic acid - C17H35COOH
CH3(CH2)16COOH
Palmitic and stearic acid is found in fats of
animals in less amount.

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These are solid and are found in fats.


(ii) Unsaturated :
Double bond is present in these fatty acid chain.
These are liquids at room temperature. Found in Oils.
These are of two types
Monounsaturated - 1 Double bond is present
Eg. Oleic acid.
Oleic acid is present in more amount in
nature.
Polyunsaturated - More than two double bond
Eg. Linoleic acid with two double bonds
Linoleinic acid with three double bonds
Arachidonic acid with four double bonds (Groundnut)
Wax :
These are esters of other alcohols of high
molecular weight instead of glycerols.
These are insoluble in water.
These are monohydric alcohols.
Some examples of waxes -
Myricye palmitate (Honeybee wax) Cetyl palmitate (Dolphin and whale wax)
Cerumen (ear wax)
Compound Lipid- Are of 4 types :
(a) Phospholipids. (b) Glycolipids.
Phospholipids :
Phosphorous is present.
ex. cell wall
Glycolipids
Lipid + Sugar = Glycolipids
Present in brain, Adrenal glands, kidney,
WBC liver, thymus, Spleen, Lungs, egg yolk
Glycolipids = 2 Fatty acid + 1 sphinocine
+ 1 galactose.
Derived lipids
By hydrolysis of fats they are obtained

Derived lipids
Types
Steroids Sterols

Steroids :
These are different from other fats.
It is insoluble in water.

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(i) Bile acids :


Present in secretion of liver.
(ii) Sex hormones :
These are androsterones.
(iii) Adrenal hormone- Eg : Aldosterone
Sterols :
They have -OH groups.
They are complex monohydroxy alcohols.
(i) Cholesterol - It is widely distributed in all cells of body.

Biological importance of Fat :


It is source of energy.
It is important for absorption of vitamin A, D, E and K.
It is important component of plasma membrane.
It act as shock absorber of body.
Calorific value 9.3 kcal.

NUCLEIC ACID
(a) These are special type of acids which are present in nucleus & cytoplasm.
(b) Control the metabolic activities of cell.
(c) They are also found in Mitochondria, centriole and chloroplast.
Types These are of 2 types
DNA (Deoxyribonucleic acid)

RNA (Ribonucleic acid)


(d) Fischer discovered Nitrogen bases in 1888

Nitrogen Base
type

Purine Pyrimidine
(e) Levan found sugar
2 type

Ribose (RNA) Decoxyribose (DNA)


Deoxyribosenuclic Acid (D.N.A.) :
(a) It is found in Nucleus.
(b) They on pneumococcus bacteria.
(c) DNA made up of 3 units-

Nitrogen base Deoxyribose Phosphric acid


Sugar (H3PO4)

Pyrimidine Purine

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(i) Thymine (i) Adenine


(ii) Cytosine (ii) Guanine
(d) Nucleoside
When nitrogen base combined with deoxyribose sugar it constitute a nucleoside.
S.No. Deoxyribonucleoside
1 Adenine + Deoxyribose Deoxyadenosine
2 Guanine + Deoxyribose Deoxyguanosine
3 Cytosine + Deoxyribose Deoxycytidine
4 Thymine + Deoxyribose Deoxythymidine

(i) Nucleotide
(a) Nitrogen base+Sugar+Phosphate Nucleotide
(b) Nucleotide is a unit of DNA.
(c) All nucleotides combined and form a chain called polynucleotides by which RNA and DNA formed.
Structure of DNA
(a) Double Helical model of DNA was proposed by biochemist J.D.Watson, British chemist
FHC Crick in 1953.
(b) DNA in double stranded structure is made up of two 5' P T 23
chains of polynucleotides. 5 4S2 A
S 4 3'
(c) DNA is a polymer of Nucleotide. 3 1 P5
P S
(d) Nucleotide are joined by 3' 5' phosphodiester bonds. 5 C G
(e) Sugar and phosphorous are alternately arranged. S
1 P5
(f) In both chains, in between A and T, 2 Hydrogen bonds
are present while in C and G 3H bonds are present. 5 P 1 G C S
3' P5
(A = T) (C G) 4 S
5'
(g) A always attach with T while C always attaches with G. 3 2
(h) Purine and pyrimidine are found in ratio 1 : 1.
cells.
(i) DNA is attached with histone protein.
(j) In prokaryotic cell and mitochondria circular DNA is
present.

Function of DNA
(i) Self - Replication or self -Duplication
DNA has the property of self - replication . It is therefore a reproducing molecule. This unique property
of DNA is at the root of all reproduction. Through its replication, DNA is acts as the key to heredity.
In the replication of DNA, the two strands of a double helix unwind and separate as a template for the
formation of a new complementary strand.
(ii) Protein Synthesis
The specific sequence of base pair in DNA represents coded information for the manufacture of
specific proteins. These code instructions first are transcribed into the matching nitrogen- base sequences
within mRNA and the instructions in such RNA subsequently are translated into particular sequence of
amino acid units within the polypeptide chains and proteins.
The major steps in the utilization of the genetic information can be represented as :
D N A Re D N A Transcript
plication
ion R N A Transcript
ion Protein

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Ribonucleic Acid (RNA) :


Found in cytoplasm as well as in nucleus.
Cytoplasm In the ribosome (heigher amount)
Chemical Nature :
Ribonucleic acid is a polymer of purine and pyrimidine ribonucleotides linked by 3' 5' phosphodiester
bridges. The number of nucleotides in RNA ranges from as few as 75 to many thousands. Although
sharing many features with DNA, RNA possesses several specific difference.
As indicated by its name, sugar in RNA to which the phosphate and nitrogen- bases are attached is
ribose rather than the deoxyribose of DNA.
Although RNA contains the ribonucleotides of adenine, guanine, and cytosine, it does not posses
thymine. Instead of thymine, RNA contains the ribonucleotides of uracil. Thus the pyrimidine components
of RNA differs from those of DNA.
RNA exists basically as a single-stranded molecule rather than as a double -stranded helical
molecule, as does DNA. However the single strand of RNA is capable of folding back on itself like a
hairpin and thus acquiring double-stranded characteristics. In these regions. A pairs with U and G pairs
with C.
Thus a given segment of a long RNA molecule might, for example, be represented as follows.
PRPRPRPRPR
| | | | |
A U G G C
where R stands for ribose ; A, U, G, and C for Adenine, Uracil, Guanine and Cytosine respectively.
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)


This type of RNA consists of single strand of variable length and serves as a template for
protein synthesis. Codon in the chromosomes.
mRNA forms complementary copy of DNA as it carries chemical messages in the form of
nitorgen-base sequence from the nucleus to the ribosomes, i.e. from DNA to cytoplasm where
proteins are synthesized. Therefore, it is called messenger RNA or mRNA
mRNA is sythesised from DNA in the nucleus.
It is called transcription.

(ii) Ribosomal RNA


A ribosome is a cytoplasmic nuucleoprotein structure which serves as the organellar machinery for
protein synthesis from mRNA templates.

On the ribosome, the mRNA and tRNA molecules interact to translate into a specific protein
molecule the information transcribed from the DNA.
rRNA constitutes the largest part of total RNA (Highest) - 80%

(iii) Transfer RNA (RNA) :


These are also called Soluble RNA.
Single stranded.
10-15% of the total RNA.
Size - Smallest 75 - 80 nucleotides only.
Synthesis - Within nucleus from DNA.
Function- It transport amino acid from cyto plasm to the site of protein synthesis.

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ENZYMES
Proteins which are used as a catalyst in biochemical reaction is known as biocatalysts.
Specific cheracteristics
Enzymes have following two specific character as :
(i) Specificity (ii) Efficiency
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 catalyzed
by more than one enzyme.
eg. Enzyme present in Yeast (Zymase) can ferment both glucose and fructose into alcohol and
also cane-sugar can be hydrolyses by invertase and sucrase enzymes.
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 cells has a highest turn over number.
(b) With having tertiary structure it can be collected as crystals.
Enzymes are denatured at higher temperature.
(c) Enzyme can be stored at low temperature as they are inactivated.
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. Scarcity of Phenylalanine hydroxylase enzyme in human body is result in Phenylketonuria
disease.
Factors affecting enzyme action :
(i) Optimum temperature and pH. Enzyme catalysed reactions have maximum rate at physiological
pH of around 7.4 and human body temperature of 37C (310 K) under one atmosphere pressure.
In fact, as the temperatue or pH is increased, the rate rises to a maximum (at 37C or pH = 7.4) and
then falls off.
(ii) Enzyme activators (co-enzymes). The
activity of certain enzymes is increased in the presence of certain substances, called co-enzymes.
It has been observed that if a protein contains a small amount of vitamin as the non-protein part, its
+ 2+ 2+
activity is enhanced considerably. The activators are generally metal ions such as Na , Mn , Cu ,
2+
Co etc. These metal ions are weakly bonded to the enzyme molecules and increase their
+
catalytic activity. For example, the enzyme, amylase, in presence of NaCl, which provides Na ion,
shows a very high catalytic activity.
(iii) Enzyme inhibitors and poisons. Just as in the case of catalysts, the activity of enzyme is slowed
down in the presence of certain substance. Such substances are called inhibitors or poisons. They
act by combining with the active functional group thereby reducing or completely destroying the
catalytic activity of the enzymes. The use of many drugs is on account of thier action as enzyme
inhibitors in our body.

NUTRIENTS
Sodium, Potassium and Chlorine
+
(i) Na is the principal mineral cation in the extracellular fluid.
+
(ii) K is the principal cation inside the cell.

(iii) Cl is the principal mineral anion in the ECF.
+ +
(iv) Na and K are essential to the maintenance of water balance and acid-base balance.
+ +
(v) Na and K are important in nerve impulse transmission.

Calcium and Phosphorus

(i) Calcium and phosphorus are deposited in bones and teeth to give them strength and rigidity.

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2+
(ii) Ca is also essential for blood coagulation, neuromuscular function, cardiac function and actions of
many enzymes and hormones.

(iii) Phosphorus enters into many compounds such as nucleic acids and phospholipids, many coenzymes
and high energy compounds like ATP.

(iv) Calcium plays an essential role in sustaining intestinal peristalsis and growth of body tissues.

Iron

(i) Iron is required for haemoglobin synthesis.

(ii) Iron is essential both for transportation of oxygen to tissues and for operation of oxidative
systems within the tissue cells.

Magnesium
(i) Magnesium is required as a catalyst for many intracellular enzymatic reactions, particularly
those relating to carbohydrate metabolism.
(ii) Mg is the central metal atom in chlorophyll
Iodine
Iodine is used in the synthesis of thyroid hormones.
Zinc
(i) Zinc is a constituent of carbonic anhydrase, present in RBCs helping in CO transport.
2
(ii) Zinc is a component to lactic dyhydrogenase, important for the interconversion between pyruvic
acid and lactic acid
(iii) Zinc is a component part of some peptidases and therefore is important for digestion of proteins
in the alimentary canal
Cobalt
(i) Cobalt helps in erythropoiesis and in the activities of some enzymes.
.
(ii) It is present in vitamin B
12
Copper
(i) Copper helps in the utilisation of iron.
(ii) Copper deficiency may produce anaemia because of failure in iron utilisation.
Molybdenum
(i) Molybdenum is a constituent of oxidase enzymes (xanthine oxidase)
(ii) Molybdenum plays an important role in biological nitrogen fixation
Fluorine
(i) Fluorine maintains normal dental enamel and prevents dental caries.
(ii) Exessive intake of fluorine cause fluorosis characterized by mottled teeth and enlarged bones.

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.

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(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.

Sr. Name of Source Deficiency


No. Vitamins Diseases

1 Vitamin A Fish liver oil, carrots, Xerophthalmia


(Retinol) butter and milk (hardening of cornea of eye)
Night blindness
2 Vitamin B1 Yeast, milk, Beri beri (loss of appetite,
(Thiamine) Green retarded growth)
Vegetables and cereals
and grams

3 Vitamin B2 Milk, egg white, Cheilosis (fissuring at corners of mouth and lips),
(Riboflavin) liver, Kidney digestive disorders and burning sensation of the skin

4 Vitamin B6 Yeast, milk, Convulsions


(Pyridoxine) egg yolk, cereals
and grams

5 Vitamin B12 Meat, fish, Pernicious anaemia (RBC deficient in haemoglobin)


(Cyanocobal- egg and curd
amine)

6 Vitamin C Citrus fruits, scurvy (bleeding gums)


(Ascorbic amla and green leafy
acid) vegetables

7 Vitamin D Exposure to sunlight, Rickets (bone deformities in children) and osteo-


(Calciferol) fish malacia (soft bones and joint pain in adults)
and egg yolk

8 Vitamin E or Eggs, Milk, Fish, Sterility (loss of sexual power and reproduction)
Jocopherolr Wheat germ oil colton
( and ) seed oil etc.
or
Antisterility
factor

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POLYMERS
The term polymer is used to describe a very large molecule that is made up of many repeating small
molecular units. These small molecular units from which the polymer is formed are called monomers.
The chemical reaction that joins the monomers together is called polymerisation. Starting from n
moleculer of a compound M, linking in a linear manner will form polymer xM(M)n2My. The nature of
linkages at the terminal units i.e. Mx and My depends upon the mode of reaction used in making the
polymers.
Homopolymers and Copolymers
Polymers which are formed by only one type of monomer are called Homopolymers. Some examples of
homopolymers and their monomers are given below :
Homopolymer Monomer
Starch Glucose
Cellulose Glucose
Glycogen Glucose
Dextrin Glucose
Inulin Fuctose
Polyethylene Ethylene
Polyvinyl chloride Vinyl chloride
Teflon Tetrafluoro ethylene
Nylon6 Caprolactam
Polystyrene Styrene
Orlon (Acrilan) Acrylonitrile
Plexiglas (Lucite) Methyl methaacrylate
Polyvinyl acetate Vinyl acetate
Polymers, which are formed by more than one type of monomers are known as copolymers. Some
examples are given below in the table:
Copolymer Monomers
Saran Vinyl chloride and vinylidene chloride
SAN Styrene and acrylonitrile
ABS Acrylonitrile, butadiene and styrene
Butyl rubber Isobutylene and Isoprene
BunaS, SBR Styrene and Butadiene
BunaN, NBR Acrylonitrile and Butadiene
Nylon66 Hexamethylen diamine and Adipic acid
Terylene Terephthalic acid and ethylene glycol

Types of copolymers
Depending upon the distribution of monomer units, the following types of copolymers are possible.
(1) Random Copolymer
If the monomer units have random distribution throughout the chain, it is called random copolymer. For
example, if the monomer A and monomer B undergo copolymerisation then the structure of the random
copolymer is
nA + nB AABABBABAAA B
segment of random copolymer
(2) Alternating Copolymer
If the two monomer units occur alternatively throughout the polymer chain, it is said to be alternating
copolymer. For example,
nA + nB ABABA B
segment of alternating copolymer
The exact distribution depends upon the proportion of the two reactant monomers and their relative
reactivities. In practice neither perfectly random nor perfectly alternating copolymers are usually
formed. However, most copolymers tend more towards alternating type but have many random
imperfections.

