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Problem Solving Strategy

of NCERT

Organic Chemistry
Questions

By

AJNISH GUPTA & BHARTI GUPTA


Professor of Organic Chemistry

(i)

Copyright 2014 by Ajnish Gupta


All rights reserved. No part of this publication may be
reproduced, stored in a database or retrieval system, or
transmitted in any form or by any means, electronic,
mechanica l, photocopying, recording, or otherwise,
without the prior written Permission of the writter.

First Indian Reprint, 2014


This edition is manufactured in Indian and is authorized for sale only in India, Bangladesh, Pakistan, Nepal,
Sri Lanka & Maldeves.
Printed & Distributed by:
Udaan Classes Pvt. Ltd.
Rainbow building, Patna
&
Madhur Satyapushpa
Shubhash Nagar, Kota
9122057123
Price: Rs. 250/-

(ii)

Preface
The guiding principle in writing this book was to create
a textbook for students- a textbook that presents the
material in a way that they learn to solve all the questions of NCERT along with the strategy to approach
the problems.
In this book we mixed all our teaching experience of 10
yea rs a long with theora tica l a nd experimenta l
knowledge to generate a hand book for all students to
reason their way to a solution rather than memorize a
multitude of facts, hoping they dont run out of memory.
If you ask your teacher, senior or friend about NCERT,
then they will surely say that NCERT questions are very
important to solve before giving board exam or any competitive exam as it is the basic theme for any board or
competitive exa m a nd nearly a ll the questions a re
derieved from NCERT only.
But the problem in NCERT organic chemistry is that
there are a lot of intermixing of concept involve in same
chapter so many students get fear of it and generally
leave it by thinking that they can score good marks or
rank without it, but they are fooling themself.
Organic chemistry is very easy and conceptual subject
and need proper understa nding of the basics a nd
stretegy to solve the questions in corret manner.
This book will prepare your right mindset for learning
Organic Chemistry. This mindset is essentially the one
that focuses you on a small number of straight forward,
repeated, fundamental concepts and helps you to apply them in different ways to solve the variety of
problems you face in NCERT or other organic problems.
Ajnish Kumar Gupta & Bharti Gupta

(iii)

Acknowledgement
We are tha nkful to all the teachers who taught us
during the concept building session of our life specially
Dr. Nizamuddin sir, senior Chandra Vijay Rao and Dr.
Vijay Pratima Mittal madam.
We have written this book to remove the fever of
organic chemistry from mind of students.
We particularly want to thank many wonderful and
talented students whom we have taught over the years
who in turn taught us how to be a good teacher and
how we can help others.
We want to make this book as user friendly as possible,
and we will appreciate any comments that will help us
to achieve this goal in future editions.
Finally, this edition has been presented before you with
efforts to make it errors free. Any that remain are our
responsibility; if you find any, please let us know so they
can be corrected in future printing.
Ajnish Gupta & Bharti Gupta
Professors of Organic Chemistry
Ajnish@OrganicChemistry.co.in
09122057123

(iv)

Table of Contents
Unit
Topic
Page. No.
1. Organic Chemistry- Some basic
principle & techniques
01 - 46
2. Hydrocarbon
47 - 78
3. Haloalkane & Haloarenes
79 - 124
4. Alcohol, Phenol & Ether
125 - 172
5. Aldehyde, Ketone & Carboxylic acid 173 - 224
6. Amines
225 - 260
7. Biomolecules
261 - 282
8. Polymers
283 - 300
9. Chemistry in everyday life
301 - 313

(v)

Dedication
Dedicated to all those students who
are in fever of organic chemistry.

(vi)

Organic Chemistry- Som e ba sic principle s a nd T echnique s

Unit

Organic ChemistrySome basic principles and Techniques

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Objective
This unit give you an understanding of Organic chemistry- Some basic principles and Techniques and covers following topics:

What is Organic chemistry, Representation of Organic compounds, Reason for the formation of large
number of organic compounds, Functional groups,
Homologue & Homologous series, Nature of C &
H, functional groups, Saturated & unsaturated molecules, Hybridiza tion, Classification of organic
compounds, Alkyl groups, IUPAC nomenclature
& Common name of Organic molecules.
Basic understanding of isomerism in organic chemistry.
Structural isomerism Chain, Position,
Function, Metamer, Tautomer. Stereoisomerism
Configurationa l & Conforma tional. Configurational Geometrical & Optical isomerism.
Electronic effects- Inductive effect, Basic concept
of resonance, General cases of resonance, Electron
flows in bond, How to draw resonating structures,
Stabiity of resonating structrue, Mesomeric effect, Hyperconjugation, Electromeric effect;
Reaction intermediate-Carbocation, Carbanion,
Free radicals, Carbene, Nitrene, Benzyne;
Concept of Acid and Base- How to find out relative Acidic & Ba sic strength, Sca le to measure
Acidic & Basic strength
Practical organic chemistry- Methods of purification of organic compounds, qualitative & quantitative analysis of organic compounds.

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Solved Example:
Example 1.
How many and bonds are present in each of the following
molecules?
(A) HC CCH = CHCH3

(B) CH2 = C = CHCH3

Strategy.
To solve such questions, always expand the structure and count
the number of & bond keeping given basic in mind.

(A)

= 10
=3

(B)
H

=9
=2

Example 2.
What is the type of hybridisation of each carbon in the following
compounds?
(A) CH3 Cl

(B) (CH 3 )2 CO

(C) CH3 CN

(D) HCONH 2

(E) CH3 CH = CHCN


Strategy.
To find the hybridization of any atom, always count the number
of bonds & lone pairs of electrons. If

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Sum of bond + lone pair of e 2 sp hybridization
Sum of bond + lone pair of e 3 sp2 hybridization
Sum of bond + lone pair of e 4 sp 3 hybridization
As carbon have no lone pair of electrons so always count the
number of bonds in deciding the hybridization of carbon
atom.

There is no role of bond in deciding the hybridization of


any atom.
H

(A) H C Cl 4 sp

(B)

O
CH 3 CCH3
sp3 sp2 sp3

(C) CH 3 C
sp

(E)

(D) HCNH 2

sp 2

CH 3 CH=CHC
sp

sp

sp

Example 3.
Write the state of hybridisation of carbon in the following
compounds and shapes of each of the molecules.
(A) H 2 C = O

(B) CH 3 F

(C) HC N

Strategy.
Similar to above question, first expand the molecule & then
count the number of bond for deciding the hybridization of
carbon.
H

(A) H

C =O
sp2

(B) H C F
3
H sp

HC

(C)

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As shape is the rea l structure of molecule which ca n be
explained with the help of hybridization.
Generally following hybridization give following shape.
sp
Linear
sp 2
Planner
sp 3
tetrahedral

So shape of A is planner, B is tetrahedral & C is linear.


Example 4.
Expand each of the following condensed formulas into their
complete structural formulas.
(A) CH 3 CH 2 COCH2 CH3

(B) CH3 CH = CH(CH2 )3 CH3

Strategy.
To expand the molecule in correct form, always keep in mind
the valencies of some common atoms such as i.e. carbon always
form 4 bonds in neutral case.

Always keep this concept for making a neutral structure.


C

H H

H H

H,

F,

H HO H H

(A) HCCCCCH

(B)

Cl ,

Br ,

H H HH

HCC=CCCCCH
HH HH H HH

Example 5.
For ea ch of the following compounds, write a condensed
formula and also their bond-line formula.
(A) HOCH 2 CH 2 CH 2 CH(CH 3 )CH(CH3 )CH3
OH

(B)

N C CH C N

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Strategy.
To write the condensed formula, always give (CH 2 )n time for
more than one CH2 unit and (CH 3 )n for CH 3 unit.
For bond line formula, write the molecule in zig-zag form.
(A) HO(CH 2 )3 CH(CH 3 )CH(CH 3 )2 (B) CH(OH)(CN)2
zig-zag form.
OH

HO

NC

CN

Example 6.
Expand each of the following bond-line formulas to show all
the atoms including carbon and hydrogen.
(A)

(B)

(C)

OH

(D)

Strategy.
In bond line formula, the number of H at each carbon = 4 no.
of visible bond.
H
H
H
C
C H
C
H
H
C
C C
H
(A) H
C
C
H C
H
H H H H
H
H

H H

H H HH HHH H

(B)

HCCCCCCCCH
H H HH HH HH

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HH

(C) HC CCC

H
CH

H OH H

H HCH HCH H

(D) HC

CH

Example 7.
Structures and IUPAC names of some hydrocarbons are given
below. Explain why the names given in the parentheses are
incorrect.
(A) CH 3 CH CH 2 CH2 CH CH CH2 CH3
CH3
CH 3 CH 3
2,5,6-Trimethyloctane
[and not 3,4,7-Trimethyloctane]
(B)

CH 3 CH 2 CH CH 2 CH CH2 CH 3
CH 2 CH3
CH3
3-Ethyl-5-methylheptane
[and not 5-Ethyl-3-methylheptane]

Strategy.
(A) In writing the IUPAC name of organic compound, always
give minimum positions to substituents i.e. use lowest
locant for substituent.
(B) In writing the IUPAC name of orga nic compound on
identical position, numbering in chain starts according to
alphabets of substituent. The alphabet which comes first
are given lower position.

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Example 8.
Write the IUPAC names of the compounds i-iv from their given
structures.
(i)

1
2
3
4
5
6
7
8
CH 3 CH 2 CH CH2 CH2 CH CH2 CH3
OH
CH 3

Strategy.
To write IUPAC name of any compound always use following
keys
(A) Use the concept of 2 prefix + 1prefix + Word root
+ 1suffix + 2suffix in sequence.
(B) Use the concept of position then alphabet then position if
functiona l group, multiple bond or substituents are
present.
(C) For giving minimum position functional group then
multiple bond then substituent.
(D) If more than one functional groups are present, then use
the concept of priority order.
(i)

1
2
3
4
5
6 7
8
CH 3 CH 2 CHCH 2 CH2 CHCH 2 CH 3
CH3
OH
6-Methyloctan-3-ol
O

(ii)

CH 3 CH 2 CCH 2 CCH 3
6
5
4 3
2 1
Hexane-2,4- dione

3 CCH2 CH 2 CH2 COH


(iii) CH
6
5 4
3
2
1
5-Oxohexanoic acid

(iv) HC CCH=CHCH=CH 2
6 5 4
3
2
1
Hexa-1,3-dien-5-yne

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Example 9.
Derive the structure of (i) 2-chlorohexane, (ii) Pent-4-en-2-ol,
(iii) 3-Nitrocyclohexene, (iv) Cyclohex-2-en-1-ol, (v) 6-Hydroxyheptanal.
Strategy.
To make the structure from given name, always take the help
of word root. Make the chain according to word root. Number
them as 1, 2, 3 .... then place the substituent, multiple bond or
functional group over it.
OH

Cl

(i)

(ii)

6
1 2 3 4 5

1 2 3 4 5
OH

(iii)

2
3
NO 2

(iv)
3

OH
4
(v) 7 6
3
5

2 1 H
O

Example 10.
Write the structural formula of :
(A) o-Ethylanisole

(B) p-Nitroaniline

(C) 2,3-Dibromo-1-phenylpentane (D) 4 -Eth yl-1 -fluo ro-2 nitrobenzene


Strategy.
For disubstituted benzene, 2nd position is considered as ortho,
3 rd position as meta & 4 th position as para with respect to first
substituent.
NH 2
OCH
3

(A)

(B)
NO 2

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(C)

F
1 2 NO
6
2
(D) 5
3
4

Br

Ph

1 2

3
Br

4 5

Example 11.
Using curved-arrow notation, show the formation of reactive
intermediates when the following covalent bonds undergo
heterolytic cleavage.
(A) CH3 - SCH3

(B) CH3 - CN

(C) CH3 - Cu
Strategy.
In heterolytic bond cleavage, bond breaks to acquire negative
charge over more electronegative atom & positive charge over
less electronegative atom.
(A) CH 3 S CH 3
(B)

CH 3 CN

(C) CH 3 Cu

CH3 + S CH 3

CH 3 + CN
CH 3 + Cu

Example 12.
Giving justification, categorise the following molecules/ions as
nucleophile or electrophile:
+

HS - , BF3 , C 2 H 5 O - , (CH 3 )3 N , Cl, CH 3 - C = O , H2 N , NO 2

Strategy.
To solve this question, remember the basic definition of nucleophile &
electrophile.
Nucleophiles- They are e rich species with complete octet with either
negative charge or with lone pair of electrons.

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Electrophiles- They are the e deficient species with either incomplete
octet, vacant orbital or +ve charge over it.
HS , C 2 H 5O , (CH3 )3 N, H 2 N

So nucleophiles are

while

electrophiles are BF3 , Cl + , CH 3 C =O, N O2


Example 13.
Identify electrophilic centre in the following:
CH 3 CH = O, CH 3CN, CH3 I.

Strategy.
Electrophilic centre is the electron deficient centre in the
molecule. They arises due to difference in electronegativity
between two atoms so electrophilic centre in above molecules
are
CH 3HC = O

H 3C C

H 3C I

Example 14.
Which bond is more polar in the following pairs of molecules:
(A) H 3 C - H, H 3 C - Br

(B) H 3 C - NH2 , H 3 C - OH

(C) H 3 C - OH, H 3 C - SH
Strategy.
Polarity of bond is judged on the basis of electronegativity
difference. Greater is the electronegativity difference, greater
is the polarity. So
(A) CBr bond is more polar than CH
(B) CO bond is more polar than CN
(C) CO bond is more polar than CS
Example 15.
In which CC bond of CH3 CH 2 CH 2 Br, the inductive effect is
expected to be the least?

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Strategy.
As inductive effect is distance dependent so ma gnitude of
inductive effect diminishes as the number of intervening bond
increases.
Hence, between 3 rd carbon & hydrogen bond exert lea st
inductive effect.
least

CH2 CH 2 CH 2 Br
H

Example 16.
Write resonance structures of CH 3 COO - a nd show the
movement of electrons by curved arrows.
Strategy.
To write resonating structure of any molecule, first write the
structure of it and then put unshared electron or ve charge on
appropriate atoms, then draw arrow one at a time moving the
electron to get the other structure.
O
CH 3 CO

O
CH 3 C=O

Example 17.
Write resonance structures of CH 2 = CH - CHO. Indicate
relative stability of the contributing structures.
Strategy.
Resonating structure of CH2 =CHCHO will be
O
CH 2 =CHCH
I

O
CH 2 CH=CHCH
II

O+
CH 2 CH=CHCH
III

Relative stability of resonating structures are judged by


generally these following points.

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(A) Neutral molecules are generally more stable than charged.
(B) Greater the number of bond, greater will be the stability.
(C) Structure with complete octet for each atom is generally
more stable than those in which atleast one atom have
incomplete octet.
(D) Structures with negative charge on electronegative atom
& positive charge on electropositive atom is more stable
than those in which electronegative atom have positive
charge & electropositive atom have negative charge.
(E) Two similar charge present neares to each other creates
electronic repulsion which destabilize the molecule but two
dissimilar cha rge present nearer to each other crea tes
electronic attraction and stabilize the molecule.
(F) Resonating structure with linear conjugation is more stable
than structure with cross conjugation.
So rela tive sta bility of resona ting structures of
CH2 =CHCHO will be I > II > III.
Example 18.
Explain why the following two structures, I and II cannot be
the major contributors to the real structure of CH 3 COOCH 3 .
O

CH 3 COCH 3
I

CH 3 C=OCH 3
II

Strategy.
Ist structure is less contributor as it has atom with incomplete
octet while IInd structure is less contributor because of charge separation
of positive & negative charge.
Example 19.
+

Explain why (CH3 )3 C is more stable than CH 3 C H2 and C H3 is


the least stable cation.

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Strategy.
Stability of carbocation is generally decided by electronic effect
such as resonance, hyperconjugation & inductive effect. Greater
is the positive electronic effects, greater is the stability. So,

(CH 3 )3 C CH 3 C H 2 CH 3
9 HC
3 HC
0 HC

Example 20.
On complete combustion, 0.246g of an organic compound gave
0.198g of carbon dioxide and 0.1014g of water. Determine the
percenta ge composition of ca rbon and hydrogen in the
compound.
Strategy.
% composition of C & H in compound will be
% of C =

12 mass of CO2 100


44 mass of compound

% of H =

2 mass of water 100


18 mass of compound

% of C =

12 0.198 100
21.95%
44 0.246

% of H =

2 0.1014 100
= 4.58%
18 0.246

Example 21.
In Dumas method for estimation of nitrogen, 0.3g of an organic
compound gave 50mL of nitrogen collected at 300K temperature
and 715mm pressure.
Strategy.
Volume of nitrogen collected at 300K and 715 mm pressure is
50 ml.
Actual pressure = 715 15 = 700 mm

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Volume of nitrogen at STP =

273 700 50
= 41.9 mL
300 760

22,400 mL of N2 at STP weighs = 28g


41.9 mL of nitrogen weighs = 28 41.9 g
22400
% of nitrogen = 28 41.9 100 17.46%
22400 0.3
Example 22.
During estimation of nitrogen present in an organic compound
by Kjeldahls method, the ammonia evolved from 0.5g of the
compound in Kjeldahls estima tion of nitrogen, neutralized
10mL of 1 M H 2 SO 4 . Find out the percentage of nitrogen in
the compound.
Strategy.
1M of 10mL H 2 SO4 1M of 20mL NH3
1000mL of 1M NH3 contains 14g N
20mL of 1M NH3 contain
So % of N

14 20
gN
1000

14 20 100
56.0%
1000 0.5

Example 23.
In Carius method of estimation of halogen, 0.15g of an organic
compound gave 0.12 g of AgBr. Find out the percentage of
bromine in the compound.
Strategy.
Molar mass of AgBr = 108 + 80 = 188 g/mol
188 g AgBr contains 80 g Br

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So 0.12 g AgBr contains

Hence, % of Br

80 0.12
g Br
188

80 0.12 100
= 34.04%
188 0.15

Example 24.
In sulphur estimation, 0.157 g of an organic compound gave
0.4813 g of barium sulphate. What is the percentage of sulphur
in the compound?
Strategy.
Molecular mass of BaSO4 = 137 + 32 + 64 = 233 g
233 g BaSO4 contains 32 g S
So, 0.4813 g BaSO4 contains
% of S

32 0.4813
gS
233

32 0.4813 100
= 42.10%
233 0.157

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Exercise Problems:
Exercise Problem 1.
Wha t are hybridisation states of each carbon atom in the
following compounds?
CH2 = C = O, CH 3 CH = CH 2 , (CH 3 )2 CO, CH2 = CHCN, C 6 H 6

Strategy.
To write the hybridiza tion of any atom, always count the
number of bond & lp of e. If
Sum of bond + lp = 2 sp hybridization
Sum of bond + lp = 3 sp2 hybridization
Sum of bond + lp = 4 sp3 hybridization
So hybridization state of each carbon atom will be
O

CH 2 =C=O
sp

CH 3 CH=CH2

sp 3

sp2

sp 2 sp2
sp2

CH 3 CCH 3
sp 3 sp2 sp3

sp2

CH 2 =CHCN
sp2

sp2

sp 2

sp

sp2

Exercise Problem 2.
Indicate the and bonds in the following molecules :
C 6 H 6 , C 6H 12 , CH2 Cl 2 , CH 2 = C = CH 2 , CH 3NO 2 , HCONHCH 3

Strategy.
To find total number of & bonds present in any molecule,
first expand the molecule and then look for single, double &
triple bond. Single bond are only bond, double bond have

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1 & 1 bond while triple bond have 1 & 1 bonds.

H
H

H H HH
H

H
HH HH

H
H
Cl

Cl

H
H
H

H
O

O
N

Exercise Problem 3.
Write bond line formulas for : Isopropyl alcohol, 2,3-Dimethyl
butanal, Heptan-4-one.
Strategy.
To draw bond line formulas of any compound, first draw the
skelelon of ca rbon taking the help of word root of IUPAC
nomenclature & then add substituent or functional group on
appropriate position in it.
OH

O
3

7 6 5 4 32 1
Iso-propyl alcohol 2,3-Dimethylbutanal Heptan-4-one
1 H

Exercise Problem 4.
Give the IUPAC names of the following compounds :
(A)

18

(B)

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CN

Organic Chemistry- Som e ba sic principle s a nd T echnique s


(C)
(E)

(D)
O
Cl

Br

Cl

(F) Cl 2 CHCH 2 OH

Strategy.
To write the IUPAC name of any compound, always use
(A) 2prefix + 1prefix + word root + 1suffix + 2suffix in
sequence.
(B) Use the concept of position then alphabet then position if
functiona l group, multiple bond or substituents are
present.
(C) For giving minimum position- Functional group- multiple
bond- Substituent.
(D) If more than one functional groups are present, then use
the concept of priority order.

(A)

(C)

CN
1
3
4
2
(B)
3-Methylpentane nitrile
5

Propylbenzene

4 5 6
7

1
3
2,5-Dimethylheptane

2 3 4
6
5
7
Cl Br
(D)
3-Bromo-3-chloroheptane
1

(E)

Cl 3 2 1 H
3-Chloropropanal

2
1
ClCHCH 2 OH

(F)

Cl
2,2-Dichloroethanol

Exercise Problem 5.
Which of the following represents the correct IUPAC name of
the compounds concerned ?
(A) 2,2-Dimethylpentane or 2-Dimethylpentane
(B) 2,4,7-Trimethyloctane or 2,5,7-Trimethyloctane

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(C) 2-Chloro-4-methylpentane or 4-Chloro-2-methylpentane
(D) But-3-yn-1-ol or But-4-ol-1-yne.
Strategy.
To solve such questions, first draw the incorrect structures from
given IUPAC name taking the help of word root of IUPAC &
the correct it using main above concept.
4
1 2 3
5
(A) 2,2-Dimethylpentane (correct)
2-Dimethylpentane (incorrect)

If more than one substituents are present in molecule, then


indicate the position of each substituent.
8
1 2 34 56 7
(B) 2,4,7-Trimethyloctane (correct)
2,5,7-Trimethyloctane (incorrect)

Always place the substituents at minimum position.


Cl
2 4
1
3
5
(C) 2-Chloro-4-methylpentane (correct)
4-Chloro-2-methylpentane (incorrect)

If position of substituents are same from both end, then


substituent with lower alphabet are given lower position.
HO

4
1 2 3
(D) But-3-yn-1-ol (correct)
But-4-ol-1-yne (incorrect)

If compound have functional group as well as multiple bond


then functional group is given lower position.

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Exercise Problem 6.
Draw formulas for the first five members of each homologous
series beginning with the following compounds.
(A) H - COOH (B) CH 3 COCH3 (C) H - CH = CH 2
Strategy.
(A) First five member of HCOOH will be
O

HCOH
I

CH 3 COH
II

CH 3 CH 2 COH
III

O
CH 3 CH 2 CH2 COH
IV

O
CH 3 CH 2 CH2 CH 2 COH
V

(B) First five member of CH 3 COCH3 will be


O
CH 3 CCH 3
I

CH 3 CCH2 CH 3
II

CH 3 CCH 2 CH2 CH 3
III
O

CH 3 CCH2 CH 2 CH 2 CH 3
IV

CH 3 CCH 2 CH 2 CH 2 CH 2 CH 3
V

(C) First five member of H CH CH 2 will be

CH 2 =CH2
I

CH 3 CH=CH 2
II

CH 3 CH 2 CH2 CH=CH 2
IV

CH 3 CH 2 CH=CH 2
III

CH 3 CH 2 CH 2 CH 2 CH=CH2
V

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Exercise Problem 7.
Give condensed and bond line structural formulas and identify
the functional group(s) present, if any, for :
(A) 2,2,4-Trimethylpentane
(B) 2-Hydroxy-1,2,3-propanetricarboxylic acid
(C) Hexanedial
Strategy.
The condensed & bond line formula of any compound can be
drawn by taking the help of word root.
CH 3

CH 3

CH 3 CCH 2 CHCH 3

(A)

CH 3
condensed form

&
bond line formula

2,2,4-Trimethylpentane
OH

HOOCCH2 CCH 2 COOH &


COOH
condensed form

(B)

OH O

HO

OH
OH
O
bond line formula

2-Hydroxy-1,2,3-propanetricarboxylic acid

HCCH 2 CH 2 CH 2 CH2 CH H

(C)

H
O
bond line formula

condensed form
Hexanedial

Functional group present in (B) are alcohol & carboxylic acid


& (C) is aldehyde while (A) do not have any functional group.

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Exercise Problem 8.
Identify the functional groups in the following compounds
NH 2

CHO

(A)

(B)
OMe
OH

OCH 2 CH 2 N(C 2 H 5 )2

(C)
Strategy.

CH=CH NO 2

Functional groups present in following compounds are


Aldehyde

CHO

Ether

(A)

OMe
OH

Phenol

NH 2

(B)

Aromatic 1amine
Ether

3amine

OCH 2 CH 2 N(C 2H 5 )2

Ethylenic double bond

(C)

CH=CH NO 2

Nitro

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Exercise Problem 9.
Which of the two: O 2NCH 2 CH 2 O- or CH 3CH2 O - is expected to
be more stable and why ?
Strategy.
Stability of any molecule depends on the dispersion of electron
density. Greater is the dispersion of charge, greater is the
stability. So,
O 2NCH 2 CH 2 O is more stable than CH3 CH 2 O because
NO 2 group withdraws electron density by I effect in first
which disperses ve charge while CH3 group donates electron
density by +I effect which intensity the negative charge.

O2N

CH2

CH2

CH3

(more stable)

CH2

(less stable)

Exercise Problem 10.


Explain why alkyl groups act as electron donors when attached
to a system.
Strategy.
Alkyl groups acts as electron donors when attached to a
bonded system of C=C bond because of hyperconjugation. In
this electronic effect CH sigma bond overlap with adjacent
bond.
H
H C CH = CH2
H
(Propene)

H
H C = CH CH 2
H+

Exercise Problem 11.


Draw the resonance structures for the following compounds.
Show the electron shift using curved-arrow notation.
(A) C 6 H 5OH

24

(B) C 6 H 5 NO 2

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(C) CH3 CH = CHCHO

(D) C 6 H 5 - CHO

(E) C 6 H 5 - CH2

(F) CH3 CH = CH C H 2

Strategy.
To write resonating structure of any molecule, first write the
structure of it and then put unshared electron or charge if
present on appropriate atom & then draw arrow one at a time
by moving the electrons to get other structures.

.OH

OH

OH

OH

OH

(A)

O O

O O

O O
N

O O
N

O
N

(B)
O

(C) CH CH = CH C H
3

CH 3 CH CH = C H

CH

CH

CH

CH

CH

CH2

CH 2

CH 2

CH 2

CH 2

(D)

(E)

(F)

CH 3 CH = CH CH 2

CH 3 CH CH = CH 2

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Exercise Problem 12.
Wha t are electrophiles and nucleophiles ? Expla in with
examples.
Strategy.
Electrophile- They are the electron deficient species which have
capacity to accept a pair of e. This electron deficiency may be
of seen as
(A) Positive charge such as H +, Cl+, Br+, NO2+ , NO+, R+, RCO+
etc.
(B) Incomplete octet such as BF3 , AlCl 3 .
(C) Vacant orbital- Such as FeCl 3 , SiCl 4 , SbCl 5 etc.
Nucle ophile - They are electron rich species which ha ve
capability to donate a pair of e. They have either ve charge or
have lone pair of electrons with complete octet.

(A) Negative charge- Such as X , OH , NH 2 , O R etc.


(B) Lone pair of e- Such as NH 3 , H 2 O, CH 3OH etc.
Exercise Problem 13.
Identify the reagents shown in bold in the following equations
as nucleophiles or electrophiles:
(A) CH3 COOH +HO CH 3 COO - + H 2 O

(B) CH3 COCH 3 +CN (CH 3 )2 C(CN)(OH)


+

(C) C 6 H 5 + CH 3 CO C 6 H 5 COCH 3
Strategy.
As stated above nucleophiles a re electron rich species with
either ve charge or with lone pair of electrons with complete
octct, while electrophiles are electron deficient species with
either positive charge, vacant orbital or incomplete octct. So,

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CH 3 COO + H 2O
(A) CH 3COOH + OH
(Nucleophile but acts as a base)

(B)

CH 3 CCH 3 + CN

CH3 CCH 3

(C)

CH3 CCH 3

CN

(Nucleophile)

OH
H+

H CCH3

CN
O
CCH 3

+ CH 3 C
(Electrophile)

Exercise Problem 14.


Classify the following reactions in one of the reaction type
studied in this unit.
(A) CH3 CH 2 Br + HS - CH3 CH 2 SH + Br
(B) (CH 3 )2 C = CH 2 + HCl (CH3 )2 ClC CH 3
(C) CH3 CH 2 Br + HO- CH 2 = CH 2 + H 2O + Br
(D) (CH 3 )3 C - CH 2 OH + HBr (CH3 )2 CBrCH2 CH2 CH 3 H 2 O
Strategy.
Organic reactions are mainly of 4 types(A) Substitution reaction- Here generally sigma bonds are
broken & corresponding new sigma bonds are formed.
+

(B) Addition reaction- Here generally pi bonds are broken &


corresponding 2 new sigma bonds are formed.

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+
C

(C) Elimination reaction- Here generally sigma bonds are


broken & corresponding new pi bonds are formed.
+
C

(D) Rearrangement reaction- Here generally attachment of


atom changes in carbon skeleton of substrate.
ABC

ACB

On the basis of first attack of reagent, substitution reaction is


of further 3 types.
(A) Nucleophilic substitution reaction
(B) Electrophilic substitution reaction
(C) Free radical substitution reaction
On the basis of first attack of reagent, addition reaction is also
of further 3 types.
(A) Nucleophilic addition
(B) Electrophilic addition
(C) Free radical addition
So,
(A) CH3 CH 2 Br HS
CH3 CH 2 SH Br
Here bond is broken & new bond is formed by attack of a
nucleophile so reaction is nucleophilic substitution reaction.
CH 3
|

Cl H
|

(B) CH3 C CH 2 HCl


CH 3 C C H2
|

CH3

Here bonds are broken & corresponding 2 new sigma bonds

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are formed by attack of an electrophile so reaction is electrophilic
addition reaction.

(C) CH3 CH 2 Br O H
CH 2 CH 2 H 2 O Br
In this reaction 2 sigma bonds are broken & corresponding a pi
bond is formed, so reaction is elimination reaction.
CH 3

CH3

(D) CH3 C CH 2 OH HBr CH 3 C CH2 CH3 H 2 O


|

CH 3

Br

Here again bond is broken and corresponding new bond


is formed by a ttack of a nucleophile & rea ction follows
nucleophilic substitution reaction, but as position of methyl
group cha nge in substra te to product, so rearra ngement
reaction is a lso seen along with nucleophilic substitution
reaction.
Exercise Problem 15.
What is the relationship between the members of following
pairs of structures ? Are they structural or geometrical isomers
or resonance contributors?
(A)

(B)

C =C
H

D
C= C
H

OH

(C) HCOH

HCOH

Strategy.
To find out structural & stereo isomers, always think for the
IUPAC name. If IUPAC of isomers a re different they a re
streuctural isomers but if they have same IUPAC name, then
they are stereoisomers.
To find out resonating structure, always look for the position
of bonding electron & non-bonding electron as position of
atoms remains same in all resonating structures.

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O

(A)

Pentan-3-one

Pentan-2-one

As they have different IUPAC name, so are structural isomers.


D

H
C= C

(B)

D
C =C

H
D
H
Trans-1,2-Deuteroethene Cis-1,2-Deuteroethene

As they have same IUPAC name but the spacial arrangement


of deuterium along C=C double bond is different, so a re
geometrical isomers.
(C)

OH

HCOH

HCOH

As position of atoms are same but have difference in position


of electrons, so are resonating structures.
Exercise Problem 16.
For the following bond cleavages, use curved-arrows to show
the electron flow and classify each as homolysis or heterolysis.
Identify rea ctive intermedia te produced as free radical,
carbocation and carbanion.
(A) CH 3O OCH3
(B)

(C)

(D)

30

O + OH

Br
+ E+

CH 3 O + OCH 3
O + H 2O

+ Br
E
+

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Strategy.
The following reaction follows

. .

(A) CH 3 O

O CH 3

..

CH 3 O + O CH3

Here sigma bond is broken homolytically to form free radicals.


O

O
+ OH

(B)

+ H 2O

Here base abstract proton heterolytically to form carbanion as


a reaction intermediate.
(C)

Br
+ Br

Here CBr bond is broken heterolytically to form carbocation


as a reaction intermediate.
E

(D)

+ E+

Here benzene attacks over an electrophile heterolytically to form


carbocation as a reaction intermediate.
Exercise Problem 17.
Explain the terms inductive and Electromeric effects. Which
electron displa cement effect explains the following correct
orders of acidity of the carboxylic acids?
(A) Cl 3CCOOH > Cl 2CHCOOH > ClCH 2 COOH
(B) CH3 CH 2 COOH > (CH 3 )2 CHCOOH > (CH3 )3 C.COOH
Strategy.
Inductive effect- It is a permanent displacement of electron
density along sigma bond and transmit along the carbon chain

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when two a tom have electronega tivity difference. This
transmission of polarity along bond is called as Inductive
effect.
+ +
+
C
C
C

C
C
C

Ele ctromeric effect- It is a temporary displacement of


electron density in carbon carbon multiple bond when a reagent
attacks over the substrate.