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(3) Block Copolymer


Polymers in which different blocks of identical monomer units alternate with each other are called block
copolymers.
For example,
BBAAAAAABBBBBBAA
segment of block copolymer
Block copolymer can be prepared by initiating the radical polymerisation of one monomer to grow
homopolymer chains, followed by addition of an excess of the second monomer.

(4) Graft Copolymer


Polymers in which homopolymer branches of one monomer unit are grafted onto a homopolymer chain
of another monomer unit are called graft copolymers. For example:
AAAAAAAAAA
B B B B
B B B B
B B B B

(Segment of a graft copolymer)


Graft copolymers are prepared by -irradiation of a homopolymer chain in the presence of a second
monomer. The high energy radiation knock out H-atoms from the homopolymer chain at random points
thus generating radical sites that can initiate polymerisation of the second monomer.

CLASSIFICATION OF POLYMERS
Polymers are classified in following ways:

(I) CLASSIFICATION BASED UPON SOURCE


(1) Natural polymers
Polymers which are obtained from animals and plants are known as natural polymers, Examples of
natural polymers are given below.
Natural polymer Monomers
1. Polysaccharide Monosaccharide
2. Proteins -L-Amino acids
3. Nucleic acid Nucleotide
4. Silk Amino acids
5. Natural Rubber (cis polyisoprene) Isoprene (2-Methyl-1, 3-butadiene)
6. Gutta purcha (trans polyisoprene) Isoprene
Natural polymers which take part in metabolic processes are known as bioplymers. Examples are
polysaccharides, proteins, RNA and DNA.

(2) Semisynthetic polymers


Polymers which are prepared from natural polymers are known as semisynthetic polymers. Most of the
semisynthetic polymers are prepared from cellulose.
Examples are: cellulose acetate, cellulose nitrate, cellulose xanthate and Rayon.

(3) Synthetic polymers


Man-made polymers, i.e. polymers prepared in laboratory are known as synthetic polymers.
Example are : PVC, polyethylene, polystyrene, nylon-6, nylon-66, nylon-610, terylene, synthetic
rubbers etc.

(II) CLASSIFICATION BASED UPON SHAPE


(1) Linear polymers
Polymer whose structure is linear is known as linear polymer. The various linear polymeric chains are
stacked over one another to give a well packed structure.

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The chains are highly ordered with respect to one another. The structure is close packed in nature,
due to which they have high densities, high melting point and high tensile (pulling) strength. Linear
polymers can be converted into fibres.
Note :
(i) All fibers are linear polymers. Examples are cellulose, silk, nylon, terylene etc.
(ii) Linear polymers may be condensation as well as addition polymers. Examples are cellulose,
Polypeptide, nucleic acid, nylon, terylene etc.

(2) Branched chain polymers


Branched chain polymers are those in which the monomeric units constitute a branched chain. Due to
the presence of branches, these polymers do not pack well. As a result branched chain polymers have
lower melting points, low densities and tensile strength as compared to linear polymers.

(3) Cross-linked or Three Dimensional network polymers


In these polymers the initially formed linear polymeric chains are joined together to form a three
dimensional network structure. These polymers are hard, rigid and brittle. Cross-linked polymers are
always condensation polymers. Resins are corss linked polymers.

CLASSIFICATION BASED UPON SYNTHESIS


(1) Condensation polymerisation
(i) They are formed due to condensation reactions.
(ii) Condensation polymerisation is also known as step growth polymerisation.
(iii) For condensation polymerisation, monomers should have at least two functional groups. Both
functional groups may be same or different.
(iv) Monomers having only two functional group always give linear polymer.
For example,

O O
Condensation
nNH2RNH2 + nHOOCRCOOH + (n1)H2O
reaction NHRNHCRC n
Polyamide
O O
O O
Condensation
nHOROH + nHO CRCOH + (n1)H2O
reaction OROCRC n
Polyester

O
Condensation n
nNH2RCOOH + 1 H2O
reaction NHRC n 2
(v) Condensation polymers do not contain all atoms initially present in the monomers.
Some atoms are lost in the form of small molecules.
(vi) Monomer having three functional groups always gives cross-linked polymer.
Examples are : Urea-formaldehyde resin, phenol-formaldehyde resin.

(3) Addition polymerisation


(i) Polymers which are formed by addition reaction are knowns as addition polymers.
(ii) If monomer is ethylene or its derivative, then addition polymer is either linear polymer of
branch-chain polymer.

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Examples are : polystyrene, polytetrafluoroethylene, polyacrylonitrile etc.


CH2=CCH=CH2
(iii) If monomer is 1, 3-butadiene or 2-substituted-1, 3-butadiene G , then
polymer is always branched chain polymer.
G G
nCH2=CCH=CH2 CH2C=CHCH2
(Monomer) (Polymer) n
(Monomer) (Polymer)
(i) G = H: 1, 3-Butadiene (i) Polybutadiene
(ii) G = CH3; 2-Methyl-1, 3-butadiene or isoprene (ii) Polyisoprene
(iii) G = Cl; 2-Chloro-1, 3-butadiene or chloroprene (iii) Polychloroprene (Neoprene)

(iv) Addition polymers retain all the atoms of the monomer units in the polymer.
(v) Addition polymerisation takes place in three steps:
Initiation, chain propagation and chain termination.
(vi) Addition polymers are called as chain growth polymers.

Types of Addition Polymerization


(A) Radical Polymerisation:
(i) Radical polymerisation takes place in the presence of radical initiators. The radical initiator may
be any of the following :
CH3 O O CH3 CH3
H2O2, CH 3COOH, KOSOOSOK CH3COOCCH 3
CH3 O O CH3 CH3
O O CH3 CH3
C6H5COOCC6H 5 and CH 3CN=NCCH 3
CN CN
(ii) Reaction intermediate of radical polymerization is a free radical.
(iii) Radical polymerization has more chance for those monomers whose free radicals are more stable.
Examples are:
O
C6H5CH=CH2, CH2=CHCl, CH2=CHO C CH3
Styrene Vinyl chloride Vinyl acetate
CH2=CCH3 G
CH 2=CHCN COCH3 CH2=CCH=CH2(G=H, CH3 and Cl)

Acrylonitrile O
(vinyl cyanide) Methyl methacrylate 2-substituted-1,3-butadiene
(iv) Radical polymer has linear as well as branched chain structure
Most of the commercial addition polymers are vinyl polymers obtained from alkenes and their
derivatives CH2=CH [G is H, C6H5, R etc.]
G
This type of polymerization is preformed by heating the monomer with only a very small amount of the
initiator or by exposing the monomer to light. The general mode of radical polymerization of vinyl
monomers is depicted below:
Chain initiation step :
Initiator In

In + CH2=CH InCH2CH
G G

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Chain propagating step :



CH2=CH+InCH2CH InCH2CHCH2CH In(CH2CH)CH
n 2CH

G G G G G G
Chain terminating step :

2In(CH 2CH)n CH2CH In(CH2CH)CH
n 2CH CHCH2
(CH2CH)n In
G G G G G G
Polymer
In vinylic polymerization, various other reaction of free radicals with some other compounds present
may compete with the parent addition chain reactions. One such reaction takes place with molecules
that can react with the growing chain to interrupt the further growth. This leads to the lowering of the
average molecular mass of the polymer. Such reagents are called as chain transfer agents and include
CCl4 , CBr4 etc.
For example, in the presence of CCl4, styrene polymerises to form plystyrene of a lower average
molecular mass which also contains some chlorine what happens here is that growing polystyrene
radical which normally would add on a monomer reacts with the chain transfer agent to end the original
chain and produces a new radical. The latter initiates a new polymerization chain and thereby forms a
new polymer as depicted below.

CH2CH + CCl4 CH2CHCl + CCl3
C6H5 C6H 5
Styrene
CCl3+CH 2=CH Cl3CCH 2CH Cl 3CCH2CH(CH2CH)
n etc.
C6H5 C6H5 C6H 5 C6H5
If the chain transfer agent a radical, which is highly unreactive, the reaction chain gets terminated
such a compound thus inhibits or arrests polymerisation. Many amines, phenols, quinones etc. act as
inhibitors. So, even traces of certain impurities, which can act as chain transfer agent or an inhibitor
can interfere with the original polymerisation chain reaction. Hence, the monomers chould be free from
such inhibitors.
In case the alkene is a diene, the following kinds of polymerisation is possible:

(1) 1, 4-polymerisation
When the polymerisation takes place at C1 and C4 of butadiene, an unbranched polymer is formed. This
product is different from that formed from an alkene having a double bond, which at each of its
carbons is substituted by different groups and hence can exist either as trans-polybutadiene or
cis-polybutadiene or a mixture as shown below.

R + CH2=CHCH=CH2 RCH2CHCH=CH2CH RCH 2CH=CHCH2

H CH2 H H
C=C and C=C
R CH2 H n R CH2 CH2 n

trans-1,4 structure cis-1,4 structure


(2) 1, 2-polymerisation
Alternatively, 1, 3-butadiene can undergo polymerisation at C1 and C2 to yield the polymeric product,
polyvinly polythene.

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4 4
CH 2 CH2
3 3
CH CH
1 2 3 4 R 1 2 2
2n CH2=CHCH=CH2 R(CH2CHCH2CH )n

The double bonds in these initial polymers can be linked by further treatment with chemicals
to modify the properties of the polymers. These reactions form the basis of the formation of
rubber.
(B) Cationic Polymerisation :
(i) Polymerisation which is initiated by an electrophile is known as cationic polymerisation.
(ii) Reaction intermediate of cationic polymerisation is a carbocation.
(iii) Carbocations can undergo rearrangement leading to the formation of a more stable carbocation.
(iv) The electrophile commonly used for initiation is BF3.OEt2.
(v) Monomers that are best able to undergo polymersation by a cationic mechanism are those with
electron - donating substituents that can stabilise the carboncation. Some examples are:

O
CH2=CHCH3 CH3C=CH2 CH2=CHOC C6H5 CH=CH2
Propene CH 3 CH3 Styrene
Isobutene Vinyl acetate
(v) It is terminated by a base.

Thus, when the initiator is cationic in nature, it would generate a cationic intermediate on addition
to the double bond for propagating the addition chain process and is termed as catioic
addition polymerisation. The process is initiated by an acid. The stages of polymerisation are depicted
below.

Chain initiation step :


H + CH2 = CH CH2 CH
G G
Chain propagating step :


CH3CH + CH2 = CH CH3CHCH2CH So on
G G G G
Chain terminating step :

A
CH3CH(CH2CH)CH2CH CH3CH(CH2CH)n CH=CH + HA
G G G G G G

Cationic polymerisation is facilitated in monomers containing electron - releasing groups. Thus, isobutylene
undergoes cationic polymerisation easily as it has two electron releasing CH3 groups that will stabilize
the intermediate carbo cation.

CH3 CH3

H + CH2 = C CH 3 CH 3 C
CH3

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CH3 CH3 CH3 CH3 CH 3 CH 3



CH3C + CH 2 =C + CH2 = C CH3CCH2CCH2C
CH 3 CH3 CH 3 CH3 CH3 CH 3

(Butyl Rubber)
(C) Anionic Polymerisation:
(i) Anionic polymerisation takes place in the presence of base or nucleopile, which is initiator in this
polymerisation.
(ii) Reaction intermediate in propagation steps are carboanion.
(iii) the suitable initiator can be NaNH2 or RLi.
(iv) Those monomers undergo anionic polymerisation reaction whose anion is stable.
Example of monomers are:

CH2=CHCl CH2=CHCN CH2=CCH3 C6H5CH=CN2


Vinyl chloride Acrylonitrile COCH3 Styrene
O
Methyl methacrylate
(v) Anionic polymerisation always give linear polymer.
(iv) Anionic polymerisation termnated by an acid.
The formation of polystyrene from styrene in the presene of potassium amide is an important
example of this category of polymerisation. The mode of anionic polymerisation is depicted below:

Chain initiation step :


K+NH2 + CH2=CH NH2CH2CHK +
X X
Chain propagating step :

+
NH2CH2CH + nCH2=CH NH2CH2(CH 2CH 2)n CH K
X X X X
Chain terminating step :
+
H
NH2CH2(CH2CH2
)n CH H2NCH2(CH 2CH2CH
)n 2

X X X X

(D) Ziegler- Natta polymerisation :


(i) Addition polymerisation which takes place in the presence of Ziegler- Natta catalyst [(C2H5)3Al
and TiCl4] is known as Ziegler- Natta polymerisation or co-ordination polymerisation.
(ii) Ziegler- Natta polymerisation always gives linear, stereo-regular polymers.
(iii) Ziegler- Natta catalyst revolutionised the field of polymer chemistry because they allow the
synthesis of stronger and stiffer polymers (due to linear geometry) that have greater resistance to
cracking and heat. High density polyethylene is prepared using a Ziegler- Natta catalyst.

CLASSIFICATION BASED ON INTERMOLECULAR FORCES (SECONDARY FORCES)


(i) Intermolecular forces present between polymeric chains are (a) Van der waals forces (b)Hydrogen
bonds and (c) Dipole - dipole attractions.
(ii) Mechanical properties such as tensile strength, elasticity, toughness etc. depend upon the
secondary force present between the polymeric chains.
(iii) Magnitude of secondary forces depends upon the size of the molecule and the number of
functional groups along the polymeric chains.
Magnitude of secondary forces is directly proportional to the length of the polymeric chain. On the

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basis of magnitude of secondary forces, polymers can be diveided into the following
Five categories.
(1) Elastomes
An elastomer is a plastic that stretches and then reverts back to its original shape. It is randomly
oriented amorphous polymer. It must have some cross-links so that the chains do not slip over one
another. Very weak Van der waal forces are present in between polymeric chains.
When elastomers are stretched, the random chains stretch out, but there are insufficient Van der Waal
forces to maintain them in that configuration and position. When the stretching force is removed, they
go back to their random shape. Elastomers have the ability to stretch out over ten times their normal
length.
Important examples are vulcanized rubbers.
Note : Addition polymers obtained from butadiene and its derivatives are elastomers.
(2) Fibres
Fibres are linear polymers in which the individual chains of a polymer are held together by hydrogen
bonds and / or dipole-dipole attraction. In the fibres, the polymeric chains are highly ordered with
respect to one another.
Due to strong intermolecular forces of attraction and highly ordered geometry, fibres have high tensile
strength and least elasticity. They have crystalline character and have high melting points and low
solubility. Examples are cellulose, nylon, terylene, wool, silk etc.
Note: (i) Condensation polymers formed from bifunctional monomers are fibres in character.
(ii) Addition polymers of alkene derivatives having strong-I group are fibres in character.

(3) Thermoplastic Polymers


Thermoplastic polymers are polymers that have both ordered crystaline regions (the regions of the
polymer in which the chains are highly ordered with respect to one another) and amorphous, non
crystalline regions (the regions of the polymer in which the chains are randomly oriented).
The intermolecular forces of attraction are in between elastomers and fibres. There are no cross-links
between the polymeric chains. Thermoplastic polymers are hard at room temperature, but when they
are heated, the individual chains can slip past one another and the polymer become soft and viscus.
This soft and viscous material become rigid on cooling. The process of heating softening and cooling
can be repeated as many times as desired without any change in chemical composition and mechanical
properties of the plastic. As a result, these plastics can be moulded into toys, buckets, telephone and
television cases.
Some common examples are : polyethene polypropylene, polystyrene, polyvinylchloride, teflon etc.
Note : Addition polymers obtained from ethylene and ethylene derivatives are thermoplastic polymers.

(4) Thermosetting Polymers


Polymers which become hard on heating are called thermosetting polymers. Thermosetting polymers
can be heated only once when it permanently sets into a solid, which cannot be remelted by heating.
Thermosetting polymers are cross-linked polymers. Greater the degree of cross- linking that exist, the
more rigid is the polymer. Cross-linking reduces the mobility of the polymer chains, causing them to be
relatively brittle materials, the hardening on heating is due to the extensive cross-linking between
different polymer chains to give a three dimensional network solid. Examples are : phenol formaldehyde
resin, urea-formaldehyde resin, melamine- formaldehyde resin.

DIFFERENCE BETWEEN THERMOPLASTIC AND THERMOSETTING POLYMERS


S.No. Thermoplatic polymers Themosetting polymers
1. Soften and melt on heating and become Become hard on heating and process is
hard on cooling i.e. process is reversible irreversible.
2. Can be moulded and remoulded and They can be moulded once and cannot
reshaped. be remoulded or reshaped.
3. They are addition polymers They are condensation polymers.
4. Structure is generally linear Structure is cross - linked.
RUBBER
1. Natural Rubber
Natural rubber is obtained from nearly five hundred different plants but the main source is a braziliensis

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tree. It is obtained in the form of milky sap known as latex. This latex is coagulated with acetic acid
and formic acid. The coagulated mass is then squeezed.
The raw natural rubber is a soft gummy and sticky mass. It is insoluble in water, dilute acids and
alkalies but soluble in non-polar solvents. It has low elasticity and low tensile strength. Natural rubberis
a polymer of 2-methyl-1, 3-butadiene (isoprene). On average, a molecule of rubber contains 5000
isoprene units held together by head to tail. All the double bonds in rubber are cis, hence natural
rubber is cis-polyisoprene.

+ + + +.....

Polymerisation(1,4 addition reaction)

n
Gutta - percha is a naturally occurring isomer of rubber in which all the double bonds trans. Thus,
gutta-percha is trans-polyisoprene.
CH3 H3C CH2
Polymerisa tion C=C
nCH 2=CCH=CH 2 1,
4 addition reaction H2C H n
It is harder and more brittle than rubber. It is filling material that dentists use in root canal treatment.
In order to give strength and elasticity to natural rubber, it is vulcanized. Heating of rubber with
sulphur or sulphur containing compound at 150oC for few hours is known as vulcanisation. The essential
feature of the vulcanisation is the formation of cross-linking between the polymeric chains. This cross-
linking gives mechanical strength to the rubber. Vulcanisation process can be enhanced in the presence
of certain organic compounds known as accelerator. The common accelerators are:
CH3 S S
CH 3
Ph NH C NH Ph NCSSCN
CH3 CH3
NH
Diphenyl guanidine Tetramethylthioureadisulph
In addition, fillers such as carbon black and zinc oxide are usually added to the crude rubber before
vulcanisation in order to imporve its wearing characteristics.

Natural rubber is used for making shoes, water - proof coats and golf balls. Vulcanised rubber is used
for manufacture of rubber bands, gloves tubing and car tyres.

SYNTHETIC RUBBER OR POLYMERISATION OF DIENES

Polymers of 1, 3 - butadienes are called synthetic rubbers because they have some of the properties
of natural rubbers including the fact that they are water proof and elastic.
Synthetic rubbers have some improved properties. They are more flexible, tougher and more durable
than natural rubber.

1. Homopolymers
Monomer of this class is 2-substituted-1, 3-butadienes.
G
CH 2=CCH=CH 2 where G=H, CH3 or Cl.
polymerisation is always carried out in the presence of Zieglar-natta catalyst which gives stereo
regular polymers.

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Page # 154 BIOMOLECULES,POLYMER & POC
+ +

Zieglar - Natta catalyst

n
cis poly (1,3 butadiene)
Neoprene was the first synthetic rubber manufactured on large scale. It is also called dieprene. Its
monomer, chloroprene (2-chlorobutadiene) is prepared from acetylene.
C
Cu2Cl2 HCl
2HCCH CH 2=CHCCH CH2=CHC=CH 2
NH Cl 4
Acetylene Vinyl acetylene Chloroprene
Chloroprene undergoes free radical polymerisation to form neoprene (polychloroprene).

Cl
Cl CH 2
Zieglar Natta
nCH=CC
2 H=CH2 C=C
Catalyst
2-chloro-1,3 butadiene CH2 CH 3
or (Trans polymer
chloroprene Trans polychloroprene
or neoprene)
Many of the properties of neoprene are similar to natural rubber but neoprene is more resistant to
action of oils, gasoline and other hydrocarbons. It is also resistant to sunlight, oxygen, ozone and
heat. It is non-inflammable.
It is used for making automobile and refrigerator parts, hoses for petrol and oil containers, insulation of
electric wires and conveyor belts.

2. Copolymers
The following synthetic rubbers are example of copolymers.
Synthetic rubber Monomers
1. Buna-S, SBR (styrene-Butadiene rubber) C6H5CH=CH2 + CH2=CHCH=CH2
(25%) (75%)
2. Buna-N, NBR (Nitrile-Butadiene rubber) CH2=CHCN + CH2=CHCH=CH2
(25%) (75%)

3. Butyl rubber CH3C=CH2 + Butadiene


CH3 2%
98%
4. ABS; Acrylonitrile, Butadiene, Styrene CH2=CHCN + CH2=CHCH=CH2
+C6H5CH= CH2
(a) Thiokol : Thiokol is made by polymerising ethylene chloride and sodium polysulphide.

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ClCH2CH2Cl + NaSSNa + ClCH 2CH2Cl

Polymerisation

CH2CH2SSCH2CH2SSCH2CH2
Thiokol rubber
The repeating unit is CH2SSCH2
Thiokol is chemically resistant polymer. It is used in the manufacture of hoses and tank linings, engine
gaskets and rocket fuel when mixed with oxidising agents.

(b) BunaS (SBR : Styrene-butadiene rubber) : Buna-S rubber is a copolymer of three moles of butadiene
and one mole of styrene. In buna-S, Bu stands for butadiene, na for symbol of sodium (Na) which is
a polymerizing agent and S stands for styrene. It is an elastomer (General purpose styrene Rubber or
GRS).

CH=CH2

nCH2=CHCH=CH2 + n CH2CH=CHCH2CHCH2
1,3-Butadiene
n
Styrene

Buna-S

Buna-S is generally compounded with carbon black and vulcanised with sulpur. It is extremely resistant
to wear and tear therefore used in the manufacture of tyres and other mechanical rubber goods. It is
obtained as a result of free radical copolymerisation of its monomers.
(c) Buna-N : It is obtained by copolymerisation of butadiene and acrylonitirile (General purpose Rubber
acrylonitirle or GRA).
CN

nCH2=CHCH=CH2 + nCH 2=CH CH2CH=CHCH 2CHCH


n
CN
It is very rigid and is very resistant to action of petrol, lubricating oil and many organic solvents. It is
mainly used for making fuel tanks.
(d) Cold Rubber : Cold rubber is obtained by polymerization of butadiene and styrene at 18o to 5oC
temperature in the presence of redox system. Cold rubber has a greater tensile strength and greater
resistance to abrasion than SBR.
NYLON
Nylon is used as a general name for all synthetic fibres forming polyamides, i.e., having a protein like
structure. A number is usually suffixed with the name nylon which refers to the number of carbon
atoms present in the monomers.
(1) NYLON -66 (Nylon six, six)
It is obtained by the condensation polymerzation of hexamethylenediamine (a diamine with six carbon
atoms) and adipic acid (a dibasic acid having 6 carbon atoms).

280C
nHOOC(CH2)4COOH + nH2N(CH2)6NH2 OC(CH2) 4CONH(CH2)6NH
High pressure
Adipic acid Hexamethylene (n1)H2O n
diamine Nylon-66

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(2) NYON-6, 10 (Nylon six, ten)


It is obtained by condensation polymerisation of hexamethylenediamine (six carbon atoms) and sebacic
acid (a dibasic acid with 10 carbon atoms).
Nylon fibres are stronger than natural fibres and so are used in making cords and ropes. The fibres are
elastic, light, very strong and flexible. They have drip dry property and retain creases. It is inert
towards chemicals and biological agents. It can be blended with wool. Nylon fibres are used in making
garments, carpets, fabrics, tyre cords, ropes etc.

(3) NYON-6 (Perlon L)


A polyamide closely related to nylon is known as perlon L (Germany) or Nylon-6 (USA). It is prepared by
prolonged heating of caprolactum at 260o-270oC. It is formed by self condensation of a large number of
molecules of amino caproic acid. Since, caprolactum is more easily available, it is used for polymerization, with
is carried out in the presence of H2O that first hydrolyses the lactam to amino acid. Subsequently, the amino
acid can react with the lactam and the process goes on and into form the polyamide polymer.
Carpolactam is obtained by Backmann rearrangement of cyclohexanone oxime.

OH O NOH

[O] [O] NH 2OH

Cyclohexane Cyclohexanol Cyclohexanone Cyclohexanone


Oxime
NOH
H 2SO4 O
Backmann O 260270C
C(CH2)5NH
rearrangement H2O
NH
(six carbon atoms in the
repeating units)
Nylon-6

(4) NYON-2 NYLON-6


It is in alternating polyamide copolymerof glycine and amino caproic acid and is biodegradable.

POLYETHYLENE
Polyethylene is of two types:
(a) Low Density Poly Ethylene (LDPE) : It is manufactured by heating ethylene at 200oC under a pressure
of 1500 atmospheres and in the presence of traces of oxygen. This polymerisation is a free radical
polymerisation.
200 C
nCH2=CH2 1500
CH2CH 2
atm.
n
The polyethylene produced has a molecular mass of about 20,000 and has a branched structure. Due
to this, polyethylene has a low density (0.92) and low melting point (110oC). That is why polyethylene
prepared by free radical polymerisation is called low density polyethylene. It is a transparent polymer
of moderate tensile strength and high toughness. It is widely used as a packing material and as
insulation for electrical wires and cables.