CH 2 =CH2 + Br

Br

Acidic character of any molecule depends on the stability of


conjugate base, so in both the cases inductive effect explains
the relative stability of conjugate base & acidic strength follows
(A) Cl 3CCOOH > Cl 2 CHCOOH > ClCH 2 COOH
The stability of conjugate base follows
Cl O
Cl

Cl

O > Cl

Cl
(3-I of Cl)

CH

O
C

O > Cl

(2-I of Cl)

CH 2

(1-I of Cl)

(B) CH3 CH 2 COOH > (CH 3 )2 CHCOOH > (CH 3 )3 CCOOH


The stability of conjugate base follows
O
CH3

CH2

O
O > CH 3

(Repulsion with
1 CH3 group)

32

CH

CH 3 O

O > CH 3

CH3
(Repulsion with
2 CH3 group)

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CH 3
(Repulsion with
3 CH3 group)

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Exercise Problem 18.
Give a brief description of the principles of the following
techniques taking an example in each case.
(A) Crystallisation

(B) Distillation

(C) Chromatography

Strategy.
(A) Crystallisation- In this process we convert an impure
compound into a pure crystals. This process is based on
the difference in the solubility of the compound and the
impurities in a suitable solvent. Here the impure compound
is dissolved in a solvent in which it is sparingly soluble at
room tempera ture but apprecia bly soluble a t higher
temperature.
Now solution is concentrated to get a nearly saturated
solution at higher temperature. On cooling the solution,
pure compound in the form of crystals separates.
The best exa mple of crysta llisa tion is iodoform
crystallisation with alcohol & benzoic a cid mixed with
naphthalene be purified by not water.
(B) Distillation- Distillation involves the process of heating a
liquid to convert it into the vapour and then condensing
the vapour to get back to the liquid.
This process of sepa ration is a pplied only for the
purification of liquid which boil without decomposition
a t a tmospheric pressure a nd contain non-vola tile
impurities. So mixture of two liquids having sufficient
difference in their boiling points can be separa ted and
purified by this process.
The best example are the separation of chloroform (bp
334K) & aniline (bp 457K) can be done by it.
(C) Chromatography- It is a technique for the separation,
purification & identification of constituents of mixtures.
Chromatography is based on the principle of selective
adsorption of components of a mixture between two phase
i.e. a stationary pha se and a moving pha se. Here the

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stationary phase can be a solid or a liquid while moving
phase is generally liquid or gas.
Exercise Problem 19.
Describe the method, which ca n be used to separa te two
compounds with different solubilities in a solvent S.
Strategy.
Two compounds with different solubilities is a solvent S can be
separated by the method called as Fractional crystallisation.
In this process, a hot saturated solution of these two compounds
is allowed to cool, the less soluble compound crystalises out
earlier than the more soluble compound. Now the crystals are
separated from the mother liquor & the mother liquor is again
concentrated and allowed to cool, then the crystal of the second
compound is obtained.
Exercise Problem 20.
What is the difference between distillation, distillation under
reduced pressure and steam distillation ?
Strategy.
This question is based on separation of compounds having
difference in boiling point. Distillation simply involves the
process of heating liquid to convert it into the vapours and the
condensation of the vapours to get back the liquid.

Simple distillation is applied only for purification of those


liquids which boil without decomposition and contains
non-volatile impurities.

Distillation under reduced pressure is applied for those


organic liquids which decomposes at a temperature below
their boiling point.

Steam distillation is simply co-distillation with water. This


technique is used to separate substance which are steam
volatile and are immiscible with water.

Exercise Problem 21.


Discuss the chemistry of Lassaignes test.

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Strategy.
Chemistry of La ssaigne s test- Orga nic compounds a re
covalently bonded so they are first converted to ions by fusing
with sodium at high temperature, then only we can test the
presence of perticular element in compound.
In this process we first prepare sodium extract & then test the
presence of elements.
Preparation of sodium extract- Here organic compounds are
first fused with sodium and heated upto red hot in ignition
tube. Then we broke the red hot ignition tube in water & filter
the solution. The filterate obtained on this is called as sodium
extract. Now this sodium extract can be used to detect the
presence of N, S, X in organic compound.
Test of Nitrogen- Here sodium extract is treated with ferrous
sulphate. If prussian blue colour is obtained, then compound
have presence of N.
Na C N
NaCN
FeSO 4 2NaOH
Fe(OH)2 Na 2 SO 4
Ferrous hydroxide
(green)

Fe(OH)2 6 NaCN
Na 4 [Fe(CN)6 ] 2 NaOH
Sodium ferrocyanide

On heating some Fe2+ ions are oxidized to Fe3+ ion


4 Fe 3 3 Na 4 [Fe(CN)6 ]
Fe4 [Fe(CN)6 ]3 12 Na
Ferric ferrocyanide
(Prussian blue)

Test of Nitrogen & Sulphur if present together.


Na C N S

NaSCN
Sodium thiocyanate

Fe 3 NaSCN
Fe(SCN)3 3Na
Blook red colour

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Test of sulphur- Here sodium extract is treated with lead
acetate. If black ppt is obtained, then compound have presence
of S.
Na S
Na 2 S
Na 2 S (CH 3COO)2 Pb

PbS

(Black ppt)

2 CH 3COONa

There is one more test of sulphur. Here sodium extract is treated


with sodium nitroprusside solution. If a violet colour ppt is
obtained, then compound have presence of S.
Na 2 S Na 2 [Fe(NO)(CN)5 ]

Na 4 [Fe(CN)5 NOS]
Sodium thionitroprusside
(violet ppt)

Test of halogen- Before testing halogens, sodium extract is


boiled with conc. HNO3 to decompose sodium cya nide or
sodium sulphide in the sodium extract, otherwise these ions
would interfere with silver nitrate test for halogen.
NaCN HNO 3
NaNO 3 HCN
Na 2 S HNO 3
NaNO 3 H 2 S

Now add AgNO3 to sodium extra ct. If white precipitate is


obtained which is soluble in ammonium hydroxide but insoluble
in HNO3, then it indicates the presence of Cl.
NaCl AgNO 3
AgCl NaNO 3
White ppt

If pole yellow ppt is obtained which is sparingly soluble in


ammonium hydroxide, then it indicate the presence of Br.
NaBr AgNO 3

AgBr

Pole yellow ppt

NaNO 3

If yellow ppt is obtained which is insoluble in ammonium


hydroxide, then it indicates the presence of iodine.
NaI AgNO 3

36

AgI

yellow ppt

NaNO 3

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Exercise Problem 22.
Differentiate between the principle of estimation of nitrogen in
an organic compound by (i) Dumas method and (ii) Kjeldahls
method.
Strategy.
Dumas method- Here a known mass of the nitrogen containing
organic compound is hea ted with excess of CuO in a n
atmosphere of CO2, then nitrogen of organic compound is
converted into N2 gas. So the volume of N2 gas thus obtained is
converted into STP and the % of nitrogen can be determined.
% N

28
Volume of N 2 at STP

100
22400 Mass of the substance taken

Kjeldahls method- Here a known ma ss of the nitrogen


containing organic compound is heated with excess of conc.
H 2 SO 4 in presence of CuSO 4 in Kjeldahls flask, then nitrogen
of organic compound is converted into (NH 4 )2 SO 4 . This
ammonium sulphate is then boiled with excess of Na OH
solution to liberate NH3 gas which is absorbed in a known excess
of standard solution of H 2 SO 4 or HCl.
The volume of acid left after absorption of ammonia is estimated
by titration against a standard alka line solution. From the
volume of the a cid used, the percentage of nitrogen is
determined by applying the mathermatical equation.
% N

1.4 Molarity of acid basicity of acid vol. of acid


Mass of substance taken

Exercise Problem 23.


Discuss the principle of estimation of halogens, sulphur and
phosphorus present in an organic compound.
Strategy.
Principle of estimation of halogens- Here a known mass of
an organic compound is heated with fuming HNO3 in the

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presence of AgNO3 in Carius tube in a furnace. By doing so,
carbon & hydrogen present in the organic compounds are
oxidised to CO2 and H2O respectively and halogen forms the
precipitate of AgX. Now this AgX is filtered, washed, dried &
weighed. So,
% of halogen =

Atomic mass of X x mass of AgX 100


Molecular mass of AgX mass of compound

Principle of estimation of sulphur- Here a known mass of an


organic compound is heated with Carius tube with sodium
peroxide on fuming HNO3. By doing so, sulphur is oxidised to
H2SO4 and precipitated as BaSO4 by adding excess of BaCl2
solution in water. Now this BaSO4 is filtered, washed, dried &
weighed.
% of S =

32 Mass of BaSO4 100


233 Mass of compound

Principle of estimation of phosphorus- Here a known mass


of an organic compounds is heated with fuming HNO3. By
doing so, phosphorus is oxidised to phosphoric acid a nd
precipita ted
as
a mmonium
phosphomolybda te
(NH 4 )3 PO4 .12 MoO3 by a dding NH 3 a nd a m monium

phosphomolybda te. Now (NH 4 )3 PO4 .12 MoO3 is filtered,


washed, dried & weighed.
% of P =

31 Mass of ammonium molybdate 100


1877 Mass of organic compound

Exercise Problem 24.


Explain the principle of paper chromatography.
Strategy.
Principle of paper chromatography- It is a type of partition
chromatography & based on principle of partition i.e. based
on continuous differentia l distribution of the va rious
components of the mixture between the stationary and the

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mobile phases.
In this process, the solution of the mixture which is to be
sepa ra ted is a pplied a s a sma ll spot a t the ba se of
chromatography paper nearly 2cm above one end of the paper
strip. Now this paper is suspended in a suitable solvent. This
solvent acts as mobile phase due to which solvent rises up the
paper.
After some time the spots of the separated coloured compounds
are visible at different heights from the position of inital spot
on the chromatogram.
The coloured components of a mixture are identified by
Retardation fa ctor, Rf value, which is fix value for every
component.

.
.

solvent front
spot
X

base line
Observation on paper chromatograph

R f value =

Distance travelled by the compound (X)


Distance travelled by the solvent (Y)

Exercise Problem 25.


Why is nitric acid added to sodium extract before adding silver
nitrate for testing halogens?
Strategy.
Conc. HNO3 is added to sodium extract before adding silver
nitrate before testing halogen is to remove NaCN or Na 2S if
present in sodium extract, otherwise they give white ppt &
black ppt with AgNO3 which creats confusion.
NaCN HNO 3
NaNO 3 HCN
Na 2 S HNO 3
NaNO 3 H 2 S

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otherwise
NaCN AgNO 3
AgCN NaNO 3
White ppt
Na 2 S AgNO 3

Ag 2 S NaNO 3
(Black ppt)

Exercise Problem 26.


Explain the reason for the fusion of an organic compound with
metallic sodium for testing nitrogen, sulphur and halogens.
Strategy.
Organic compounds are covalently bonded so the detection of
element is not easy so, they are first fused with sodium to convert
them into ion, which we get by easy chemical test.
Na C N
NaCN

Na S
Na 2 S
Na X
NaX
Exercise Problem 27.

Name a suitable technique of separation of the components


from a mixture of calcium sulphate and camphor.
Strategy.
Suitable technique used for separation of components from
mixture of calcium sulphate & comphor is sublimation.
As camphor is sublimable but CaSO4 is not so sublimation of
the mixture gives camphor on the side of funnel while CaSO4
is left in the china dish.
Exercise Problem 28.
Explain, why an organic liquid vaporises at a temperature below
its boiling point in its steam distillation ?
Strategy.
In steam distillation process, the mixture consisting of the
organic liquid and water boils when the sum of the vapour

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pressure of the organic liquid and that of water becomes equal
to the atmospheric pressure.
Atmospheric pressure = Vapour pressure of the liquid + Vapour
pressure of the water.
Since, vapour pressure of the liquid is lower than atmospheric
pressure, the organic liquid vaporises at lower temperature than
its boiling point.
Exercise Problem 29.
Will CCl 4 give white precipitate of AgCl on heating it with
silver nitrate? Give reason for your answer.
Strategy.
No, CCl4 will not give white precipitate of AgCl on heating
with AgNO3 because CCl4 is covalently bonded compound and
will not ionize to give Cl ion required for the formation of
AgCl as precipitate.
Exercise Problem 30.
Why is a solution of potassium hydroxide used to absorb carbon
dioxide evolved during the estimation of carbon present in an
organic compound?
Strategy.
As carbon dioxide is slightly acidic in nature, therefore it will
react with strong base like KOH to form K2CO3 & from the
weight of CO2 obtained, % of carbon in the organic compound
can be calculated.
KOH CO2
K2 CO3 H2 O
% of C =

12 weight of CO2 formed


100
Weight of substance taken

Exercise Problem 31.


Why is it necessary to use acetic acid and not sulphuric acid
for acidification of sodium extract for testing sulphur by lead
acetate test?

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Strategy.
When H2SO4 is used for acidification of sodium extract for
testing sulphur by lead acetate test, then lead acetate itself react
with H2SO4 to form white ppt of lead sulphate.
(CH 3 COO)2 Pb H 2 SO 4
PbSO 4 CH 3COOH
White ppt

Hence, this white ppt of PbSO4 will interfere with the following
test of sulphur.
(CH 3 COO)2 Pb NaS
PbS CH 3 COONa
Black ppt

However, if acetic acid is used, it does not react with lead acetate, so it
will not interfere in the test.
Exercise Problem 32.
An orga nic compound conta ins 6 9 % ca rbon a nd 4 .8 %
hydrogen, the remainder being oxygen. Calculate the masses
of carbon dioxide and water produced when 0.20 g of this
substance is subjected to complete combustion.
Strategy.
Calculation of mass can be done by following formula.
% of C =
69 =

12 Mass of CO2 formed


100
44 mass of substance taken

12 Mass of CO2 formed


100
0.2

So, mass of CO2 formed = 0.506 gram.


% of H =

2 Mass of H2 O formed
100
Mass of substance taken

2 Mass of H 2 O formed
100
18 0.2
So, mass of H2O formed = 0.0864 g.
4.8 =

42

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Organic Chemistry- Som e ba sic principle s a nd T echnique s


Exercise Problem 33.
A sample of 0.50 g of an organic compound was treated
according to Kjeldahls method. The ammonia evolved was
absorbed in 50ml of 0.5 M H 2 SO 4 . The residual acid required
60 mL of 0.5 M solution of NaOH for neutralisation. Find the
percentage composition of nitrogen in the compound.
Strategy.
Volume of H2SO4 taken = 50 mL of 0.5 M H2SO4
= 25 mL of 1.0 M H2SO4
Volume of alkali used for neutralization of excess acid
= 60 mL of 0.5 M NaOH
= 30 mL of 1.0 M NaOH
As, H 2 SO 4 2 NaOH
Na 2 SO 4 2 H 2 O
So, 1 mole of H2SO4 = 2 mole of NaOH
Hence, 30 mL of 1.0 M NaOH = 15 mL of 1.0 M H2SO4

Volume of acid used by ammonia = 2515 = 10 mL

% of Nitrogen =

1.4 N 1 Vol. of acid used


Mass of organic compound

% of Nitrogen =

1.4 2 10
56.0
0.5

Exercise Problem 34.


0.3780 g of an organic chloro compound gave 0.5740 g of silver
chloride in Carius estimation. Calculate the percentage of
chlorine present in the compound.
Strategy.
Mass of organic compound taken = 0.3780 g.
Mass of AgCl formed = 0.5740 g.

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43

Organic Chemistry- Som e ba sic principle s a nd T echnique s


% of Cl =

Mass of AgCl formed


35.5

100
143.5
Mass of substance taken
35.5
0.5740

100 = 37.566%
143.5
0.3780

Exercise Problem 35.


In the estimation of sulphur by Carius method, 0.468 g of an
organic sulphur compound a fforded 0 .66 8 g of barium
sulphate. Find out the percenta ge of sulphur in the given
compound.
Strategy.
Mass of organic compound taken = 0.468 g.
Mass of BaSO4 formed = 0.668 g.
% of S =

32
Mass of BaSO 4 formed

100
233
Mass of substance taken
=

32
0.668

100 = 19.60%
233
0.468

Exercise Problem 36.


In the organic compound CH 2 = CH - CH 2 - CH 2 - C CH, the
pa ir of hydridised orbita ls involved in the formation of :
C 2 - C 3 bond is:
(A) sp - sp2

(B) sp - sp3

(C) sp 2 - sp3

(D) sp 3 - sp3

Strategy.
To find out hybridised orbital first write hybridization of each
carbon & then report your answer.
So, hybridised orbitals involved in the formation of C2C3 bond
is sp2sp3.

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Organic Chemistry- Som e ba sic principle s a nd T echnique s


Exercise Problem 37.
In the Lassaignes test of nitrogen in an organic compound,
the Prussian blue colour is obtained due to the formation of :
(A) Na 4 [Fe(CN)6 ]

(B) Fe 4 [Fe(CN)6 ]3

(C) Fe 2 [Fe(CN)6 ]

(D) Fe 3 [Fe(CN)6 ]4

Strategy.
In the Lassaignes test for nitrogen in an organic compound,
the Prussian blue colour is obtained due to forma tion of
Fe 4 [Fe(CN)6 ]3 .
FeSO 4 2 NaOH
Fe(OH)2 Na 2 SO 4
Fe(OH)2 6 NaCN
Na 4 [Fe(CN)6 ] 2 NaOH
4 Fe 3 3 Na 4 [Fe(CN)6 ]
Fe 4 [Fe(CN)6 ]3 12 Na

Exercise Problem 38.


Which of the following carbocation is most stable ?
+

(A) (CH 3 )3 C .CH2


+

(C) CH3 CH 2 CH 2

(B) (CH3 )3 C
+

(D) CH3 CH CH 2 CH 3

Strategy.
Greater is the number of hyperconjugating structure, greater
is the sta bility of carbocation. So (CH 3 )3 C is most stable
carbocation.
CH 3
CH 3 CCH 2
CH 3
(0 HC)

CH 3
CH 3 C
CH 3
(9 HC)

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45

Organic Chemistry- Som e ba sic principle s a nd T echnique s


CH 3 CH 2 CH2
(2 HC)

CH 3 CHCH 2 CH3
(5 HC)

Exercise Problem 39.


The best and latest technique for isolation, purification and
separation of organic compounds is :
(A) Crystallisation

(B) Distillation

(C) Sublimation

(D) Chromatography

Strategy.
The best & latest technique for isolation, purification &
separation of organic compound is chromatography.
Exercise Problem 40.
The reaction :
CH 3 CH2 I +KOH(aq) CH 3CH2 OH +KI

is classified as :
(A) electrophilic substitution (B) nucleophilic substitution
(C) elimination

(D) addition

Strategy.
The reaction is classified as nucleophilic substitution reaction
as nucleophile (OH) attacks over carbon directly attached to I
to replace it with itself.
CH 3 CH2 I

CH 3 CH 2 OH + KI

HO

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Hydrocarbon

Unit

Hydrocarbon

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47

Hydrocarbon

Objective
This unit give you an understanding of Hydrocarbons
and covers following topics:

48

IUPAC nomenclature of hydrocarbons, its classification & isomerism involved in it.


Various methods of preparations of alkanes, alkenes, alkynes & aromatic hydrocarbons.
Methods to distinguish between alkane, alkene,
alkyne & aromatic hydrocarbons on the basis of
physical & chemical properties.
Chemical reactions of alkane, alkene, alkyne &
aromatic hydrocarbons.
Aromaticity, directing influence of substituents in
monosubstituted benzene ring.
Learn about carcinogenicity & toxicity.

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Hydrocarbon

Solved Example:
Example 1.
Write structures of different cha in isomers of a lkanes
corresponding to the molecular formula C 6 H 14 . Also write their
IUPAC names.
Stategy.
Whenever you have to draw the structures from a known
molecular formula, always follow these steps.
(A) Calculate DU
(B) Make the skeleton of carbon in decreasing order
(C) Take the help of chemically different H or position
So, structure possible for C 6 H 14 will be

Hexane

2-Methylpentane

2,2-Dimethylbutane

3-Methylpentane

2,3-Dimethylbutane

Example 2.
Write structures of different isomeric a lkyl groups
corresponding to the molecular formula C 5 H11 . Write IUPAC
names of alcohols obtained by attachment of OH groups at
different carbons of the chain.
Stategy.
To write the structures of different alkyl groups from a known
molecular formula, add a hydrogen & find DU first. DU will
give a clear cut picture, whether we have to think double bond,
ring or not.

If DU is zero, then compound will have no multiple bond


or ring.

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49

Hydrocarbon

If DU is one, then compound will have either 1 double


bond or a ring.

If DU is two, then compound will have 1 triple bond or 2


double bond or 1 ring with 1 double bond or 2 rings.

So, alkyl group possible for the molecular formula C 5 H11 are

Alcohol obtained by attaching OH group over these alkyl


groups are as follows.
OH
Pentan-1-ol

OH
Pentan-3-ol

OH
Pentan-2-ol
OH
3-Methylbutan-1-ol

OH
OH
3-Methylbutan-2-ol

2-Methylbutan-2-ol
OH

HO
2-Methylbutan-1-ol

2,2-Dimethylpropan-1-ol

Example 3.
Write IUPAC names of the following compounds:
(i)

(CH 3 )3 CCH 2 C(CH 3 )3

(ii) (CH3 )2 C(C 2 H5 )2

(iii) tetra-tert-butylmethane

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Hydrocarbon
Stategy.
Whenever you have to write the IUPAC name of compound
written in condensed form, first write in bond line
representation & then use the general concept of IUPAC
nomenclature i.e. use the concept of 2prefix + 1prefix + word
root + 1suffix + 2suffix is sequence.
(CH 3 )3 C CH 2 C(CH3 )3

(i)

(Bond line form)

(Condensed form)

1 2 3 4 5
2,2,4,4-Tetramethylpentane
(CH3 ) 2 C(C 2 H5 )2

(ii)

(Condensed form)
34 5

(Bond line form)

1
3,3-Dimethylpentane

(iii) tetra-tert butylmethane

1 2 3 4

3,3-Bis-(dimethylethyl)-2,2,4,4-tetramethylpentane
Example 4.

Write structural formulas of the following compounds:


(i)

3, 4, 4, 5-Tetramethylheptane (ii) 2,5-Dimethyhexane

Stategy.
Whenever you have to draw structures from given compound,
always take the help of word root. With the help of it, first

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51

Hydrocarbon
draw the skeleton & then on it, attach the substituent, multiple
bond or functional group, whatever it is mensioned.
(i)

23 45 6
7

(ii)

3 45 6

Example 5.
Write structures for each of the following compounds. Why
are the given names incorrect? Write correct IUPAC names.
(i)

2-Ethylpentane

(ii) 5-Ethyl-3-methylheptane

Stategy.
As told earlier, first draw the structure & then think for correct
& incorrect name.
1
2
5
6
23 4
3
1
5
4
(i)
2-Ethylpentane
3-Methyl hexane
(Incorrect)
(correct)
In this case longest chain is of 6 carbon atom & not of 5 carbon
atom.
1

23 4 5 6
7

65 4 3 2
1

(ii) 5-Ethyl-3-methylheptane 3-Ethyl-5-methylheptane


(Incorrect)
(correct)
When position of substituent from both the ends are identical,
then substituent with lower alphabets are given lower position.
Example 6.
Sodium salt of which acid will be needed for the preparation
of propane? Write chemical equation for the reaction.
Stategy.
Sodium salt of carboxylic acid on treatment with soda lime,
decarboxylate to give alkane as a product with one carbon less
from the substrate. So, to prepare propane, you can use either
acid.

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Hydrocarbon
(i)

Butanoic acid
COOH

(ii) 2-Methylpropanoic acid


NaOH/CaO

CO
2

COOH

NaOH/CaO

CO
2

Example 7.
Write IUPAC names of the following compounds:
(i)

(CH 3 )2 CH CH = CH CH 2 CH
CH3 CH CH
C2H 5

(ii)
(iii) CH2 = C(CH 2 CH 2 CH 3 )2
(iv) CH 3CH2 CH2 CH2

CH 2 CH 3

CH3 - CHCH = C - CH2 - CHCH 3


CH 3

Stategy.
To write IUPAC name of compound from structure, always
follows following concept.
(A) Use the concept of 2prefix + 1 prefix + word root +
1suffix + 2suffix.
(B) Use the concept of position then alphabet & then position
if functiona l group, multiple bond or substituents are
present.
(C) For giving minimum position functional group -multiple
bond - substituent.
(D) If more than one functional groups are present, then use
the concept of priority order.

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53

Hydrocarbon
CH 3

(i)

(ii)

CH 3 CHCH=CHCH 2 CH
1
2
3
4
5 6
H 3CCHCH
8
7
CH 2 CH 3
9
10
2,8-Dimethyldeca-3,6-diene

2 3 4
8
5 6 7
1
Octa-1,3,5,7-tetraene

1
2 3
4
5
(iii) CH 2 =CCH 2 CH2 CH 3
CH 2 CH 2 CH3
2-Propylpent-1-ene
10 9 8 7
(iv) CH 3CH2 CH2 CH2
CH 2 CH 3
6 5
43
2
1
H3 CCHCH=CCH2 CHCH 3
CH 3
4-Ethyl-2,6-dimethyldec-4-ene

Example 8.
Calculate number of sigma () and pi ( ) bonds in the above
structures (i-iv).
Stategy.
To calculate the number of sigma & pi bond in any molecule,
first write the molecule in expanded form & then look for single,
double & triple bond. Single bond is only of bond. Double
bond contains 1 & 1. Triple bond have 1 & 2 bonds.

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Hydrocarbon
H
HCH
H

(i)

H C C C = C C C H
bond = 33
bond = 2

H H H H H
H H
HCCCH
H
H

(Expanded form)

H C C H
H H

(ii)

H
C = C C = C C = C C = C

H H H H H H

bond 17
bond 4

H H H
CCCH

(iii)

C =C
H

bond 23
bond 1

H HH
H H

HCCCH
H H H

H H H H

H H

HCCCCH HCCH

(iv)

H H H
H
H C C C
H H H

H
H H H

bond 41
bond 1

C C C C H
H H
H
HCH
H

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55

Hydrocarbon
Example 9.
Write structures and IUPAC names of different structural
isomers of alkenes corresponding to C 5 H 10 .
Stategy.
To draw the structure from molecular formula, as we have
discussed earlier, first calculate DU, then make the skeleton of
carbon in decreasing order & finally take the help of chemically
different position on that skeleton to make double bond over it.
So alkene with molecular formula C 5 H 10 will be

Pent-1-ene

Pent-2-ene

2-Methylbut-2-ene

2-Methylbut-1-ene

3-Methylbut-1-ene

Example 10.
Draw cis and trans isomers of the following compounds. Also
write their IUPAC names :
Stategy.
When two same atom or groups are present in the same side of
double bond, then we asign the configuration cis, and if
opposite, then we called as trans.
H

(i)

Cl

C =C

C =C

Cl
Cl
cis-1,2-Dichloroethene

H
Cl
trans-1,2-Dichloroethene

H 3C

CH 3

H 3C

C 2 H5

H 5C 2

C= C

(ii)

H 5C2

cis-3,4-Dimethylhex-3-ene

56

C2H 5
C =C
CH 3

trans-3,4-Dimethylhex-3-ene

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Hydrocarbon
Example 11.
Which of the following compounds will show cis-trans
isomerism?
(i)

(ii) CH 2 = CBr2

(CH 3 )2 C = CH - C 2 H5

(iii) C 6 H 5 CH = CH - CH3

(iv) CH3 CH = CClCH 3

Stategy.
Those compounds which have restriction in rota tion &
restricted atom have different substituent, shows geometrical
isomeris.
(i)

H3 C

C2H 5
C =C
H

H3 C

will not show cis-trans isomerism as two methyl group on


restricted atom are same.
H

(ii)

Br
C=C
Br

will not show cis-trans isomerism as two hydrogens as well as


bromines on restricted atom are same.
C 6 H5

(iii)

CH 3

C6H 5

C =C
H
cis

H
C =C

H
trans

CH 3

will show cis-trans isomerism as two groups on restricted atoms


are different.
H3 C

(iv)

CH3
C =C

H
cis

Cl

H3 C

Cl
C =C

H
trans

CH 3

will show cis-trans isomerism as two groups on restricted atoms


are different.

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57

Hydrocarbon
Example 12.
Write IUPAC names of the products obtained by addition
reactions of HBr to hex-1-ene
(i)

in the absence of peroxide and

(ii) in the presence of peroxide.


Stategy.
This question is based on the knowledge of Markownikoff rule
& Anti-Markownikoff rule.
Markownikoff rule When unsymmetrical alkene or alkyne
is treated with unsymmetrical reagent, during electrophilic
addition reaction, then positive part of reagent will attached
to that carbon which have more number of hydrogen while
negative part of the reagent will attached to that carbon which
will have less number of hydrogen.
Br
HBr

Hex-1-ene

2-Bromohexane

Anti-Markownikoff rule When unsymmetrical alkene or


alkyne is trea ted with HBr in presence of peroxide, then,
hydrogen will attached to that carbon which have less number
of hydrogen while bromine will attached to that carbon which
will have more number of hydrogen.
Br
HBr/Peroxide
Hex-1-ene
Example 13.

1-Bromohexane

Write structures of different isomers corresponding to the 5 th


member of alkyne series. Also write IUPAC names of all the
isomers. What type of isomerism is exhibited by different pairs
of isomers?
Stategy.
To solve such question, first make the skeleton of carbon in
decreasing order of number of carbon and then take the help
of chemically different position to place triple bond over it.

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Hydrocarbon
By doing so, we will get following alkynes of 5th member of
alkyne series.
Hex-1-ene
(I)

Hex-3-yne
(III)

4-Methylpent-2-yne
(V)

Hex-2-yne
(II)

4-Methylpent-1-yne
(IV)

3-Methylpent-1-yne
(VI)

3,3-Dimethylbut-1-yne
(VII)

Whenever you have to find the isomeric relationship between


pair of compounds, always remember these basic concepts.

Chain isomers have difference in main chain or side chain


of carbon, keeping chemical reaction same.

Positional isomers have difference in position of functional


group, multiple bond or substituent, keeping no change
in chemical reaction & main chain or side chain of carbon.

Functional isomers have difference in chemical reactions.

Metamers have difference in carbon skeleton along


polyvalent atom.

Tautomer have difference in position of H.


So,
I, II & III are positional isomers.
IV, V & VI are positional isomers.
I, II & III with respect to IV, V, VI & VII are chain isomers.

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59

Hydrocarbon
Example 14.
How will you convert ethanoic acid into benzene?
Stategy.
To solve this question, first think for the conversion of ethanoic
acid to ethyne, as ethyne on high temperature trimerize to give
benzene as the product. So, conversion followsO

Cl /h

NaOH/CaO

2
CH3 C OH
CH 4
CH 3 Cl
Decarboxylation
Monochlorination

Na/dry ether

Cl /h

reaction

chlorination

2
CH3 Cl
CH 3 CH3
CH3 CH2 Cl
Wurtz
Mono

Br
addition
reaction

alc KOH
2
CH3 CH 2 Cl
CH 2 =CH 2
CH 2 CH 2
Elimination
reaction

alc KOH
Elimination
reaction

Br

Br

NaNH

2
C H2 CH 2 CH 2 =CHBr
HC CH

Br

Br

Elimination
reaction

Red hot Fe tube


HC CH

873 K

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Hydrocarbon

Exercise Problems:
Exercise Problem 1.
How do you account for the formation of ethane during
chlorination of methane ?
Stategy.
Halogenation of alkane is a free radical substitution reaction.
Cl /h

2
CH4
CH3 Cl HCl

Mechanism of such reaction proceed in 3 steps.


(A) Chain initiation step:
Cl

. .

Cl

2 Cl

(B) Chain propagation step:


H

. . .

H C

H + Cl

HC

+ HCl

. . .

CH 3 + Cl

Cl

CH 3 Cl + Cl

(C) Chain termination step:

..
..
..

Cl + Cl
CH 3 + CH 3
CH 3 + Cl

Cl 2
CH 3 CH 3
CH 3 Cl

From the above mechanism, it is clear that in chain termination


step, two CH 3 combines to form ethane as side product.

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61

Hydrocarbon
Exercise Problem 2.
Write IUPAC names of the following compounds :
(a) CH3 CH = C(CH 3 )2
(b) CH2 = CH - C C - CH3
(c)
(d)

CH 2 CH 2 CH = CH 2

CH3

(e)
(f)

OH
CH 3 (CH 2 ) 4 CH(CH2 )3 CH 3
CH 2 CH(CH 3 )2

(g)

CH 3 CH = CH CH2 CH = CH CH CH 2 CH = CH 2
C2H 5

Stategy.
To write IUPAC name of compound from structure, always
follows following concept.
(A) Use the concept of 2prefix + 1 prefix + word root +
1suffix + 2suffix.
(B) Use the concept of position then alphabet & then position
if functiona l group, multiple bond or substituents are
present.
(C) For giving minimum position functional group -multiple
bond -substituent.
(D) If more than one functional groups are present, then use
the concept of priority order.

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Hydrocarbon
CH3

(A) CH 3 CH=CCH3
4
3
2 1
2-Methylbut-2-ene
1 2 3
4
(C)
Buta-1,3-diene

(B)

(D)

H2 C=CHC CCH 3
1 2
3 4 5
Pent-1-en-3-yne

4
3
2
1
CH 2 CH 2 CH=CH 2
4-Phenylbut-1-ene

4 3
5

2 CH 3
(E)
6 1 OH
2-Methylphenol

(F)

10
9
8
7
6
5
4
3
2
1
CH 3 CH 2 CH2 CH 2 CH 2 CHCH2 CH 2 CH 2 CH 3
CH2 CHCH 3
CH 3
5-(2-Methylpropyl)decane

10
9
8
7
6 5
4
3
2
1
(G) CH 3 CH=CHCH 2 CH=CHCHCH2 CH=CH 2
C 2 H5
4-Ethyldeca-1,5,8-triene

Exercise Problem 3.
For the following compounds, write structural formulas and
IUPAC names for all possible isomers having the number of
double or triple bond as indicated :
(a) C 4H 8 (one double bond)
(b) C 5 H 8 (one triple bond)
Stategy.
Whenever you have to draw the structures from a known
molecular formula, always follow these steps.
(A) Calculate DU

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63

Hydrocarbon
(B) Make the skeleton of carbon in decreasing order
(C) Take the help of chemically different H or position. On the
basis of this a and b are
(a)

(b)

But-1-ene

But-2-ene

2-Methylpropene

Pent-1-yne

Pent-2-yne

3-Methylbut-1-yne

Exercise Problem 4.
Write IUPAC names of the products obtained by the ozonolysis
of the following compounds:
(i)

Pent-2-ene

(ii) 3,4-Dimethylhept-3-ene

(iii) 2-Ethylbut-1-ene

(iv) 1-Phenylbut-1-ene

Stategy.
Ozonolysis is a chemical method to find position of C=C or
C C bond in unknown compound. To find out the product

of ozonolysis, break the C=C bond & add two oxygen, one
at each double bonded carbon atom to get aldehyde or ketone
as general product.
C

O+O

Alkene

(Aldehyde or Ketone)

(i)
Pent-2-ene

2 1 H
Ethanal

3
+ H 1
2
Propanal

4 32

(ii)
3,4-Dimethylhept-3-ene

64

1
Butanone

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+ O
Pentan-2-one

Hydrocarbon
O

(iii)

(iv)
Exercise Problem 5.
An alkene A on ozonolysis gives a mixture of ethanal and
pentan-3-one. Write structure and IUPAC name of A.
Stategy.
To get back from aldehyde, ketone to alkene in ozonolysis
reaction, write the structure of aldehyde or ketones in such a
way that their oxygen atoms pointing toward each other. Then
join the two ends of these through a double bond by removing
oxygen atom to get alkene.
2
1 O+ O
H
Ethanal
Pentan-3-one

4 5
1
2 3
3-Ethylpent-2-ene
(A)

Exercise Problem 6.
An alkene A contains three C C, eight C H bonds and
one C C bond. A on ozonolysis gives two moles of an
aldehyde of molar mass 44 u. Write IUPAC name of A.
Stategy.
Alkenes that contains 3 CC, 8 CH bonds & 1 CC bond
will be.