(b) High Density Poly Ethylene (HDPE) : It is prepared by the use of Zieglar - Natta catalyst at 160C
under pressure of 6 to 7 atmosphere.
The polymer is linear chain, hence it has high density (0.97) and has high melting point (130oC). That
is why it is called high density polyethylene. It is a translucent polymer. It has greater toughness,
hardness and tensile strength than low density polyethylene. It is used in the manufacture of containers
(buckets, tubes), house wares, bottles and toys.

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PLASTICISER
A plasticiser is an organic compound that dissolves in the polymer and allows the polymer chains
to slide past one another. This makes polymer more flexible. Dibutylphthalate is a commonly use
plasticiser.

CO(CH2)3CH 3

CO(CH2)3CH 3

MELAMINE - FORMALDEHYDE RESIN


This resin is formed by condensation polymerisation of melamine and formaldehyde.

H2N N NH 2 H2N N NHCH2OH H2N N NHCH 2



+ HCHO
Polymerisation
N N N N N N

NH 2 NH2 NH2 n
(Intermediate) Melamine-formaldehyde polymer

It is a quite hard polymer and is used widely for making plastic crockery under the name melamine. The
arti cles made from thi s polymer do not break even when dropped from consi derabl e
height.

BAKELITE
Phenol-formaldehyde resins are obtained by the reaction of phenol and formaldehyde in the presence
of either an acid or a basic catalyst. The reaction starts with the initial formation of ortho and para-
hydroxymethyl phenol derivatives, which further react with phenol to form compouds where rings are
joined to each other with CH2 groups. The reaction involves the formation of methylene bridges in
ortho, para or both ortho and para positions. Linear or cross - linded materials are obtained depending
on the conditions of the reaction.

OH OH OH
CH 2OH
H+or OH

+ HCHO +

(Intermediate) CH2OH
o-and p-hydroxymethyl phenol

OH
OH OH
CH2OH
Polymerisation CH2
n

n
Linear polymer
Novolac

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OH OH
OH OH OH
CH2OH
Polymerisation
n + n CH 2 CH2 CH2 CH2

CH2OH
CH2 CH2

CH 2 CH2 CH2 CH2

OH OH OH
Cross-linked polymer (Bakelite)
POLYESTERS
Dacron is a common polyester, prepared using ethylene glycol and terephthalic acid. The reaction is
carried out at 140o to 180o C in the presence of zinc acetate and Sb2O3 as catalyst.

nHOCH2CH2OH + nHO2C CO2H OCH2CH2C C


n
O O
Dacron

The terylene fibre (Dacron) is crease resistant and has low moisture absorption. It has high tensile
strength. It is mainly used in making wash and wear garments, in blending with wood to provide better
crease and wrinkle resistance.

BIODEGRADABLE POLYMERS
By far the largest use of synthetic polymers is as plastic. A major portion of it is used as throwaway
containers and packing materials. Since plastics do not disintergrate by themselves, they are not
biodegradable over a period of time. Non-biodegradability is due the carbon-carbon bonds of
addition polymers which are inert to enzyme catalysed reaction. These polymers create pollution
problem.
Biodegradable polymers are the polymers that can be broken into small segments by enzyme catalysed
reactions using enzymes produced by microorganisms. In biodegradable polymers, bonds that can be
broken by the enzymes are inserted into the polymers. Therefore, when they are buried as waste,
enzymes present in the ground can degrade the polymer.
One method involves inserting hydrolysable ester group into the polymer. For example, when acetal (I)
is added during the polymerzation of alkene, ester group is inserted into the polymeric chains.

O
OCH2CH2 Peroxide
nRCH=CH2 + nCH2=C CH2CHCH2COCH2CH2CH 2CH 2
OCH2CH2
n
R
Ester linkage attacked by enzyme

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Aliphatic polyesters are important class of biodegradable polymers. Some examples are described
below:

(1) Poly - Hydroxybutyrate-CO--Hydroxyvalerate (PHBV)


It is a copolymer of 3-hydroxybutanoic acid and 3 hydroxypentanoic acid, in which the monomer units
are connected by ester linkages.
CH3CH(OH)CH2COOH + CH3CH2CH(OH)CH2COOH

(
OCHCH ) where R = CH3,C2H5
2 CO
n

R O

The properties of PHBV very according to the ratio of both the acids. 3-Hydroxybutanoic acid provides
stiffness and 3-hydroxypentanoic acid imparts flexibility to the co-polymer. It is used in specialty
packaging, orthopaedic devices and even in controlled drug relase. When a drug is put in a capsule of
PHBV. It is released only after the polymer is degraded. PHBV also undergoes bacterial degradation in
the environment.

(2) POLY (GLYCOLIC ACID) AND POLY (LACTIC ACID)


They constitute commercially successful biodegradable polymers such as sutures. Dextron was the
first bioadsorbable suture made for biodegradable polyesters for post - operative stitches.

MOLECULAR MASS OF POLYMER


Normally, a polymer contains chains of varying lengths and therefore, its molecular mass is always
expressed as an average. In contrast, natural polymers such as protein contains chain of identical
length and hence, have definite molecular mass.
The molecular mass of a polymer is expressed as

(a) Number average molecular mass ( M n)

Mn
NM i i

N i
i

Where Ni is the number of molecules of molecular mass Mi

(b) Weight average molecular mass ( M w)

Mw
NM i i

NM
i
i i

Where Ni is the number of molecules of molecular mass Mi. Methods such as light scattering and
ultracentrifuge depend on the mass of individual molecules and yield weight average molecular masses.

Mn is determined by employing methods which depend upon the number of molecules present in the
polymer sample viz. Colligative properties like osmotic pressure.

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The ratio of the weight and number average molecular masses ( M w/ M n) is called Poly Dispersity Index

(PDI). Some natural polymers, which are generally monodisperesed, the PDI is unity (i.e. M w= Mn ).
In synthetic polymers, which are always polydispersed, PDI > 1 because is always higher than

M n.

COMMON POLYMERS

Monomer Repeating unit Polymer

1. CH2=CH2 CH2CH2 Polyethylene


Ethylene

CH3

2. CH3CH=CH2 CH2C H2 Polypropene

Propene

3. C 6H 5CH=CH 2 CH 2CH Polystyrene


Styrene
C6H 5

4. CF2=CF2 CF2CF2 Polytetrafluoro


Tetrafluoroethylene ethylene (PTFE), Teflon

Cl

5. CH2=CHCl CH2CH Polyvinyl Chloride (PVC)

Vinyl chloride

CN

6. CH2=CHCN CH2CH Polyvinyl cyanide,

Vinyl cyanide or poly acrylonitrile, Acrylonitrile Orlon.

H3C O COOCH3

7. CH 2=CCOCH 3 CH2C Polymethyl metha acrylate,


Methyl methacrylate
CH3

Plexiglas, Lucite

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O OCOCH 3

8. CH2=CHOCCH 3 CH2CH Polyvinyl Acetate

Vinyl acetate

9. CH2 =CHCH=CH2 CH2CHCHCH2 Polybutadiene,


1, 3-butadiene Buna rubber

Cl

10. CH2=CHCl (vinyl chloride) CH2CHCCl2CH2 Saran

+
CH2=CCl2 (Vinylidene chloride)

C6H5 CN

11. C6H5CH=CH2 (Styrene) CH 2CH CHCH2 SAN

+
CH2=CHCN (acrylonitrile)

12. CH2=CHCN + CH2=CHCH=CH2 ABS


+
C6H5CH=CH2

CH3

13. CH2=CCH 2+CH 2=CCH=CH2 Butyl rubber

CH3

14. C6H5CH=CH2+CH2=CHCH=CH2 Buna-S, SBR

15. CH2=CHCN + C6H5CH=CH2 Buna-N, NBR

Cl Cl

16. CH 2=CCH=CH 2 CH2C =CHCH2 Neoprene

Cloroprene

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COOH
O O

17. + HOCH2CH2OH C COCH2CH2O Poly(ethylene

COOH

terephthalate,
Terylene, Dacron or Mylar

COOH OH
O O

18. + C CO O Kodel Polyster

COOH OH

O
COH
19. O +HOCH2CH2OH C COCH2CH2O Polyethylene
COH O O

phthatate alkyd resin


(Glyptal)

O O

20. (CH2)5 C NH(CH2)5C Nylon-6

NH

Caprolactam

O O

21. NH2(CH2)6NH2 NH(CH2)6NHC(CH2)4C Nylon-66

Hexamethylenediamine
+

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BIOMOLECULES,POLYMER & POC Page # 163

O O

HOC(CH2)4COH

Adipic Acid

O O

22. NH 2 NH2 NH NHC C Kelvar

1, 4-Diaminobenzene
+

O O

ClC CCl

Terephthaloyl chloride

OH

23. + HCHO Bakelite or resol

24. NH2CNH2 + HCHO Urea-formaldehyde resin

NH2

N N
25. + HCHO Melamine-

H2N N NH2

Malamine formaldehyde resin

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PRACICAL ORGANIC CHEMISTRY


(A) FUNCTIONAL GROUP ANALYSIS

1. Unsaturation : Alkenes & alkynes :


(a) Bayers test : Cold dil alk. KMnO4 decolourisation test
Purple colour Colourless + MnO2 (Brown ppt)
(b) Br2 water decolourisation test
Violet colourless of Br2 Colourless

2. Terminal alkynes :
Confirmed by ppt of Acetylide ion with NaNH2 or AgNO2 or Cu2Cl2NH4OH

3. Alkyl halides :
(a) If they are capable of carbocation formation then they will give ppt with AgNO3.
(b) Beilsteins test : A green colour is imported to the flame if small amount of organic compound
is taken on copper wire.

4. Alcohol :
(a) Cerric ammonium nitrate Give red colour
(b) Boil with acetic acid & conc. H2 SO4 fruity smell

(c) 2-alkanol & ethanol also give Iodoform test Yellow ppt. of CH3I on reaction with I2 + O H

5. Aldehyde & ketones :


2,4-Dinitrophenyl hydrazize (or) Braddys reagent give yellow, orange or red colour with ald. & Ketones
(2, 4-DNP)

6. Aldehydes :
(a) Tollens test Silver mirror
(b) Fehlings test {except benzaldehyde} Red colour
(c) Benedicts test Red colour
(d) Schiffs dye colour regeneration test Pink colour
(e) Gly ppt. with HgCl2.

7. Ketones :
(a) methyl ketones give haloform test
(b) -hydroxy Ketones give Tollens & Fehling tests too.

8. Carboxylic acids :
(a) Brisk effervescence with aq. NaHCO3 solution.
(b) HCOOH alone gives silver mirror test with Tollens reagent.
(c) Blue litmus red
(d) give fruity smell of reaction with alcohols.

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9. Phenols :
(a) Violet colouration with neural Fecl3
(b) Liebermann test
(c) White ppt. with Br2 water
(d) Brisk effervescence with aq. NaHCO3 is observed in case of Nitrophenols.

10. Primary amines :


(a) Carbylamine reaction Isonitriles have very distinctive foul odors
(b) Hoffmann mustard oil reaction Oily liquid with mustard like smell.

11. Aromatic 1 amine diazo test

12. Amide boil with NaOH NH3

13. Nitrobenzene Mullikqn Baker test Treat it with ZnNH4Cl then boil with Tollens reagent Silver
mirror will appear

14. Proteins :
(a) Biuret test : Also used for urea Alkaline solution of protein treated with a drop of aq CuSO4
when bluish violet colour is obtained
(b) Ninhydrin test: Protein treated with a puridine solution of ninhydrin give colour ranging from deep blue
to violet pink.

DIFFERENTATION TEST

D1. 1, 2 & 3 alcohols :


(a) Lucas test : Lucas reagent is conc. HCl + ZnCl2
(b) Victor Meyers test (RBC test)
(i) 1 Alcohol Blood red colour
(ii) 2 Alcohol Blue
(iii) 3 Alcohol Colourless

D2. 1, 2 & 3 amines :


(a) Hinsbergs reagent
(i) 1 Amine yield a clear solution from which upon acidification an insoluble material separated.
(ii) 2 Amine yield an insoluble compound which is unaffected by acid
(iii) 3 Amine yield insoluble compound
(b) Reaction with HNO2.

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1. Natural rubber is a polymer of


(1) Chloroprene (2) Isoprene
(3) 1,3-Butadiene (2) None
2. Hydroylsis of sucrose is called
(1) saponification (2) Inversion
(3) Esterification (2) Hydration
3. In vulcanization of rubber
(1) Sulphur reacts to form a new compound
(2) Sulphur cross-links are introduced
(3) Sulphur forms a very thin protective layer over rubber.
(2) All statements are correct.
4. Which of the following belong to the class of natural polymers ?
(1) Proteins (2) Cellulose
(3) Rubber (4) All of the above
5. The reaction of glucose and red P + HI is called
(1) Sandmeyers reaction (2) Reformatsky reaction
(3) Gattermanns reaction (4) Reduction
6. The reagent used in Ruff degradation is :
(1) baeyers reagent (2) Tollens reagent
(3) Fentons reagent (4) Benedicts reagent
7. Number of possible isomers of glucose is:
(1) 10 (2) 14
(3) 16 (4) 20
8. Glucose reacts with acetic anhydride to form
(1) Monoacetate (2) Tetra acetate
(3) Penta acetate (4) Hexa acetate
9. Glucose or aldohexose contains
(1) ONe CHO group
(2) Five OH groups
(3) One primary alcoholic group and four secondary alcoholic groups
(4) All are correct
10. When glucose is heated with nitric acid, the product is
(1) Gluconic acid (2) Glucaric acid
(3) Glycolic acid (4) Oxalic acid
11. Cane sugar is made of
(1) 5 membered glucose ring and 5 membered fructose ring
(2) 6 membered glucose ring and 6 membered fructose ring
(3) 6 membered glucose ring and 5 membered fructose ring
(4) 6 membered galactose ring and 6 membered fructose ring

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(A) ELEMENTAL ANALYSIS
Lassaigne Method (Detection of Elements)

Element Sodium Extract (S.E.) Confirmed Test Reactions

S.E. + FeSO4 + NaOH, FeSO4 + 2NaOH Fe(OH)2 + Na2SO4


Nitrogen Na + C + N NaCN(S.E.) boil and cool, Fe(OH)2 + 6NaOH Na4[Fe(CN)6]+ 2NaOH
BIOMOLECULES,POLYMER & POC

+ FeCl3 + conc. HCl Na4[Fe(CN)6] + FeCl3 Fe4[Fe(CN)6]3 + 3NaCl


Blue or green colour Prussian blue
(i) S.E. + sodium nitro
prusside (A) (i) Na2S + Na2[Fe(CN)5NO] Na4[Fe(CN)5NOS]
A deep violet colour (A) deep violet
Sulphur 2Na + S Na2S(S.E.) (ii) S.E. + CH3COOH (ii) Na2S +(CH3COO)2Pb PbS 2CH3COONa
+ (CH3COO)2 Pb black ppt.
A black ppt.
S.E. + HNO3 + AgNO3
(i) White ppt. soluble
in aq. NH3 confirms Cl NaX + AgNO3 AgX
(ii) Yellow ppt. ppt.
Halogen Na + Cl NaCl(S.E.) partially soluble in

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aq. NH3 confirm Br
(iii) Yellow ppt. AgCl + 2NH3(aq) [Ag(NH3)2]Cl
in soluble in aq. NH3 white ppt. soluble
confirms I
As in test for nitrogen;
instead of green or blue
Nitrogen colour, blood red NaCNS + FeCl3 [Fe(CNS)]Cl2 +NaCl
and Sulphur Na+C+N+S NaCNS(S.E.) colouration confirms blood red colour
together presence of N and S
both

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Page # 167
Page # 168 BIOMOLECULES & POLYMERS

EXERCISE I OBJECTIVE PROBLEMS (JEE MAIN)


1. Which of the following monosaccharides is a
Q.7 The pH value of the solution in which a
pentose-
particular amino acid does not migrate under
(A) Glucose (B) Fructose the influence of electric field is called its-
(C) Ribose (D) Galactose
(A) Eutectic point
Sol. (B) Neutralisation point
(C) Isoelectric point
(D) Effusion point
Sol.
Q.2 Ring structure of glucose is due to formation
of hemiacetal and ring formation between-
(A) C1 and C5 (B) C1 and C4
(C) C1 and C3 (D) C2 and C4
Sol.
Q.8 The number of essential amino acids for the
growth & maintenance of life is-
(A) 1 (B) 2
(C) 4 (D) 8
Q.3 Glucose is- Sol.
(A) Monosaccharide (B) Disaccharide
(C) Trisaccharide (D) Polysaccharide
Sol.

Q.9 Secondary structure of proteins refers to-


Q.4 Hydrolysis of sucrose is called- (A) Mainly denatured proteins and structure of
(A) Esterification (B) Saponification prosthetic group
(C) Inversion (D) Hydration (B) Three dimensional structure specially the
Sol. bond between amino acid residues that are
distant from each other in polypeptide chain
(C) Linear sequence of amino acid residue in
the polypeptide chain
(D) Regular folding patterns of continuous
Q.5 Starch is changed into disaccharide in presence portion of the polypeptide chain
of- Sol.
(A) Amylase (B) Maltase
(C) Lactase (D) Zymase
Sol.
Q.10 A pigment protein in animals is-
(A) Chlorophyll (B) Insulin
(C) Keratin (D) Haemoglobin
Q.6 The disaccharide present in milk is- Sol.
(A) Sucrose (B) Maltose
(C) Lactose (D) Cellobiose
Sol.

Q.11 The main structural feature of proteins is-


(A) An ester linkage
(B) An ether linkage
(C) The peptide linkage (D) All

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BIOMOLECULES & POLYMERS Page # 169
Sol. Q.18 The enzyme pepsin hydrolyses-
(A) Proteins to peptides
(B) Fats to fatty acids
(C) Glucose to ethyl alcohol
(D) Polysaccharides to monosaccharides
Sol.
Q.12 -Helical structure refers to the-
(A) Primary structure of protein
(B) Secondary structure of protein
(C) Tertiary structure of protein
(D) Quaternary structure of proteins
Sol. Q.19 Which one is the complimentary base of adenine
in one strand to that in the other strand of
DNA-
(A) Cytosine (B) Guanine
(C) Uracil (D) Thymine
Sol.
Q.13 Simplest amino acid is-
(A) Lysine (B) Glycine
(C) Leucine (D) Alanine
Sol.

Q.20 The base present in RNA but not found in DNA


is-
(A) Thymine (B) Uracil
(C) Adenine (D) Guanine
Q.14 Kwashirokor is a disease caused by the
Sol.
deficiency of-
(A) Vitamins (B) Hormones
(C) Blood (D) Essential amino acids
Sol.
Q.21 Calorific value is in the order-
(A) Fats > Proteins > Carbohydrates
(B) Carbohydrates > Fats > Protein
(C) Fats > Carbohydrates > Protein
Q.15 Hair, finger, nails, hoofs etc. are all made of- (D) Protein > Fats > Carbohydrates
(A) Fat (B) Vitamins Sol.
(C) Proteins (D) Iron
Sol.

Q.22 Ptyalin of saliva acts in:


Q.16 Mark the globular protein in the following- (A) Slightly acidic medium
(A) Collagen (B) Slightly alkaline medium
(B) Myoglobin or Haemoglobin (C) Neutral medium
(C) Myosin (D) Fibroin (D) All types of medium
Sol. Sol.

Q.17 The end product of protein digestion is- Q.23 Deficiency of vitamin A results in:
(A) Peptides (B) Peptones (A) Scurvy (B) Night blindness
(C) Protones (D) -Amino acids (C) Beri-beri (D) Rickets
Sol. Sol.

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Page # 170 BIOMOLECULES & POLYMERS
Q.24 Riboflavin deficiency causes- Q.31 Milk protein is-
(A) Scurvy (B) Pellagra (A) Lactose (B) Myosin
(C) Beri-beri (D) Cheilosis (C) Casein (D) Pepsin
Sol. Sol.

Q.32 Cobalt as a rare element is essential in the


Q.25 Sunshine vitamin is: synthesis of this vitamin:
(A) E (B) C (C) D (D) A (A) Vitamin C (B) Vitamin D
(C) Vitamin B1 (D) Vitamin B12
Sol.
Sol.

Q.26 A good source of vitamins A and D is:


Q.33 Which of the following is an essential amino
(A) Whole cereal (B) Cod liver oil
acid?
(C) Yeast (D) Water melon (A) Serine (B) Cysteine
Sol. (C) Glycine (D) Phenylalanine
Sol.

Q.27 Vitamin B takes part in :


(A) increase in blood pressure Q.34 Vitamin necessary for blood clotting is:
(B) decrease in blood pressure (A) E (B) C
(C) activating bone marrow (C) K (D) D
(D) maturation of RBCs Sol.
Sol.

Q.35 Scurvy is a disease caused by:


Q.28 Ascorbic acid is called as: (A) a virus
(A) Vit. C (B) Vit. A (B) deficiency of vitamin E
(C) Vit. D (D) Vit. B (C) deficiency of ascorbic acid
Sol. (D) deficiency of vitamin D
Sol.

Q.29 Cyanocobalamin is the chemical name of:


(A) Vitamin B1 (B) Vitamin B2 Q.36 Which pairing is found in DNA-
(C) Vitamin B6 (D) Vitamin B12 (A) Adenine with thymine
Sol. (B) Thymine with guanine
(C) Guanine with adenine
(D) Uracil with adenine
Sol.
Q.30 Continuous bleeding from an injured part of body
is due to deficiency of:
(A) Vitamin A (B) Vitamin E
(C) Vitamin B (D) Vitamin K
Sol. Q.37 The acidic characters of DNA and RNA are due
to:
(A) purine bases (B) sugar molecules
(C) pyrimidine bases (D) phosphoric group

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BIOMOLECULES & POLYMERS Page # 171
Sol. Q.43 Which of the following is not a reducing sugar-
(A) Sucrose (B) Galactose
(C) Glucose (D) Lactose
Sol.

Q.38 According to the Chargaffs law:


(A) A + T = G + C (B) T + A = C
AG
(C) A + T + G = C (D) 1
CT Q.44 The sulphur containing essential amino acids
Sol. bonded together in long peptide chains form-
(A) Hydrocarbons (B) Nucleic acids
(C) Organic acids (D) Proteins
Sol.

Q.39 T hose ami no aci ds w hi ch c an not b e


synthesised by animal bodies are called-
(A) Non - essential (B) Essential
(C) Energy yielding (D) Active
Sol. Q.45 Find out the example of phosphoprotein-
(A) Plasma membrane(B) Casein of milk
(C) Haemoglobin (D) Mucin of saliva
Sol.

Q.40 DNA molecule is formed of-


(A) Pentose sugar, pyrimidines and purines
(B) Pentose sugar: Phosphoric acid, pyrimidines
and purines Q.46 If a portion of DNA code is CAT, the anticodon
(C) Pentose sugar, phosphoric acid, and purines
(D) Chloridepentose sugar, phosphoric acid and for this code on t RNA will be-
pyrimidines, (A) GUA (B) GTA
Sol. (C) ATG (D) AUG
Sol.

Q.41 In DNA if 10% of guanine is present, how much


thymine is present? Q.47 How many carbon atoms can be found in a
(A) 10% (B) 20% monosaccaride-
(C) 40% (D) 80% (A) 5-6 (B) 3-5
Sol. (C) 3-7 (D) 1-5
Sol.

Q.42 In mammals carbohydrates are stored in the


form of- Q.48 The nucleotides of one polynucleotide chain
(A) Lactic acid in muscles are joined together by-
(B) Glycogen in liver and muscles (A) Weak hydrogen bonds
(C) Glucose in liver and spleen (B) Disulphide bonds
(D) Glycogen in liver and spleen (C) Phospho-diester bonds
Sol. (D) Glycosidic bonds
Sol.

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Page # 172 BIOMOLECULES & POLYMERS
Q.49 If 30% of an organisms DNA is thymine, then: Sol.
(A) 70% is purine (B) 20% is guanine
(C) 30% is adenine
(D) Both (B) and (C) are correct
Sol.
Q.55 Characters are transferred from parents to
offspring through-
(A) RNA (B) DNA
(C) Lipid (D) Protein
Q.50 Deoxyadenylic acid, deoxyguanylic acid, Sol.
deoxythymidylic acid & deoxycytidylic acid are-
(A) Necleotides of DNA
(B) Fatty acids
(C) Necleosides of DNA
(D) Nucleotides of RNA
Q.56 Which of the following groups includes all
Sol.
essential amino acids for man-
(A) Leucine, methionine, lysine & valine
(B) Tryptophan, phenylalanine, glycine &
glutamine
(C) Glutamine, valine & arginine
Q.51 Which of the following substances is involved (D) Phenylalanine , valine , lysine, glycine
in all energy transformation reactions in a living tyrosine
system- Sol.
(A) Calcium (B) Phosphate
(C) Cyclic AMP (D)Creatinephosphate
Sol.

Q.57 Base is not found in DNA is-


(A) Uracil (B) Adenine
(C) Guanine (D) Cytosine
Q.52 The base sequence for a nucleic acid segments Sol.
is given as GAG, AGG, GGA , CGA,& CCA , from
this it can be definetely concluded that it is a
segment of-
(A) tRNA (B) mRNA
(C) DNA (D)Data not sufficient
Q.58 The similarity between DNA & RNA is that both-
Sol.
(A) Are polymers of nucleotides
(B) Are always double stranded
(C) Have similar kind of sugar
(D) Have similar type of pyrimidine bases
Sol.
Q.53 Nucleic acids are made of:
(A) Proteins (B) nucleotides
(C) amino acids (D) nucleosides
Sol.
Q.59 Semi conservative method of DNA duplication
means-
(A) Newly synthesized DNA is conserved only
in one cell cycle
Q.54 A nucleoside is: (B) Newly synthesized DNA molecules have one
(A) base + sugar strand from the parent DNA molecule
(B) base + phosphate (C) Replication of DNA results in the formation
(C) sugar + phosphate of only one stranded daughter DNA
(D) base + sugar + phosphate (D) Only one strand of DNA molecule form RNA

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BIOMOLECULES & POLYMERS Page # 173
Sol. Sol.

Q.65 The fibre obtained by the condensation of


Q.60 In DNA, guanine pairs with:
(A) Cytosine (B) Thymine hexamethylene diamine and adipic acid is-
(C) Adenine (D) Uracil (A) Dacron (B) Nylon 66
Sol. (C) Rayon (D) Teflon
Sol.

Q.61 Which of the following is not a copolymer-


(A) Plexiglass (B) Buna-S Q.66 Of the following which is a step growth poly-

(C) Nylon-66 (D) Dacron mer-


Sol. (A) Bakelite (B) Polyethylene
(C) Teflon (D) PVC
Sol.