But-1-ene

But-2-ene

2-Methylpropene

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65

Hydrocarbon
But from the question, it is indicated that A on ozonolysis
gives 2 moles of aldehyde of molar mass 44u i.e. CH 3 CHO.
So alkene must be symmetrical & hence
CH 3 CH
Ethanal

O+O

CHCH3

CH3 CH=CHCH 3
But-2-ene

Exercise Problem 7.
Propanal and pentan-3-one are the ozonolysis products of an
alkene? What is the structural formula of the alkene?
Stategy.
To get back from aldehyde, ketone to alkene in ozonolysis
reaction, write the structure of aldehyde or ketones in such a
way that their oxygen atoms pointing toward each other. Then
join the two ends of these through a double bond by removing
oxygen atom to get alkene.
3 2

2 1
3
4 5

1 O+O
H
Propanal
Pentan-3-one

6 5 2 1
43
3-Ethylhex-3-ene

Exercise Problem 8.
Write chemical equa tions for combustion rea ction of the
following hydrocarbons:
(i)

Butane

(ii) Pentene

(iii) Hexyne

(iv) Toluene

Stategy.
Chemical equations for combustion reaction of hydrocarbon
followsy
y

C x H y x O 2
xCO 2 H2 O
4
2

So,

66

10
10

C 4 H10 4 O 2
4 CO 2 H2 O
4
2
Butane

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Hydrocarbon

C 4H 10 6.5 O 2
4 CO 2 5 H 2 O

10
10

C 5 H10 5 O2
5 CO 2 H2 O
4
2
pentane

C 5 H 10 7.5O 2
5 CO 2 5 H 2 O

10
10

C 6 H 10 6 O 2
6 CO 2 H2 O
4
2
Hexyne

C 6 H 10 8.5 O 2
6 CO 2 5H 2 O

CH3
Toluene

or C 7 H 8 7

8
8
O2
7 CO2 H 2 O

4
2

C 7 H 8 9 O 2
7 CO 2 4 H 2 O

Exercise Problem 9.
Draw the cis and trans structures of hex-2-ene. Which isomer
will have higher b.p. and why?
Stategy.
Cis & Trans structures of hex-2-ene are

cis-Hex-2-ene
trans-Hex-2-ene
Boiling point of any molecule depends on its intermolecular
forces i.e. hydrogen-bonding, dipole moment & vander waal
interaction.

In case of isomers, greater is the hydrogen bonding and or dipole


moment, greater is the boiling point so, cis form have move
boiling point than trans.

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67

Hydrocarbon
Exercise Problem 10.
Why is benzene extra ordinarily stable though it contains three
double bonds?
Stategy.
Benzene have extra ordinary stability inspite of 3 double bonds
due to its aromatic character. Due to aromaticity, there is cyclic
delocalization of electron density in the molecule and due to
this delocalization of electrons, molecule become stable.

Resonating structure

Resonance hybrid

Benzene

Exercise Problem 11.


What a re the necessary conditions for any system to be
aromatic?
Stategy.
The necessary conditions for a system to be aromatic are
(A) System should be cyclic
(B) Each atom of the cycle must be sp or sp2 hybridized.
(C) Molecule as a whole must be planner or nearly planner.
(D) Tota l number of electrons in the ring must be
(4n 2) e in number i.e. follow Huckels rule.

Exercise Problem 12.


Explain why the following systems are not aromatic?
(i)

CH 2

(ii)

(iii)

Stategy.
As we have discussed in the above question, for a compound
to be aromatic, molecule must satisfy all the four conditions i.e.

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Hydrocarbon
(i)

CH 2 is not aromatic as one of the carbon atom in

the ring is sp3.


(ii)

is not aromatic again, as one of the carbon atom in


the ring is sp3.

(iii)

is not aromatic as total number of electrons in the


ring is 8 and not follow (4n 2) electron rule i.e. Huckels
rule.

Exercise Problem 13.


How will you convert benzene into
(i)

p-nitrobromobenzene

(iii) p-nitrotoluene

(ii) m-nitrochlorobenzene
(iv) acetophenone?

Stategy.
Following conversion take place as below.
Br
?

(i)
NO 2
Br

Br

Br2 /AlCl 3

conc.H 2SO 4

Bromination

HNO 3

CH3
+

NO 2

NO 2 (minor)
(major)

Now from the fractional distillation, p-nitrobromobenz ene


should be separated out.
In this reaction, you have to perform first bromination reaction
followed by nitration because bromine is ortho-para directing
in nature & nitro group is meta directing in nature.

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69

Hydrocarbon
Cl

(ii)

NO 2
NO 2
conc.H 2 SO 4 /HNO 3

NO 2
Cl 2 /FeCl 3

Cl
In this reaction you have to first perform nitration followed by
chlorination as NO2 is meta directing group.

CH 3

(iii)

NO 2
CH 3
CH 3Cl

CH3
conc.H 2SO 4

AlCl 3

NO 2

HNO 3

CH 3
+

(minor)

NO 2
(major)
Now from fractional distillation, p-nitrotoluene should be
separated out.

Here again first alkylation has to perform as CH3 is orthopara directing in nature.
O

(iv)

CH 3

It is simply the acelation reaction of benzene which can be


done with the help of acid halide or acid anhydride in presence
of AlCl3.
COCH 3
CH 3 COCl/AlCl 3 or
(CH 3CO)2O/AlCl 3

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Hydrocarbon
Exercise Problem 14.
In the alkane H 3 C - CH2 - C(CH3 )2 - CH2 - CH(CH3 )2 , identify
1, 2, 3 carbon atoms and give the number of H atoms bonded
to each one of these.
Stategy.
On the basis of attachment of carbon with other carbon, carbon
is categorise into 4 types.
(A) Primary carbon (1C) It is the carbon attached with none
or 1 carbon.
(B) Secondary carbon (2C) It is the carbon attached with 2
carbon.
(C) Tertiary carbon (3C) It is the carbon attached with 3
carbon.
(D) Quaternary carbon (4C) It is the carbon attached with
4 carbon.
Hydrogens present on 1C, 2C & 3C are called as 1H, 2H &
3H respectively. So,
1
1
CH3
CH 3
1H = 15
1
2
2
1
CH 3 CH 2 CCH 2 CHCH3 2H = 4
4
3
3H = 1
CH3
1
Exercise Problem 15.
What effect does branching of an alkane chain has on its boiling
point?
Stategy.
Boiling point of any molecule depends on its intermolecular
force of attraction i.e. H-bonding, dipole moment, vander waal
force of attraction.
As in alkane, H-bonding & dipole moment is absent, so deciding
factor is vander waal force of attraction.
As va nde r wa al force of attraction surfa ce area and

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71

Hydrocarbon
decrea ses with increase in bra nching. So boiling point also
decreases with increase in branching.
Exercise Problem 16.
Addition of HBr to propene yields 2-bromopropane, while in
the presence of benzoyl peroxide, the same reaction yields 1bromopropane. Explain and give mechanism.
Stategy.
Addition of HBr to propene yield 2-Bromopropane as a product
while in presence of benzoyl peroxide, 1-Bromo propane is
formed because nature & mechanism of chemical reaction in
both the cases are different.
Addition of HBr in absence of peroxide follow carbocationic
mechanism and follow Markownikoff rule while addition of
HBr in presence of peroxide follow free radical mechanism &
follow anti-Markownikoff rule.
Br
|

HBr CH CHCH
CH3 CH=CH 2
3
3
Mechanism:

HBr

+ Br

Br
CH 3 CH = CH2

CH 3 CH=CH2

CH3 CH CH 3
HBr/(PhCO)2O 2

Br

CH 3 CH CH 3

CH3 CH 2 CH 2 Br

Mechanism:
O

..
. ..

PhCO

OCPh

Ph + H

2 Ph

CO

2 Ph + 2 CO 2

Ph H + Br

CH 3 CH=CH2 + Br

CH 3 CHCH 2 Br

CH 3 CHCH 2 Br + H

Ph

72

Br

. . .
.
.
.
..
O

CH3 CH 2 CH 2 Br

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Hydrocarbon
Exercise Problem 17.
Write down the products of ozonolysis of 1,2-dimethylbenzene
(o-xylene), How does the result support Kekule structure for
benzene?
Stategy.
To solve this question, first think for the both resonating
restructure of o-xylene. i.e.

1,2-Dimethyl benzene (o-xylene)

Now perform ozonolysis reaction on both these structures.


O O

Ozonolysis

O O

2 H3 C C C H + H C C H
O O

Ozonolysis

O O

H 3 C C C CH3 + 2 H C C H

So, overall ozonolysis product of 1,2-Dimethylbenzene are


O O

O O

O O

CH3 C C H + H C C H + CH 3 C C CH 3

As these three products can not be obtained from a single Kerule


structure, so it indicates that o-xylene is a resonance hybrid of
two Kerule structures.
Exercise Problem 18.
Arrange benzene, n-hexane and ethyne in decreasing order of
acidic behaviour. Also give reason for this behaviour.
Stategy.
Acidic character of any molecule depends on the stability of
conjugate base. Greater is the stability of conjugate base, greater
is the acidic strength.

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73

Hydrocarbon

Benzene

Conjugate base
(I)

Conjugate base
II

n-hexane

HC CH
Ethyne

HC C
Conjugate base
III
As conjugate base follows the order III > I > II as I of C C >

I of C=C while CC
follows the order

HC

have +I nature, so acidic character


CH >

Ethyne

>

Benzene

n-hexane

Exercise Problem 19.


Why does benzene undergo electrophilic substitution reactions
easily and nucleophilic substitutions with difficulty?
Stategy.
As benzene ring is electron rich due to presence of 6 delocalized
electrons in it, so it attacks over the electron deficient centre
(E+) to give electrophilic substitution reaction more easily but
these delocalized electron repels electron rich species (Nu)
to give any chemica l rea ction, so nucleophilic substitution
reaction takes place with more difficulty.
E
E+
Benzene
Electrophile substituted benzene
Exercise Problem 20.
How would you convert the following compounds into
benzene?
(i) Ethyne
(ii) Ethene
(iii) Hexane

74

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Hydrocarbon
Stategy.
(i)

?
HC CH
Red hot Fe tube
HC CH

873 K

It is simply the trimerization of ethyne to form benzene at high


temperature in Fe tube.
?
(ii) CH 2 =CH 2

Br

Br2

Br

alc KOH

CH2 =CH 2
CH2 CH 2 CH 2 =CHBr
CCl
4

Elimination
reaction

NaNH /liq NH

red hot Fe tube

2
3
CH2 =CHBr
HC CH

873K

Here ethenes a re first converted to ethyne, then use


trimerization of it to form benzene.
(iii)

Cr2O 3 /V2 O 5

Mo2 O 3 Al 2O 3 (1020Atm, 773K)

n-alkane having 6 or more carbon atoms on heating at 773 K


at 1 0-2 0 atmospheric pressure in presence of va nadium,
molybdenum or chromium supported over a lumina get
dehydrogenate to give aromatic rings. This reaction is called as
aromatization reaction or reforming reaction.
Exercise Problem 21.
Write structures of all the alkenes which on hydrogenation give
2-methylbutane.
Stategy.
To solve such question, first draw the skeleton of carbon of
alkane or cycloalkane. Then think for chemically different
position and place double bond over it. So, structure of 2Methylbutane is

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75

Hydrocarbon
It has 3 chemically different positions.

So, alkene which on hydration give 2-methylbutane are


2-Methylbut-1-ene 2-Methylbut-2-ene 3-Methylbut-1-ene
Exercise Problem 22.
Arrange the following set of compounds in order of their

decreasing relative reactivity with an electrophile, E


(a) Chlorobenzene, 2,4-dinitrochlorobenzene,
p-nitrochlorobenzene
(b) Toluene , p - H 3C C 6 H 4 NO 2 , p - O 2 N C 6 H4 NO 2 .
Stategy.
Reactivity of aromatic ring over an electrophile depends on
the availabe electron density in the benzene ring. Greater is the
available electron density in aromatic ring, greater will be the
reactivity of the molecule towards an electrophile. This electron
density of ring is controlled by electronic effect, i.e. resonance,
hyperconjugation & Inductive effect.
Electron donating group of any form (+M, HC or +I) increases
the electron density in ring while electron withdrawing group
of any form (M or I) decreases the electron density in the
ring, so
(A) Reactivity order of following compounds towa rds an
electrophile follows
Cl
Cl
Cl
I
I
NO 2
M
>
>
M
M
NO 2
NO 2
(Chloro
(p-Nitrochloro
(2,4-Dinitrochloro
benzene)
benzene)
benzene)

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Hydrocarbon
CH3 (HC)

CH3 (HC)
>

NO 2 (M)
>

M
NO 2
(p-Nitrotoluene)

(B)
(Toluene)

(M)
NO 2
(p-nitrobenzene)

Exercise Problem 23.


Out of benz ene, m-dinitrobenzene and toluene which will
undergo nitration most easily and why?
Stategy.
Nitration is a lso an exa mple of electrophile substitution
reaction, so its reactivity over aromatic ring also depends on
the available electron density in aromatic ring. Greater is the
available electron density in aromatic ring, greater will be the
reactivity, so toluene has higher reactivity towards nitration in
compa rison to benzene & dinitrobenzene as CH3 donates
electron density in aromatic ring by hyperconjugation.
Reactivity order followsCH 3 + HC
>
(Toluene)

NO 2M
>

(Benzene)

M
NO 2
(m-Dinitrobenzene)

Exercise Problem 24.


Suggest the name of a Lewis a cid other than anhydrous
aluminium chloride which can be used during ethylation of
benzene.
Stategy.
Ethylation of benzene is usually carried out in presence of
anhydrous AlCl3 but many other Lewis acids such as FeCl3,
SnCl4, SbCl5 can also be used for this reaction, as they are also
capable of generating electrophile for alkylation reaction.

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77

Hydrocarbon
CH 2 CH 3
CH 3CH 2 Cl/FeCl 3

Exercise Problem 25.


Why is Wurtz reaction not preferred for the preparation of
alkanes containing odd number of carbon atoms? Illustrate
your answer by taking one example.
Stategy.
When alkyl halide is treated with Na is presence of dry ether,
then alkane is formed as a product. This reaction is called as
Wurtz reaction.
Na/dry ehter

RX
RR

Mechansim:
R X

R + R RR

As in this reaction, alkyl free radical combines with other alkyl


free radicals to give alkane with double the number of carbon
in alkyl group. So wurtz reaction is preferred to prepare alkane
with even number of carbon.
But, if we use two different alkyl halide in reaction chamber,
then mixture of products will be formed by combination of
free radicals.
Na/dry ehter

RX + R' X
RR + R 'R' + RR'

As the yield of a single product is very low so this reaction is


not preferred for the preparation of alkane with odd number
of carbon. ExampleNa
CH3 Cl + CH 3 CH 2 Cl
CH 3 CH 3 + CH 3CH2 CH2 CH3
dry ehter

+ CH 3CH2 CH3

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Haloalkane & Haloarenes

Unit

Haloalkane & Haloarenes

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79

Haloalkane & Haloarenes

Objective
This unit give you an understanding of Haloalkanes
and Haloarenes and covers following topics:

80

IUPAC nomencla ture of ha loa lka nes a nd


haloarenes with its classifications.
Various methods of preparations of haloalkanes
and haloarenes.
Physical properties dealing melting point, boiling
point and its solubility in water.
Chemical reactions of haloalkanes and haloarenes.
Applications of organometallic compound with
highlight of environmental effects of polyhalogen
compound.

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Haloalkane & Haloarenes

Solved Example:
Example 1.
Draw the structures of all the eight structural isomers that have
the molecular formula C 5 H 11Br. Name each isomer according
to IUPAC system and classify them as primary, secondary or
tertiary bromide.
Strategy.
This type of questions can be done by taking longest chain of
carbon containing substituent and then replacing methyl group
one by one at other carbons to obtain all isomers.

For all primary isomers


1

Br
2
I
1-Bromopentane

Br
II
1-Bromo-2-methylbutane

Br

Br
IV
III
1-Bromo-3-methylbutane 1-Bromo-2,2-dimethylpropane

For all secondary isomers


Br
V
2-Bromopentane

Br
VI
3-Bromopentane

Br
VII
2-Bromo-3-methylbutane

For all tertiary isomers


Br
VIII
2-Bromo-2-methylbutane

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81

Haloalkane & Haloarenes


Example 2.
Write IUPAC names of the following:
H
H
Br

H3 C

(i)

CH 3
H
Br

CH3
H
Br
H
H 3C

H3 C

(iv)

H
H
Br
H

CH 3
H
Br

H 3C

H3 C

(v)

(ii)

H 3C

H3 C

(iii)

(vi)

CH 3
H
Br

Strategy.
For writting IUPAC name of any organic compound, always
write 2 Prefix + 1 Prefix + Word root + 1 Suffix + 2 Suffix
in sequencial order.

2Prefix tells about position of substituents with its name


if present.

1 Prefix tells about cyclic or acyclic nature of main chain


of carbon.

Word root tells about main chain of carbon containing


functional group, multiple bond or substituent at minimum
position.

1 Suffix tells about saturation or unsaturation in CC,


C=C or C C bond.

2 Suffix tells about main functional group.

If stereochemistry is involve in question, then use Cis/Trans to


indicate its stereochemistry.

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Haloalkane & Haloarenes


1
H 3C

H
4H
H
5
Br
(i)
H 3C
Trans-4-Bromopent-2-ene

H 3C

(iii)

23

1
2

CH 3

CH 3
3H
4
H
Br
(ii)
H 3C
3-Bromo-2-methylbut-1-ene
H 3C

3 H
H 5 4 Br
H 3C

Cis-4-Bromo-3-methyl
pent-2-ene

4
H3 C

H
2 H
(v)
H 3 1 Br
H
Trans-1-Bromobut-2-ene

12

4
3

CH 3
H
H 2 Br
H 1
(iv)
Cis-1-Bromo-2-methyl
but-2-ene
CH 3
12 H
H
Br
(vi)
H 3
3-Bromo-2-methylpropene
H

Example 3.
Identify all the possible monochloro structural isomers expected
to be formed on free ra dica l monochlorina tion of
(CH 3 )2 CHCH2 CH3 .
Strategy.
Monochlorination under the presence of light is used to identify
the type of H atom which are chemically different in alkanes.
As the given molecule contains 4 different H so it will give 4
monochloro product.
5
CH 3

4
CH 3 CHCH 2 CH 3
3
2
1

CH 3
CH 3 CHCH 2 CH 2 Cl

CH 3
CH 3 CH CH CH 3
Cl

1-Chloro-3methylbutane

2-Chloro-3-methylbutane

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83

Haloalkane & Haloarenes


CH3
CH 3 C CH 2 CH 3
Cl

2-Chloro-2-methylbutane

CH3
Cl CH 2 CH CH2 CH3

1-Chloro-2-methylbutane

Chemically different H can be observe by writting the IUPAC


name of substituted mono chloro product. If replacement of H
by Cl leads to different IUPAC name of compound, then H
will be chemically different, otherwise it will be chemically
same.
Example 4.
Write the products of the following reactions:
(i)

H
+ HBr
H H

(ii)

CH 3 CH2 CH = CH2 + HCl

CH2 C = CH 2 +HBr Peroxide

(iii)

Strategy.
This example tells about the reaction of C=C bond with HX
in absence or presence of peroxide.
Ph

(i)

Ph
+ HBr

H Br CH 3

Mechanism HBr H + Br

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Haloalkane & Haloarenes


1st face
Ph

H
+H

(ii)

Ph +

CH 3 Br
nd

face

CH 3 CH2 CH = CH 2 + HCl

Br
Ph

H
Ph

CH 3

CH 3

H
(S)

Br
(R)
Racemic mixture
Cl
CH 3 CH 2 CH CH3

Mechanism HCl H + Cl

CH 3 CH 2 CH=CH2 + H

CH 3 CH 2 CHCH3

Cl
1 st face
+

CH 3 CH 2 CHCH3
2

nd

CH 3 CH 2

CH 3
H
(S)

Cl

+
H

face
CH 3 CH 2

CH3
Cl
(R)

Racemic mixture
Peroxide
(iii) PhCH 2 CH = CH 2 + HBr
PhCH 2 CH 2 CH 2 Br

Reaction of HBr to alkene under the presence of peroxide


proceeds through free radical mechanism.
Here we use hypothetical benzoyl peroxide to explain the
mecha nism, as it is commonly used as peroxide for
generation of free radicals.
O

Ph C O O C Ph
Ph + H

Br

O
2 Ph C O

2Ph + 2CO 2

Ph H + Br

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85

Haloalkane & Haloarenes


Br
PhCH 2 CHCH2 + PhCH2 CHCH2 Br
(Less stable)
(More stable)

PhCH CH=CH +Br.


2

.Ph

PhCH 2 CHCH2 Br

Ph

PhCH 2 CH 2 CH 2 Br

Example 5.
Haloalkanes react with KCN to form alkyl cyanides as main
product while AgCN forms isocyanides as the chief product.
Explain.
Strategy.
This question is based on ionic & covalent nature of cynide
and some short of knowledge of inorganic compound.
KCN is predominantly ionic and provides cyanide ion in
solution. Although both carbon & nitrogen atoms are in position
to donate electron pairs, the attack takes place mainly through
carbon atom and not through nitrogen atom since CC bond is
more stable than CN bond.
H
D

Cl KCN NC

T
(R)

H
D
T
(S)

Mechanism :
KCN K + CN

H
NC

D C
T

2
Cl SN NC

H
D
T

However, AgCN is mainly covalent in nature and nitrogen is


free to donate electron pair forming isocyanide as the main
product.

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Haloalkane & Haloarenes


Hypothetically
H
Cl

AgCN

CN

H
AgCN

D
T

D
T(S)
2

SN
Cl AgCl
CN

H
D
T
(S)

Example 6.
In the following pairs of halogen compounds, which would
undergo SN 2 reaction faster?
CH 2 Cl and

Cl;

I and

Cl

Strategy.
Always remember tha t SN 2 rea ction proceeds through
transition state.

Easiar the formation of TS, faster the SN 2 reaction will be.


TS can be favoured by 1 alkyl halide, better leaving group
& aprotic solvents.

Here in 1st case,

CH 2 Cl is 1 alkyl halide. Therefore

TS will be formed easily & SN 2 reaction will be faster as


compared to
Nu

Cl which in 2 in nature.

H
SN2
C H
Cl

Nu H
C H
Cl
TS

H
C H
Nu

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87

Haloalkane & Haloarenes

In

2 nd case iodine

will be a better leaving group because of


its large size and therefore it will be released at a faster
rate in the presence of incoming nucleophile than chlorine.
2
therefore
I will undergo faster SN reaction.

Example 7.
Predict the order of reactivity of the following compounds in
S N 1 and S N 2 reactions:
(i)

The four isomeric bromobutanes

(ii) C 6 H 5CH2 Br, C 6 H 5 CH(C 6 H5 )Br,


C 6 H 5CH(CH 3 )Br, C 6H 5 C(CH 3 )(C 6H 5 )Br

Strategy.
(i)

As we have already discussed that SN 2 reaction proceeds


through transition state. Easiar the formation of TS, faster
the SN 2 reaction will be i.e. more reactive via SN 2 . This
TS can be favoured by 1 alkyl halide, better leaving group
& aprotic solvent. When there is competition between two
1 alkyl halide then less hindered 1 alkyl halide react faster
with SN 2 because TS formation will be again easy.

Therefore reactivity order for 4 isomeric bromobutane via SN2


will be.
Br
CH 3
CH 3
CH 3CH2 CH2 CH2 Br CH3 CHCH 2 Br CH3 CH 2 CHCH3 CH 3CBr
CH 3

As SN 1 rea ction proceeds through forma tion of


carbocation so those factors which stabilize the carbocation
stability, they will surely favour SN 1 reaction also. These
factors include hindrance in alkyl halide (3 > 2 > 1),
better leaving group and protic solvent.

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Haloalkane & Haloarenes


Therefore reactivity order for 4 isomeric bromobutane via SN 1
will be just opposite of SN 2 i.e.
CH 3

CH 3

CH 3

CH 3CBr CH 3CH2 CHBr CH 3CHCH 2 Br CH 3CH2 CH 2CH2 Br


CH 3

(ii) Simila r factors can again decide whether they contain


aromatic ring or not.
Reactivity order of SN 2 will be

Ph CH 2 Br

CH3

Ph

Ph CH Br

Ph CH Br

(Less Hindered

More hindered)

Ph
Ph C Br
CH 3

Reactivity order for SN 1 will be


Ph
Ph
CH 3
Ph C Br Ph CH Br Ph CH Br Ph CH 2 Br
CH3
(More stable carbocation
Less stable carbocation formation)

Example 8.
Identify chiral and achiral molecules in each of the following
pair of compounds.
H

(i)

H3 C
Br

H
H 3C
Br
OH

(i)

HO H

(ii) H3 C

(i)

(ii)

H 3C
CH 3

Br

CH 3
OH
(ii)

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89

Haloalkane & Haloarenes


(iii) CH 3CHCH 2 CH 3 CH 3 CH2 CH 2CH2 Br
Br (i)
(ii)
Strategy.
Chira l molecule are those which contain dissymmetry in
molecule i.e. no plane of symmetry & centre of symmetry is
present in the molecule. If molecule have any type of symmetry
then they are considered as achiral.

If a molecule ha s only one chiral carbon i.e. a ll 4


substituents are different then they are considered as chiral
molecule, no matter in which representation molecule is
written as it has no POS or COS.
H

(i)

(Chiral as all 4 atoms/groups of atoms


H3 C
Br OH attached to central Carbon is different)
H
H3 C
Br

(Achiral as central Carbon contain


two bromine atoms)
Br

HO H

(ii)

(iii)

H3 C

(Chiral as all four atoms/groups


are different)
CH 3

H3 C

CH 3

H OH

(Achiral as two same ethyl groups are


attached to central Carbon)

CH 3 CHCH 2 CH 3 (Chiral as all four atom/groups of


atoms are different)
Br

CH3 - CH 2 - CH 2 - CH 2 - Br

90

(Achiral as no carbon have all


the four substituent different)

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Haloalkane & Haloarenes


Example 9.
Although chlorine is an electron withdrawing group, yet it is
ortho-, para- directing in electrophilic aromatic substitution
reactions. Why?
Strategy.
It should alway kept in mind that orienta tion in aromatic
substitution is controlled by resonance because of stabilization
of intermediate carbocation and reactivity is controlled by
inductive effect.

As we all know chlorine withdraws electron density


through inductive effect due to difference in
electronegativity of carbon & chlorine but release electrons
through resonance if chlorine is attached to carbon which
has double bond.

Although by inductive effect, chlorine destabilizes the


intermediate carbocation formed during the electrophilic
substitution.
Cl

Cl
+ E+

H
E

But as chlorine have 3 lone pairs & due to one of the lone pair
it stabilizes the carbocation by resonance.

As this effect is more pronounced at ortho & para position


because carbon directly attach with chlorine have positive
cha rge in ortho & pa ra substitution & no positive on
carbon directly attached with chlorine in meta substitution.
Cl

:Cl
+E

H
E

+Cl

H
E

Cl
+

H
E

Cl

H
E

(Extra stability due to more resonance structure )

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Haloalkane & Haloarenes


Cl

Cl
+E+

Cl

Cl

H
H
E
+ E
(No extra stability)

:Cl

Cl
+E

Cl

Cl+

H
E

Cl

+
+

E H E H E H E H
(Extra stability due to more resonance structure)

Although inductive effect which is stronger than resonance


cause net electron withdrawl & cause net deactivation,
the resonance effect oppose the inductive effect for ortho
& para position and promote the attack of E at ortho &
para position because of extra stability by resonance.

92

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Intext Problem:
Intext Question 1.
Write structures of the following compounds:
(i)

2-Chloro-3-methylpentane

(ii) 1-Chloro-4-ethylcyclohexane
(iii) 4-tert. Butyl-3-iodoheptane
(iv) 1,4-Dibromobut-2-ene
(v) 1-Bromo-4-sec. butyl-2-methylbenzene.
Strategy.
Structure of any organic compound follow the same basic
pattern of nomenclature i.e. 2 Prefix + 1 Prefix + Word root +
1 Suffix + 2 Suffix.
(i)

2-Chloro-3-methylpentane
2 Prefix
Cl
1 2

(ii)

3 4

Word root 1suffix

1-Chloro-4-ethylcyclohexane
1Prefix Word root 1suffix

2 Prefix

Cl
1 2
6
5 4 3

(iii) 4-tert. Butyl-3-iodoheptane


Word root 1suffix

2 Prefix
2
1

6
3 4 5
I

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Haloalkane & Haloarenes


(iv) 1,4-Dibromobut-2-ene
2 Prefix Word root 1suffix
2

Br
1

4
3

Br

(v) 1-Bromo-4-Sec butyl-2-methylbenzene


2 Prefix

6
5

1 Prefix +word root + 1 suffix

Br
1 2 CH
3
4

Intext Question 2.
Why is sulphuric acid not used during the reaction of alcohols
with KI?
Strategy.
Sulphuric acid is not used during the reaction of alcohol with
KI because sulphuric a cid is dehydra ting agent along with
oxidizing agent. It will produce alkene instead of alkyl halide
so 95% phosphoric acid is used to form alkyl iodide in reaction
with alcohol & KI.
HypotheticallyH 2 SO4 H + HSO4

CH 3 CH 2 OH +H

+ H HSO 4

CH 2 CH 2 O
H

CH2 = CH2
H H 2 O
H 2SO 4

But in presence of H3 PO4 which is weak acid


H3 PO 4

94

H + H 2 PO 4

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CH 3 CH 2 OH + H

+ H

CH 3 CH 2 O

I
H 2O

CH3 CH 2 I

It also converts KI to corresponding HI which are then oxidised


to I2 therefore H2SO4 is not used for replacement of OH group
by I.
Intext Question 3.
Write structures of different dihalogen derivatives of propane.
Strategy.
Dihalogen derivative of propane means 2 hydrogen of propane
are replaced by 2 halogens. Four structures can be obtained by
replacing 2H by 2 Cl. these are
CH 3 CH2 CHCl 2
I

CH 3 CCl 2 CH 3
II

CH 3 CH CH2

CH 2 CH 2 CH 2

Cl
III

Cl

Cl

Cl
IV

Intext Question 4.
Among the isomeric alkanes of molecular formula C 5 H 12 ,
identify the one that on photochemical chlorination yields
(i)

A single monochloride.

(ii) Three isomeric monochlorides.


(iii) Four isomeric monochlorides.
Strategy.
Photochemical chlorination in alkane tells about the type of
chemically different hydrogen. Therefore first draw all the
isomers and then look for chemically different H.
Isomers of C5H12 will be
I

II

III

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(i)

A single monochloride means, only one type of H is present


in alkane. Therefore molecule will be III
Cl 2
h

Cl

(ii) 3 isomeric monochloride means 3 types of chemica lly


different H is present therefore it will be I
Cl

Cl

Cl 2
h

Cl

(iii) Similarly 4 isomeric monochlorides means 4 types of


chemically different H is present, Therefore it will be II
Cl
+

Cl 2
h

Cl
+

+ Cl
Cl

Intext Question 5.
Draw the structures of major monohalo products in each of
the following reactions.
OH
+ SOCl 2

(i)

CH2 CH 3

(ii)

(iii)

(iv)

O2N
CH 2 OH
HO

Br2 , heat or
UV light

+ HCl heat

CH 3
+ HI

(v) CH3 CH 2 Br + NaI

(vi)

96

heat
+ Br2 UV
light

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Strategy.
This question tells about the importance of reaction mechanism.
OH
+ SOCl 2

(i)

Cl

Mechanismm:O

O
+ Cl S Cl HCl

O
O S SO
Cl
2
Cl (SN i )
(By nucleophilic
substitution internal)

Br

(ii)

Br2 , heat
or, light

O2N

O2N

Mechanism:Br

Br

2 Br

Br
Br
O2N

+ Br

HBr O N
2

O2N

(iii)

(Free radical)
(By Free radical formation)

OH HCl, Heat
HO

Cl
HO

Mechanism:-

HO

OH + H +

H H O
2
+ H
HO

O
HO

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+

CH3

(iv)

Cl
HO
(By SN 1 reaction)

Cl

HO

CH 3
I

+ HI

Mechanism CH3 +
+H

+ CH 3

CH 3
I

(By electrophilic addition)

(v) CH3 - CH 2 - Br + NaI


CH 3 - CH2 - I
Mechanism:NaI Na + I

CH 3 CH 2 Br

H3 C
I

H
Br

CH3 CH 2 I

H
(By SN 2 reaction)
+ Br2

(vi)

heat/UVlight

Mechanism:
Br

Br

2 Br

H
Br
HBr

Br

Br

(Allylic free radical Substitution)

98

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Intext Question 6.
Arrange each set of compounds in order of increasing boiling
points.
(i)

Bromometha ne,
Dibromomethane.

Bromoform,

Chlorometha ne,

(ii) 1-Chloropropane, Isopropyl chloride, 1-Chlorobutane.


Strategy.
Boiling point of any organic molecule depends on hydrogen
bonding, vander waal force of attraction i.e. molecular mass,
surface area, dipole moment in decreasing order. This means
the role of H-bonding is more contributing than molecular mass
than dipole-dipole interaction.
(i) This question is ba sed on molecular mass. More the
molecular mass more will be the boiling point.

CHBr3 > CH 2 Br2 > CH3 Br > CH 3 Cl

(ii) This is based on molecular mass along with surface area.


Cl >

Cl

Cl
>

Intext Question 7.
Which alkyl halide from the following pairs would you expect
to react more rapidly by an SN 2 mechanism? Explain your
answer.
(i)

CH 3CH2 CH 2 CH2 Br or CH3 CH 2 CHCH 3


Br

CH 3

(ii)

CH 3CH2 CHCH 3 or H3 CCBr


Br
CH 3

(iii) CH 3CHCH 2 CH 2 Br or CH 3 CH 2 CHCH 2 Br


CH 3
CH 3

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Strategy.
As earliar said , SN 2 reaction proceeds through transition state.
More favourable the formation of TS, more reactive the molecule
via SN 2 . This TS is more favourable in less hindered alkyl halide
so
(i)

CH3 - CH 2 - CH 2 - CH 2 - Br

Br
CH 3 CH2 CH CH 3

1 alkyl halide

2 alkyl halide

(more favourable for TS)

(Less favourable for TS


due to steric factor)

Therefore CH3 CH 2 CH 2 CH 2 Br is more reactive than


Br
CH 3 CH2 CH CH 3 .
Br

(ii)

CH 3
CH 3 C Br

CH 3 CH2 CH CH 3

CH 3

2 alkyl halide

3 alkyl halide

(more favourable)

(Less favourable as 3 methyl


group causes steric hindrance)
Br

Therefore CH 3 CH2 CH CH 3 is more reactive than


CH 3
CH 3 C Br
CH 3

100

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CH 3
(iii) CH 3 CH CH 2 CH 2 Br
1 alkyl halide
(more favourable)
substituted methyl group is far form
halogen so creat less steric hindrance
CH 3
CH3 CH 2 CH CH2 Br
1 alkyl halide
Substituted methyl group is near
by halogen so create more hindrane
CH 3
hence CH 3CHCH 2 CH 2Br is more reactive than

CH 3
CH 3CH2 CHCH 2Br

Intext Question 8.
In the following pairs of halogen compounds, which compound
undergoes faster S N 1 reaction?
Cl

(i)

Cl
and
Cl

(ii)

and

Cl

Strategy.
As earlia r sa id SN 1 rea ction proceed with formation of
carbocation as an intermediate. So more stable the carbocation,
more favourable the SN 1 reaction will be.

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Cl

(i)

3 carbocation
(more stabilized by 3 +I effect & 9 HC)

Cl

2 carbocation
(Less stable)

Cl

Therefore

is more reactive than

Cl

Cl

(ii)

2 carbocation
(more stable)
+

Cl

1 carbocation
(Less stable)

Cl

Therefore

is more reactive than


Cl

Intext Question 9.
Identify A, B, C, D, E, R and R 1 in the following:
Br + Mg dry ether
R Br + Mg

dry ether

A
D2 O

H 2O

CH 3 CHCH3
D

CH 3 CH 3
H 2O
Mg
D
E
CH3 Na/ether R'X
CH 3
CH 3 CH 3

102

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For SN1

Haloalkane & Haloarenes


Strategy.
This question is based on reaction of organometaic compounds.
Br + Mg

dry ether
(Preparation
of GR)

Mg Br
A

H 2O
(R eaction of GR
by acidic H)

D O

CH 3 CH CH 3 + Mg dry CH3 CH CH3 2 CH 3 CH CH3


ether
Br
Mg (Reaction of G R D
(Preparation
RBr

CH 3 CH 3
CH 3 C C CH3
CH 3 CH3

Br
C

of G R)

Na /ether
(Wurtz
reaction)

CH 3

by acidic D)

Mg

CH3 C X
(G R)
CH 3
(R1X)

CH 3
H2 O
CH 3 C Mg
CH 3
(R eaction of GR
CH 3
by acidic H)
D

CH3
CH3 C Mg X
CH3
D

CH 3
C H
CH 3
E

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Exercise Problems:
Exercise Problem 1.
Name the following halides according to IUPAC system and
classify them as alkyl, allyl, benzyl (prima ry, secondary,
tertiary), vinyl or aryl halides:
(i)

(CH 3 )2 CHCH(Cl)CH3

(ii)

CH3 CH 2 CH(CH 3 )CH(C 2 H 5 )Cl

(iii)

CH 3 CH 2 C(CH 3 )2 CH 2 I

(iv)

(CH 3 )3 CCH 2 CH(Br)C 6H 5

(v)

CH3 CH(CH 3 )CH(Br)CH 3

(vi)

CH3 C(C 2 H 5 )2 CH 2 Br

(vii) CH 3 C(Cl)2 (C 2 H 5 )CH 2CH3


(viii) CH3 CH = C(Cl)CH 2 CH(CH 3 )2
(ix)

CH3 CH = CHC(Br)(CH 3 )2

(x)

p - ClC 6H 4 CH 2 CH(CH 3 )2

(xi)

m - ClCH 2 C 6 H 4 CH 2C(CH3 )3

(xii) o - Br - C 6 H 4 CH(CH3 )CH2 CH3


Strategy.
CH3 Cl
(i) CH 3 CH CH CH 3
4
3
2
1

2-Chloro-3-methylbutane (2 alkyl halide)


CH3 Cl
(ii) CH 3 CH2 CH CH C 2 H5 or

104

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CH 3 Cl
CH 3 CH 2 CH CH CH 2 CH 3
6
5
4
3
2
1
3-Chloro-4-methylhexane
(2 alkyl halide)

CH3
CH3 CH2 C CH 2 I
2
(iii)
4
3
1
CH3
1-Iodo-2,2-dimethylbutane (1 alkyl halide)
Br
CH3
CH 3 C CH 2 CH C6 H 5
3
4
2
1
(iv)
CH3
1-Bromo-3,3-dimethyl-1-phenylbutane
(2 benzylic halide)

CH 3 Br

(v)

CH 3 CH CH CH 3
4
3
2
1
2-Bromo-3-methylbutane (2 alkyl halide)
C2H 5

(vi) CH 3 C CH2 Br
C2H 5

or

4
5
CH2 CH3
3
CH 3 C CH2 Br
CH2 CH3
1
2
3-Bromomethyl-3-methylpentane
(1 alkyl halide)

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Cl
(vii) CH 3 C CH 2 CH 3 or
C2H 5
Cl
1
3 2
CH 3 C CH2 CH3
CH2 CH3
4
5
3-Chloro-3-methylpentane (3 alkyl halide)

Cl CH 3
CH 3 CH = C CH 2 CH CH3
(viii)
1
2
3 4
5
6
3-chloro-5-methylhex-2-ene (2 vinyl halide)
Br
CH 3 CH = CH C CH 3
1
2
3 4
5
(ix)
CH 3
4-Bromo-4-methylpent-2-ene (3 Allyl halide)
1

CH 2 CH CH3

(x)

CH 3

Cl
1-Chloro-4-(2-methylpropyl)benzene
Aryl halide

(xi)

106

CH 3
1
2
CH 2 C CH 3
3
3
2 CH 3
1 CH 2 Cl
1-Chloromethyl-3-(2,2-dimethylpropyl)benzene
1 Benzyl Halide

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H3 C CH CH 2 CH 3
2 Br
(xii)
1
1-Bromo-2-(1-methylpropyl)benzene
Aryl Halide

Exercise Problem 2.
Give the IUPAC names of the following compounds:
(i)

CH 3 CH(Cl)CH(Br)CH 3

(ii) CHF2 CBrCIF


(iii) ClCH 2 C CCH 2 Br
(iv) (CCl 3 )3 CCl
(v) CH 3 C(p - ClC 6 H 4 )2 CH(Br)CH 3
(vi) (CH 3 )3 CCH = C(Cl)C 6 H 4 I - p
Strategy.
Cl

Br

(i)

CH 3 CH CH CH 3 2-Bromo-3-chlorobutane
4
3
2
1

(ii)

F Br
2 1
HC C Cl 1-Bromo-1-chloro-1,2,2-trifluoroethane
F F

4
3 2 1
(iii) Cl CH 2 C C CH 2 Br 1-Bromo-4-chlorobut-2-yne

Cl
Cl Cl C Cl
2
1,1,1,2,3,3,3-heptachloro-21
(iv) Cl C
C Cl
trichloromethylpropane
3
Cl Cl C Cl
Cl

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Cl

(v)

Br
1
3 4
2
CH3 C CH CH 3

Cl
3-Bromo-2,2-bis-(4-chlorophenyl) butane
CH 3 CH 3 3 2
CH 3 C CH 4
I
1
(vi)
CH 3
1-Iodo-4-(1,2,2-trimethylpropyl)benzene

Exercise Problem 3.
Write the structures of the following orga nic ha logen
compounds.
(i)

2-Chloro-3-methylpentane

(ii) p-Bromochlorobenzene
(iii) 1-Chloro-4-ethylcyclohexane
(iv) 2-(2-Chlorophenyl)-1-iodooctane
(v) Perfluorobenzene
(vi) 4-tert-Butyl-3-iodoheptane
(vii) 1-Bromo-4-sec-butyl-2-methylbenzene
(viii) 1,4-Dibromobut-2-ene
Strategy.
Cl

Cl

4
3
5
2
(i)
1
(ii)
2-Chloro-3-methylpentane

108

Br
p-Bromochlorobenzene

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Cl
1 2
4 3

(iii)

1-Chloro-4-ethylcyclohexane

(iv)

Cl
8
2 3 4
6
1
5 7
2-(2-chlorophenyl)-1-iodooctane
I

(v)

(vi)

F
F
Perfluorobenzene
1 2

4 6 7
5
I
4-tert-Butyl-3-iodoheptane

(vii)

Br
1 2

3
4
1-Bromo-4-sec-butyl
-2-methylbenzene
5

Br

(viii)

4 Br
1 2 3
1,4-Dibromobut-2-ene

Exercise Problem 4.
Which one of the following has the highest dipole moment?
(i)

CH 2 Cl 2

(ii) CHCl 3 (iii)

CCl 4

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Strategy.
CH2 Cl 2 > CHCl 3 > CCl 4
(1.60D) (1.03D) (0D)

Exercise Problem 5.
A hydrocarbon C 5 H 10 does not react with chlorine in dark but
gives a single monochloro compound C 5 H9 Cl in bright sunlight.
Identify the hydrocarbon.
Strategy.
Cl 2 / Dark
No reaction
C 5 H10
Cl 2 /h
A
C5 H 9Cl (Single monochloro product)
only one type of H
CH3
CH3
Cl 2 / h
so, CH 3 C CH3
CH3 C CH2 Cl
CH3

CH3

Exercise Problem 6.
Write the isomers of the compound having formula C 4 H 9 Br .
Strategy.
Isomers of C 4 H 9 Br

Br

Br

Br

Br
II

III

IV

Exercise Problem 7.
Write the equations for the preparation of 1-iodobutane from
(i)

1-butanol

(ii) 1-chlorobutane

(iii) but-1-ene.

110

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Strategy.
HI

(i)

OH

(ii)

Cl

KI

B H /THF
H2O 2/OH

(iii)

HI

OH

2 6

Exercise Problem 8.
What are ambident nucleophiles? Explain with an example.
Strategy.
Ambident nucleophiles are those which can attack from two
or more than two place resulting in formation of two or more
products.
Ex

O
R C NH

O
R C = NH

Here N or O may attack to any electron deficient center to give


product.
Exercise Problem 9.
Which compound in each of the following pairs will react faster
in SN 2 reaction with OH ?
(i)

CH3 Br or CH 3 I

(ii) (CH 3 )3 CCl or CH 3Cl

Strategy.
(i) CH3 I > CH3 Br
Here I is better leaving group than Br
(ii)

CH3
CH 3 Cl > CH3 C Cl
CH3

Steric hindrance is less in first case so nucleophile can easily


attack over it.

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Exercise Problem 10.
Predict a ll the a lkenes tha t would be formed by
dehydrohalogenation of the following ha lides with sodium
ethoxide in ethanol and identify the major alkene.
(i)

1-Bromo-1-methylcyclohexane

(ii) 2-Chloro-2-methylbutane
(iii) 2,2,3-Trimethyl-3-bromopentane.
Strategy.
Br
HBr
EtONa/EtOH

(i)

+
(minor) (major)

Cl

EtONa/EtOH

(ii)

(iii)

HCl

Br

+
(minor) (major)

EtONa/EtOH
HBr

+
(E)
(major)

(Z)

Exercise Problem 11.


How will you bring about the following conversions?
(i)

Ethanol to but-1-yne

(ii) Ethane to bromoethene


(iii) Propene to 1-nitropropane
(iv) Toluene to benzyl alcohol
(v) Propene to propyne
(vi) Ethanol to ethyl fluoride
(vii) Bromomethane to propanone
(viii) But-1-ene to but-2-ene
(ix)

1-Chlorobutane to n-octane

(x)

Benzene to biphenyl

112

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Strategy.
(i)

OH

OH

(ii)

HI

HC CH/NaNH 2
(1 eq)

Br
HI

Br
Br2 /h

Br

Br2 / h

Br
Br

KOH/alc

NO 2

(iii)

OH HI

B 2H 6
H 2O 2 / OH

CH3

I AgNO 2

NO 2

CH 2 OH

(iv)
CH 3

CH 2 Cl

CH 2 OH

H2 O /

Cl 2 /h

(v)
Br
Br2 /CCl 4

Br NaNH2
liq NH 3

(vi)

OH
HF/BF

OH

(vii) H C Br
3

i) CH3 -C -H
Mg/Ether
H 3 C Br
CH 3 MgBr

ii) H3O+

OH
CH 3 CH CH3

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OH
O
Cu/
CH 3 C CH3
CH 3 CH CH3

(viii)
H O/H+

OH

H SO (conc)

2
4

Cl

(ix)

Cl Na/THF

Wurtz reaction

(x)
Na
Ether

(Fitting reaction)

Exercise Problem 12.


Explain why
(i)

the dipole moment of chlorobenzene is lower than that of


cyclohexyl chloride?

(ii) alkyl halides, though polar, are immiscible with water?


(iii) Grignard reagents should be prepared under anhydrous
conditions?
Strategy.
(i)

Chlorobenzene have partica l double bond cha racter in


C Cl bond but chlorocyclohexane have fully single bond
character.
As q d
so d decreases, decreases.

(ii) RX is polar in nature due to electronegativity difference of


C & X but bulky alkyl group make RX immiscible due to
non polar nature.

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(iii) Grignard reagent should be prepared under anhydrous
condition because of its reactivity with proton to form RH.
Exercise Problem 13.
Give the uses of freon 1 2, DDT, carbon tetrachloride and
iodoform.
Strategy.
Use of Freon-12
Freon 12 (CCl 2 F2 ) is used for aerosol propellants, refrigeration
& air conditioning purposes.
Use of DDT
DDT is used as an insecticides espacially for mosquito.
Use of CCl 4
CCl 4 is used in manufacture of refrigerants & propellants for

aerosol. It is used as a solvent in many organic reaction along


with fire extinguisher.
Use of iodoform
Iodoform is generally used as an antiseptic.
Exercise Problem 14.
Write the structure of the major organic product in each of the
following reactions:
(i)

CH 3CH2 CH2 Cl + NaI

(ii)

(CH 3 )3 CBr + KOH

Acetone
Heat

ethanol
Heat

(iii) CH 3CH(Br)CH 2 CH 3 +NaOH

water

aq. ethanol
(iv) CH3 CH 2 Br + KCN

(v) C 6 H 5ONa + C 2 H 5 Cl

(vi) CH 3 CH 2 CH 2 OH + SOCl 2

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peroxide
(vii) CH3 CH 2 CH = CH 2 + HBr

(viii) CH3 CH = C(CH 3 )2 + HBr

Strategy.
acetone
(i) CH3 CH 2 CH 2 Cl + NaI
CH3 CH 2 CH2 I

(ii)

CH 3
CH 3
Ethanol
CH 3 C Br +KOH
CH 3 C = CH 2

CH 3

Br
OH
H2O
(iii) CH 3 CH CH 2 CH 3
CH 3 CH CH 2 CH 3
aq acetone
(iv) CH3 CH 2 Br + KCN

CH 3 CH2 CN

O CH2 CH3

(v)

C 6 H5 ONa + CH3 CH 2 Cl

(vi) CH 3 CH 2 CH 2 OH + SOCl 2
CH 3 CH 2 CH 2 Cl
Peroxide CH CH CH CH Br
(vii) CH3 CH 2 CH = CH 2 + HBr
3
2
2
2

Br
(viii) CH 3 CH = C
+ HBr
CH 3 CH2 C CH 3
CH 3
CH3

CH 3

Exercise Problem 15.


Write the mechanism of the following reaction:
EtOH-H O

2
nBuBr + KCN
nBuCN

Strategy.
Br + KCN

116

EtOH H 2 O

CN

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Haloalkane & Haloarenes


KCN K + + CN

CN
Br

CN

CN

Br

Exercise Problem 16.


Arrange the compounds of each set in order of rea ctivity
towards SN 2 displacement:
(i)

2 - Br omo -2 - me th y lbu ta n e, 1 -B ro mop en t a n e,


2-Bromopentane

(ii) 1 -Bromo-3 -methylbuta ne, 2-Bromo-2 -methylbuta ne,


2-Bromo-3-methylbutane
(iii) 1-Bromobutane, 1-Bromo-2,2-dimethylpropane, 1-Bromo2-methylbutane, 1-Bromo-3-methylbutane.
Strategy.
(i) Br

(ii)

Br

Br

Br

>

(decreasing order of SN2 )

>
Br

>

>

(decreasing order of SN 2 )

Br

(iii) Br

> Br

>

Br

> Br

Exercise Problem 17.


Out of C 6 H 5 CH 2 Cl and C 6 H 5 CHClC 6 H5 , which is more easily
hydrolysed by aqueous KOH?
Strategy.
CH2 Cl

CH 2
(Less stable)

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117

Haloalkane & Haloarenes


Cl
CH

CH
(More stable)

As II have more stable carbocation so hydrolysis of II is faster


than I
Exercise Problem 18.
p-Dichlorobenzene has higher m.p. and solubility than those
of o- and m-isomers. Discuss.
Strategy.
Melting points mainly depents upon packing so
Cl

Cl
>

Cl

Cl

Cl

>

Cl

Exercise Problem 19.


How the following conversions can be carried out?
(i)

Propene to propan-1-ol

(ii) Ethanol to but-1-yne


(iii) 1-Bromopropane to 2-bromopropane
(iv) Toluene to benzyl alcohol
(v)

Benzene to 4-bromonitrobenzene

(vi)

Benzyl alcohol to 2-phenylethanoic acid

(vii)

Ethanol to propanenitrile

(viii) Aniline to chlorobenzene


(ix)

2-Chlorobutane to 3, 4-dimethylhexane

(x)

2-Methyl-1-propene to 2-chloro-2-methylpropane

(xi)

Ethyl chloride to propanoic acid

118

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Haloalkane & Haloarenes


(xii)

But-1-ene to n-butyliodide

(xiii) 2-Chloropropane to 1-propanol


(xiv) Isopropyl alcohol to iodoform
(xv)

Chlorobenzene to p-nitrophenol

(xvi) 2-Bromopropane to 1-bromopropane


(xvii) Chloroethane to butane
(xiii) Benzene to diphenyl
(xix) tert-Butyl bromide to isobutyl bromide
(xx)

Aniline to phenylisocyanide

Strategy.
OH

(i)

H2O 2/OH
) B

BH

2 6

OH

(ii)

OH

OH

Br2

CCl 4

H2 SO 4

180C

Br

Br

alc KOH

Br

NaNH

NaNH2
CH 3 -CH2 -I
HC CH

HC C Na

CH3 CH 2 C CH
?

Br

(iii)

Br

alc KOH/80
Br

CH 3

HBr

Br

CH2 OH
?

(iv)
CH 3

CH2 Cl
Cl 2/h

CH2 OH
aq KOH

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119

Haloalkane & Haloarenes


NO 2
?

(v)

Br

NO 2

Br

Br2/FeBr3

HNO 3+H2SO 4

Br

CH 2 - OH

Ph CH 2 C OH
?

(vi)

CH2 OH

COOH

KMnO 4 /OH

COCl

PCl 5

CH2 COOH

(i) CH 2 N 2 /Ag 2 O

(ii) H 2 O /H

?
(vii) CH 3 - CH 2 - OH
CH 3 - CH2 - C N

SOCl

KCN
2
CH3 CH 2 OH
CH 3CH 2 Cl
CH3 CH 2 C N

Cl

NH 2
?

(viii)

NH 2

(ix)

Cl

Cl

NaNO 2/HCl

0-5C

Cl

N 2Cl
KCl

(Sandmeyer reaction)
?

Na/Et O
(Wurtz reaction)

120

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?

(x)

Cl

HCl

Cl

(Markownikoff rule)
OH

(xi)

Cl

(xii)

OH

H O/H+

KCN

CN

Cl

I
-

BH

H2O 2 /OH
) B

3 (

HI

OH

Cl

OH

(xiii)
Cl

alc KOH/80C

OH

(xiv)

B2H6 (

H2O 2 /OH
) 3B

OH

CHI 3

OH

NaOH/I 2

CH 3 C ONa + CHI 3

OH

Cl
?

(xv)

NO 2

Cl

OH
KOH/
High T

CH 3COCl

O
O
OCCH 3 OCCH 3
NO 2+

OH

H 2O/H +

NO 2

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NO 2

121

Haloalkane & Haloarenes


Br

(xvi)

Br

Br

HBr/(PhCO) O

alc KOH/

2 2

Br

(xvii)

Cl
Na/THF

Cl
(Wurtz reaction)
?

(xviii)

Cl
Cl /FeCl

2
3

Na/Ether
(Fitting reaction)

CH 3
CH 3
?
(xix) CH 3 C Br
CH 3 CH CH 2 Br
CH 3
CH 3
CH 3
EtOH/
CH 3 C Br
CH 3 C = CH 2
CH 3

CH 3
CH 3
HBr

CH 3 C = CH 2 (PhCO)2 O2 CH 3 CH CH 2 Br

N C

NH 2
?

(xx)

NH 2

N C
CHCl 3/KOH

Exercise Problem 20.


The treatment of alkyl chlorides with aqueous KOH leads to
the formation of alcohols but in the presence of alcoholic KOH,
alkenes are major products. Explain.

122

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Strategy.
Trea tment of alkyl chloride with a queous KOH leads to
formation of alcohol because OH is a good nucleophile but in

presence of alcoholic KOH give alkene because OR is a good


base which is formed due to acid-base reaction.
KOH K + + OH

In presence of H 2 O

H O H + OH OH + H 2 O

In presence of ROH

R O H +OH RO +H 2 O

Due to bulky size of RO , it will abstract proton to give alkene


as a product.
Exercise Problem 21.
Primary alkyl halide C 4 H 9 Br (a) reacted with alcoholic KOH
to give compound (b). Compound (b) is reacted with HBr to
give (c) which is an isomer of (a). When (a) is reacted with
sodium metal it gives compound (d), C 8 H18 which is different
from the compound formed when n-butyl bromide is reacted
with sodium. Give the structural formula of (a) and write the
equations for all the reactions.
Strategy.
C 4 H9 Br
A
Primary alkyl halide

alc KOH

Isomers of C 4 H9 Br
Br ,
1 Alc

Br
2 Alc

HBr

C
Isomer of A
Na
C 8 H18
D
Different from the reaction of
n-butyl bromide with Na.
B

Br ,

,
1 Alc

Br
3 Alc

Br should not be taken as A because it is already said.


So only one primary alkylhalide is present & it is

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123

Haloalkane & Haloarenes


Br

A=

Br

HBr

Br alc KOH

Na
dry ether

Exercise Problem 22.


What happens when
(i)

n-butyl chloride is treated with alcoholic KOH,

(ii) bromobenzene is treated with Mg in the presence of dry ether,


(iii) chlorobenzene is subjected to hydrolysis.
(iv) ethyl chloride is treated with aqueous KOH,
(v) methyl bromide is treated with sodium in the presence of
dry ether,
(vi) methyl chloride is treated with KCN?
Strategy.
alc KOH
Cl

(i)
Br

Mg/dry ether

(ii)

Mg

Br

(Grignard reagent)

Cl

(iii)

HO

No reaction will occur at room temperature

because C Cl bond has double bond character but at


62 3k a nd 30 0 atm, phenol will be obta ined in basic
medium.
aq KOH
(iv) CH 3 - CH 2 - Cl

CH3 - CH 2 - OH

Na/dry ether

(v) CH3 - Br
Wurtz reaction CH 3 - CH 3
KCN
(vi) CH 3 - Cl

CH 3 - CN

124

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Alcohol, Phenol & Ether

Unit

Alcohol, Phenol & Ether

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125

Alcohol, Phenol & Ether

Objective
This unit give you a n understanding of Alcohol,
Phenol & Ether and covers following topics:

126

IUPAC nomenclature of alcohol, phenol & ethers.


Classification of alcohol, phenol & ethers.
Preparation of alcohol, phenol & ether.
Physical properties of alcohol, phenol & ether.
Chemical reactions of alcohol, phenol & ether.
Some commercially important alcohols.

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Alcohol, Phenol & Ether

Solved Example:
Example 1.
Give IUPAC names of the following compounds:
(i) CH 3 CH CH CH CH 2 OH (ii) CH 3 CH O CH 2 CH 3
Cl CH 3 CH 3
CH 3
H3 C

OH

CH 3

(iii)

(iv)

NO 2
OC 2 H 5

Strategy.
(i)

(ii)

5
4
3
2
1
CH 3 CH CH CH CH2 OH
Cl CH 3 CH 3
4-Chloro-2,3-dimethylpentan-1-ol
3
2
CH 3 CH O CH 3 CH 3
1
CH3
2-Ethoxypropane

OH
H3 C 6 1 2 CH
3

(iii)

3
4
2,6-Dimethylphenol
NO 2
OC H
2 1 2 5

(iv)

1-Ethoxy-2-nitrocyclohexane

Example 2.
Give the structures and IUPAC names of the products expected
from the following reactions:
(a) Catalytic reduction of butanal.

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127

Alcohol, Phenol & Ether


(b) Hydration of propene in the presence of dilute sulphuric
acid.
(c) Reaction of propanone with methylmagnesium bromide
followed by hydrolysis.
Strategy.
O
H

Catalytic reduct ion

OH
Butan-1-ol
(Reduction can be carried out
by LiAH 4 or NaBH4)

(A)

H 2 O / H 2 SO 4

(B)

OH
Propan-2-ol

(C)

CH 3MgBr

OMgBr

H 2O

OH
2-Methylpropan-2-ol

Example 3.
Arrange the following sets of compounds in order of their
increasing boiling points:
(a) Pentan-1-ol, butan-1-ol, butan-2-ol, ethanol, propan-1-ol,
methanol.
(b) Pentan-1-ol, n-butane, pentanal, ethoxyethane.
Strategy.
Boiling point of compount depends on extent of hydrogen
bonding with other molecule and molecular weight. Lower the
molecular weight, lower the boiling point & larger the hydrogen
bonding, larger the boiling point, so order of increasing boiling
point follow.
OH
(A) CH 3OH< CH 3CH 2 OH<CH3 CH 2 CH 2 OH <CH 3 CH 2 CHCH3
< CH3 CH 2 CH 2 CH 2 OH < CH 3CH2 CH2 CH2 CH2 OH

128

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Alcohol, Phenol & Ether


(B) CH3 CH 2 CH 2 CH 3 < CH 3 CH 2 OCH 2 CH 3 <
O
CH 3 CH 2 CH2 CH 2 CH<CH3 CH2 CH 2 CH2 CH 2 OH

Example 4.
Arrange the following compounds in increasing order of their
acid strength: Propan-1-ol, 2,4,6-trinitrophenol, 3-nitrophenol,
3,5-dinitrophenol, phenol, 4-methylphenol.
Strategy.
Acidic strength depends on the stability of conjugate base, more
stable the conjugate base, more acidic the molecule will be.

CH3 CH2 CH2 OH CH3 CH2 CH2 O


(Conjugate base destabilize due to +I of Alkyl group)

OH
O 2N

O2N

NO 2

NO 2

NO 2
NO 2
(Conjugate base is stabilize due to M &
I of NO2 along with ortho effect)
OH

NO 2
NO 2
(Conjugate base is stabilized due to I of NO2)
OH
O

O 2N

NO 2

NO2
O 2N
(Conjugate base is stabilize due to two I of NO2)

OH

(Conjugate base is stabilized due to


resonance with phenyl group)

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129

Alcohol, Phenol & Ether


OH

CH 3
CH 3
(Conjugate base is destabilize due to
+I nature of methyl group)

So Increasing order of acid strength follows


OH

OH
<

CH 3CH 2CH2 OH <

OH
<
NO 2

CH3

OH

OH

<

<
O2N

O2N

NO 2

NO 2
NO 2

Example 5.
Write the structures of the major products expected from the
following reactions:
(a) Mononitration of 3-methylphenol
(b) Dinitration of 3-methylphenol
(c) Mononitration of phenyl methanoate.
Strategy.
OH

(A)

Mononitration

CH3

Electrophilic substitution in disubstituted benzene in which both


groups are electron donating, then more powerful donating
group decide the orientation. So,

130

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Alcohol, Phenol & Ether


More powerful due to + M

OH

CH3

Less powerful due to hyper conjugation & + I

So
OH

OH

OH

NO 2

OH
+

O2N

CH 3
NO 2
1,2,3 substitution 1,2,4 substitution 1,2,4 substitution
(without IUPAC) (without IUPAC) (without IUPAC)
CH 3

CH 3

CH 3

1,2,3 has more steric crowding so both product of 1,2,4 will be


the major product.
OH

(B)

OH
Mono
nitration

CH3

O2N

OH

O 2N

CH 3

CH 3
NO 2

Mono
nitra tion

OH
CH 3
NO 2

In trisubstituted benzene also, most electron donating group


will decide the orientation of incomming substituent.
O
OCH

(C)

O
OCH

Mono
nitration

O
OCH
NO 2

(1,2-substitution)
NO 2
(minor)
(1,4-substitution)
(major)

1,4 substituted compound will be major due to less Vander


wall repulsion.

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131

Alcohol, Phenol & Ether


Example 6.
The following is not an appropriate reaction for the preparation
of t-butyl ethyl ether.
CH3
CH 3
C 2 H5 ONa + CH3 C Cl
CH3

(i)

CH3 C OC 2 H5
CH 3

What would be the major product of this reaction ?

(ii) Write a suitable reaction for the preparation of t-butylethyl


ether.
Strategy.

(i)

CH 3
CH 3
C 2 H 5ONa
CH 3 C Cl
CH 3 C = CH2
CH 3

C 2 H 5 ONa is a strong base so abstract proton to give elimination

product as a major one via E 2 mechanism.


Cl
CH 3 C CH 2
CH 3 H

OEt

CH 3 C = CH2
CH 3

(ii) t-butylethyl ether as a major product can be obtained by


SN2 reaction between crowded nucleophile & least crowded
alkyl halide. i.e.
CH 3
CH 3 C ONa + CH 3 CH 2 Cl
CH 3

CH 3
CH 3 C O CH2 CH3
CH 3
(t-butylethyl ether)

Example 7.
Give the major products that are formed by heating each of
the following ethers with HI.
CH3

(i)

132

CH 3 CH 2 CH CH 2 O CH2 CH3

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(ii)

CH 3
CH 3 CH 2 CH 2 O C CH2 CH 3
CH 3

(iii)

CH2 O

Strategy.
CH3
CH 3
+
HI
(i) CH 3CH2 CHCH 2 OCH 2 CH 3
CH 3CH2 CHCH 2 OCH 2 CH 3
H

CH 3
+
CH 3 CH 2 CHCH2 OCH2 CH 3 I

SN 2

CH 3
CH 3 CH 2 CHCH2 OH
+
CH 3 CH 2 I

I is a good nucleophile so it will atta ck at lea st sterically


hindered C.

CH3

(ii)

CH 3CH 2CH2 OCCH2 CH3


CH3

HI

CH 3

CH3 CH 2 CH 2 OCCH 2 CH 3
H CH 3

CH 3
CH 3CH2 CH2 OCCH 2 CH 3
H CH 3
+

CH 3 CH 2 CH 2 OH
+
CH3
CH3 CCH 2 CH 3
+

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133

Alcohol, Phenol & Ether


CH 3
CH 3 CCH2 CH 3
+

CH 3
I

CH3 CCH 2 CH3


I

Protonation leads to formation of 3 carbocation which is most


stable so reaction proceeds via formation of intermediate.
(iii)

CH2 O

HI

CH 2 O
H
+

CH 2 + HO

CH2 O
H
+

CH2

CH2I

Protonation leads to formation of benzyl carbocation which is


resonace stabilize so I will attack over it.

134

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Alcohol, Phenol & Ether

Intext Problem:
Intext Question 1.
Classify the following as primary, secondary and tertia ry
alcohols:

(i)

CH 3
CH 3 C CH2 OH
CH 3

(ii) H 2 C = CH CH 2 OH
OH
CH CH 3

(iii) CH3 CH 2 CH 2 OH

CH 2 CH CH3
OH

(v)

(iv)

(vi)

CH 3
CH = CH C OH
CH 3

Strategy.
Primary (1) alcohol is that alcohol which is attached to primary
carbon, secondary (2) alcohol is that one which is attached to
secondary carbon while tertiary (3) alcohol is one which is
attached to tertiary carbon.
(i)

CH 3
CH 3 C CH 2 OH (Primary alcohol)
CH 3

(ii)

CH 3 = CH CH 2 OH (Primary alcohol)

(iii) CH 3 CH2 CH2 OH (Primary alcohol)


OH
CH CH 3

(iv)

(Secondary alcohol)

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135

Alcohol, Phenol & Ether


(v)

CH2 CH CH 3
(Secondary alcohol)
OH

(vi)

CH 3
CH = CH C OH
(Tertiary alcohol)
CH 3

Intext Question 2.
Identify allylic alcohols in the above examples.
Strategy.
Allylic alcohol is that alcohol which is attached to allylic position

So. CH2 = CH - CH 2 - OH &

CH3
CH = CH C OH
are allylic
CH3

alcohol.
Intext Question 3.
Name the following compounds according to IUPAC system.