Q.62 Polymerisation in which two or more chemi-


cally different monomers take part is called- Q.67 Bekelite is-
(A) Addition polymerisation (A) Addition polymer (B) Elastomer
(B) Copolymerisation (C) Thermoplastic (D) Thermosett
(C) Chain polymerisation Sol.
(D) Homopolymerisation
Sol.

Q.68 Perlon is-


(A) Rubber (B) Nylon
(C) Terylene (D) Orlon
Sol.
Q.63 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
Q.69 Nylon-6, 6 is made by the polycondensation
(D) 1,3,5-Triamino-2,4,6-triazine
of-
Sol.
(A) Adipic acid + Hexamethylene diamine
(B) Phthalic acid + Glycerol
(C) Phenol + Formaldehyde
(D) Urea + Formaldehyde
Sol.
Q.64 Carprolactum is used to prepare which of the
polymer-
(A) Nylon 66 (B) Melamine
(C) Nylon 6 (D) PMMA

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Page # 174 BIOMOLECULES & POLYMERS
Q.70 An example of a natural biopolymer is- Q.76 The example of thermosetting plastic and
(A) Teflon (B) Neoprene thermoplastic polymer respectively is-
(C) Nylon-66 (D) DNA (A) Polystyrene, polyvinyl chloride
Sol. (B) Bakelite, polystyrene
(C) Polythene, polyacrylonitrile
(D) Polystyrene, urea formaldehyde resin
Sol.

Q.71 Natural silk is a-


(A) Polypeptide (B) Polyacrylate
(C) Polyester (D) Polysaccharide Q.77 Which of the following is wrong-
Sol. (A) PMMA is called plexiglass
(B) PTFE is called teflon
(C) SBR is called natural rubber
(D) LDPE is called low density polyethylene
Sol.

Q.72 Peptide bond is a key feature in-


(A) Polysaccharide (B) Proteins
(C) Nucleotide (D) Vitamins
Sol. Q.78 Which is not a rubber polymer-
(A) Neoprene (B) Gutta percha
(C) Buna-S (D) P.M.M.A.
Sol.

Q.73 Neoprene rubber is obtained by the polymer-


ization of -
(A) 1, 3-Butadiene
(B) 2- Methyl -1, 3-butadiene
Q.79 Match List I [polymers] with List II
(C) 2- Chloro -1, 3 butadiene
[monomers] and choose the correct answer
(D) Styrene and butadiene from the codes given below the list-
Sol. ListI [Polymer] ListII [Monomer]
A. P.A.N. a. Chloroethene
B. Natural rubber b. Caprolactum
C. Nylon6 c. Isoprene
D. P.V.C. d. Acrylonitrile
Code is-
Q.74 Which of the following is not a natural poly-
A B C D
mer-
(A) Starch (B) Cellulose (A) d c b a
(C) Glyptal (D) Glycogen (B) a b c d
Sol.
(C) c d a b
(D) b a c d
Sol.

Q.75 Which of the following is natural polymer-


(A) Polyisoprene
(B) Polybutadiene
(C) Polyethylene terephthalate Q.80 Which of the following is an addition polymer-
(D) Polyethylene (A) SBR (B) Glyptals
Sol.
(C) Terylene (D) Nylons
Sol.

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BIOMOLECULES & POLYMERS Page # 175

Exercise - II
1. Given structure is ? (A) Aldopentose (B) Ketohexose
HC O (C) Ketoheptose (D) Aldohexose
| Sol.
H C OH
|
H C OH
|
H C OH
|
CH2OH 4. Which of the following is D-glyceraldehyde ?
D ribose HC=O H
(A) Aldopentose (B) Aldohexose
(A) HOCH2 OH (B) HO CH2OH
(C) Ketopentose (D) Aldotetrose
Sol. H HC=O
CH2OH
(C) HO H (D) A and B both
HC=O
Sol.
2. Given structure ?
CH 2 OH
|
C O
|
HO C H 5. D-Glucose and L-Glucose are:
| (A) enantiomers
H C OH (B) Distereomers
|
H C OH (C) D-Glucose is optically active and L-Glucose is
| optically inactive.
H C OH (D) Not isomers
|
CH 2 OH Sol.
D sedoheptul ose
(A) Aldopentose (B) Ketohexose
(C) Ketoheptose (D) Ketohexose
Sol.

6. D-Glucose will form same osazone with -


(A) D-Mannose (B) D-Fructose
(C) D-Allose (D) Both (A) and (B)
Sol.
3. Given structure is ?

HC O
|
HO C H
|
HO C H
|
H C OH 7. Relation between D-Glucose & D-Fructose is -
| (A) C2-epimer (B) C3-epimer
H C OH (C) Functional isomer (D) Positional isomers
|
CH2OH Sol.
D mannose

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Page # 176 BIOMOLECULES & POLYMERS
8. Which of following is Oligosaccharides ? Sol.
(A) Glucose (B) Fructose
(C) Sucrose (D) Starch
Sol.

Br2
13. D-Glucose Product in known as -
H2O

(A) D-Glucitol (B) D-Gluconic acid


(C) D-Glucaric acid (D) Tartaric acid
9. Which of the following is D-Glyceraldehyde ? Sol.

CH2OH CHO
(A) H OH (B) H OH
CH CH2 OH
CHO CHO
(C) H OH (D) HO H
CH3 CH3
HO HO
Sol. 14. D-Glucose D-Fructose (X)
(A) D-Allose (B) D-Altrose
(C) D-Mannose (D) D-Glucose
Sol.

10. C2-epimer of D-Glucose is -


(A) D-Glucose (B) D-Allose
(C) D-Altrose (D) D-Mannose 15. D-Glucose Product is -
5HIO4

Sol. (A) 4HCO2H1CO2, HCHO (B) 5HCO2H, HCHO


(C) 4HCO2H1CO2, HCHO (D) 5HCHO, HCO2H
Sol.

11. C3-epimer of D-Glucose is -


(A) D-Glucose (B) D-Allose
(C) D-Altrose (D) D-Mannose
Sol.
16. Which of following pair give same Osazone-
(A) D-Glucose, Fructose (B) D-Glucose, D-Mannose
(C) D-Allose, D-Altrose (D) All
Sol.

12. Which of following Carbohydrate is Aldohexose ?


(A) D-Mannose (B) D-Glucose
(C) D-Fructose (D) Both (A) and (B)

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BIOMOLECULES & POLYMERS Page # 177

Comprehension (Q.17 to Q.20) Sol.

CH2 OH

H O H

H
(A) OH H
17. Relation between (A) and (B) is -
(A) Anomers (B) Positional isomer
HO HO (C) Functional isomer (D) Enantiomer
Sol.
H OH

CH2 OH

H O HO

H
(B) 18. Structure of B-D-Gluco pyronose is -
OH H
(A) A (B) B
(C) C (D) D
Sol.
HO H

H OH

O
HO CH2 OCH3 19. Which of compound not undergo mutarotation -
(A) A (B) B
(C) C (D) D
Sol.

H OH H CH2 OH
(C)

H OH
20. How many mole of acetic anhydride will
consumed when it reacts with compound (A)
O (A) 3 (B) 4
HO CH2 OH
(C) 5 (D) 6
Sol.

H OH H H
(D)

H OH

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Page # 178 BIOMOLECULES & POLYMERS
21. 25. In an amino acid, the carboxylic group ionises
CH2OH at p
ka1
= 2.34 and ammonium ion at
ka2
p = 9.60. The iso electric point of the amino
C=O
acid is at pH -
(A) 5.97 (B) 2.34
H OH (C) 9.60 (D) 6.97
(i) NaBH4
HO H (P) Sol.
(ii) H , H2O
H OH

CH2OH
D-sorbose
Number of stereioisomer of product (P) is -
(A) 4 (B) 10 26. Which statement is incorrect about peptide
(C) 12 (D) 16 bond ?
Sol. (A) CN bond length in proteins is loger than usual
bond length of CN bond
(B) Spectroscopic analysis shows planer structure
of C NH bond
||
O
(C) CN bond length in proteins is smaller than usual
22. The main structural features of proteins is
bond length of CN bond
-
(D) None of these
(A) Ester linkage (B) Ether linkage
Sol.
(C) Peptide linkage (D) All of these
Sol.

27. A triglyceride can have how many different


acyl groups ?
23. Which compound can exist in a dipolar
(A) 3 (B) 2
(Zwitterion) structure ?
(C) 1 (D) 4
(A) C6H5CH2CH(N=CH2)COOH
Sol.
(B) (CH3)2CHCH(NH2)COOH
(C) C6H5CONHCH2COOH
(D) HOOCCH2CH2COCOOH
Sol.

28. Which one of the following is natural polymer-


(A) Starch (B) Nylon-6
(C) Kodel (D) Buna-S, SBR
Sol.
24. Vitamins C is chemically -
(A) Ascorbic acid (B) Citric acid
(C) Aspirin (D) Aspartic acid
Sol.

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BIOMOLECULES & POLYMERS Page # 179
29. Which of the following is homopolymer ? Sol.
(A) Starch (B) Polystyrene
(C) Orlon (D) All of these
Sol.

34. Intermolecular force present in nylon-66 is-


(A) vander Waal (B) Hydrogen bond
30. Which of the following monomers can
(C) Dipole-Dipole interactions
undergoes radical, cationic as well as anionic
polymerisation with equal ease ? (D) Sulphide linkage
Sol.
(A) CH3 C CH2 (B) C6H5CH=CH2
|
CH3
(C) CH2=CHCN (D) CH2=CH2
Sol.

35. Nylon-66 is made by using -


(A) Phenol (B) Benzaldehyde
(C) Adipic acid (D) Succnic acid
Sol.

31. Zieglar-Natta catalyst is -


(A) R3Al (B) TiCl4
(C) R3Al + TiCl4 (D) R3B + TiCl2
Sol.

36. Polymer which has amide linkage is -


(A) Nylon-66 (B) Terylene
(C) Teflon (D) Bakelite
Sol.

32. Monomer of Teflon is -


(A) Monochloroethene
(B) 1,2-Difluoroethene
(C) 1, 1, 2-Trifluoroethene 37. Bekelite is prepared by the reaction between-
(D) Tetrafluoroethene (A) Phenol and formaldehyde
Sol. (B) Ethylene glycol and dimethylphthalate
(C) Urea and formaldehyde
(D) Tetramethylene glycol and hexamethylene
diamine
Sol.

33. Orlon is polymer of -


(A) Styrene (B) CF2=CF2
(C) Vinyl chloride (D) Acrylonitrile

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Page # 180 BIOMOLECULES & POLYMERS
38. Natural rubber is a polymer of - Sol.
(A) Butadiene (B) Ethyne
(C) Styrene (D) Isoprene
Sol.

43. Which one of the following is a polyamide?


(A) Teflon (B) Nylon-66
(C) Terylene (D) Bakelite
Sol.

39. Terylene is a condensation polymer of ethylene


glycol and
(A) Benzoic acid (B) Phthalic acid
(C) Salicylic acid (D) Terephthalic acid
Sol.

44. Glycosidic linkage is present in -


(A) Sucrose (B) Maltose
(C) Lactose (D) All
Sol.

40. Cellulose acetate is a -


(A) Natural polymer
(B) Semisynthetic polymer
(C) Synthetic polymer
(D) Plasticiser 45. Which of the following amino acid has lowest
Sol. is isoelectric point ?
(A) Lysine (B) Aspartic acid
(C) glycine (D) Alanine
Sol.

41. A condenation polymer among the following


polymers is - 46. Protein on hydrolysis give -
(A) Teflon (B) Polystyrene (A) -amino acid (B) -amino acid
(C) PVC (D) Dacron (C) -amino acid (D) All
Sol. Sol.

47. Which of the following aminoacid is optically


42. In elastomer, intermolecular forces are - inactive -
(A) Nil (B) Weak (A) Glycine (B) Alanine
(C) Strong (D) Very strong (C) Valine (D) Leucine

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BIOMOLECULES & POLYMERS Page # 181
Sol. 51. Which of following is structure of -D-
Glucopyranose ?

CH2 OH

H O H

H
(A)
OH H

48. Peptide linkase is present is - HO HO


(A) Protein (B) Nylon-6, 6
(C) Sucrose (D) both (A) & (B)
H OH
Sol.
CH2 OH

H HO
O

H
(B)
OH H

HO H
49. Product obtained by hyrolysis of lactose are-
(A) Glucose & fructose (B) Glucose, mannose H OH
(C) Mannose & fructose (D) Galactose, Glucose
Sol.
O
HOCH2 OH

(C)

H H H H

OH OH
50. Which of following is amino acid ?
(A) NH2CH2CO2H
(B) NH2CH2CH2CO2H
(C) NH2CH2CH2CH2CO2H (D) All
Sol.
CH2 HO O
CH2 HO

(D)

H OH H OH

H OH

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Page # 182 BIOMOLECULES & POLYMERS
Sol. 56. Which one of the following is non-reducing
sugar ?
(A) Glucose (B) Arabinose
(C) Fructose (D) Sucrose
Sol.

52. Which of the following is fully fluorinated polymer ?


(A) Neoprene (B) Teflon
(C) Thiokol (D) PVC
Sol.

57. Which one of the following is reducing sugar?


(A) Starch (B) Cellulose
(C) Glycogen (D) Fructose
Sol.