(i)

CH2 OH
CH 3 CH 2 CH CH CH CH 3
CH2 Cl
CH3

(ii)

CH 2 OH
CH 3 CH CH 2 CH CH CH 3
OH
CH 3

OH

(iii)
Br

(iv) H2 C = CH CH CH 2 CH 2 CH3
OH

136

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Alcohol, Phenol & Ether


(v)

CH 3 C = C CH2 OH
CH 3 Br

Strategy.

(i)

1
CH 2 OH
5
4
3 2
CH 3 CH 2 CH CH CH CH3
CH2 Cl
CH3
3-Chloromethyl-2-(methylethyl)pentan-1-ol

(ii)

1
CH 2 OH
6
5
4
3 2
CH 3 CH CH 2 CH CH CH3
CH3
OH
2,5-Dimethylhexane-1,3-diol

(iii)

OH
1 2
3 Br
3-Bromocyclohexanol

1
2
3
4
5
6
(iv) CH 2 = CH CH CH 2 CH 2 CH 3
OH
Hex-1-en-3-ol

(v)

4
3 2 1
CH 3 C = C CH 2 OH
CH 3 Br
2-Bromo-3-methylbut-2-en-1-ol

Intext Question 4.
Show how are the following alcohols prepared by the reaction
of a suitable Grignard reagent on methanal ?
CH 2 OH

(i)

CH 3 CH CH 2 OH
CH 3

(ii)

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137

Alcohol, Phenol & Ether


Strategy.
Grignard reagent have nucleophilic centre at R so it can attack
over partial positive carbon of carbonyl compound to give
addition product.
As methanal contain CH 2 group so RMgx of R can be
CH 3

MgBr

CH 3 CH MgBr for first &

for second

Mechanism;
+

O MgBr

(i)

CH 3 CH MgBr +H C H
CH 3

CH 3 CH C H
CH 3 OH

CH 3 CH CH2 OH
CH 3
+

O MgBr

MgBr O
+H C H

(ii)

H 2 O /H

H 2O
H

OH
+

Intext Question 5.
Write structures of the products of the following reactions:
(i)

CH 3 CH = CH 2
O

(ii)

H 2O /H

CH 2 C OCH 3 NaBH
4
O

(iii) CH 3 CH 2 CH CHO

NaBH 4

CH 3

138

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Alcohol, Phenol & Ether


Strategy.
H 2O

(i)

CH 3 CH = CH 2

CH 3 CH CH 3

OH
CH 3 CH CH 3

OH
CH 2 C O CH 3 NaBH 4
O

(ii)

H 2O

CH 2 C O CH3
O

NaBH 4 is a reducing agent for aldehyde, ketone & acid halide

but do not reduce ester.


O

(iii) CH 3 CH 2 CHCH
CH 3

NaBH 4

CH3 CH 2 CHCH 2 OH
CH3

Intext Question 6.
Give structures of the products you would expect when each
of the following alcohol reacts with (a) HCl ZnCl 2 (b) HBr
and (c) SOCl 2 .
(i)

Butan-1-ol

(ii) 2-Methylbutan-2-ol
Strategy.
OH

(i)

OH

(ii)

HCl - ZnCl 2

Cl

HBr
SOCl 2

HCl - ZnCl 2
HBr
SOCl 2

Br
Cl

Cl
Br
Cl

HCl ZnCl 2 is called as Luca s reagent which is used to

distinguish 1, 2, & 3 alcohol. 3 alcohol give instant white

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139

Alcohol, Phenol & Ether


ppt, 2 alcohol needs 2-5 minute time but 1alcohol react slowly
at room temperature and needs nearly 30 minute for ppt.
Intext Question 7.
Predict the major product of acid catalysed dehydration of
(i)

1-methylcyclohexanol and

(ii) butan-1-ol
Strategy.
OH
H 2SO 4
H 2 O

(i)

OH

(ii)

H
(major)

H 2 SO 4

O
H

H+

H
+

H
(major)

Intext Question 8.

Ortho a nd para nitrophenols are more acidic than phenol.


Draw the resonance structures of the corresponding phenoxide
ions.
Strategy.
OH
NO 2 H +

O
N

O
O

O
N

O
N

O
N

OH

O
N

O
H+

N
O

140

N
O

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O
N

Alcohol, Phenol & Ether


O

N
OO

N
O O

N
O O

N
O O

N
O O

order of acidic character follows


OH

OH
>

NO 2

OH
>

NO 2
(ortho have intramolecular H-bonding
so have less acidic character)

Intext Question 9.
Write the equations involved in the following reactions:
(i)

Reimer-Tiemann reaction

(ii) Kolbes reaction


Strategy.
Equations involving Reimer-Tiemann reaction is
OH

OH
CHCl 3 /KOH

(i)

OH
CCl 4 /KOH

CHO

COOH

(ii) Equation involving Kolbes reaction


OH

OH
(i) CO 2 /NaOH
(ii) H 2 O /H

COOH

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141

Alcohol, Phenol & Ether


Intext Question 10.
Write the reactions of Willia mson synthesis of 2 -Ethoxy-3methylpentane starting from ethanol and 3-methylpentan-2ol.
Strategy.
(A) Preparation of 2-Ethoxy-3-methylpentane from ethanol.
Cl

OEt
NaOH

EtOH +

EtO H OH EtO
Cl

OEt

EtO

(B) Prepa ra tion of 2 -Ethoxy-3 -methylpentane from 3 methylpentan-2-ol.


OH
+ CH3 CH 2 Cl NaOH

OH

O
OH

O CH2 CH3

CH 3 CH 2 Cl

Method B is better one to obtain 2-Ethoxy-3-methylpentane


because of less crowding at alkyl halide as some elimination
product is also obtained in method A.
Intext Question 11.
Which of the following is an appropriate set of reactants for
the preparation of 1-methoxy-4-nitrobenzene and why?
ONa

Br

(i)

+ CH3 ONa
NO 2

142

(ii)

+ CH 3Br
NO 2

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Alcohol, Phenol & Ether


Strategy.
Mechanism of (i) reaction follows
Br

Br OCH 3 OCH 3
CH 3 O

(Method I)
N

NO 2
O

N
O

Mechanism of (ii) reaction follows


O

OCH 3
+ CH3 Br

(Method II)

N
O

NO 2

(i) Method is more appropriate because due to presence of


-NO 2 at p-position, partial positive charge is present at C
directly attached to Br. So any nucleophile can attack over it to
give substitution product. But in (ii) case O is resonance
stabilized so is a weak nucleophile & not capable of attacking
over CH 3 Br .
Intext Question 12.
Predict the products of the following reactions:
(i) CH3 CH 2 CH 2 OCH3 +HBr (ii)

(iii)

OC 2 H 5 Conc.H SO
2
4
Conc.HNO 3

OC 2 H 5
+ HBr

HI
(iv) (CH 3 )3COC 2 H5

Strategy.

..

(i) CH3 CH 2 CH2 OCH3 + H+

+
CH 3 CH2 CH 2 OCH 3
H

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143

Alcohol, Phenol & Ether

+
Br
CH3 CH 2 CH 2 OCH 3
CH 3 CH 2 CH2 OH + CH 3 Br

..
OC H
2

H
+
OC 2 H 5

H+

(ii)

H
+
OCH 2 CH3

OH

Br

OC 2 H 5

(iii)

NO 2

+ CH 3CH2 Br

OC 2 H 5
NO 2

OC 2 H 5
+
NO 2

(iv) (CH 3 )3 COC 2 H5

H+

+
(CH 3 )3COC 2H 5
H

+
(CH 3 )3 COC 2 H 5

CH 3
CH3 C + + C 2 H 5 OH

CH 3

CH 3
CH 3 C +
CH 3

CH 3
CH3 C

CH 3

144

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Alcohol, Phenol & Ether

Exercise Problems:
Exercise Problem 1.
Write IUPAC names of the following compounds:

(i)

(ii)

CH3
CH 3 CH CH C CH 3
CH 3 OH CH3

H 3 CCHCH 2 CHCHCH 2 CH 3
OH
OH C 2 H 5

(iii) CH 3 CH CH CH 3
OH OH
(iv) HO CH 2 CH CH 2 OH
OH

(v)

CH 3
OH

CH 3

(vi)
OH

CH 3

(vii)

OH

(viii)

CH 3

CH 3

(ix) CH 3 O CH2 CH CH 3
CH 3

CH 3
OH

(x) C 6 H 5 O C 2H 5

(xi) C 6 H 5 O C 7 H 15 (n-)
(xii) CH 3 CH2 O CH CH 2 CH 3
CH3

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Alcohol, Phenol & Ether


Strategy.

(i)

(ii)

CH
5
4
3 2 31
CH 3 CH CH C CH 3 2,2,4-Trimethylpentan-3-ol
CH3 OH CH3

1
2
3
4
5
6
7
CH 3 CH CH2 CH CH CH 2 CH3
OH
OH C 2 H 5
5-Ethylheptane-2,4-diol

1
2
3
4
(iii) CH 3 CH CH CH 3 Butane-2,3-diol
OH OH

1
2
3
(iv) HO CH 2 CH CH 2 OH Propane-1,2,3-triol
OH
CH 3
4
CH 3
3
2 1 OH
1 2
(v)
(vi)
OH
2-Methylphenol
4-Methylphenol
CH
5 3
6
4
(vii)
3
2 1 OH
CH 3
2,5-Dimethylphenol

CH3
6 1 OH
5
2
(viii)
4
3 CH3
2,6-Dimethylphenol

1
2
3
(ix) CH 3 O CH2 CH CH 3 1-Methoxy-2-methylpropane
CH3

(x) C 6 H 5 - O - C 2 H 5 Ethoxy benzene


(xi) C 6 H 5 - O - C 7 H 15 (n-) 1-Phenoxyheptane
2
3
4
(xii) CH 3 CH2 O CH CH 2 CH 3 2-Ethoxybutane
1
CH 3

146

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Exercise Problem 2.
Write structures of the compounds whose IUPAC names are
as follows:
(i)

2-Methylbutan-2-ol

(ii)

1-Phenylpropan-2-ol

(iii) 3,5-Dimethylhexane-1,3,5-triol
(iv)

2,3-Diethylphenol

(v)

1-Ethoxypropane

(vi)

2-Ethoxy-3-methylpentane

(vii) Cyclohexylmethanol
(viii) 3-Cyclohexylpentan-3-ol
(ix)

Cyclopent-3-en-1-ol

(x)

3-Chloromethylpentan-1-ol

Strategy.
(i)

OH

2-Methylbutan-2-ol

(ii) 1-Phenylpropan-2-ol Ph

OH

(iii) 3,5-Dimethylhexane-1,3,5-tiol
OH

(iv) 2,3-Diethylphenol

HO

OH OH

CH 2 CH 3
CH 2 CH 3

(v) 1-Ethoxypropane CH 3 - CH 2 - O - CH 2 - CH 2 - CH3


(vi) 2-Ethoxy-3-methylpentane
(vii) Cyclohexylmethanol

OCH2 CH3

CH2 OH

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Alcohol, Phenol & Ether


OH

(viii) 3-Cyclohexylpentan-3-ol

(ix) Cyclopent-3-en-1-ol
(x)

HO

3-Chloromethylpentan-1-ol HO
Cl

Exercise Problem 3.
(i)

Draw the structures of all isomeric alcohols of molecular


formula C 5 H 12 O and give their IUPAC names.

(ii) Classify the isomers of a lcohols in a bove question as


primary, secondary and tertiary alcohols.
Strategy.
(i) Isomeric alcohol of molecular formula C 5 H 12 O are

2
3 1
Pentan-1-ol
I

32 1

OH
3-methyl
butan-1-ol
IV

HO

4
1 2 3
2-Methyl
butan-1-ol
VII

148

OH

OH

4 2 1
5
3
Pentan-2-ol
II

32 1

OH
3-Methyl
butan-2-ol
V
OH
2
3
1
2,2-Dimethyl
propan-1-ol
VIII

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4 3 2
1
OH
Pentan-3-ol
III

2 3 4
OH
2-Methyl
butan-2-ol
VI
1

Alcohol, Phenol & Ether


(ii) I

Primary alcohol

II

Secondary alcohol

III Secondary alcohol

IV

Primary alcohol

VI

Tertiary alcohol

Secondary alcohol

VII Primary alcohol

VIII Primary alcohol

Exercise Problem 4.
Explain why propanol has higher boiling point than that of
the hydrocarbon, butane?
Strategy.
Propanol has higher boiling point than buta ne because of
presence of intermolecular H-bonding. Additional energy is
required to break that H-bonding.
CH 3 CH 2 CH 2 O
H

H
O CH2 CH2 CH 3

Exercise Problem 5.
Alcohols a re compa ratively more soluble in water tha n
hydrocarbons of comparable molecular masses. Explain this
fact.
Strategy.
Solubility of any molecule in water depends upon extent of
hydrogen bonding with water. Alcohol form H-bonding with
water but hydroca rbon does not. So alcohol ha ve more
solubility in water than hydrocarbon.
HO
HO
R
H
Exercise Problem 6.

What is meant by hydroboration-oxidation reaction? Illustrate


it with an example.
Strategy.
Hydroboration-oxidation reaction means addition of borane
to a n a lkene followed by reaction with hydroxide ion &
hydrogen peroxide.

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Alcohol, Phenol & Ether


CH 3 CH = CH 2

(i) BH 3
(ii) H 2O 2 /OH

CH3 CH2 CH 2 OH

CH 3 - CH 2 - CH 2 - BH2

CH3-CH = CH2

CH 3 - CH = CH 2

H - BH 2
CH 3 -CH=CH 2

(CH 3 -CH 2 -CH 2 )3 -B


H 2O 2 /OH

(CH 3 -CH 2 -CH 2 )2 -B-H

3 CH 3 CH 2 CH2 OH

Exercise Problem 7.
Give the structures and IUPAC names of monohydric phenols
of molecular formula, C 7 H 8O.
Strategy.
Monohydric phenol with moecular formula C 7 H 8 O will be
OH
OH

CH3

2-Methylphenol

OH
CH 3
3-Methylphenol

CH3
4-Methylphenol

Exercise Problem 8.
While separating a mixture of ortho and para nitrophenols by
steam distillation, name the isomer which will be steam volatile.
Give reason.
Strategy.
Ortho-nitrophenol will be steam volatile because of presence
of intramolecular hydrogen bonding in it.
O

N
O
O-Nitrophenol

150

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Exercise Problem 9.
Give the equations of reactions for the preparation of phenol
from cumene.
Strategy.
CH3
CH CH 3

OH

O
+ CH3 C CH 3

i) O 2
ii) H 2 O /H +

CH3
H3 CCH

CH 3
H 3CCOOH
O2

CH 3

CH 3
H3 C C O O H

CH3
CH 3 C O

H 3C C O O H

H + /H 2 O

CH3
CH 3 C O
+

H2 O
H

CH3
O
CH3C
OH

OH

CH3 C CH 3 +

Exercise Problem 10.


Write chemical reaction for the preparation of phenol from
chlorobenzene.
Strategy.
Cl

OH
NaOH
623K,300Atm

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Alcohol, Phenol & Ether


H + H
O

Cl
H OH
H 2O

OH

H 2 O

Benzyne

Exercise Problem 11.


Write the mechanism of hydration of ethene to yield ethanol.
Strategy.
CH 3 = CH

H 2O /H +

CH 3 CH2 OH
+

CH 2 = CH2 H CH 3 CH2

H 2O

H
CH 3 CH 2 O H
+

CH 3 CH2 OH

Exercise Problem 12.


You are given benzene, conc. H 2 SO 4 and NaOH. Write the
equations for the preparation of phenol using these reagents.
Strategy.
SO 3H
conc.H 2 SO 4

OH

i) NaOH
ii) H +

Exercise Problem 13.


Show how will you synthesise:
(i)

1-phenylethanol from a suitable alkene.

(ii) cyclohexylmetha nol using a n a lkyl ha lide by a n


S N 2 reaction.
(iii) pentan-1-ol using a suitable alkyl halide?
Strategy.
(i)

152

Alkene ?

Ph CH CH 3
OH

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Ph CH = CH 2

H 2 O /H +

Ph CH CH 3
+

SN

(ii) Alkyl halide

H+

OH
Ph CH CH 3

CH 2 OH

CH 2 Br

CH 2 OH

NaOH

(iii) Alkyl halide

H2O

OH

CH 3 -CH 2 -CH 2 -CH 2 -CH2 -Br KOH CH3 -CH2 -CH 2 -CH 2 -CH 2 -Br

Exercise Problem 14.


Give two reactions that show the acidic nature of phenol.
Compare acidity of phenol with that of ethanol.
Strategy.
+

OH

ONa
Na

+
+

NaOH

1
H2
2

ONa
+ H 2O

These two reactions shows the acidic nature of phenol because


phenol looses its proton to form phenoxide ion.
Comparision of acidic character is done on the basis of stability
of conjugate base. More stable the conjugate base, more acidic
the molecule will be.
O

OH
H

CH 3 CH 2 OH

CH3 CH2 O

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Phenoxide ion is resonance stabilized with phenyl ring but due
to + I nature of alkyl group CH 3 CH 2 O is relative unstable.
So phenol is more acidic than ethanol.
Exercise Problem 15.
Explain why is ortho nitrophenol more acidic than ortho
methoxyphenol ?
Strategy.
Acidic strength is based on stability of conjugate base. So
OH
NO 2 H +

O
N

OH

OCH 3 H +

O
OCH3

Conjugate base of ortho-nitrophenol is more stable due to


electron withdrawing nature of NO 2 but conjugate base of
ortho-methoxyphenol is less stable due to + M nature of -OCH3 ,
which creats electronic repulsion.
Exercise Problem 16.
Explain how does the OH group atta ched to a carbon of
benzene ring activate it towards electrophilic substitution?
Strategy.
OH group attached to carbon of benzene ring activate the
ring towards electrophilic substitution because of + M nature
of OH. Here OH group increases the electron density at ortho
& para position.
OH

154

OH

OH

OH

OH

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OH

- E+
-

OH
E

OH
+

Exercise Problem 17.


Give equations of the following reactions:
(i)

Oxidation of propan-1-ol with alkaline KMnO 4 solution.

(ii) Bromine in CS2 with phenol.


(iii) Dilute HNO 3 with phenol.
(iv) Treating phenol with chloroform in presence of aqueous
NaOH.
Strategy.

(i) CH 3 CH2 CH2 OH


OH

alkaline KMNO 4

OH
Br2 /CS 2

(ii)

CH3 CH2 C OH

OH
Br

Br
OH

OH
dilute HNO 3

(iii)
OH

(iv)

OH
CHCl 3 /NaOH

OH

NO 2

NO 2

CHO

alkaline KMnO 4 is a strong oxidising agent which convert


primary alcohol into carboxylic acid.

CS 2 is a non-pola r medium, so in this medium only

monosubstitution occur but in presence of H 2 O which is


polar medium, tribromo compound will be formed.

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Phenol react with chloroform in presence of any base to


give salicyldehyde and this reaction is called as ReimerTiemann reaction.

Exercise Problem 18.


Explain the following with an example.
(i)

Kolbes reaction.

(ii) Reimer-Tiemann reaction.

(iii) Williamson ether synthesis. (iv) Unsymmetrical ether.


Strategy.
(i)

Kolbe reaction Conversion of phenol into salicylic acid


in presence of CO 2 is called as Kolbe reaction.
OH

OH
CO 2

COOH

Salicylic acid
+

OH

OH

O H

O
CO

O
O
H COH

OH

COOH

(ii) Reimer-Tiemann reaction Conversion of phenol into


salicyldehyde in presence of chloroform and base is called
Reimer-Tiemann reaction.
OH

OH
CHCl 3 /KOH

CHO

Salicyldehyde
Cl
Cl
OH
ClCH H O ClC
ClCCl
2
Dichlorocarbene
Cl
Cl

..

OH

O
KOH

156

O
ClC Cl

Cl
CCl

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O

Cl
CCl H OH

Cl
CCl
H

O
KOH

OH
O
O
OH
H
COH
CH
CHO
H

(iii) Willia mson ether synthe sis Formation of ether by


reaction of alkyl halide with an alkoxide ion is called as
Williamson ether synthesis.
CH 3 CH 2 Br

CH 3ONa

CH 3 CH 2 O CH 3

H
2
CH 3 O + H 3 C C Br SN CH 3 O CH 2 CH 3
Methoxyethane
H

(iv) Unsymmetrical ether Unsymmetrical ether is that ether


which is formed by condensatiion of two different alcohols i.e.
both alkyl part along oxygen atom are different.
CH 3 CH2 O H +H O CH 2 CH 3

H 2O

CH3 CH2 O CH2 CH 3


R
R
(Both R is same so symmetrical)

CH 3 CH 2 O H+ H O CH 3

CH 3 CH 2 O CH 3
R
R
(Both alkyl group is different so
unsymmetrical ether)
H 2O

Exercise Problem 19.


Write the mechanism of acid dehydration of ethanol to yield
ethene.
Strategy.
CH 3 CH 2 OH

H 2 SO 4/

CH 2 = CH2

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Alcohol, Phenol & Ether


Mechanism
H2 SO 4

H+ + HSO 4

H
CH 3 CH2 OH +H+

HSO 4

CH 2 CH 2 O H H SO CH 2 = CH2
+
2
4
(E2 )
H

Exercise Problem 20.


How are the following conversions carried out?
(i)

Propene Propan-2-ol.

(ii) Benzyl chloride Benzyl alcohol.


(iii) Ethyl magnesium chloride Propan-1-ol.
(iv) Methyl magnesium bromide 2-Methylpropan-2-ol.
Strategy.
(i)

OH

H2 O / H

H 2O

OH

H +

(ii)

CH 2 Cl

CH 2 OH

CH 2 Cl

CH 2 OH

KOH
2
SN

?
(iii) CH3 CH 2 MgCl
CH 3 CH 2 CH 2 OH

O
CH3CH2 MgCl + H C H

CH 3 CH 2 CH 2 OH

158

CH 3 CH2 CH2 O Mg Cl

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H 2 O /H +

Alcohol, Phenol & Ether


OH

?
(iv) CH 3 MgBr

O
CH 3MgBr + CH 3 C CH3

O MgBr

H 2O /H +

OH

Exercise Problem 21.


Name the reagents used in the following reactions.
(i)

Oxidation of a primary alcohol to carboxylic acid.

(ii) Oxidation of a primary alcohol to aldehyde.


(iii) Bromination of phenol to 2,4,6-tribromophenol.
(iv) Benzyl alcohol to benzoic acid.
(v) Dehydration of propan-2-ol to propene.
(vi) Butan-2-one to butan-2-ol.
Strategy.
(i)

?
Primary alcohol
Carboxylic acid.

Reagent for this oxidation shows by strong oxidizing agents


such as
1. KMnO 4 /

2.

K 2 Cr2 O 7

3. CrO 3

? aldehyde
(ii) Primary alcohol

Reagent used for this oxidation shows by mild oxidizing agents


such as
1. Pyridinium chlorochromate (PCC)
2. Pyridinium dichromate (PDC)
OH

(iii)

Br

OH

Br

Br

Here bromination should be carried out in polar solvent such

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Alcohol, Phenol & Ether


as water, which make phenol into phenoxide that activate the
ring very much.
OH
Br2 /H 2 O

Br

OH

Br

CH2 OH

(iv)

Br

O
COH

Strong oxidising reagent should be used for it such as


1. KMnO 4 /
OH

(v)

2.

K 2 Cr2 O 7

Any dehydrating reagent can be used for it such as


1. H 2 SO 4

2.

H 3 PO 4

3. Al 2 O 3

4.

ThO 2

(vi)

OH

Any reducing agent which reduces ketone to alcohol can be


used for it such as
1. NaBH 4

2. LiAlH 4

3. Al-isopropoxide(MPV reduction)
Exercise Problem 22.
Give reason for the higher boiling point of ethanol in comparison
to methoxymethane.
Strategy.
Boiling point depends on extent of hydroden bonding for nearly
same molecular weight compound. More the H-bonding, more
will be the boiling point. Ethanol form intermolecular Hbonding but methoxymethane can not.

160

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Alcohol, Phenol & Ether


HO

HO

HO

CH 2 CH 3 CH 2 CH 3 CH2 CH3

Exercise Problem 23.


Give IUPAC names of the following ethers.
(i)

C 2 H5 OCH 2 CH CH 3

(ii) CH3 OCH 2 CH 2 Cl

CH 3

(iii) O 2N C 6 H 4 OCH3 (p)


H3 C

(iv) CH3 CH 2 CH 2 OCH3

CH3

(v)

(vi)
OC 2 H 5

OC 2 H 5

Strategy.
(i)

1
2
3
C 2 H5 O CH 2 CH CH3 1-Ethoxy-2-methylpropane
CH 3

(ii)

2
1
CH 3 O CH2 CH 2 Cl 1-chloro-2-methoxyethane

(iii) O 2 N C6 H 4 OCH 3 (p) 1-Methoxy-4-nitrobenzene


or
O2N 4

1
3 2

O CH 3

3
2
1
(iv) CH 3 CH 2 CH 2 O CH 3 1-Methoxypropane

(v)

2
4-Ethoxy-1,1-dimethylcyclohexane
4 3
OC 2 H 5

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Alcohol, Phenol & Ether


(vi)

Ethoxybenzene
OC 2 H 5

Exercise Problem 24.


Write the names of reagents and equations for the preparation
of the following ethers by Williamsons synthesis:
(i)

1-Propoxypropane

(ii) Ethoxybenzene

(iii) 2-Methoxy-2-methylpropane (iv) 1-Methoxyethane


Strategy.
(i)

?
X
CH3 CH2 CH2 O CH 2 CH 2 CH3

CH 3 CH 2 CH 2 O K + CH 3 CH2 CH2 Cl

SN

CH3 CH2 CH2 O CH2 CH2 CH3

(ii) X

O CH 2 CH 3

OK
+ CH 3 CH2 Cl

(iii)

OCH3

OK
+ CH 3 Cl

(iv) X

OCH3

OCH3
+

CH3 CH 2 O K +CH 3 Cl

162

O CH2 CH3

CH 3CH 2 OCH3

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Alcohol, Phenol & Ether


Exercise Problem 25.
Illustrate with examples the limitations of Williamson synthesis
for the preparation of certain types of ethers.
Strategy.
Williamson ether synthesis is an example of SN 2 reaction. Here
alkyl halide is allowed to react with sodium alkoxide.
2
R' X SN

RO

R R'

Rate of SN 2 reaction decreases for alkyl halide if it is more


crowded i.e.
1 RX > 2 RX > 3 RX
So for better result of ether, primary alkyl halide is choosen.
As alkoxide is nucleophile as well as base so for secondary &
tertiary alkyl halide some elimination product can also be formed
along with substitution. In case of 3 alkyl halide alkene is the
only product instead of ether. Such as
CH 3
CH 3 C Br
CH 3

CH 3

CH 3 ONa

CH 3 C = CH 2 + CH 3 OH

Mechanism:CH 3
CH 3O CH 3 C Br
H CH 2

CH 3
E2

CH 3 C = CH2

So Limitation of williamson ether synthesis is the choose of


primary alkyl halide for preparation of ether.
Exercise Problem 26.
How is 1-propoxypropane synthesised from propan-1-ol? Write
mechanism of this reaction.
Strategy.
?
CH3 CH2 CH 2 OH
CH 3 CH 2 CH2 OCH 2 CH 2 CH3

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Alcohol, Phenol & Ether


Reaction:CH 3 CH 2 CH2 OH +CH3 CH 2 CH2 I

NaOH

CH 3 CH 2 CH 2 OCH2 CH 2 CH3

Mechansim:+

CH 3 CH2 CH2 O H + OH
CH 3CH2 CH2 O + CH 3 CH 2 CH 2 I

SN

CH 3 CH2 CH2 O Na
2

CH 3 CH 2CH2 OCH 2 CH 2 CH 3

Exercise Problem 27.


Prepa ration of ethers by acid dehydra tion of secondary or
tertiary alcohols is not a suitable method. Give reason.
Strategy.
Dehydra tion of secondary & tertiary alcohol proceeds via
formation of ca rboca tion. This carbocation ha ve acidic
hydrogen at position. So another alcohol molecule has choice
to attack over carbocation or abstract H. It is due to steric
hindrance, possibility of attack over carbocation is very less so
it will abstract H and form alkene as a product instead of
ether.
CH 3
CH 3 COH
CH 3

CH 3

CH 3

CH 3 CO

CH 3 C +
+ H H 2O
CH

CH 3

CH 3
CH 3
CH 3 CCH 2
+

164

CH 3 COH
CH3

CH 3 CH3
CH 3 COCCH3
CH3 CH3
(Less favourable)

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CH 3
CH 3 COH
CH3

CH 3
CH 3 CCH 2
+

CH 3
CH 3 CCH 2
(More favourable)

Exercise Problem 28.


Write the equation of the reaction of hydrogen iodide with:
(i)

1-propoxypropane

(ii) methoxybenzene and


(iii) benzyl ethyl ether.
Strategy.
(i)

HI
CH3 CH 2 CH 2 - O - CH 2 - CH 2 - CH 3
?

CH 3 CH 2 CH2 O CH2 CH2 CH3

H I

H
+

CH3 CH2 CH 2 O CH 2 CH2 CH3

H
+

CH 3 CH 2 CH 2 O CH2 CH2 CH3

(ii)

CH 3 CH 2CH2 OH
+
CH 3CH2 CH2 I

O CH 3 HI ?

O CH3 H I

O CH 3 I 2
SN
H

OH + CH 3I

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Alcohol, Phenol & Ether


CH2 O CH 2 CH 3 HI ?

(iii)

CH2 O CH 2 CH 3

HI

CH 2 O CH 2 CH 3
H
+

CH
+

CH2 O CH 2 CH 3

+ CH 3 CH2 OH

H
+

CH 2 I

CH 2
I

Exercise Problem 29.


Explain the fact that in aryl alkyl ethers (i) the alkoxy group
activates the benzene ring towards electrophilic substitution
and (ii) it directs the incoming substituents to ortho and para
positions in benzene ring.
Strategy.
Alkoxy group activates the benzene ring towards electrophilic
substitution reaction because of +M nature of OR. OR will
increase the electron density a t ortho & pa ra position so
available electron density in ring is high so attack of electrophile
become easy.
OR

OR
E+

OR

OR

OR

E
+

OR

OR

OR

Activation & deactivation of benzene ring is based on available

166

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Alcohol, Phenol & Ether


electron density of substituted benzene & without substituted
benzene. If any group donate electron density to ring then it
will activate the ring for electrophilic substitution and if any
group withdraws electron density of benzene then it will
deactivate the ring for electrophilic substitution.
Halogens are exceptional which deactivate the ring but are
ortho-para directing group. But in general, activator are orthopara directing while deactivators are meta directing in nature.
Exercise Problem 30.
Write the mecha nism of the rea ction of HI with
methoxymethane.
Strategy.
HI
CH3 O CH 3
?

+
CH 3 O CH3 H I CH 3 O CH 3 I
H

CH3 OH +CH3 I

Exercise Problem 31.


Write equations of the following reactions:
(i)

Friedel-Crafts reaction-alkylation of anisole.

(ii) Nitration of anisole.


(iii) Bromination of anisole in ethanoic acid medium.
(iv) Friedel-Crafts acetylation of anisole.
Strategy.
(i)

Friedel-Craft reaction- alkylation of anisole.


OCH 3
RX/AlX 3

OCH3
R
(Minor)

OCH3
+
R
(Major)

Me chanism Mechanism of a ll electrophilic substitution

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167

Alcohol, Phenol & Ether


reaction follows in three steps
(A) Formation of an electrophile
X
R X + Al X
X

R + +AlX4
(Electrophile)

(B) Attack of an electrophile


OCH3
R

OCH3
+ R

OCH3

OCH3
+

+ R

(Stable)

(Least stable)

R
(stable)

(C) Deprotonation
OCH 3
H R

OCH3

OCH 3
+ R
H

OCH3
R

Due to +M nature of -OCH3 group, electron density at ortho


& para position is high so ortho & para product will be formed
as major products.
(ii) Nitration of anisole
OCH 3

OCH 3
NO 2
(Minor)

OCH3
+
NO 2
(Major)

Mechanism
Similar to above question mechanism follows three steps
(A) Formation of an electrophile
(B) Attack of an electrophile
(C) Deprotonation

168

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Alcohol, Phenol & Ether


O

O
O
+
H O N H O + N
2
O
O
O
H
Nitronium ion
(Electrophile)
+
+
OCH3 OCH 3 OCH3

H O S O H + H O N
O

OCH 3 OCH 3

OCH 3 +
OCH 3

NO

NO 2
2

OCH3

NO 2

(iii) Bromination of anisole in ethanoic acid medium.


OCH 3

OCH 3
Br

Br2 / CH 3 COOH

OCH3
+

(Minor)

Br
(Major)

Mechanism is similar again and follows same three steps


(A) Formation of an electrophile
(B) Attack of an electrophile
(C) Deprotonation
+

OCH 3 OCH 3

OCH 3 +
OCH 3
NO 2
NO 2

OCH3 OCH 3 OCH3

OCH3
+
NO 2

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169

Alcohol, Phenol & Ether


Anisole undergoes bromina tion even in a bsence of
FeCl 3 or FeBr3 . It is due to the activation of benzene by +M
nature of methoxy group. Para product will be major due to
less vander-wall repulsion between -OCH 3 & Br.
(iv) Friedel-Crafts acetylation of anisole
OCH 3

OCH3

O
CH 3 C Cl /AlCl 3

O
OCH 3
CCH3

(Minor)

CCH3
O
(Major)

Mechanism is similar again i.e.


(A) Formation of an electrophile
(B) Attack of an electrophile
(C) Deprotonation
O
CH 3 C Cl + AlCl 3
OCH 3

O
+ CH3 C +

OCH 3

+ CH3 C+

O+

O
CH 3 C +
OCH 3
+ COCH 3
OCH3

CH 3 C
OCH 3

O
C CH 3

OCH 3

H CR

CCH3
O
O
Friedel-Craft acylation is carried out in presence of acid halide
& lewis a cid such a s AlCl 3 , FeCl 3 etc. which ma ke a cyl
carbocation, which is an electrophile for acylation reaction. As
ortho & para position is more electron rich so ortho & para
product will be formed as product.

170

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Alcohol, Phenol & Ether


Exercise Problem 32.
Show how would you synthesise the following alcohols from
appropriate alkenes?
CH 3

(i)

OH

OH

(iii)

OH

(ii)

(iv)

OH

Strategy.
(i)

Alkene ?

or

(ii) Alkene

+ H O
2

OH

H +

OH

H2 O / H+

or

(iii) Alkene

OH

OH

H 2O /H +

OH

H 2O
H

(iv) Alkene

OH

H 2O

OH
H 2O /H +

H2 O
H

OH

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171

Alcohol, Phenol & Ether


H+

H+

H2 O

OH

H +

Exercise Problem 33.


When 3-methylbutan-2-ol is treated with HBr, the following
reaction takes place.
Br
CH 3 CH CH CH 3
CH3 OH

HBr

CH 3 C CH 2 CH 3
CH 3

Give a mechanism for this reaction.


Strategy.

CH 3 CH CH CH 3
CH 3 OH

HBr

CH 3 CH CH CH 3
CH3 O
H

CH3 CH CH CH 3
CH 3

CH 3 -C-CH-CH 3
CH3

CH3 -C-CH2 -CH 3


CH3

Br
Br

CH 3 -C-CH 2 -CH 3
CH 3

Carbocation have special property to rearrange itself for better


stability. so 2 carbocation rearranges to 3 carbocation then
Br attack to give final product.

172

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Aldehyde, Ketone & Carboxylic acid

Unit

Aldehyde, Ketone & Carboxylic acid

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173

Aldehyde, Ketone & Carboxylic acid

Objective
This unit give you an understanding of Aldehyde ketone & Carboxylic acid and covers following topics:

174

IUPAC nomenclature of aldehyde, ketones & carboxylic acid.


Structures of carboxyl groups.
Preparation of aldehyde & ketones.
Physical properties of aldehyde & ketones.
Chemical reactions of aldehyde & ketones.
Use of aldehyde & ketones.
Methods of preparation of carboxylic acid & its derivatives.
Chemical reactions of carboxylic acid & its derivatives.
Use of carboxylic acid.

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Aldehyde, Ketone & Carboxylic acid

Solved Example:
Example 1.
Give na mes of the reagents to bring about the following
transformations:
(i)

Hexan-1-ol to hexanal

(ii) Cyclohexanol to cyclohexanone


(iii) p-Fluorotoluene to p-fluorobenzaldehyde
(iv) Ethanenitrile to ethanal
(v) Allyl alcohol to propenal
(vi) But-2-ene to ethanal
Strategy.
O

(i)

OH

In this conversion primary alcohol has to convert into aldehyde,


so weak oxidizing agent can only be used, other wise further
oxidation occur & final product will be carboxylic acid. Reagent
used can be
(A) Pyridinium chlorochromate (PCC)
(B) Pyridinium dichromate (PDC)
OH

(ii)

O
?

Any general oxidising agent can do it well. It may be


(A) K 2 Cr2 O7 /H +
(B) KMnO 4 /H +
(C) CrO3 /H+
(D) Aluminium tertiary butoxide in acetone (oppanauer
oxidation)

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175

Aldehyde, Ketone & Carboxylic acid


CH 3

CHO
?

(iii)
F

Conversion of a methyl group attached to benzene ring into


the formyl group can be done by oxidation with Cr (VI) oxide
in acetic anhydride in the presence of strong acid or with a
solution of chromyl chloride (CrO 2 Cl 2 ) in CCl 4 or CS 2 which
is also called Etard reaction.
CH 3

CHO
i) CrO2 Cl 2 , Ac 2O
ii) H 2O /H

(iv) CH 3 C

DIBAL-H

CH 3 C H

Nitriles can be best converted into aldehyde by the help of


diisopropylaluminium hydride (DIBALH) at 78C.
O
CH 3 C

(v)

DIBAL-H

OH ?

CH 3 C H

H
O

This can be done by


(i) Pyridinium chlorochromate (PCC)
(ii) Pyridinium dichromate (PDC)
(iii) MnO 4 (Selective for conversion of allylic or benzylic
alcohol to aldehyde/ketone.
(vi)

O
CH 3 C H

This can be done by reductive ozonolysis of alkene.

176

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Aldehyde, Ketone & Carboxylic acid


O3

H 3C O
H

O CH

O H
Ozonide

Zn H 2O

O
2 CH 3 C H

Example 2.
Arrange the following compounds in the increasing order of
their boiling points:
CH 3 (CH2 )2 CHO, CH 3 CH 2 CH 2 CH 2 OH,
H 5 C 2 OC 2 H 5 , CH 3 (CH 2 )3 CH 3

Strategy.
Boiling point depends on following factors in decreasing order
for nearly same mol. wt.
Intermolecular H-bonding > Intramolecular H-bonding > Dipole
moment > Vander waal force.
So increasing order of boiling points of following molecules
follows.
CH3 CH 2 CH 2 CH 2 CH 3 < H5 C 2 OC 2 H5 <
CH3 CH 2 CH 2 CHO < CH 3 CH 2 CH 2 CH 2 OH
Example 3.

Would you expect benzaldehyde to be more reactive or less


rea ctive in nucleophilic addition reactions than propanal?
Explain your answer.
Strategy.
Nucleophilic addition reaction of carbonyl compounds depends
on two factors.
(A) Steric hindrance along carbonyl carbon- Less the steric
hindrance a long ca rbonyl ca rbon, more ea sy for a
nucleophile to attack over it.
(B) Electronic factor- More the partial positive charge over
carbonyl carbon more easy for a nucleophile to attack over it.
So due to smaller size of ethyl group and weak +I nature of
ethyl group in propanal, carbonyl carbon of propanal have
more partial positive charge than larger size of phenyl and +M
nature of phenyl in benzaldehyde which decreases the partial

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177

Aldehyde, Ketone & Carboxylic acid


positive charge over carbonyl carbon of benzaldehyde. So
reactivity of benzaldehyde is less than that of propanaldehyde.
O
H

O
H

O
H

O
H

O (+M of phenyl group)


CH3 CH 2 CH
(+I of ethyl group)

Example 4.
An orga nic compound (A) with molecula r formula
C 8 H8 O forms an orange-red precipitate with 2,4-DNP reagent
and gives yellow precipitate on heating with iodine in the
presence of sodium hydroxide. It neither reduces Tollens or
Fehlings reagent, nor does it decolourise bromine water or
Baeyers reagent. On drastic oxidation with chromic acid, it
gives a ca rboxylic a cid (B) ha ving molecula r formula
C 7 H 6 O 2 . Identify the compounds (A) and (B) and explain the
reactions involved.
Strategy.

C 8 H8 O
A

2,4-DNP

Orange red ppt presence of


aldehyde or ketones.
I 2 /NaOH
Yellow ppt Iodoform test for
presence of COCH3 group.
Tollen's
No reduction Absence of aldehyde,
reagent
so it must be ketone.
Fehling
No reduction Absence of aldehyde,
solution
so it must be ketone.
Bromine
No decolourization Absence of
water
C=C or C Cbond.
Baeyer
No decolourization Absence of
reagent
C=C or C Cbond.
C 7 H6 O 2
Chromic
Carboxylic acid
acid
B

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Aldehyde, Ketone & Carboxylic acid


As C 8 H8 O has DU = 5 with high degree of unsaturation. So
we may think a phenyl group. So A will be
O

2,4-DNP

NN
NO 2

H 3C

CH 3

Ph

I 2 /NaOH

NO 2

Ph COONa +CHI3
COOH

H2 CrO 4

Example 5
Write chemical reactions to affect the following transformations:
(i)

Butan-1-ol to butanoic acid

(ii) Benzyl alcohol to phenylethanoic acid


(iii) 3-Nitrobromobenzene to 3-nitrobenzoic acid
(iv) 4-Methylacetophenone to benzene-1,4-dicarboxylic acid
(v) Cyclohexene to hexane-1,6-dioic acid
(vi) Butanal to butanoic acid.
Strategy.
(i)

O
?

OH

OH

It is an oxidation reaction so such oxidation can be carried out


by
(a) CrO 3 - H 2 SO 4 (Jones reagent) (b) CrO 3
(c) KMnO 4 /H +

(d) KMnO4 /OH

(e) K 2 Cr2 O 7
(ii)

CH 2 OH

CH 2 COOH
?

Number of carbon can be increased by introducing CN group


so transformation can be carried out by

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179

Aldehyde, Ketone & Carboxylic acid


CH2 OH

CH2 Br

HBr

CH 2 CN

KCN
KBr

H2 O

CH 2 COOH

H 2O /H

COOH

Br
?

(iii)

NO 2

NO 2

COOH group can also be attached by Grignard reagent.


Br

MgBr

COOMgBr
CO 2

Mg/THF

NO 2

NO 2

NO 2

(iv)

H3 C

NO 2

COOH

CH 3

COOH

H 2 O /H +

HOOC

This transformation can be carried out using oxidation with


KMnO 4 .
O
O
+
KMnO 4 / KOH
COOH
H O/H
OK 2
CH 3
H3 C
KOOC
HOOC
(v)

COOH
COOH

Alkene can be ozidized to acid in presence of hot KMnO 4 .


KMnO 4 /H +

(vi)

COOH
COOH
O

OH

Oxidation of aliphatic aldehyde to acid can be carried out in


presence of
(a) Tollens reagent (b) Fehling solution(c) Benedict solution

180

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Aldehyde, Ketone & Carboxylic acid

Intext Problem:
Intext Question 1.
Write the structures of the following compounds.
(i)

- Methoxypropionaldehyde

(ii) 3-Hydroxybutanal
(iii) 2-Hydroxycyclopentane carbaldehyde
(iv) 4-Oxopentanal
(v) Di-sec. butyl ketone
(vi) 4-Fluoroacetophenone
Strategy.

(i)

(iii)

OCH 3
0 H
O

OH O

(ii)

CHO
OH
12

2 1 H

(iv)

(v)
sec butyl group
Intext Question 2.

4 3

2 1 H
O

2 1O
CH 3
(vi) 3
F4

Write the structures of products of the following reactions:


O
C

(i)

+ C2H 5

Cl

Anhyd. AlCl 3
CS 2

(ii) (C 6H 5 CH 2 )2 Cd + 2 CH3 COCl


(iii) H C C C H
3

Hg 2 + ,H 2SO 4

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181

Aldehyde, Ketone & Carboxylic acid


CH 3
1. CrO 2Cl 2

(iv)

2. H 3O +

NO 2

Strategy.
O

(i)

+ C2H 5
O

Cl

Anhydrous AlCl 3

Cl

C 2 H5 C Cl +AlCl
Cl

C 2 H 5 C + + AlCl 4

+H

+ C2H 5 C+

(ii)

C2H 5

CS 2

O
C 2 H5

O
(C 6 H 5CH2 )2 Cd + 2CH3 C Cl

H+

Et

O
C6H 5 C Cl + C 6H 5 CH 2 Cd CH 2 C6 H5

O
CH 3 C CH 2 C 6 H5

(iii) CH C C H
3
CH3 C CH

Hg 2+ ,H 2 SO 4

Hg 2+

CH3C

O
CH 3 C Cl
CH 2 C 6 H5

CH
Hg +

182

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Aldehyde, Ketone & Carboxylic acid


H + H
O
H 2O
CH
CH3C CH

CH3C

Hg +

Hg

H + H
O

OH

CH 3 C=CH

CH3 C=CHHg

O
CH 3 CCH 2 Hg

Hg
O
CH 3 CCH 2 Hg

[H]

CH 3 CCH 3

CHO

CH3
i)CrO 2 Cl 2

(iv)

(Etard reaction)

ii)H 2O /H +

NO 2
Intext Question 3.

NO 2

Arrange the following compounds in increasing order of their


boiling points.
CH 3 CHO, CH3 CH 2 OH, CH 3 OCH 3 , CH 3CH2 CH3

Strategy.
Boiling points depends upon following factors in decreasing
order
H-bonding > dipole-dipole interaction > Vander waal force
so increasing order of boiling points of following compounds
follows
O
CH 3 CH 2 CH3 < CH3 OCH3 < CH 3 CH < CH3 CH2 OH

Intext Question 4.
Arrange the following compounds in increasing order of their
reactivity in nucleophilic addition reactions.
(i)

Ethanal, Propanal, Propanone, Butanone.

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183

Aldehyde, Ketone & Carboxylic acid


(ii) Benzaldehyde, p-Tolua ldehyde, p-Nitrobenzaldehyde,
Acetophenone.
Strategy.
(i)

Nucleophilic addition reaction depends on mainly two


factors.
(a) Steric factor Steric factor , Reactivity
(b) Electronic factors partial +ve charge over carbon ,
Reactivity

So increasing order of reactivity follows


O

CH 3 -C-CH 2 -CH 3 < CH 3 -C-CH 3 < CH 3 -CH 2 -C-H < CH3 -C-H

(ii) Aldehydes are more reactive than ketone due to steric factor
& electronic factors. Electron withdrawing group present
in carbonyl compound increases the partial positive charge
on carbonyl carbon but electron donating group decreases
the reactivity due to decrease in partial +ve charge. So,
O
C CH 3
<

CHO

CHO

<

CHO

<

CH3

NO 2

Intext Question 5.
Predict the products of the following reactions:
(i)

O
H+
+ HO NH2

(ii)

O2N
O
+ NH2 NH

NO 2

O
+
(iii) R CH = CH CHO + NH 2 C NH NH 2 H

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Aldehyde, Ketone & Carboxylic acid


O
CH 3 + CH CH NH H+
3
2
2

(iv)
Strategy.
(i)

O
H+
+ HO NH 2
+

OH

H+

OH
+

OH
H
+NOH
H

(ii)

OH
2H

OH
H
+NOH
H

H 2NOH

NH

NOH

O2N
O
+ NH2 NH

NO 2
O
NO 2
H 2 NN
H

OH
H NO
2
NN
NO 2
H

NO 2

OH

NO 2

NN
H H

NO 2

NO 2
NN
H

NO 2

O
H+
?
(iii) R CH = CH CHO +H2 N C NH NH 2

O
OH
+
H
RCH=CHCH
RCH=CHCH
+

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185

Aldehyde, Ketone & Carboxylic acid


O

OH H2 N-N-C-NH2

OH H
O
RCH=CHCHNNCNH2
H

RCH=CHCH

H +

1
OH H
O
O
3
2
RCH=CHCHNNCNH 2 CH 3 CH=CHCH=NNCNH 2
H
H
O
CH 3 + CH CH NH H+
3
2
2

(iv)

OH

O
CH 3 H

+ CH3

OH H
C NCH2CH3
CH 3

OH
+ CH 3 H 2 N-CH 2 -CH 3
H

1
OH H
2
3
C NCH 2 CH3

C=NCH 2 CH 3
CH 3

CH3

Intext Question 6.
Give the IUPAC names of the following compounds:
(i)

PhCH 2 CH 2 COOH

(ii) (CH 3 )2 C = CHCOOH


NO 2
COOH

CH 3

(iii)

186

COOH

(iv)

O2N

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NO 2

Aldehyde, Ketone & Carboxylic acid


Strategy.
(i)

3
2
1
Ph CH 2 CH2 COOH 3-Phenylpropanoic acid

(ii)

4
3 2
1
CH 3 C = CH COOH 3-Methylbut-2-enoic acid
CH 3

CH3
COOH
12
2-Methylcyclopentane-1-carboxylic acid

(iii)

NO 2
6 COOH
5
1
(iv)
2,4,6-Trinitrobenzenecarboxylic acid.
O 2 N 4 3 2 NO 2

Intext Question 7.
Show how each of the following compounds can be converted
to benzoic acid.
(i)

Ethylbenzene

(ii) Acetophenone

(iii) Bromobenzene

(iv) Phenylethene (Styrene)

Strategy.
CH 2 CH 3

COOH

(i)

Compound with atleast one hydrogen at ca rbon directly


attached to benzene when treated by hot KMnO 4 give benzoic
acid as a product, so
CH 2 CH 3

COOH

KMnO 4 /

(ii)

COOH
CH 3

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187

Aldehyde, Ketone & Carboxylic acid


Compound containing COCH3 group of aldehyde or ketone
give iodoform reaction on treatment with I 2 /NaOH , which
on hydrolysis in acidic medium give acid as a product, so
O

O
CH 3

I 2 /NaOH

Br

(iii)

OH

COOH
?

Br

MgBr
Mg/THF

(iv)

O
O Na H2 O /H

CH = CH2

COOMgBr

CO 2

H 2O /H

COOH
+

COOH

Compound with atleast one H at the carbon directly attached


to benzene on oxidation with hot KMnO 4 give benzoic acid,
no matter, it is attached to single, double bond or any substituent.
CH = CH 2

COOH

KMnO 4 /

Intext Question 8.
Which acid of each pair shown here would you expect to be
stronger?
(i)

CH3 CO 2 H or CH 2 FCO 2 H

(ii) CH 2 FCO 2 H or CH 2 ClCO 2 H


(iii) CH 2 FCH2 CH2 CO 2 H or CH 3CHFCH 2 CO 2 H
(iv) F3C

188

COOH or H 3C

COOH

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Aldehyde, Ketone & Carboxylic acid


Strategy.
Acidic strength depends upon stability of conjugate base. More
stable the conjugate base, more easily it will be formed from
loosing proton from acid, so stronger is the acid.
(i)

CH3 COOH & CH 2 F COOH

O
O
+
H
CH 3 C OH
CH 3 C O
(I)

O
O
H +
F CH 2 C OH
F CH 2 C O
(II)

Due to I nature of F, conjugate base of II is more stable so


acidic order follows.
F CH 2 COOH > CH3 COOH

(ii) CH2 FCOOH & CH2 ClCOOH


O
O
H +
F CH 2 C OH
F CH 2 C O
(I)

O
O
H +
Cl CH 2 C OH
Cl CH 2 C O
(II)

Due to stronger I nature of F than Cl, conjugate base of I is


more stable than II so acidic order follows.
F CH 2 COOH > Cl CH2 COOH

(iii) CH2 FCH 2 CH 2 COOH or CH 3 CH F CH 2 CO 2 H


FCH 2 CH 2 CH 2 COOH

O
FCH2 CH 2 CH2 CO
(I)

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189

Aldehyde, Ketone & Carboxylic acid


O
O
+
H
CH 3 CH CH 2 C OH
CH3 CH CH 2 C O
F

(II)

Inductive effect is distance dependent, so I of F in (II) is more


stronger than that of I of (I) due to closer distance from negative
carboxylate ion so acidic order follow.
CH 3 CH CH 2 CO 2 H > F CH 2 CH 2 CH 2 CO 2 H
F

(iv) F3C

COOH or H 3C

COOH

O
C O

COOH
H +

CF3

CF3
(I)

COOH

COO
H +

CH 3

CH 3
(II)

Due to I nature of -CF3 , conjugate base of (I) is more stable


but in (II) case, conjugate ba se in less stable due to +I &
Hyperconjugation of -CH 3 group. So acidic order follows.
COOH

COOH
>

CF3

CH3

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Aldehyde, Ketone & Carboxylic acid

Exercise Problems:
Exercise Problem 1.
What is meant by the following terms ? Give an example of the
reaction in each case.
(i)

Cyanohydrin

(ii)

Acetal

(iii) Semicarbazone

(iv) Aldol

(v)

(vi) Oxime

Hemiacetal

(vii) Ketal

(viii) Imine

(ix) 2,4-DNP-derivative

(x)

Schiffs base

Strategy.
(i)

Cyanohydrin When aldehyde or ketone is treated with


HCN, then a compound is obtained in which same carbon
ha ve CN & OH group. That compound is called as
cyanohydrin.
OH

HCN

H/R

CN H/R
Cyanohydrine

(ii) Acetal When aldehyde is treated with ROH, than first


hemiacetal is formed which latter converted to a compound
in which same carbon is attached to two alkoxy group.
This compound is called as acetal.
O
R

+ OH

ROH / H+

OH
H

R ORH

RO
R

ROH

R ORH

OH
H

OH

OR

ROH

ROH

OR OR
R

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H/R

191

Aldehyde, Ketone & Carboxylic acid


(iii) Semicarbazonewhen aldehyde or ketone is treated with
semicarbazide then a compound is obtained and is called
as semicarbazone.
O
O + H 2NNCNH 2
R/H
H
R

OH
H
R/H

OH
O
H
NNCNH2
R/H
H/R H

NNCNH 2
H/R H

NNCNH2
R/H
H
(Semicarbazone)

(iv) Aldol Those aldehyde which have hydrogen when


treated with base, give -hydroxyaldehyde as product.
This -hydroxyaldehyde have a ldehydic & alcoholic
group. So it is called as Ald + ol = Aldol.
O
CH 3 C H OH

OH
O
CH 3 CH CH 2 C H

O
HO CH2 C H

O
CH 2 C H

O
H C = CH 2

O
O
HC=CH 2 CH 3 CH

OH
O
CH 3 CHCH2 CH
-hydroxyaldehyde (Aldol)

(v) Hemiacetal When aldehyde react with one equivalent


of alcohol, then a compound is obtained, in which same
carbon have OH & OR group. This compound is called
as hemiacetal.

192

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O

ROH / H +

+ OH

ROH

OH

H H +

H
OR
(Hemiacetal)

(vi) O xime When a ldehyde or Ketone is trea ted with


hydroxylamine then a compound is obta ined in which
C=N is present & N have OH group in it. This
compound is called as Oxime.
R
O
R/H

NOH

H
H
OH
R
NOH
NOH
+
NOH
H
R
H/R
H/R
R/H Oxime

(vii) Ke tal When ketone is treated with two molecule of


alcohol then a compound is obtained in which same carbon
is attached with 2 alkoxy group. That type of compound
is called as Ketal.
+

O
R

OH

H
ROH

ROH

OH

R H + R
OR R

H+
H 2O

ROH

R ORRH +

RO

OR

R
R
Ketal

(viii) Imine When aldehyde or ketone react with ammonia,


then a compound is formed in which C=N is present and
N have H present in it. This compound is called as imine.
O

O
R

H/R

H
+
NH
R
H/R H

NH 3

OH
R
H
H 2O
NH
NH
R
H/R
R/H
(Imine)

(ix) 2,4-DNP derivative When aldehyde or ketone is treated


with 2,4-DNP then a compound is obtained which is called
as 2,4-DNP derivative.

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Aldehyde, Ketone & Carboxylic acid


R
O
R/H

H
H

R
NN

NN

NO 2

H NO 2
2,4-DNP

NO 2

R/H
H NO 2
2,4-DNP derivative

(x) Schiffs base When aldehyde or ketones are treated with


primary aliphatic amine than a compound is obtained in
which C=N is formed with alkyl group at N. Such
compound is called as schiffs base
O

O
H/R

H
+
NR
R
H/R H

RNH 2

OH
R
H
H 2O
NR
NR
R
H/R
R/H
(Schiff's base)

Exercise Problem 2.
Name the following compounds according to IUPAC system
of nomenclature:
(i)

CH3 CH(CH 3 )CH 2 CH 2 CHO

(ii) CH3 CH 2 COCH(C 2 H 5 )CH 2 CH 2Cl


(iii) CH3 CH = CHCHO
(iv) CH3 COCH 2 COCH3
(v) CH3 CH(CH3 )CH 2 C(CH3 )2 COCH3
(vi) (CH3 )3 CCH 2 COOH
(vii) OHCC 6 H 4CHO - p
Strategy.
(i)

194

CH 3
O
CH 3 CH CH 2 CH 2 C H 4-Methyl pentanal
5
4
3
2
1

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O

(ii)

4
5
6
CH 3 CH2 C CH CH 2 CH 2 Cl
1
2
3
C 2H 5

6-Chloro-4-ethyl
hexan-3-one

O
(iii) CH 3 CH = CH C H But - 2 - enal
4
3
2
1

(iv) CH 3 C CH2 C CH3 Pentan-2, 4-dione


1
2 3
4 5
CH3

CH 3 O
(v) CH 3 CH CH 2 C C CH 3 3,3,5-Trimethylhexan-2-one
3
6
5
4
2 1
CH 3

CH 3
O
(vi) CH 3 3C CH2 C OH 3,3-Dimethylbutanoic-acid
2
4
1
CH 3
CHO
1
2
(vii)
4-Hydroxybenzenecarbaldehyde
43
OH

Exercise Problem 3.
Draw the structures of the following compounds.
(i)

3-Methylbutanal

(ii) p-Nitropropiophenone
(iii) p-Methylbenzaldehyde
(iv) 4-Methylpent-3-en-2-one
(v) 4-Chloropentan-2-one
(vi) 3-Bromo-4-phenylpentanoic acid
(vii) p,p-Dihydroxybenzophenone
(viii) Hex-2-en-4-ynoic acid

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Aldehyde, Ketone & Carboxylic acid


Strategy.
CH 3

O
(i) 3-Methylbutanal CH 3 CH CH 2 C H
4
3
2
1

(ii) p-Nitropropiophenone

O2N
CHO

(iii) p-Methylbenzaldehyde
CH 3

(iv) 4-Methylpent-3-en-2-one

(v) 4-Chloropentan-2-one

O
2 1
5 4 3
Cl O

5 4 3 2 1

Ph
3 2 1 OH
(vi) 3-Bromo-4-phenylpentanoic acid
4
5
Br O

O
C

(vii) p,p-Dihydroxybenzophenone HO

(viii) Hex-2-en-4-ynoic acid

5
6

3
4

OH

1 OH

Exercise Problem 4.
Write the IUPAC names of the following ketones and aldehydes.
Wherever possible, give also common names.
(i)

CH3 CO(CH 2 )4 CH 3 (ii) CH 3 CH 2 CHBrCH 2 CH(CH 3 )CHO

(iii) CH3 (CH2 )5 CHO

196

(iv) Ph CH = CH - CHO

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CHO

(v)

(vi) PhCOPh

Strategy.
Structure
(i)

Common Name

O
CH 3 C CH 2 CH 2 CH2 CH2 CH3
Heptan-2-one
Br

(ii)

CH 3 O

CH 3 CH 2 CH CH 2 CH C H
6
5
4
3
2
1
4-Bromo-2-methylhexanal

O
(iii) CH 3 CH2 CH2 CH2 CH 2 CH2 C H
7
6
5
4
3
2
1
Heptanal
O
(iv) Ph CH = CH C H
3
2
1
3-Phenylprop-2-enal

Cinnamaldehyde

CHO

(v)

Cyclopentane carbaldehyde
O
Ph C Ph
(vi) Diphenylmethanone

Benzophenone

Exercise Problem 5.
Draw structures of the following derivatives.
(i)

The 2,4-dinitrophenylhydrazone of benzaldehyde

(ii) Cyclopropanone oxime


(iii) Acetaldehydedimethylacetal

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Aldehyde, Ketone & Carboxylic acid


(iv) The semicarbazone of cyclobutanone
(v) The ethylene ketal of hexan-3-one
(vi) The methyl hemiacetal of formaldehyde
Strategy.
Ph

(i)

(ii)

Ph

NN
O + NN
NO 2
NO 2
H
H
H NO 2
H NO 2
Benzaldehyde 2,4-DNP 2,4-Dinitrophenylhydrazone
of benzaldehyde
H

NOH
NOH
H
Cyclopropanone Hydroxylamine Cyclopropanone oxime
O

CH 3 O

CH 3 OH /

H
(iii) H3 C
Acetaldehyde

O+

OCH 3

H
H
Acetaldehydedimethylacetal
O

N N C NH 2
H
Cyclobutanone Semicarbazide

(iv)

N N C NH 2
H
Semicarbazone of
cyclobutanone

(Hexan-3-one)
H
(v)
O

H
O

(Ethane-1,2-diol)

(vi)

198

CH 3OH(1 eq)/H

H
H
Formaldehyde

Ethylene ketal of hexan-3-one


+

OH OCH3

H
H
Methylhemiacetal of formaldehyde

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Exercise Problem 6.
Predict the products formed when cyclohexanecarbaldeyde
reacts with following reagents.
(i)

PhMgBr and then H 3 O+

(ii) Tollens reagent


(iii) Semicarbazide and weak acid
(iv) Excess ethanol and acid
(v) Zinc amalgam and dilute hydrochloric acid
Strategy.
O
H

(i)

i) PhMgBr

ii) H 3O +

O MgBr

O
H PhMgBr

Ph

OH
+

H 3O

O
H Tollen's reagent

(ii)

Tollens reagent is silver ammonical nitrate which is a mild


oxidiz ing agent. Tollens reagent oxidiz es a ldehyde into
carboxylic acid. so
O

O
H

Tollen's reagent

O Ag

H 2 N N C NH 2 /H +

(iii)

O
H

H
H

O
N N C NH 2
H

H+

N N C NH 2
H

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199

Aldehyde, Ketone & Carboxylic acid


O
+
H EtOH (excess) /H ?

(iv)

OH

O
H H+

+ H EtOH
H+

OH
OEt
+
H H

H 2O

OEt

OEt

OEt

+ H EtOH
H+

(v)

Zn Hg / HCl

Zinc amalgam & dilute hydrochloric acid is called as reagent


of clemmenson reduction which reduces aldehyde & ketone
to alkane.
O
CH 3
H Zn Hg /HCl
Exercise Problem 7.
Which of the following compounds would undergo aldol
condensation, which the Canniz zaro reaction and which
neither? Write the structures of the expected products of aldol
condensation and Cannizzaro reaction.
(i)

Methanal

(ii) 2-Methylpentanal

(iii) Benzaldehyde

(iv) Benzophenone

(v) Cyclohexanone

(vi) 1-Phenylpropanone

(vii) Phenylacetaldehyde

(viii) Butan-1-ol

(ix) 2,2-Dimethylbutanal
Strategy.
Those aldehyde which have - H when treated with base give
-hydroxy aldehyde, which is called as aldol, and condensation

200

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is called as aldol condensation. Such as
O
OH
O
OH
CH 3 C H
CH 3 CH CH2 C H

aldol

O
O
OH
HCCH 2 H O HCCH 2
2
H

O
HC=CH 2

O
O
H OH
CH3 CHCH2 CH

O
O
HC=CH 2 CH 3 CH

OH
O
CH 3 CHCH2 CH

Those aldehyde which do not have - H when treated with


base then disproportination reaction occur. One molecule of
aldehyde is reduced to alcohol while other is oxidize to acid.
Such reaction is called as Cannizzaro reaction. Such as
O
O
NaOH
H C H
H C ONa + CH 3 OH
O
HCH

OH

O
HCH
OH

O
O
HC H+HCH
OH

O
O
HCOH+HCH
H

O
O
HCO H + HCH
H

O
HCONa + CH 3OH

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Aldehyde, Ketone & Carboxylic acid


(i)

O
O
OH
H C H
H C O + CH 3OH (Show cannizzaro
Methanal
reaction)

Mechanism of reaction is shown in above example.

(ii)

OH

CHO

CHO

2-methylpentanal

CHO

H 2O/H

CHO

CHO

OH CHO
(Show aldol reaction)

OH
H
Ph
H
(iii) Ph
OH
(Benzaldehyde)

O
Ph

H Ph
OH

Ph

Ph

O
O H +Ph

H
OH

OH + Ph

H
OH

O
Ph
O + PhCH 2 OH
(Show cannizzaro reaction)

(iv)

OH

Ph
Ph
Benzophenone

No a ldol nor canniz z a ro beca use

benzophenone is not aldehyde & nor ketone with H.

202

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O

H OH

OH
H 2O

(v)

OH

Show aldol reaction


O

(vi)

H OH
Ph

H OH
Ph

OH

O
HOH

Ph

(vii)

Ph

O
H

Ph Ph
Ph Ph
(Show aldol type raction)

O
H
Ph

O
Ph

H OH

Ph Ph
O

OH

Ph Ph
(Show aldol reaction)
OH

(viii)

No aldol, no cannizzaro, as substrate


OH
Butan-1-ol
is neither aldehyde nor ketone with or without H.
O

(ix)

OH

H
2,2-Dimethylbutanal
O

H
OH

H
OH
O
O H +

O H +
(show cannizzaro reaction)

O
OH +

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203

Aldehyde, Ketone & Carboxylic acid


Exercise Problem 8.
How will you convert ethanal into the following compounds?
(i)

Butane-1,3-diol

(ii) But-2-enal

(iii) But-2-enoic acid


Strategy.
O

(i)

H3 C

HO

OH
Butane-1,3-diol

Ethanal

O
OH
O
NaBH
OH
CH 3 C H
CH 3 CH CH2 C H [H] 4
Aldol
Ethanal condensation
OH
OH
CH3 CH CH 2 CH 2
Butane-1,3-diol

(ii)

O
CH 3 C H

O
?

H
But-2-enal

O
CH 3 C H

OH H O
CH CH C H E CB
1

O
CH 3 CH = CH C H
But-2-enal

OH
CH3
Aldol
con densation

O
(iii) CH 3 C H
O
CH 3 C H

204

O
?

OH
But-2-enoic acid

OH
Aldol

OH H O
CH3 CH CH C H H O
2
O
CH 3 CH = CH C H

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Tollen's
O
O
reagent
CH 3 CH = CH C H [O]
CH 3 CH = CH C H

Exercise Problem 9.
Write structural formulas and names of four possible aldol
condensation products from propanal and butanal. In each
case, indicate which aldehyde acts as nucleophile and which
as electrophile.
Strategy.
O
O
CH 3 CH 2 C H + CH 3 CH 2 CH 2 C H

OH

O
CH 3 CH C H
H

OH

CH3 CH CHO
Nucleophile

CH3 CHCHO + CH 3 CH 2 CHO


(Nucleophile)

(Electrophile)

OH
CH 3 CH 2 CHCHCHO
CH3

CH 3CHCHO + CH3 CH 2 CH2 CHO


(Nucleophile) (Electrophile)

OH
CH 3 CH 2 CH2 CHCHCHO
CH 3

O
CH 3 CH 2 CHCH OH CH3 CH 2 CHCHO
H

(Nucleophile)

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Aldehyde, Ketone & Carboxylic acid


CH 3 CH 2 CHCHO + CH 3CH2 CHO
(Electrophile)
(Nucleophile)

OH
CH 3 CH 2 CHCHCHO
CH2 CH 3

CH 3CH2 CHCHO + CH 3 CH 2 CH 2 CHO


(Electrophile)
(Nucleophile)

OH
CH 3 CH 2CH2 CHCHCHO
CH2 CH3

Exercise Problem 10.