53. The monomer of the polymer


CH3 CH3

CH2 C CH2 C
is
CH3 CH3 58. In solution glucose exist in how many isomeric
forms ?
CH3 (A) Two (B) Sixteen
(A) CH2 C (B) CH3CH=CHCH3 (C) Three (D) Four
Sol.
CH3

(C) CH3CH=CH2 (D) CH3 C C CH3


| |
CH3CH3
Sol.
59. Reducing property of monosaccharide is due
to the presence of
(A) -OH group (B) Keto group
(C) Acetal group
(D) Anomeric hydroxyl group
Sol.
54. Buna-S is a polymer of -
(A) butadiene only (B) Butadiene and styrene
(C) Styrene only (D) Butadiene and nitryl
Sol.

60. Which one of the following carbohydrates will


show mutarotation ?
(A) Sucrose (B) Maltose
55. Maximum number of monosaccharide units (C) Lactose (D) Both (B) & (C)
present in oligosaccharides is Sol.
(A) 8 (B) 15
(C) 10 (D) 40
Sol.

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61. Glucose and mannose are 63. Glucose molecule reacts withX number of
(A) Anomers (B) Positional isomers molecule of phenylhydrazine to yield osazone.
(C) Functional isomers (D) Epimers The value of X is
Sol. (A) Three (B) Two
(C) One (D) Four
Sol.

62. Which of the following pairs are epimers


CHO CHO 64. Which of the following reagents cannot
distinguish between glucose and fructose ?
H C OH HO C H (A) Tollens reagent (B) Fehling solution
C OH and HO C H (C) Bendict solution (D) All of these
H
(A) Sol.
H C OH HO C H

CH2OH CH2OH
CH2OH CHO
C=O C OH 65. Cellulose is a polymer of
H
(A) Glucose (B) Fructose
HO C H HO C H (C) Ribose (D) Sucrose
OH and H C OH Sol.
H C
(B)
H C OH HO C H
CH2OH CH2OH

CHO CHO

H C OH H C OH
66. Which of the following is an example of
(C) H C OH and HO C H
Ketohexose ?
H C OH H C OH (A) Mannose (B) Galactose
(C) Maltose (D) Fructose
CH2OH CH2OH Sol.

CHO CHO

H C OH HO C H

(D) H C OH and HO C H
HO C H H C OH
67. When glucose reacts with bromine water, the
CH2OH CH2OH main product is
Sol. (A) Acetic acid (B) Saccharic acid
(C) Glyceraldehyde (D) Gluconic acid
Sol.

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68. All monosaccharide ........ Tollens reagent 73. Peptide linkage is
O O
(A) oxidises (B) reduces
(A) (B)
(C) condense with (D) add to C O C NH 2
Sol.
O O
(C) (D)
C NH NH 2 C NH
Sol.

69. The number of chiral centres in (+) glucose is


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

74. Complete hydrolysis of cellulose gives


(A) L-glucose (B) D-fructose
(C) D-ribose (D) D-glucose
Sol.
70. Protein is polymer of
(A) Amino acid (B) -Amino acid
(C) -Amino acid (D) -Amino acid
Sol.

75. Number of chiral carbons in -D-(+)-glucose


is
(A) six (B) three
(C) four (D) five
71. Amino acid may be
Sol.
(A) Neutral (B) Basic
(C) Acid (D) Any one of these
Sol.

76. The pair of compounds in which both the


compounds give positive test with Tollens reagent
is
72. The given structure of -amino acid will exist
(A) glucose and sucrose
at which pH ?
(B) fructose and sucrose
COOH (C) acetophenone and hexanal
(D) glucose and fructose
NH 3 C H Sol.

R
(A) 7 (B) 14
(C) 2-3 (D) 12
Sol.
77. Among cellulose, polyvinyl chloride, nylon, and
natural rubber, the polymer in which the
intermolecular force of attraction is the
weakest is
(A) polyvinyl chloride (B) natural rubber
(C) nylone (D) cellulose

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Sol. 82. Identify the non reducing sugar
OH
O
OH
H H
H
(A) HO
OH OH
H
OCH3 CH2OH
78. D-Glucose & L-Glucose are O
(A) Enantiomers (B) Diastereomers H3CO H O OH
(C) Epimers (D) Anomers H H
Sol. (B) (C) OH OH H
H
H 3CO OH
H 3CO H OH

OH
O
OH
H
79. Identify the pair of Epimers (D) HO OCH3
(A) D-Glucose & D-Fructose
(B) D-Glucose & L-Glucose OH
(C) D-Glucose & D-Mannose Sol.
(D) D-Glucose & D-Glucose
Sol.

83. Write the names of monomers of the following


polymers :
H H O O
(i) | | || ||
80. The number of Stereogenic centres in [
N(CH2)6NC(CH2)4Cn ]
-D-Glucose are
(A) 4 (B) 5
O H
(C) 3 (D) 2 || |
Sol.
(ii)
C(CH2)5Nn
[ 2CF2
(iii) CF ]n
Sol.

81. -D-Glucose and -D-Glucose are


(A) Epimers (B) Anomers 84. Classify the following as addition and
(C) Enantiomers (D) Acetals condensation polymers: Terylene, Bakelite,
Sol. Polyvinyl chloride, Polythene.
Sol.

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EXERCISE III SUBJECTIVE PROBLEMS (JEE ADVANCED)


Comprehension (Q.1 to Q.3) 2. What is the structure of L-Glucose ?
It is convenient at times to represent the
cyclic structures of a monosaccharide without CHO CHO
specifying whether the configuration of the
anomeric carbon atom is or . When we HO H H OH
do this, we shall use formulas such as the
H OH HO H
following
HO H H OH
CH2OH (A) (B)
CH2OH HO H H OH
H O O
HO
H OH
HO H CH2OH CH2OH
HO HO OH
H OH OH CHO
Indicates or (three-dimensional view H OH
not specified)
HO H
1. Which of the following represents the anomer
of the compound shown ? H OH
(C) (D) None of these
O HO H
HOCH 2 H
H H CH2OH
H OH Sol.

HO OH

O O
HOCH 2 H HOCH2 OH
OH H H H
(A) H OH (B) H H
HCOH
H OH HO OH ||
COH
O
H OH HO H
H OH, the given is enol form of
OHHO 3.
(C) HOCH
H2 H (D) None of these
H OH
H H CH2OH
Sol. (A) D-glucose (B) D-mannose
(C) D-fructose (D) All of these
Sol.

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MCQ : 6. Which of following compound give positive Tollens
4. Which of the following pair forms the same osazone test ?
with phenylhydrazine
(A) D-Glucose and D-Fructose OH OH
(B) D-Fructose and D-Mannose OH OH
(C) D-Glucose and D-Mannose O O
(D) D-Glucose and D-Galactose OH (B) OCH3
(A)
Sol.
OH OH
OH OH

OH
OH OCH 3
O

(C) OCH3
5. The correct statement(s) about the following OH
sugars X and Y is (are) OH
CH2OH
OH CH2OH
H O H O
HOH2C H O
H
OH H H HO H
H H
HO H O CH2OH O
(D) OH H OH OH H
H OH OH H

(X) OH H H OH

CH2OH Sol.

CH2OH H O H
H
H O O H HO
H OH
OH H
HO H OH H
H OH
(Y) Match the column :
(A) X is a reducing sugar and Y is a non-reducing 7. Column-I Column-II
sugar (A) Nylon -6, 6 (P) Condensation polymerization
(B) X is a non-reducing sugar and Y is a reducing (B) styrene (Q) Addition polymerization
sugar (C) Bakellite (R) Homo polymer
(C) The glucosidic linkages in X and Y are and (D) Teflon (S) Co-polymer
, respectively Sol.
(D) The glucosidic linkages in X and Y are and
, respectively
Sol.

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Page # 188 BIOMOLECULES & POLYMERS
8. Column-I 9. Column-I
(A) H3O
Sucrose
CH2OH (B) H3O
Maltose
O
H H (C) Lactose H3O
H
(A) Column-II
OH H
HO OH (P) Product is glucose + Fructose
(Q) Product is 2 Glucose
H OH (R) Product is Glucose + Galactose
CH2OH (S) Oligo saccharides
O Sol.
H OH
H
(B)
OH H
HO H

H OH

CH2OH
O
H OCH3
H
(C) HO OH H
H

H OH

CH2OH CH2OH
O O
HO OH
H H
(D) OH H OH H
H O H
10. Column-I Column-II
H OH H OH (A) Terylene (P) Condensation polymerization
Column-II (B) Stryrene (Q) Addition polymerization
(P) It will undergo osazone formation (C) Bakellite (R) Homo polymer
(Q) When undergo acetylation reaction with acetic (D) Teflon (S) Co-polymer
anhydride molecular weight Sol.
increases by 210
(R) It is reducing sugar
(S) It is known as -D-Glucopyranose
(T) It is not reducing sugar & not show the
mutarotation
Sol.

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EXERCISE IV PREVIOUS YEARS PROBLEMS

LEVEL I JEE MAIN


Q.4 The reason for double helical structure of DNA
is operation of [AIEEE-2003]
Q.1 The functional group, which is found in amino (A) Hydrogen bonding
acid is - [AIEEE-2002] (B) Electrostatic attractions
(A) COOH group (B) NH2 group (C) vander Waals forces
(C) CH3 group (D) Both (A) and (B) (D) Dipole-dipole interaction
Sol. Sol.

Q.5 Coordination compounds have great importance


in biological systems, In this context which of
the following statements is incorrect ?
Q.2 RNA contains - [AIEEE-2002] [AIEEE-2004]
(A) Urasil, Ribose (A) Chlorophylls are green pigments in plants
(B) Thiamine, Ribose and contain calcium
(C) Cytocine, Deoxyribose (B) haemoglobin is the red pigment of blood
(D) Adenine, Deoxyribose and contains iron
Sol. (C) Cyanocobalamin is B12 and contains cobalt
(D) CarboxypeptidaseA is an enzyme and
contains zinc
Sol.

Q.3 Complete hydrolysis of cellulose gives


[AIEEE-2003]
(A) D-glucose (B) L-glucose Q.6 Which base is present in RNA but not in DNA ?
(C) D-fructose (D) D-ribose [AIEEE-2004]
Sol. (A) Uracil (B) Cytosine
(C) Guanine (D) Thymine
Sol.

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Page # 190 BIOMOLECULES & POLYMERS
Q.7 Insulin production and its action in human body Q.10 The pyrimidine bases present in DNA are
are responsible for the level of diabetes. This [AIEEE 2006]
compound belongs to which of the following (A) cytosine and guanine
categories ? [AIEEE-2004] (B) cytosine and thymine
(A) A co-enzyme (B) A hormone (C) cytosine and uracil
(C) An enzyme (D) An antibiotic (D) cytosine and adenine
Sol. Sol.

Q.8 Identify the correct statement regarding


enzymes : [AIEEE-2004]
(A) Enzymes are specific biological catalysts
that can normally function at very high Q.11 The term anomers of glucose refers to
temperatures (T~ 1000 K) [AIEEE 2006]
(B) Enzymes are normally heterogeneous (A) a mixture of (D)-glucose and (L)-glucose
catalysts that are very specific in their action (B) enantiomers of glucose
(C) Enzymes are specific biological catalysts (C) isomers of glucose that differ in configura
that cannot be poisoned tion at carbon one (C-1)
(D) Enzymes are specific biological catalysts (D) isomers of glucose that differ in configura
that possess well-defined active sites tions at carbons one and four (C-1 and
Sol. C-4)
Sol.

Q.9 In both DNA and RNA, heterocylic base and


phosphate ester linkages are at
[AIEEE-2005] Q.12 The secondary structure of a protein refers
(A) C2' and C5 ' respectively of the sugar to [AIEEE 2007]
molecule (A) -helical backbone
(B) C5' and C2 ' respectively of the sugar (B) hydrophobic interactions
molecule (C) sequence of -amino acids
(C) C5' and C1 ' respectively of the sugar (D) fixed configuration of the polypeptide
molecule backbone
(D) C3 ' and C5 ' respectively of the sugar Sol.
molecule
Sol.

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Q.13 -D-(+)-glucose and -D-(+)-glucose are Q.17 The presence or absence of hydroxy group on
[AIEEE 2008] which carbon atom of sugar differentiates RNA
(A) epimers (B) anomers and DNA ? [AIEEE 2011]
(C) enantiomers (D) conformers (A) 1st (B) 2nd (C) 3er (D) 4th
Sol. Sol.

Q.14 The two functional groups present in a typical


carbohydrate are : [AIEEE 2009] Q.18 Which one of the following statements is
(A) OH and COOH (B) CHO and COOH correct ? [AIEEE-2012]
(C) > C = O and OH (D) OH and CHO (A) All amino acids are optically active
Sol. (B) All amino acids except glycine are optically active
(C) All amino acids except glutamic acid are optically active
(D) All amino acids except lysine are optically active
Sol.

Q.15 Which amino acid is chiral ? [AIEEE-2009]


(A) Alanine (B) Valine
(C) Prolline (D) Histidine
Sol.
Q.19 Which of the following compounds can be
detected by Molischs test ? [AIEEE-2012]
(A) Sugars (B) Amines
(C) Primary alcohols (D) Nitro compounds
Sol.

Q.16 Biuret test is not given by - [AIEEE 2010]


(A) proteins (B) carbohydrates
(C) polypeptides (D) urea
Sol.

Q.20 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
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Page # 192 BIOMOLECULES & POLYMERS
Sol. Sol.