An orga nic compound with the molecula r formula
C 9 H 10 O forms 2,4-DNP derivative, reduces Tollens reagent and
undergoes Cannizzaro reaction. On vigorous oxidation, it gives
1,2-benzenedicarboxylic acid. Identify the compound.
Strategy.
2, 4-DNP

C 9 H10O

2,4-DNP derivative Presence of


aldehyde or ketonic group.

Tollen's
Reduce it Presence of aldehyde.
reagent
Cannizzaro
+Ve Presence of aldehyde without H.
reaction
C
COOH
[O]
Presence of skeleton
COOH
C

As compound have DU=5, so compound will be


CHO
CH2 CH3

206

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Exercise Problem 11.
An organic compound (A) (molecular formula C 8 H 16 O 2 ) was
hydrolysed with dilute sulphuric acid to give a carboxylic acid
(B) and an alcohol (C). Oxidation of (C) with chromic acid
produced (B). (C) on dehydration gives but-1-ene. Write
equations for the reactions involved.
Strategy.
C 8H 16 O 2
A
C
Alcohol

C
Alcohol

H 2O / H +

CrO 3
[O]

Carboxylic acid + alcohol


B
C

H2 O

As dehydration of C leads to but-1-ene so alcohol must have


4C. As the alcohol on oxidation give acid, so alcohol must be
butan-1-ol. B is butanoic acid & A is ester.
O

H 2O/H

CH 3CH2 CH2 COCH 2 CH 2 CH 2 CH 3


(A)
CH 3 CH 2CH2 COOH
(B)
CH 3CH2 CH 2CH2 OH
(C)

Exercise Problem 12.


Arrange the following compounds in increasing order of their
property as indicated:
(i)

Acetaldehyde, Acetone, Di-tert-butyl ketone, Methyl tertbutyl ketone (reactivity towards HCN)

(ii) CH3 CH 2 CH(Br)COOH, CH 3CH(Br)CH 2 COOH,


(CH 3 )2 CHCOOH,CH 3 CH 2CH 2COOH (acid strength)

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Aldehyde, Ketone & Carboxylic acid


(iii) Benzoic acid, 4-Nitrobenzoic acid, 3,4-Dinitrobenzoic acid,
4-Methoxybenzoic acid (acid strength)
Strategy.
(i)

Reactivity of carbonyl compounds towards nucleophilic


addition reaction depends on main two factors.
(a) Steric factor i.e. lesser the steric hindrance along
carbonyl carbon, easier for nucleophile to attack.
(b) Electronic factor i.e. greater the partial positive charge
along carbonyl carbon, easier for nucleophile to attack.

So increasing order of reactivity to HCN for different carbonyl


compounds follows
CH3 O CH 3
CH 3 C C C CH3
CH3
CH 3
Di-tert-butyl ketone
O
CH 3 C CH 3
acetone

<

O CH 3
CH3 C C CH 3
CH 3

<

methyl tert-butyl ketone


O
< CH 3 CH
acetaldehyde

(ii) Acidic strength depends on stability of conjugate base. As


the stability of conjugate base increases, corresponding
acidic strength increases. so
Br
Br
CH 3 CH 2 CHCOOH
Br
CH 3 CHCH 2 COOH

CH 3
CH 3 CHCOOH

208

CH 3 CH 2 CH COO
(I)
Br
CH 3 CH CH2 COO
(II)

CH 3
CH 3 CH COO
(III)

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CH 3 CH 2 CH2 COOH

CH3 CH 2 CH 2 COO
(IV)

Stability to conjugate base follows III < IV < II < I so acid


strength also follows III < IV < II < I.
(iii) Same concept is also used for aromatic compounds too.
i.e.
COO

COOH

(I)
COOH

COO

NO 2

NO 2 (I, M)
(II)

COOH

COO

NO
NO 2 2

NO 2 (I)
NO 2 (I, M)
(III)

COOH

COO

OCH 3(+M, I)
(IV)

OCH 3

Stability of conjugate base follows IV < I < II < III, so acidic


strength also follows IV < I < II < III
Exercise Problem 13.
Give simple chemical tests to distinguish between the following
pairs of compounds
(i)

Propanal and Propanone

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Aldehyde, Ketone & Carboxylic acid


(ii) Acetophenone and Benzophenone
(iii) Phenol and Benzoic acid
(iv) Benzoic acid and Ethyl benzoate
(v) Pentan-2-one and Pentan-3-one
(vi) Benzaldehyde and Acetophenone
(vii) Ethanal and Propanal
Strategy.

(i)

O
Tollen's test
Black ppt
CH 3 CH 2 CH NaOH/I
2
No Yellow ppt
(Propanal)
O

Tollen's test

CH 3 CCH 3
(Propanone)

I 2 /NaOH

Yellow ppt

O
CH3 NaOH /I2

(ii)

No ppt

ONa + CHI

(Yellow ppt)

(Acetophenone)

O
NaOH /I2

No yellow ppt

(Benzophenone)
OH

(iii)

NaHCO 3

No salt & no evolution of CO 2

(Phenol)

COOH
NaHCO 3

COONa
+ CO 2 (evolution of CO 2 )

(Benzoic acid)

210

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(iv)

O
COH NaHCO

CO 2 evolution is seen

(Benzoic acid)
O
COEt NaHCO
3

No CO 2 evolution

(Ethyl benzoate)

(v)

I 2 /NaOH

ONa + CHI 3
yellow ppt

(Pentan-2-one)
I2 / NaOH

No yellow ppt

O
(Pentan-3-one)
O

(vi)

CH I /NaOH
2

No yellow ppt

(Benzaldehyde)

O
C CH3 I /NaOH
2

O
C ONa + CHI 3
yellow ppt

O
I 2 / NaOH
yellow ppt
(vii) CH3 C H
(Ethanal)

O
I /NaOH
CH3 CH2 C H 2
No yellow ppt
(Propanal)

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Aldehyde, Ketone & Carboxylic acid


Exercise Problem 14.
How will you prepare the following compounds from benzene?
You may use any inorganic reagent and any organic reagent
having not more than one carbon atom.
(i)

Methyl benzoate

(ii) m-Nitrobenzoic acid

(iii) p-Nitrobenzoic acid

(iv) Phenylacetic acid

(v) p-Nitrobenzaldehyde.
Strategy.

(i)

O
C OCH3

(Benzene)

(Methyl benzoate)
CH 3

CH 3 Cl /AlCl 3
(Friedel-craft
alkylation )

KMnO 4 /H +

O
+
CH 3OH / H
COH (Esterification)

(oxidation)

O
COCH 3

COOH

(ii)

(Benzene)

NO 2
(m-nitrobenzoic acid)

CH3
CH 3Cl/AlCl 3
(Friedel-craft
alkylation)

KMnO 4 /H +
oxidat ion

COOH
HNO 3 /H 2 SO 4
Nitra tion

COOH

(iii)

NO 2

212

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COOH
NO 2

Aldehyde, Ketone & Carboxylic acid


CH3
CH 3Cl/AlCl 3
(Friedel-craft
alkylation)

CH 3

CH3
NO 2

HNO 3 /H 2SO 4

CH 3
+

NO 2
(Separation by fractional distilation)

COOH
KMnO 4 /H +

NO 2

NO 2
CH2 COOH
(Phenylacetic acid)

(iv)

CH3
CH 3Cl/AlCl 3
(Friedel-craft
alkylation)

CH2 Cl

CH 2 Cl

Cl 2 /h
(Free radical
substitution)

CH 2 CN

CH2 COOH
+

H 2O/H
(Hydrolysis)

KCN
(Nucleophilic
substitution)

CHO
?

(v)

NO 2 (p-nitrobenzaldehyde)
CH3
CH 3Cl/AlCl 3

HNO 3 /H 2 SO 4

CH 3
NO 2

(Friedel-craft
alkylation)

CH3

CHO

CH 3
+
NO 2

(i) CrO 2 Cl 2
(ii) H 2O/H

NO 2

NO 2

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Aldehyde, Ketone & Carboxylic acid


Exercise Problem 15.
How will you bring about the following conversions in not more
than two steps?
(i)

Propanone to Propene

(ii)

Benzoic acid to Benzaldehyde

(iii)

Ethanol to 3-Hydroxybutanal

(iv)

Benzene to m-Nitroacetophenone

(v)

Benzaldehyde to Benzophenone

(vi)

Bromobenzene to 1-Phenylethanol

(vii) Benzaldehyde to 3-Phenylpropan-1-ol


(viii) Benzaldehyde to - Hydroxyphenylacetic acid
(ix)

Benzoic acid to m-Nitrobenzyl alcohol

Strategy.

(i)

O
CH 3 C CH 3
Propanone

O
CH 3 C CH3

(ii)

CH3 CH = CH 2
Propene
OH

LiAlH 4
H 3O +
(R eduction)

CH 3 CH = CH2

CHO

COOH ?
Benzoic acid
O
COH SOCl

Benzaldehyde

O
CCl H / Pd - BaSO
2
4
(Rosenmuld
reduction)

214

H 2 SO 4 /

CH 3 CH CH 3 Elimination

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CHO

Aldehyde, Ketone & Carboxylic acid


(iii) CH 3 CH 2 OH
Ethanol

CH 3 CH 2 OH

OH
O
CH 3 CH CH2 C H
3-Hydroxybutanal

PCC
oxidation

O
NaOH
CH 3 C H aldol reaction

OH
O
CH 3 CH CH2 C H
COCH 3
?

(iv)

NO 2
m-nitroacetophenone

Benzene

COCH 3

COCH 3

CH 3COCl /AlCl 3

HNO 3 /H 2 SO 4

(F.C. acylation)

(Nitration)

CHO

NO 2

O
?

(v)

Benzaldehyde

Benzophenone

OH
H PhMgBr

Br

O
Cu

OH
?

(vi)
Bromobenzene

Br

CH CH3
1-Phenylethanol
O

Mg/THF

i) CH 3 C H
MgBr
+
ii) H 2O /H

OH
CH CH 3

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215

Aldehyde, Ketone & Carboxylic acid


CHO

Ph
?

(vii)

CH 2 CH 2 CH 2 OH

Benzaldehyde

Ph CH = O

3-Phenylpropan-1-ol

(CH 3CO)2 O/CH 3COONa


Perkin's react ion

Ph CH = CH COOH

CHO

LiAlH 4

Ph CH = CH COOH

Ph CH 2 CH2 CH2 OH

OH O
?

(viii)

Benzaldehyde

CHO

CH C OH
- Hydroxyphenylacetic acid

OH

OH
+
H O/H
CHCN 2

HCN

COOH

CHCOOH

CH 2 OH
?

(ix)
Benzoic acid

COOH

NO 2
m-nitrobenzyl alcohol

COOH

HNO 3 / H 2 SO 4

CH2 OH
LiAlH 4

NO 2

NO 2

Exercise Problem 16.


Describe the following:
(i)

Acetylation

(ii) Cannizzaro reaction

(iii) Cross aldol condensation (iv) Decarboxylation

216

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Aldehyde, Ketone & Carboxylic acid


Strategy.
(i)

Acetylation When aromatic compounds are treated with


CH3 COCl in presence of AlCl3 , it gives acetyl substituted
aromatic compound. Such reaction is called as acetylation.
O
C CH 3

Ex.

CH 3 C Cl /AlCl 3

Cl

C CH 3 C CH 3
+

CH 3 C Cl +AlCl AlCl CH3 C +


Cl

(ii) Cannizzaro reaction When aldehyde without H is


trea ted with a ny ba se, then it will undergoes self
oxidation-reduction i.e. disproportionation reaction to give
alcohol & salt of carboxylic acid. Such reaction is called as
Cannizzaro reaction.
O
O
Na OH
HCH
HCONa + CH 3OH
O
O
OH
HCH
HC H
OH

O
HCH

O
HCO H + CH3 O

O
HCO H + CH 3 O

O
HCONa+CH3OH

(iii) Cross aldol condensation When one aldehyde having


H is treated with base in presence of another aldehyde
which may or may not have H then condensation occur
between these two ca rbonyl compounds. Such
condensation is called as cross aldol condensation.
O

CH3CH + CH3CH2CH

CH3 O
OH

CH 3CH=C CH

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217

Aldehyde, Ketone & Carboxylic acid


O
O
O
O
CH3CH
OH
CH3CHCHCH
CH3CHCH
CH3CHCHO
CH3
H
HO H

OH CH3 O
OH CH3 O
O
OH
CH3CH=CCH CH3CHC CH
CH3CHC CH
CH3
H
, - Unsaturated aldehyde

(iv) Decarboxylation When compound containing carboxylic


acid group is treated with soda-line (NaOH+CaO) then
CO 2 is losed. Such reaction is called as decaroxylation.
NaOH/CaO
CH3 - COOH
CH 4

When strong electron withdra wing group is present a t


position of carboxylic acid then decarboxylation occur on just
heating.
O
CH 3 C CH3

O
O
CH 3 C CH2 C OH

Exercise Problem 17.


Complete each synthesis by giving missing starting material,
reagent or products.
CH 2 CH3

(i)

COOH
KMnO 4
KOH, heat

(ii)

COOH

O
C

(iii) C 6 H5 CHO H 2NCONHNH2 (iv)


O

(v)

218

[Ag(NH 3 )2 ]+

CHO

CHO

(vi)

SOCl 2
heat

NaCN/HCl

COOH

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Aldehyde, Ketone & Carboxylic acid


(vii)

C 6 H 5CHO
dil. NaOH
+
CH 3CH2 CHO

(viii) CH 3COCH 2 COOC 2 H 5

NaBH 4
H

CrO 3

(ix)

OH

(x)

CH2

CHO

(i) O

3
(xi) (ii) Zn H O 2
2

Strategy.
CH 2 CH 3

(i)

COOK

KMnO 4
KOH/Heat

KMnO 4 is a strong oxidising agent which oxidizes CH bond


of alkyl substituted benzene containing atleast one C at the
head with atleast one H at it to benzoic acid.

COOH

(ii)

SOCl 2

COOH

O
CCl
CCl
O

SOCl 2 is used to form acid halide from carboxylic acid.

(iii)

O
O H
CH H N C N NH
2
2
O

(iv)

O
CH = N N C NH 2
H
O

Ph C Cl / AlCl 3
Friedel-cra ft reaction

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219

Aldehyde, Ketone & Carboxylic acid


O

(v)

(vi)

Ag (NH 3 )2

CHO Tollen's reagent

CHO

COO

OH
CN
(Cyanohydrine
H
COOH formation)

NaCN/HCl

COOH

O
O
dil NaOH
(vii) PhC H +CH 3 CH 2CHO
Ph CH = C C H
CH 3
(Cross aldol condensation)
O
O
OH
O
(i) NaBH 4
CH3CHCH 2COC 2 H5
(viii) CH 3CCH2 COC 2 H5
+
(ii) H

NaBH 4 is selective reducing agent for aldehyde & Ketones &


Acid halide. It does not reduce ester.

(ix)

OH

CrO 3

CrO 3 is used for oxidation of alcohols. 2 alc oxidize to ketone

in presence of CrO 3 .
(x)

(i) BH

CH 2 (ii) H O3 /NaOH
2 2

CHO

(iii) PCC

Alkene is first converted into alcohol by hydroboration


oxydation method, then it is oxidized to aldehyde by PCC.
(xi)

(i) O 3
(ii) Zn H 2 O

As only one carbonyl compound is formed by ozonolysis so,


join 2 similar carbonyl compound to form alkene.

220

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Aldehyde, Ketone & Carboxylic acid


O + O

Exercise Problem 18.


Give possible explanation for each of the following:
(i)

Cyclohexanone forms cyanohydrin in good yield but 2,2,6trimethylcyclohexanone does not.

(ii) There are two NH2 groups in semicarbazide. However,


only one is involved in the formation of semicarbazones.
(iii) During the preparation of esters from a carboxylic acid
and an alcohol in the presence of an acid catalyst, the water
or the ester should be removed as soon as it is formed.
Strategy.
(i)

Reactivity of carbonyl compounds mainly depends on two


factors
(a) Electronic factors greater the partial positive charge
over carbonyl ca rbon, better for a nucleophile to
attack.
(b) Steric fa ctor lesser the steric hindrance a round
carbonyl carbon, better for a nucleophile to attack.

As cyclohexanone has more partial positive charge along with


less steric hindrance so form cyano hydrine.
O

HO

CN

HCN

But 2,2 ,6-Trimethylcyclohexanone has less partial positive


charge & more steric hindrance so no cyanohydrine formation
is observed for it.
O
HCN

No reaction

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221

Aldehyde, Ketone & Carboxylic acid


O
O
R
1
H 2
O+
NNCNH2
NNCNH2
H
(ii) R/H
R/H
H
H
Semicarbozide
Semicarbozone
As lone pair of electron of N 1 is in resonance with C=O bond
so is dolocalized. Therefore its nucleophilic charactor is very
less. On the other hand lone pair electron of N 2 is localized &
can attack more easily on carbonyl carbon because of good
nucleophilic character. Therefore only one -NH 2 is involved
in formation of semicarbazone.
R

(iii) Esterification formation of ester from carboxylic acid &


alcohol in presence of acid is a reversible reaction.
O
O
H+
RCOR + H 2O
RCOH + ROH

As we remove the water or ester from the reaction mixture,


the reaction proceeds in forward direction forming more &
more ester by Le-chatellier principle.
Exercise Problem 19.
An orga nic compound conta ins 69 .7 7% carbon, 1 1.63 %
hydrogen a nd rest oxygen. The molecular mass of the
compound is 86. It does not reduce Tollens reagent but forms
an addition compound with sodium hydrogensulphite and give
positive iodoform test. On vigorous oxidation it gives ethanoic
a nd propa noic acid. Write the possible structure of the
compound.
Strategy.

Tollen's
An organic reagent Ve Absence of aldehyde group
compound
O
NaHSO 3
C=69.77%
Addition product Reaction of R-C-H/R
H=11.63%
O
I2 /NaOH
O=100
+Ve Presence of C CH 3
(69.77+11.63) [O]
CH 3 COOH + CH 3CH2 COOH
=18.56%

222

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Aldehyde, Ketone & Carboxylic acid


From the data first calculate the molecular mass, then obtain
the formula & then from the rea ction, compound can be
obtained.
Elem. % of
Elem.
C
69.77
H
11.63
O
18.56

At.
mass
12
1
16

Relative
atomic mass
69.77/12=5.8
11.63/1=11.63
18.56/16=1.16

Simple ratio
of moles
5.8/1.16=5
11.63/1.16=10
1.16/1.16=1

whole
no. ratio
5
10
1

hence compound will be C 5 H 10 O i.e.


O
CH 3 CH2 CH2 C CH 3

O
CH 3 -CH 2 -CH 2 -C-CH 3

Tollen's
Ve
test
OH
NaHSO 3
CH3 CH2 CH2 C CH 3
I 2 /NaOH
[O]

SO 3 Na
CH3 CH2 CH2 COO Na + + CHI3
CH3 COOH + CH3 CH 2 COOH

Exercise Problem 20.


Although phenoxide ion has more number of resonating
structures than carboxylate ion, carboxylic acid is a stronger
acid than phenol. Why?
Strategy.
Acidic strength does not depends on number of resonating
structure but depends on stability of conjugate base.
Although phenoxide ion has more number of resonating
structure than carboxylate ion but here negative charge is
present on C atom making very less contribution for stability
due to weak M of phenyl group. On the other hand carboxylate

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223

Aldehyde, Ketone & Carboxylic acid


ion has only two resonating structure but both are equivalent
& O have ve charge making more stable due to strong M of
CO group.
O

(Less contributing)
O
RC O

O
RC=O

Equivalent structure with ve charge on O is more contributing.


As conjugate base of carboxylate is more stable than phenoxide
so carboxylic acid is more acidic than phenol.

224

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Amines

Unit

Amines

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225

Amines

Objective
This unit give you an understanding of Amines and
covers following topics:

226

Structures of amines.
Classification of amines.
Nomenclature of amines.
Preparation of amines.
Physical properties of amines.
Chemical reactions of amines.
Methods of preparation of diazonium salt & its
chemical reactions
Important diazonium salt in synthesis of aromatic
compounds.

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Amines

Solved Example:
Example 1.
Write chemical equations for the following reactions:
(i)

Reaction of ethanolic NH3 with C 2 H 5 Cl .

(ii) Ammonolysis of benzyl chloride and reaction of amine so


formed with two moles of CH3 Cl.
Strategy.
C 2 H5 Cl

(i)

NH 3
2

SN
HCl

C 2 H 5NH2

C 2H 5 Cl
HCl
2
(SN )

(Ethylchloride) (Ethylamine)

C 2 H 5 NH
C 2 H5

(N-Ethylethanamine)

C H Cl

2 5
C 2 H 5 NC 2 H5
C 2 H 5 NH
HCl
2
(SN )
C2H 5
C 2H 5
(N-Ethylethanamine)
(N,N-Diethylethanamine)

C 6 H 5CH2 Cl

(ii)

NH 3
HCl
(SN1)

Benzylchloride

C 6H 5 CH 2NH2
Benzylamine

CH 3Cl
HCl
(SN 2 )

C 6 H 5CH2NCH 3
H
N-methylphenyl
methanamine

CH Cl

C 6 H5 CH 2 N CH 3 3
C 6 H5 CH 2 N CH 3
HCl
H
2
CH 3
(SN )
N-methylphenyl
N,N-Dimethylphenyl
methanamine
methanamine

Example 2.
Write chemical equations for the following conversions:
(i)

CH 3 CH 2 Cl into CH 3 CH2 CH2 NH 2

(ii) C 6 H 5 CH2 Cl into C 6 H 5 CH2 CH2 NH 2

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227

Amines
Strategy.
(i)

CH 3CH2 Cl

(ii)

KCN
2
SN

LiAlH

4
CH 3 CH 2 C N Reduction
CH3 CH 2 CH 2 NH2

C 6 H5 CH2 Cl KCN
C 6 H 5 CH 2 C
2
SN

H 2/Ni

C 6H 5 CH2 CH 2 NH 2

Example 3.
Write structures and IUPAC names of
(i)

the amide which gives propana mine by Hoffmann


bromamide reaction.

(ii) the amine produced by the Hoffma nn degradation of


benzamide.
Strategy.
(i)

As propanamine contains 3 carbon atoms hence amide


which form this amine must have 4 carbon.
O
Br2 /NaOH
CH 3 CH 2 CH2 C NH2 Hoffmann CH 3 CH 2 CH2 NH 2
Butanamide
Propanamine
bromide
O

(ii)

C NH 2 Br2 /NaOH
Benzamide

NH 2
Aniline

Ph C N H OH Ph C NH

Br Br

Ph C N Br OH
H

H
O
Ph NH 2

228

H 2O

Ph N = C = O

Ph C N Br

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Amines
Example 4.
Arra nge the following in decreasing order of their basic
strength:
C 6 H 5NH2 , C 2 H 5 NH 2 , (C 2 H 5 )2 NH, NH3

Strategy.
Basic strength depends upon the availability of electron pair
on nitrogen atom. More the available electron, more the basic
molecule will be. So basic strength of following compounds
follows.
NH 2
CH 3 CH2 N H > CH 3 CH 2 NH 2 > NH 3 >
2+I

CH 2 CH 3

+I

Resonance

Example 5.
How will you convert 4-nitrotoluene to 2-bromobenzoic acid ?
Strategy.
COOH
Br

CH 3
?

NO 2

CH 3
Br2

CH 3
CH3
CH 3
Br NaNO2 /HCl
Br H 3PO 2
Br Sn /HCl
05C

NO 2
NO 2
step I

step II

NH 2

step III

N 2 Cl

step IV

CH 3
COOH

KMnO
/OH
Br
Br
4
step V

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229

Amines
Note step I is bromination which is govern by CH3 group.
It is because of the reason that in disubstituted benzene when
one group is EDG & other is EWG, the EDG will decide the
position of incomming electrophile.
Step II is reduction which convert NO 2 into NH2 .
Step III is diazotization which convert NH2 into N 2 Cl.
Step IV is removal of N 2 .
Step V is oxidation.

230

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Amines

Intext Problem:
Intext Question 1.
Classify the following amines as primary, secondary or tertiary:
N(CH 3 )2

NH 2

(i)

(ii)

(iii) (C 2 H 5 )2 CHNH 2

(iv) (C 6H 5 )2 NH

Strategy.

Primary amine is that amine in which N is attached to


alkyl group from one side & two H from other sides i.e.
R NH2 .

Secondary amine is that amine in which N is attached to


two alkyl group & one H.

Tertiary amine is that amine in which N is attached with


3 alkyl group from all side.

So,
NH 2

(i)

H3 C N CH 3

Primary amine (ii)

3 amine

H
(iii) CH 3CH2 C NH 2 1amine (iv) CH 3 CH 2 NH 2 amine
CH 2 CH 3
CH2 CH 3

Intext Question 2.
(i)

Write structures of different isomeric amines corresponding


to the molecular formula, C 4 H 11 N.

(ii) Write IUPAC names of all the isomers.


(iii) What type of isomerism is exhibited by different pairs of
amines?

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231

Amines
Strategy.
(i)

Isomeric amines of C 4H 11 N are

NH 2

NH 2

II

I
NH 2
III

IV

NH 2 (1 amines)

VI

H
N
VII

(ii) I

N
(2 amines)

VIII

Butan -1-amine

II

Butan-2-amine

III

2-Methylprop-1-amine

IV

2-Methylprop-2-amine

N-Methylpropan-1-amine

VI

N-methylproan-2-amine

(3 amines)

VII =

N-Ethylethanamine

VIII =

N,N-Dimethylethanamine

(iii) (I, III) (I, IV) are chain isomer


(II, III) (II, IV) are chain isomer
(I & II) (III & (IV) are positional isomer
1 amines are functional isomers with 2 & 3 amines.
V, VI & VII are metamers.

232

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Amines
Intext Question 3.
How will you convert
(i)

Benzene into aniline

(ii) Benzene into N, N-dimethylaniline


(iii) Cl (CH 2 )4 Cl into hexan-1, 6-diamine?
Strategy.
NH 2
?

(i)
Benzene

Aniline

NO 2
HNO 3 / H 2 SO 4
Nitration

NH 2

Sn/HCl
reduction

H3 C N CH3
?

(ii)
Benzene

N,N-Dimethylaniline

NO 2
HNO 3 /H 2 SO 4

NH 2

Sn/HCl
reduction

Nitration

CH 3I
1 eq

NH2
H 2N
(Hexane-1,6-Diamines)

(iii) Cl (CH ) Cl
2 4

Cl (CH 2 )4 Cl

CH 3I
(1 eq)

HNCH 3 H3 CNCH 3

KCN

LiAlH

4
NC (CH 2 )4 CN reduction

H 2 N CH 2 (CH 2 )4 CH 2 NH 2

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233

Amines
Intext Question 4.
Arrange the following in increasing order of their basic strength:
(i) C 2 H 5 NH 2 , C 6 H5 NH 2 , NH 3 , C 6H 5 CH 2 NH 2 and (C 2 H 5 )2 NH
(ii) C 2 H 5 NH 2 , (C 2 H 5 )2 NH, (C 2 H 5 )3 N,C 6 H 5NH 2
(iii) CH3 NH 2 , (CH 3 )2 NH, (CH3 )3 N,C 6 H 5 NH 2 , C 6H 5 CH 2 NH 2 .
Strategy.
CH 2 NH 2

NH 2
< NH 3<

(i)

< CH3 CH2 NH 2 < CH 3 CH 2 NH


CH 2CH3

NH 2

CH 2 CH 3

< CH3 CH2 NH2 < CH 3 CH 2 NCH 2 CH 3

(ii)

CH 2 CH 3
< CH 3 CH 2 NH

NH 2

CH 2NH2

<

(iii)

CH3
< CH3 N < CH 3 NH 2 < CH 3 N H
CH3

CH 3

Intext Question 5.
Complete the following acid-ba se reactions and name the
products:
(i)

CH 3 CH 2 CH 2 NH 2 +HCl

(ii) (C 2 H5 )3 N + HCl

Strategy.
(i)

CH 3 CH 2 CH2 NH2 +HCl

CH 3 CH 2 CH 2 NH 3Cl

(ii)

234

(C 2H 5 )3 N + HCl

CH3 CH 2 N CH 2 CH 3 Cl
CH2 CH3

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Amines
Intext Question 6.
Write reactions of the final alkylation product of aniline with
excess of methyl iodide in the presence of sodium carbonate
solution.
Strategy.
CH3 I
+
H 3 C N CH3

NH2

CH 3 I(excess)
HI

NH2

CH 3 I
HI

CH I

NCH3CH 3 I
CH3

NCH3 3
HI
H

CH3
+

NCH3 I
CH3

Intext Question 7.
Write chemical reaction of aniline with benzoyl chloride and
write the name of the product obtained.
Strategy.
NH 2

O
Cl

Aniline Benzoylchloride

O
Cl

+ H2 N

HCl

N
H
N-phenylbenzenecarboxylate

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235

Amines
Intext Question 8.
Write structures of different isomers corresponding to the
molecular formula, C 3 H9 N. Write IUPAC names of the isomers
which will liberate nitrogen gas on treatment with nitrous acid.
Strategy.
Isomers of C 3 H 9 N
2C + 2 - H + N
= O System is saturated with only
2
single bonds without ring. So
DU =

NH2 ,

1 Amines are

NH 2

H CH 3
H

2 amine is

3 amine is CH 3 N CH 3
CH 3
1 amines librate N 2 gas on treatment with HNO 2 . So they
are
(a) propan-1-amine

(b) propan-2-amine

Intext Question 9.
Convert
(i)

3-Methylaniline into 3-nitrotoluene.

(ii) Aniline into 1,3,5-tribromobenzene.


Strategy.
(i)

Convertion
NH2

CH 3
?

NO 2
CH 3
3-Methylaniline 3-Nitrotoluene

236

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Amines
N2 Cl

NH 2
NaNO 2 / HCl

CH 3

KNO 2

05C

NH 2

NO 2

CH3

Br

CH 3

Br

(ii)

Br
1,3,5-Tribromobenzene

Aniline
NH2

Br

Br2

NH 2
N 2 Cl
Br H PO Br
Br NaNO 2 Br
3
2

H2 O

Br

HCl

Br

Br

Br

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237

Amines

Exercise Problems:
Exercise Problem 1.
Write IUPAC names of the following compounds and classify
them into primary, secondary and tertiary amines.
(i)

(CH3 )2 CHNH 2

(ii) CH3 (CH2 )2 NH 2

(iii) CH3 NHCH(CH 3 )2

(iv) (CH3 )3 CNH2

(v) C 6 H 5NHCH3

(vi) (CH3 CH 2 )2 NCH3

(vii) m - BrC 6 H 4 NH2


Strategy.
SN.
(i)

Structure

IUPAC Name Nature of amine


Propan-2-amine

1 amine

(ii) CH3 CH 2 CH2 NH2 Propan-1-amine

1 amine

N-Methyl
propan-2-amine

2 amine

CH 3 CH NH 2
CH 3

(iii) CH 3 N CH CH 3
H CH3
CH 3

(iv) CH 3 C NH 2
CH 3
(v)

N CH 3
H

(vi) CH 3 -CH 2 -N-CH 2 -CH 3


CH 3
NH2
(vii)
Br

238

2-Methyl
propan-2-amine

1 amine

N-Methylaniline

2 amine

N-Ethyl-N-methyl 3 amine
ethanamine

3-Bromoaniline

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1 amine

Amines
Exercise Problem 2.
Give one chemical test to distinguish between the following
pairs of compounds.
(i)

Methylamine and dimethylamine

(ii) Secondary and tertiary amines


(iii) Ethylamine and aniline
(iv) Aniline and benzylamine
(v) Aniline and N-methylaniline.
Strategy.
(i)

Test for distinction between

CH 3 NH2 & CH 3 N H
CH 3
Methylamine librate N 2 gas on treatment with nitrous acid but
dimethylamine does not, because it is a test of primary amine.

(ii) Secondary & tertiary amines


Secondary amines on treatment with NaNO 2 /HCl give yellow
oily drop of nitroso compounds but tertiary amine does not
react with NaNO 2 /HCl .
(iii) Ethylamine & aniline
Aniline on reaction with NaNO 2 /HCl at low temperature
followed by addition of -naphthol give red dye which is test
of aromatic primary amine but ethylamine librates N 2 gas and
does not give dye test.
(iv) Aniline & Benzylamine
Aniline on reaction with NaNO 2 /HCl at low temperature
followed by addition of -naphthol give red dye which is test
of aromatic primary amine but benzylamine do not give such
test as it is aliphatic amine.

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239

Amines
(v) Aniline & N-methylaniline
Aniline on reaction with NaNO 2 /HCl at low temperature
followed by a ddition of -naphthol give red dye but Nmethylanilinc give yellow oily drop of nitroso compounds with
treatment with NaNO2/HCl.
Exercise Problem 3.
Account for the following :
(i)

pK b of aniline is more than that of methylamine.

(ii) Ethylamine is soluble in water whereas aniline is not.


(iii) Methylamine in water rea cts with ferric chloride to
precipitate hydrated ferric oxide.
(iv) Although amino group is o and p directing in aromatic
electrophilic substitution reactions, aniline on nitration
gives a substantial amount of m-nitroaniline.
(v) Aniline does not undergo Friedel-Crafts reaction.
(vi) Diazonium salts of aromatic amines are more stable than
those of aliphatic amines.
(vii) Gabriel phthalimide synthesis is preferred for synthesising
primary amines.
Strategy.
Reason for
(i)

pK b of aniline is more than that of methylamine or in other

words, aniline is more acidic than methylamine because


of stability of its conjugate base.
Stable the conjugate base, more acidic the molecule will
be.
NH 2

NH
H

240

(Resonance stabilization of
negative charge)

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Amines
+
CH 3 NH2 H CH3 NH2 (Inductive effect destabilize
negative charge)

(ii) Ethylamine is soluble in water because of H-bonding with


wa ter but a niline is not beca use of repulsion of
hydrophobic part of phenyl group.
CH 3 CH 2 N H
H

O H
H

(iii) As methylamine is more basic than water so it abstract


proton from water & generate OH.
This OH reacts with Fe3+ and form hydrated ferric oxide.