Q. 25 Buna-N synthetic rubber is a copolymer of -


Q.21 Nylon threads are made of [AIEEE-2003]
(A) Polyamide polymer (B) Polyethylene polymer [AIEEE 2009]
(C) Polyvinyl polymer (D) Polyster polymer Cl
Sol. (A) H2C = CH CH = CH2
H2C = CH C = CH2 and
(B) H2C=CH CH = CH2 and H5C6 CH = CH2
(C)H2C = CH CN and H2C = CH CH = CH2
H2C = CH C = CH2
(D) H2C = CH CN and
CH3
Sol.

Q.22 Which of the following is a polyamide ?


[AIEEE-2005]
(A) Nylon-66 (B) Teflon
(C) Bakelite (D) Terylene
Sol.
Q.26 The species which can best serve as an
initiator for the cationic polymerization is
[AIEEE-2012]
(A) HNO3 (B) AlCl3
(C) BuLi (D) None of these
Sol.

Q.23 Which of the following is fully fluorinated


polymer- [AIEEE-2005]
(A) Teflon (B) Neoprene
(C) PVC (D) Thiokol
Sol.
Q.27 Synthesis of each molecule of glucose in
photosynthesis involves: [AIEEE-2013]
(A) 5 molecules of ATP
(B) 18 molecules of ATP
(C) 10 molecules of ATP
(D) 8 molecules of ATP
Sol.

Q.24 Bakelite is obtained from phenol by reacting


with [AIEEE 2008]
(A) CH3CHO (B) CH3COCH3
(C) HCHO (D) (CH2OH)2

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LEVEL II JEE ADVANCED


1. Which of the following pairs given positive Tollens 4. Cellulose upon acetylation with excess acetic
test ? [IIT 2004] anhydride/H2SO4 (catalytic) gives cellulose
(A) Glucose, sucrose (B) Glucose, fructose triacetate whose structure is
(C) Hexanal, acetophenone [IIT 2007]
(D) Fructose, sucrose
Sol. AcO

H OO
AcO H
OAcH
O O H
H
AcO H H OAc
OAcH
(A) O O H
H
H H OAc
O AcH
O H
H OAc

2. The two forms of D-glucopyranose obtained from


the solution of D-glucose are called : AcO
[IIT 2005] H OO
(A) isomer (B) anomer AcO H
(C) epimer (D) enantiomer OH H
O O H
Sol. H
AcO H H OH
OH H
(B) O O H
H
H H OH
OH H
O H
H OH

AcO AcO AcO

H OH H OH H OO
H H H
(C) OAcH OAcH OAcH
O O O H
3. Column-I Column-II
[IIT 2006] H OAc H OAc H OAc
(A) Cellulose (P) natural polymer
(B) nylon-6, 6 (Q) synthetic polymer AcO AcO AcO
(C) protein (R) amide linkage
H OH H OH H OO
(D) sucrose (S) glycoside linkage H H H
Sol. (D) H H H H H H
O O O H
OAcOAc OAc OAc OAcOAc

Sol.

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Page # 194 BIOMOLECULES & POLYMERS
5. Among cellulose, poly (vinyl chloride), nylon 7. The correct statement about the following
and natural rubber, the polymer in which the disaccharide is
intermolecular force of attraction is weakest [IIT 2010]
is :
[IIT 2008] OH
(A) nylon (B) Poly (vinyl chloride) O CH2OH O
H H H
(C) cellulose (D) natural rubber H (a) (b)
Sol. OH H H HO
OH OCH2CH2O CH2OH

H OH OH H
(A) Ring (a) is pyranose with -glycosidic link
(B) Ring (a) is furanose with -glycosidic link
(C) Ring (b) is furanose with -glycosidic link
(D) Ring (b) is pyranose with -glycosidic link
Sol.

6. The correct statement(s) about the following


sugars X and Y is (are) [IIT 2009]

CH 2-OH
O
H O
H HOH2C H
H
OH H OHOH CH2OH 8. The following carbohydrate is [IIT 2011]
HO O

OH H H
H OH OH
H O
(X) CH2OH HO
H O
CH2OH H HO OH
H H
O H HO OH OH
H O H H
H
OH H H OH H (A) a ketohexose (B) an aldohexose
HO (C) an -furanose (D) an -pyranose
Sol.
H OH
(Y)
(A) X is a reducing sugar and Y is a non-reducing
sugar
(B) X is a non-reducing sugar and Y is a reducing
sugar
(C) The glucosidic linkages in X and Y are and
, respectively
(D) The glucosidic linkages in X and Y are and
, respectively
Sol.
9. Give the structures of the products in the following
H
reaction Sucrose A+B [IIT 2000]
Sol.

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10. Give the structure of the products in the 14. Following two amino acids liosine and
following reaction [IIT 2000] glutamine form dipeptide linkage. What
are two possible dipeptides ?
NOH
|| NH2 NH2
| |
H
C
* D
Polymerisation
n
* [] H2N
+
COOH HOOC COOH
[IIT 2003]
Sol.
Sol.

11. Aspartame, an artificial sweetener, is a peptide


and has the following structure :
15. The structure of D-glucose is as follows :
[IIT 2004]
CH2C6H5 CHO
|
H2NCHCONHCHCOOCH3
| H OH
CH2COOH HO H
[IIT 2001] OH
H
(i) Identify the four functional groups.
(ii) Write the zwitter ionic structure. H OH
(iii) Write the structure of the amino acids obtained
from the hydrolysis of aspartame. CH2OH
(i v) Which of the two amino aci ds i s more (a) Draw the structure of L-glucose
hydrophobic? (b) Give the reaction of L-glucose with Tollens
Sol. reagent
Sol.

12. Write the structure of alanine at pH = 2 and 16. Which of the following disaccharide will not
pH = 10. [IIT 2002] reduce Tollens reagent ?
Sol. (A)
CH2OH CH2OH

O O
HO HH OH

H HO H HO
H O H

OH H OH H
13. Write down the heterogeneous catalyst involved
in the polymerization of ethylene. [IIT 2003] (B)
Sol. CH2OH CH2OH

O O
HO HH OH

H HO OH H
H O H

OH H H OH

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Page # 196 BIOMOLECULES & POLYMERS
Sol.
20. The substituents R1 and R2 for nine peptides
are listed in the table given blow. How many of
these peptides are positively charged at
pH = 7.0? [IIT 2012]

H3NCHCONHCHCONHCHCONHCHCOO
H R1 R2 H
17. Monomer A of a polymer on ozonolysis yields
two mol es of HCHO and one mol e of Peptide R1 R2
CH3COCHO. I H H
(a) Deduce the structure of A. II H CH3
(b) Write the structure of all cis-form of polymer III CH 2COOH H
of compound A. [IIT 2005] IV CH2CONH2 (CH2)4NH2
Sol. V CH2CONH2 CH2CONH 2
VI (CH2)4NH2 (CH2)4NH2
VII CH 2COOH CH2CONH 2
VIII CH2OH (CH2)4NH2
IX (CH2)4NH2 CH3
Sol.

18. What is the total number of basic grops in


the following form of lysine ? [IIT 2010] 21. The total number of lone-pairs of electrons in
melamine is [IIT(Advance) 2013]
+
H3N CH 2.CH 2.CH 2.CH 2 O Sol.
CHC

H 2N O
Sol.

22. A tetrapeptide has COOH group on alanine.


This produces glycine (Gly), valine (Val), phenyl
alanine (Phe) and alanine (Ala), on complete
19. When the following aldohexose exists in its hydrolysis. For this tetrapeptite, the number
D-configuration, the total number stereoisomers of possible sequencess (primary structures) with
in its pyranose form is [IIT 2012] NH2 group attached to a chiral center is
CHO Sol. [IIT(Advance) 2013]
CH2
CHOH
CHOH
CHOH
CH2OH
Sol.

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ANSWER KEY
EXERCISE - I
Ques. 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20

Ans. C A A C A C C D D D C B B D C B D A D B

Ques. 21 22 23 24 25 26 27 28 29 30
Ans. C A B D C B D A D D

Ques. 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50

Ans. C D D C C A D D B B C B A D B A C C D A

Ques. 51 52 53 54 55 56 57 58 59 60
Ans. B D B A B A A A B A

Qus . 61 62 63 64 65 66 67 68 69 70 71 72 73 74 75
An s . A B C C B A D B A D A B C C A
Qus . 76 77 78 79 80
An s . B C D A A

EXERCISE - II
1. A 2. C 3. D 4. C 5. A 6. D 7. C
8. C 9. B 10. D 11. B 12. D 13. B 14. C
15. B 16. D 17. A 18. B 19. C 20. C 21. B
22. C 23. B 24. A 25. A 26. A 27. A 28. A
29. D 30. B 31. C 32. D 33. D 34. B 35. C
36. A 37. A 38. D 39. D 40. B 41. D 42. B
43. B 44. D 45. B 46. D 47. A 48. D 49. D
50. D 51. B 52. B 53. A 54. B 55. C 56. D
57. D 58. C 59. D 60. D 61. D 62. C 63. A
64. D 65. A 66. D 67. D 68. B 69. A 70. B
71. D 72. C 73. D 74. D 75. D 76. D 77. B
78. A 79. C 80. B 81. B 82. D
83. (i) Hexamethylene diamine and adipic acid, (ii) Caprolactam, (iii) Tetrafluoroethene
84. Addition polymers : Polyvinyl chloride, Polythene
Condensation polymers : Terylene, Bakelite

EXERCISE-III
1. B 2. A 3. D 4. ABC 5. BC 6. ABD
7. AP, S; BQ, R; CP, S; DQ,R 8. AP,Q,R,S; BP,Q,R; CT Ans; DP,R
9. APS; BQS; CRS 10. APS; BQR; CPS; DQR

EXERCISE - IV
Level-I
Q.No. 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19
Ans. D A A A A A B D D B C A B C A,B,C,D B B B A

20 21 22 23 24 25 26 27
B A A A C C B B

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Level-II
1. B 2. B 3. AP,S; BQ,R; CP,R; DS 4. A
5. D 6. BC 7. A 8. B

H
9. Sucrose D-glucose+D-fructose
H O 2

CHO CH2OH
|
CHO
H OH
HO H HO H
H OH H OH
H OH H OH

CH2OH CH2OH
NOH
|| O O
||
10. H Polymerisation
NH
[
C(CH ]n
2 )5NH

caprolactum nylon-6 (D)


(c)
CH2C6H5
1 | 3 4

11. H2NCHCONHCHCOO CH3


| 2

CH2COOH
CH2C6H5
Aspartamine + |
H3NCHCONHCHCOOCH 3
(i) NH2gp.(1)amino gp. (ii) |
COOH gp. (2) carboxyl gp. CH2COO
CONH gp. (3) 2amide gp.
COOH gp. (4) ester gp.
CHC 6H 5
CH2C6H5 |
HO H | OH H H2NCHCOOH+H2NCHCOOH+CH3OH
H2NCHCO NHCHCO O CH3 | (B)
(iii) |
Hydrolysis
CH2COOH
CH 2COOH
(A)

(iv) B is more hydrophobic due to presence of larger organic gp., benzyl gp. (C6H5CH2).

12. At pH = 2 At pH = 12

R 3 Al TiCl4
13. nCH 2 = CH 2 (
CH )n Zi eglar Natta catalyst (R 3 Al + Ti Cl 4 ) acts as
Zieglar Natta Catalyst 2CH2

heterogenous catalyst. While Willikinsons Catalyst ((Ph3P)3.RhCl) acts as homogenous catalyst.

O
14. Peptide linkage is and it is formed by the condensatoin between NH2 group and
NHC
COOH group as follows :

COH+HNH CNH
H2O
O O
In given amino acids liosine and glutamine the two possible dipeptides are formed as follows:

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BIOMOLECULES & POLYMERS Page # 199
(i) When both NH2 gp. to COOH are condensed

NH H H NH
+
H2N COH HOC COOH

O O
2H2O

O
COOH
HN
NH
H2N
O

(ii) When -NH2 of both amino acids is used but in one terminal COOH gp. lacking -NH2 gp. is
used.

O O

HN H HOC COH

H2N COH H HN

O 2H2O

O=C COOH
HN
NH
H2N C

15. (a) The structure of L-glucose can be drawn by reversing the position of H and OH at the
second last C-atom of D-glucose given i.e.,

CHO

H OH
HO H
H OH
*
H OH
Carbon used for determination
CH2OH of D & L configuration, i.e., most
distant asymmetric carbon from
D-glucose CHO gp.

Hence structure of L-glucose will be :

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Page # 200 BIOMOLECULES & POLYMERS

CHO

HO H
H OH
HO H
*
HO H

CH2OH

Position of H and OH at C* is opposite to that in D.


(b) With Tollens reagent the terminal CHO group oxidised to COOH group as :

CHO COO

HO H HO H
H OH H OH
Tollen's
HO H HO H
reagent
* *
HO H HO H

CH2OH CH2OH

16. In structure (a), one ring has a free hemiacetal group, will hydrolyse into open chain in aqueous
solution and therefore will reduce Tollens reagent. Structure b has only acetal groups, will not hydrolyse
in aqueous solution into open chain, will not reduce Tollens reagent.

CH3 O
| O3 ||
17. (a) H2C=CCH=CH 2 2HCHO+CH3CCHO
ZnH2O
isoprene

CH2 CH2CH2 CH 2
C=C C=C
(b) Isopene H3C H H3C H
natural rubber

18. 2 19. 8 20. 4

21. 0006

H2N N NH2

N N Melamine
NH 2
Lone pairs of electrons in malamine is 6.

22. 0004
Phe Gly Val Ala
Phe Val Gly Ala
Val Gly Phe Ala
Val Phe Gly Ala
(Glycine has no chiral centre)

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