..

CH3 N H 3 OH
CH 3 NH2 + H OH
FeCl 3
Fe3 3Cl

2 Fe 3 6 OH
2 Fe(OH)3 or

Fe 2 O3 .3 H2 O
Hydrated ferric oxide
(brown ppt)

(iv) m-Nitroa niline forma tion occur due to formation of

anilinium ion in which -NH 3 is m-directing.


+

NH2

NH 3

HNO 3 /H 2 SO4

NO 2

NH3

NH 2
H

NO 2

NO 2

(v) Aniline react with lewis acids such as FeCl 3 , AlCl 3 to form
a complex which deactivate the benzene ring. So this
deactivated benzene ring do not give Friedel-craft reaction.
NH 2 +AlCl 3

H Cl
+
N Al Cl
H Cl
Complex formation

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241

Amines
(vi) Gabriel phthalimide synthesis is very useful method for
the synthesis of pure primary amine. Here phthalimide is
first converted into potassium salt which on heating with
alkyl halide, give N-alkylphthalimide which on hydrolysis
give primary amine is pure form.
O
NH

O
+ RI

EtOH/KOH

O
Phthalimide

NR

NK
Salt

O
N-alkylphthalimide

RNH 2 +

COOH

H2 O

COOH
1amine Phthalic acid

Exercise Problem 4.
Arrange the following:
(i)

In decreasing order of the pK b values:


C 2 H 5 NH 2 , C 6H 5 NHCH 3 , (C 2 H 5 )2 NH and C 6 H 5NH 2

(ii) In increasing order of basic strength:


C 6 H 5NH2 , C 6 H 5 N(CH 3 )2 , (C 2 H 5 )2 NH and CH 3 NH 2

(iii) In increasing order of basic strength:


(a) Aniline, p-nitroaniline and p-toluidine
(b) C 6 H 5NH2 , C 6 H 5 NHCH 3 , C 6 H5 CH 2 NH 2
(iv) In decreasing order of basic strength in gas phase:
C 2 H 5 NH 2 , (C 2 H 5 )2 NH, (C 2 H 5 )3 N and NH 3

(v) In increasing order of boiling point:


C 2 H 5 OH, (CH3 )2 NH, C 2 H 5 NH 2

(vi) In increasing order of solubility in water:


C 6 H 5NH2 , (C 2 H 5 )2 NH, C 2 H5 NH 2

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Amines
Strategy.
Arrange the following
(i)

In decreasing order of pK b value.

pK b value is inversaly proportiona l to ba sic strength so

decreasing order of pK b follows.


NH 2 H N CH 3
> CH 3 CH 2 NH 2 > CH 3 CH 2 N CH2 CH3
H

>

(ii) Increasing order of basic strength follows


NH 2 H 3 C N CH 3
<

< H 3C NH 2 < CH 3 CH 2 N H
CH 2 CH 3

(iii) Increasing order of basic strength follows


NH2

NH 2

NH2

<

(a)

NO 2
p-nitroaniline aniline
NH 2

(b)

<
CH3
p-toluidine

H N CH 3
<

CH 2 NH 2

<

(iv) Decreasing order of basic strength in gas phase follows


CH 3 -CH2 -N-CH 2 -CH 3 >CH3 -CH2 -N-H >CH 3 -CH 2 -NH 2 >NH3
CH2CH 3
CH 2CH3

(v) Increasing order of boiling point follows


CH 3 N CH 3 < CH 3 CH 2 NH 2 < CH 3 CH2 OH
H

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243

Amines
(vi) Increasing order of solubility in water follows
NH2
< CH 3 CH2 N H < CH3 CH 2 NH 2
CH 2 CH 3

Exercise Problem 5.
How will you convert:
(i)

Ethanoic acid into methanamine

(ii)

Hexanenitrile into 1-aminopentane

(iii) Methanol to ethanoic acid


(iv) Ethanamine into methanamine
(v)

Ethanoic acid into propanoic acid

(vi) Methanamine into ethanamine


(vii) Nitromethane into dimethylamine
(viii) Propanoic acid into ethanoic acid?
Strategy.
ConversionO

(i)

CH 3 C OH
Ethanoic acid

O
CH 3COH

(ii)

NH 3/

CH 3 NH 2
Methanamine

O
Br2 /KOHa
CH 3CNH Hoffmann
CH 3NH 2
bromide

CN ?

CN H2 O/H+

NH 2

Partial
hydrolysis

Br2 /OH

NH 2 Hoffmann

bromamide
reaction

NH 2

244

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Amines
(iii) CH 3 OH
Methanol

CH 3 OH

O
CH 3 C OH
Ethanoic acid

HI

CH 3 I

(iv) CH 3 CH 2 NH2
Ethanamine

(v)

Br2 /NaOH

O
CH 3 C OH
Ethanoic acid

H 2O

CH 3 CN H+ CH 3 C OH

CH 3 NH 2
Methanamine

NaNO2 /HCl
H 2O /

CH 3 CH 2 NH2

CH 3 NH 2

KCN

CH 3 CH 2 OH

KMnO 4 /H +

O
O
NH 3 /
CH 3 C NH2
CH 3 C OH

O
CH 3 CH2 C OH
Propanoic acid

O
LiAlH 4
KCN
HI
CH 3 CH2 I
CH 3 C OH
CH 3 CH2 OH
O
+
H 2O / H
CH 3 CH2 CN
CH 3 CH 2 C OH
?

(vi) CH 3 NH2
Methanamine

CH3NH 2

NaNO 2
HCl

CH 3 CH 2 NH2
Ethanamine

CH 3Cl

KCN

CH 3 CN

CH 3 CH 2 NH2

LiAlH 4

H 2O
H+

O
CH 3 C OH
NH 3 /
O

CH 3 C NH 2

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245

Amines
(vii) CH3 NO 2
Nitromethane

CH 3 N CH 3
H
Dimethylamine
CH I

3
CH 3 NO 2 Sn /HCl CH 3 NH2 (1 eq)
CH3 N CH 3
H

O
(viii) CH 3 CH2 C OH
Propanoic acid

O
CH 3 C OH
Ethanoic acid

Br2

NaOH

CH 3 CH 2 C OH CaO

CH 3 CH 3 h CH3 CH 2 Br

O
CH 3 C OH

KMnO 4 /H

KOH

CH 3 CH 2 OH

Exercise Problem 6.
Describe a method for the identification of primary, secondary
and tertiary amines. Also write chemical equa tions of the
reactions involved.
Strategy.
Primary, secondary & tertiary amines ca n be identified by
nitrous acid test.
A. Sample

NaNO 2 /HCl

Formation of brisk effervesence.

Presence of 1 aliphatic amine

B.

Sample NaNO 2 /HCl


05C

-naphthol

orange red dye obtained.

Presence of 1 aromatic amine

C.

Sample

NaNO 2 /HCl

yellow oily drop obtained.

Presence of 2 aliphatic & aromatic amine

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Amines
D. Sample

NaNO 2 /HCl

No change/No reaction.

Presence of 3 aliphatic amine

E.

Sample NaNO 2 / HCl Green/brown salt.


05C

Presence of 3 aromatic amine

Chemical reactions
(A) RNH2
(B) ArNH2

(C)

NaNO 2 /HCl

NaNO 2 /HCl

(R/Ar)2NH

RCl + N2
ArN2Cl

NaNO 2 / HCl

-naphthol

HO
N=N

R/ArNN=O
R/Ar

NR NaNO 2 /HCl R
N
R
R
Exercise Problem 7.

(D)

N=O

Write short notes on the following:


(i)

Carbylamine reaction

(ii) Diazotisation
(iii) Hofmanns bromamide reaction
(iv) Coupling reaction
(v) Ammonolysis
(vi) Acetylation
(vii) Gabriel phthalimide synthesis.
Strategy.
Short notes on
(A) Carbylamine reaction It is used to test primary amine
whether aliphatic or aromatic. When primary amine is

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247

Amines
heated with chloroform in presence of KOH then
isocyanide is obtained, which have foul smell. This reaction
is called as carbylamine reaction.
R/Ar NH2

KOH /CHCl 3

R/Ar NC
(Isocyanide with foul smell)

(B) Diazotization When aromatic primary amine is treated


with NaNO 2 / HCl a t low temperature (0 - 5C), then
diazonium salt will be obtained. This reaction is called as
diazotization reaction.
+

NH 2

N 2 Cl
NaNO 2 / HCl
05C

(C) H ofmanns bromide re action When a mide group


containing compounds are treated with Br2 in presence
of KOH, then amine are obtained. This reaction is called
as Hofmanns bromide reaction.
O
R C NH 2

Br2 /KOH

RNH2 + K 2 CO 3 + KBr + H 2O

(D) Coupling reaction When phenol or aniline are treated


with diazonium salt, then they couple each other to form
a dye. This electrophilic substitution reaction is called as
coupling reaction.
OH

Ph N 2Cl
P

NH 2

= 8 10

N=N

(Orange dye)

NH 2

N=N

(Yellow dye)

PhN 2Cl
P

248

HO

= 47

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Amines
(E) Ammonolysis When alkyl halide is treated with NH3 ,
then cleavage of CX bond by ammonia take place. This
reaction is called as ammonolysis.
R
NH
RX HX3

RNH2

RX

(1Amine)

RNH

RX

RNR

RX

RNRX

R
R
R
(2Amine) (3Amine) (overall product)

Here 1 amine thus obtained behave as a nucleophile and


further attack over RX to give 2, 3 & finally quaternary
ammonium salt as a product.
(F) Acetylation It is a process of reaction of R NH2 of
O
O
O
ROH with CH 3 C Cl , CH 3 C O C CH3 to form
R NHCOCH3

or

O
R O C CH3

to decrea se the

reactivity of NH2 or OH group i.e. substitution of


O
CH 3 C group in place of H of NH2 or OH is called

acetylation.
O
NH 2

HN C CH3

CH 3 C Cl

OH

O
O C CH 3

CH 3 C Cl

(G) Ga brie l-Phthalimide synthe sis Ga briel phthalimide


synthesis is used to form primary amine. Here phthalimide
is trea ted with EtOH/KOH to form potassium salt of
phthalimide which on heating with alkyl halide followed

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249

Amines
by alka line hydrolysis give prima ry a mine. It ha s a
limita tion tha t a roma tic prima ry amine ca n not be
prepared by this reaction as no SN 2 reaction occur over
ArX.
O

O
EtOH

NH KOH
O

O
+R X

NK

SN

H O

2
NR NaOH

COONa

R NH 2 +
(1amine)

COONa

Exercise Problem 8.
Accomplish the following conversions:
(i)

Nitrobenzene to benzoic acid

(ii) Benzene to m-bromophenol


(iii) Benzoic acid to aniline
(iv) Aniline to 2,4,6-tribromofluorobenzene
(v) Benzyl chloride to 2-phenylethanamine
(vi) Chlorobenzene to p-chloroaniline
(vii) Aniline to p-bromoaniline
(viii) Benzamide to toluene
(ix) Aniline to benzyl alcohol.
Strategy.
Accomplish the following conversions
(i)

Nitrobenzene to benzoic acid.

In this interconversion you have to convert NO 2 group into


COOH group.
This type of question can be done by converting the substrate
into diazonium salt.
The process will be as follow.

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Amines
NH2

NO 2

N 2 Cl

NaNO 2 /HCl
0-5C
Diazotization

Sn/HCl
(Reduction)

Nitrobenzene

KCN
Nucleophilic
Substitution

COOH

CN
H 2O / H +
Hydrolysis

Benzoic acid

(ii) Benzene to m-bromophenol


As bromine as well as hydroxyl group are ortho-para directing
in nature so you can not directly do this interconversion. For
this you have to first substitute a hydrogen of benzene to meta
directing group such as NO 2 . The conversion follows like this
NO 2
conc. H2 SO4 /HNO 3

NO 2
Br2 /AlCl 3

Nitration

Bromination

Br

Benzene
OH

Sn/HCl
Reduction

N2 Cl
KOH
Nucleophilic
substition

Br
m-bromophenol

NH2
NaNO /HCl
2

Diazotization

Br

Br

(iii) Benzoic acid to aniline


This question can be done by either way
(a) First convert benzoic acid into amide then take the
help of hoffmann bromamide reaction.
COOH

CONH 2
NH3 /

Benzoic acid

NH 2

Br2 /NaOH
Hoffmann bromamide reaction

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251

Amines
(b) First convert benz oic a cid into benz ene by
decarboxylation & then take the help of nitration &
reduction.
NH 2

COOH
conc. H 2 SO 4 /HNO 3

CaO/NaOH
Decarboxylation

NH 2

Sn/HCl
Reduction

Nitration

Aniline

Benzoic acid

(iv) Aniline to 2,4,6-Tribromofluorobenzene


Direct fluorination is explosive in nature so take the help of
fluorination on diazoniam salt. This interconversion occur as
follows.
NH2

Br
Br2 / H 2O

NH 2
N 2 Cl
Br NaNO / HCl Br
Br
2
Diazotization

Bromination

Aniline

Br
Br

Br

Br NaBF /
4
Fluorination

Br
2,4,6-Tribromofluoro benzene

(v) Benzyl chloride to 2-phenylethanamine


This question can be done by taking the help of SN 2 reaction
followed by reduction.
CH 2 CN

CH 2 Cl
KCN
SN 2

CH 2 CH 2 NH 2

H 2 / Ni
reduction

Benzyl chloride

2-Phenylethanamine

(vi) Chlorobenzene to p-chloroaniline


As chlorine is ortho-para directing group, so we can take the
help of nitration and then reduction.

252

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Amines
Cl

Cl

Cl

conc.H 2 SO4 /HNO 3

Chlorobenzene

Sn/HCl
Reduction

NO 2

NH 2
p-chloroaniline

(vii) Aniline to p-bromoaniline


We can not do directly bromination as +M of NH 2 is very
high, so first we reduces its reactivity. So this interconversion
follows by this way.
NHCOCH 3

NH 2
(CH 3CO)2 O
Nucleophilic
substitution

NHCOCH 3

Br2 /AlCl 3
Bromination

H 2O/H
hydrolysis

Br
p-Bromoaniline

Br

Aniline

NH 2
+

(viii) Benzamide to toluene


This interconversion can take place by following way.
O
CNH 2

O
CH

C N

P2 O 5
Dehydration

Benzamide

DIBAL - H
Partial
Reduction

CH 3

Zn Hg / HCl
Clemmenson
reduction

Toluene

78C

(ix) Aniline to benzyl alcohol.


This interconversion can take place by taking the help of
diazonium salt.
The interconversion will be
NH 2
N 2 Cl
NaNO 2 /HCl
05C
Diazotization

Aniline

CN

KCN
Nucleophilic
substit ution

DIBAL-H
Partial reduction

78C
CH 2 OH

CHO
H 2 /Ni
reduction

Benzyl alcohol

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253

Amines
Exercise Problem 9.
Give the structures of A, B and C in the following reactions:
(i)

OH

NaOH+Br

NaCN
2
CH3 CH 2 I
A
B
C
Partial hydrolysis
H O/H+

NH

CuCN
2
3
(ii) C 6 H 5N 2 Cl
A
B
C

LiAlH

HNO

KCN
4
2
(iii) CH3 CH 2 Br

A
B
C
0C

NaNO 2+HCl
H2O/H+
Fe/HCl
(iv) C 6 H 5NO2
A

C
273K

NH

NaNO /HCl

3
NaOBr
2
(v) CH3 COOH
A
B

HNO

C H OH

Fe/HCl
2
6 5
(vi) C 6 H 5NO 2

A
B
C
273K

Strategy.
(i) CH 3CH2 I

NaCN
SN

OH
CH3 CH 2 CN Partial
A
hydrolysis

CH 3CH2 NH 2
C

(ii)

C 6 H5 N 2 Cl

CuCN
Nucleophilic
substitution

O
CH 3 CH 2 C NH 2
B
Na OH /Br2
Hofmann bromamide
reaction

H O / H+

C 6 H5 CN 2
C 6 H 5 COOH
Hydrolysis
A
B
C 6 H 5 CONH2
C

NH 3

(iii) CH 3CH2 Br KCN CH 3 CH 2 CN LiAlH4 CH 3CH2 CH 2NH 2


Reduction
SN 2
A
B
CH 3 CH 2 CH 2 OH
C

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HNO 2
0C

Amines
(iv) C 6 H5 NO 2

Fe/HCl
reduction

C6 H5 NH 2
A

NaNO 2/HCl
273K

C6 H 5N 2 Cl
B

C 6 H 5OH
C

(v)

CH 3COOH

NH 3

H 2 O/H +

NaOBr

CH3 CONH2
Hoffmann
A
bromamide reaction
NaNO 2 /HCl

CH3 OH
C

CH 3 NH 2
B

HNO 2
(vi) C 6 H5 NO 2 Fe/HCl C 6H 5 NH 2
C 6 H5 N 2 Cl
reduction
273K
A
B

N=N

OH

C 6H 5OH

Diazo-coupling
reduction

Exercise Problem 10.


An aromatic compound A on trea tment with aqueous
ammonia and heating forms compound B which on heating
with Br2 and KOH forms a compound C of molecular formula
C 6 H7 N. Write the structures and IUPAC names of compounds
A, B and C.

Strategy.
Such type of questions can be done by first making an equation
from statement so that everything is visible by our eyes. The
equation for this statement will be
aq NH 3 /

A
Aromatic
Compound

Br2 / KOH

C6 H 7 N
C
Molecular
formula

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255

Amines
The deciding reaction will be B to C a s it is a Hoffma nn
bromamide reaction i.e. conversion of amide into amine.
As A on treatment with NH3 give B (Amide) so A must be
carboxylic acid. So overall reaction will be
O

COH

C NH 2

NH 2

Br2 /KOH

aq NH 3 /

A
Benzene carboxylic
acid

Exercise Problem 11.


Complete the following reactions:
(i)

C 6 H 5NH2 + CHCl 3 + alc.KOH

(ii) C 6 H 5N 2 Cl + H 3 PO 2 + H 2 O
(iii) C 6 H 5NH2 + H 2 SO 4 (conc.)
(iv) C 6 H 5 N 2Cl + C 2 H5 OH
(v) C 6 H 5NH2 + Br2 (aq)
(vi) C 6 H 5NH2 + (CH 3CO)2 O
(i) HBF

(vii) C 6 H 5 N 2Cl
(ii) NaNO /Cu.
2

Strategy.
(i)

C 6 H 5NH2 + CHCl 3 + alc KOH

This rea ction is carbylamine reaction. This state that when


primary amine on treatment with chloroform in presence of
base, give isonitrile with foul smell. So product of reaction is
C 6 H5 NH 2

256

CHCl 3 / KOH

C 6 H 5NC
Iso-nitrile

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Amines
(ii) C 6 H 5 N 2Cl +H 3 PO2 + H 2 O

This is conversion of benzene diazonium salt into benzene using


H 3PO 2 . So overall reaction will be.
H 3PO 2 /H 2 O

C 6 H5 N 2 Cl

(iii) C 6 H 5 NH2 + H 2 SO 4 (conc.)

This is simply the acid-base reaction and overall reaction will


be
C 6 H5 NH 2

conc. H 2SO 4

(C 6 H5 NH 3 )2 SO 4

(iv) C 6H 5N 2Cl + C 2H 5OH

This is a special case of conversion of benzene diazonium salt


into benzene using ethanol.
N 2 Cl
C2 H 5 OH

(v) C 6 H 5NH2 + Br2 (aq)

This is simply bromination of aniline in polar protic solvent.


The overall reaction will be
NH 2
Br2 (aq)

Br

NH 2
Br
Br

(vi) C 6 H 5NH2 + (CH3 CO)2 O

The use of acetic anhydride is to reduce the reactivity of aniline.


The overall reaction will be

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257

Amines
O
HNCCH 3

NH2
(CH 3 CO)2 O

(vii) HBF4 is used to repla ce Cl into sa lt of BF4 . La ter


NaNO 2 attack over diazonium salt to give nitrobenzene
as product.

N 2 BF4

N2 Cl
HBF4

NO 2

NaNO2/Cu/

Exercise Problem 12.


Why cannot aromatic primary amines be prepared by Gabriel
phthalimide synthesis?
Strategy.
Ga briel-phthalimide synthesis is use to prepare primary
aliphatic amine as salt of phthalimide attack over alkyl halide
to form alkyl substituted phthalimide by SN 2 mecha nism.
When we take aryl halide, it has partial double bond character
between C & halogen so SN 2 reaction will not take place. So
aromatic primary amine is not formed.
O
NH KOH
O

O
+ RX

N K SN 2
O

ArX

NR

H 2 O/H +

RNH2

O
No reaction

Exercise Problem 13.


Write the reactions of (i) aromatic and (ii) aliphatic primary
amines with nitrous acid.

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Amines
Strategy.
Nitrous acid rea cts differently with a romatic & aliphatic
primary amine.
NH2

N2 Cl
HNO 2

NH2

OH
HNO 2

Exercise Problem 14.


Give possible explanation for each of the following:
(i)

Why are amines less acidic than alcohols of comparable


molecular masses?

(ii) Why do primary amines have higher boiling point than


tertiary amines?
(iii) Why are aliphatic amines stronger bases than aromatic
amines?
Strategy.
(i)

Acidic strength depends on stability of conjugate base.


Greater is the stability of conjugate base, greater is the
stability. Negative charge over N is less stable than negative
charge over O, so amines are less acidic than alcohol of
comparable molecular mass such as CH 3 NH 2 < CH 3OH in
acidic strength.

(ii) Boiling point depends on H-bonding. Primary amine shows


H-bonding but tertiary amine do not show H-bonding. So
some extra energy is required to break this H-bonding in
1 amine so have more boiling point.
(iii) Basic strength depends on available electron density over
donating atom. Greater is the available electron density
over donating atom, greater is the basic strength. As alkyl

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259

Amines
group in aliphatic amine donates electron density towards
nitrogen and increases the available e density by +I while
phenyl group is aroma tic a mine withdra ws electron
density from nitrogen by M, So aliphatic amines are more
basic than aromatic amines.
NH 2

NH 2
>

in basic strength.

260

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Biomolecules

Unit

Biomolecules

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261

Biomolecules

Objective
This unit give you an understanding of Biomolecules
and covers following topics:

262

Carbohydrates- Its classification & nomenclature.


Glucose- Its structure preparation & chemical reactions.
Fructose- Its structures preparation & chemical reactions.
Disaccharides- Sucrose, Maltose, Lactose.
Polysaccharides- Starch, Cellulose.
Importance of carbohydrates.
Proteins- Its structures.
Classification & name of amino acids.
Enzymes
Vitamines
Nucleic acids- Structure & its biological functions.
DNA & RNA.

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Biomolecules

Intext Problem:
Intext Question 1.
Glucose or sucrose are soluble in water but cyclohexane or
benzene (simple six membered ring compounds) are insoluble
in water. Explain.
Strategy.
Solubility of any molecule in water depends on H-bonding with
water molecule & dipole moment. Greater is the extent of Hbonding or dipole moment, greater is the solubility in water.
Glucose & sucrose can form H-bonding with water molecule
hence soluble but cyclohexane & benzene are non-polar and do
not form H-bonding with water and hence insoluble in water.
Intext Question 2.
What are the expected products of hydrolysis of lactose?
Strategy.
La ctose is a disaccha ride formed by combina tion of two
monosaccharide units - D-Galactose & - D-Glucose. Hence
hydrolysis of lactose give its monosaccharides - D-Galactose
& - D-Glucose.
CH 2 OH
CH 2 OH
O
HOH
HO H
H H O OH
O
OH H H
H OH H H
H OH
-D-Galactose
CH2 OH
HO H O OH
H OH H H
H OH
-D-Galactose

H OH
-D-Glucose

Lactose
H2 O

CH 2 OH
H H O OH
HO OH H H
H OH
-D-Glucose

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Intext Question 3.
How do you explain the absence of aldehyde group in the
pentaacetate of D-glucose?
Strategy.
Free aldehyde group in any molecule react with hydroxylamine
to form oxime as a product but pentaacetate of D-glucose does
not react with hydroxylamine indicating the absence of free
aldehyde group.
CH2 OAc
O OAc
H H
AcO OAc H H

Hydroxylamin e

No reaction.

H
OAc
Penta acetate of D-Glucose
Intext Question 4.

The melting points and solubility in water of amino acids are


generally higher than that of the corresponding halo acids.
Explain.
Strategy.
Amino acids are those molecules in which same carbon have
COOH & NH2 group. So in aqueous medium, it exist as zwitter
ion

COOH
R

NH 2
H

COO
R

NH 3

H
Zwitter ion

Due to strong dipolar interaction they have high melting point


& solubility in water.
In case of holo acids i.e. HF, HCl, HBr & HI, they have polarity
but not as strong as zwitter ions of amino acid, so they have
less melting point & solubility in water.

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Intext Question 5.
Where does the water present in the egg go after boiling the
egg?
Strategy.
This question is based on denaturation of protein i.e. when an
egg is boiled, its globular protein gets denatured and water
present in egg probably gets either absorbed or adsorbed during
this denaturation & gets disappears.
Intext Question 6.
Why cannot vitamin C be stored in our body?
Strategy.
This question is asked to check the knowledge of soluble &
insoluble a vitamines.
As Vitamic-C (Ascorbic acid) is water soluble so it is regularly
excreted in urine from the body and can not be stored.
Intext Question 7.
What products would be formed when a nucleotide from DNA
containing thymine is hydrolysed?
Strategy.
To solve such question, first think for the atta chment of
nitrogenous bases of DNA & RNA along with sugars.
When nucleotide from DNA is hydrolysed, it will give its sugar
component i.e. deoxyribose suga r; phosphoric a cid &
nitrogenous bases i.e. Guanine (G), Adenine (A), Thymine (T)
& cytosine (C).
Base
Sugar Phosphate

H2 O
+
n H

Nitrogenous base + H3 PO 4 + Sugar.

Nucleotide

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Biomolecules
Intext Question 8.
When RNA is hydrolysed, there is no relationship among the
qua ntities of different bases obtained. What does this fact
suggest about the structure of RNA?
Strategy.
This question is to check the knowledge of single stranded
structure of RNA.
As we know that DNA molecules has a double strand structure
and four complementary nitrogenous bases paired with each
other.
Cytocine (C) pairs with Guanine (G) while Thymine (T) pairs
with Adenine (A).
Due to such pairing structure, DNA produces the products in
definite molar ratio.
But in case of RNA, base pairing is not observed, So RNA on
hydrolysis, different quantities of bases are observed.
This fact suggest about single stranded structure of RNA.

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Exercise Problems:
Exercise Problem 1.
What are monosaccharides?
Strategy.
Monosaccharides are the smallest unit of sugars which can
not be further hydrolysed. They have carbon ranges from C3
C7. On the basis of aldehydic or ketonic group present, they
are simply consider as aldose or ketose sugar of following types.
C 3
Triose

C 4
Tetrose

C 5
Pentose

C 6
Hexose

C 7
Heptose

Exercise Problem 2.
What are reducing sugars?
Strategy.
Reducing sugars are those sugars which have presence of either
aldehyde, ketone or hemiacetal linkage while non-reducing
sugars are those which have only acetal linkage in it.
All monosaccharides & disa ccha rides (except sucrose) are
reducing sugar.
In terms of chemical reaction, they reduces Fehling solution &
Tollens reagent.
Exercise Problem 3.
Write two main functions of carbohydrates in plants.
Strategy.
There are many functions of carbohydrates in plants but the 2
main functions are
(i)

Made cell wall of the plant which is made up of cellulose,


which is a polysaccaride.

(ii) Carbohydrates are stored in the form of starch, which is


also a polysaccharide as a reserve food material.

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Exercise Problem 4.
Classify the following into monosaccharides and disaccharides.
Ribose, 2-deoxyribose, maltose, galactose, fructose and lactose.
Strategy.
As we know that monosaccharides are smallest unit of sugar
which can not hydrolysed but disa ccharide are simply the
compound formed by combination of 2 monosaccharide units.
Ribose, 2 -Deoxyribose, Ga la ctose & Fructose a re
monosaccharide while Maltose & Lactose are disaccharides.
O

HOH 2 C
H

OH
H

H
OH OH
Ribose

CH2 OH
HO H O OH
H OH H H
H OH
Galactose

HOH 2 C
H

OH
H

OH H
2-Deoxyribose

HOH 2 C

H HO

CH 2 OH
OH H
Fructose

HO

CH 2 OH
CH 2 OH
O
H H
H
H H O OH
O
OH H H (Maltose)
HO OH H
H OH
-D-Glucose
CH2 OH
HO H O
H OH H H
H OH
-D-Galactose

268

H OH
-D-Glucose
CH 2OH
H H O OH
(Lactose)
O
OH H H
H OH
-D-Glucose

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Exercise Problem 5.
What do you understand by the term glycosidic linkage?
Strategy.
Glycosidic linkage is simply the ether linkage between two
monosaccharide when combines to form disaccha ride or
polysaccharides.
CH2 OH
H H O H
HO OH H

HOH2 C
O

H HO

CH 2 OH
OH
H
H OH
-D-Fructose
-D-Glucose
Glycosidic linkage
(Sucrose)

Exercise Problem 6.
What is glycogen? How is it different from starch?
Strategy.
Glycosen is a polysaccharide or simply the carbohydrate which
is stored in animal body. It is generally stored in liver, muscle
& brain. When body needs glucose, enzymes break down the
glycogen to glucose. On the other ha nd, sta rch is a
polysaccha ride which is stored in plants. It consists of two
components i.e. amylose & amylopectin. Amylose is water
soluble component and makes nearly 15-20% part of starch
while amylopectin is water insoluble component & ma kes
nearly 80-85% part of starch.
Exercise Problem 7.
What are the hydrolysis products of
(i)

sucrose and

(ii) lactose?

Strategy.
To solve such question, you must know the structure of sucrose
& lactose.

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Biomolecules
CH 2OH
H H O H HOH 2C O H
H HO
O
CH 2 OH
HO OH H
OH H
H OH
-D-Fructose
-D-Glucose
(Sucrose)
+

H O

2
H
CH2 OH
H H O H
HOH2 C O OH
+
H HO
HO OH H OH
HO
CH 2 OH
OH H
H OH
-D-Glucose
-D-Fructose

CH2 OH
CH2 OH
O OH
HO H O
NH
O
OH H H
H OH H H
H OH
-D-Galactose

H OH
-D-Glucose

H2 O H +

CH 2OH
CH 2 OH
HO H O OH
H H O OH
+
H OH H H
HO OH H H
H OH
-D-Galactose

H OH
-D-Glucose

Exercise Problem 8.
What is the basic structural difference between starch and
cellulose?
Strategy.
The basic structural difference between starch & cellulose is
seen in nature of glucose molecules.

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Starch consists of amylose & amylopectin, which are made up
of -D-Glucose unit. Here amylose unit consist of linear chains
of glucose linked in C1C4 manner wheras amylopectin consists
of these linear chains further linked in C1C6 manner.
Cellulose consist of only -D-Glucose molecules that are linked
to each other in C1C4 manner.

CH 2 OH
CH2 OH
CH 2 OH
O
O
O H
H H
H
H 5
H
H
H
H
4
1
4
1
4
1
O OH H
O
O
OH H
OH H O
H

OH
-Link

OH

OH

-Link

Amylose

CH 2 OH
CH2 OH
O
O H
H H
H
H
H
4
1
4
1
O OH H
O
OH H
H

OH

OH
O

-Link

Branch at C 6

CH2 OH
CH2
CH 2 OH
O
O
H H
H
H 5
H
H H O H
H
4
1
4
1
4
1
O OH H
O
O
OH H
OH H O
H

OH

H
H OH
-Link
-Link
Amylopectin

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OH

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Biomolecules
HOH2 C
HOH 2 C
HOH 2 C
H
O OH

O O

O O OH

O O OH

OH
OH

OH
-links

Cellulose

Exercise Problem 9.
What happens when D-glucose is treated with the following
reagents?
(i)

HI

(ii) Bromine water (iii) HNO 3

Strategy.
(i)

As we know that D-Glucose have aldehyde & alcoholic


group, so HI reduces both functional group to convert it
into alkane.
CHO
H
OH
HO
H
HI
OH
H
OH
H
Hexane
CH2 OH
D-Glucose
(ii) Bromine water is a mild oxidising agent which convert
only aldehyde group to carboxylic acid.
CHO
OH
H
OH
OH
CH2 OH
D-Glucose

H
HO
H
H

272

Bromine w ater

COOH
OH
H
OH
OH
CH2 OH
Gluconic acid

H
HO
H
H

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(iii) HNO3 is a strong oxidising agent which convert aldehyde
as well as CH2OH group into carboxylic acid.
CHO
OH
H
OH
OH
CH2 OH
D-Glucose

H
HO
H
H

HNO 3

COOH
OH
H
OH
OH
COOH
Glucaric acid

H
HO
H
H

Exercise Problem 10.


Enumerate the rea ctions of D-glucose which cannot be
explained by its open chain structure.
Strategy.
Following reactions can not be explained by open cha in
structure of D-Glucose.
(i)

2,4DNP
Glucose
Ve

Schiff base
(ii) Glucose
Ve
NaHCO

(iii) Glucose 3 No reaction.


NH OH

2
(iv) Pentaacetate of glucose
No reaction.

(v) Formation of & -alkyl glucosides can not be explained


by its open chain structure. These glycosides can only be
formed when we assume its ring structure.
Exercise Problem 11.
What are essential and non-essential amino acids? Give two
examples of each type.
Strategy.
Essential amino acids are those amino acids which can not be
synthesised in the body and must be taken from outer source

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Biomolecules
i.e. from diet. Out of 20 naturally occuring amino-acids, 10 are
essential amino acids. They are
(i)

Valine

(ii)

Leucine

(iii) Isoleucine

(iv) Arginine

(v) Lysine

(vi) Threonine

(vii) Methionine

(viii) Phenylalanine

(ix) Tryptophan

(x)

Histidine

Non-essential amino acids, are those amino acids which can


be synthesised in the body itself and not needed from outer
source. 10 non-essential amino acids are
(i)

Glycine

(ii)

Alanine

(iii) Glutamine

(iv) Glutamic acid

(v) Aspartic acid

(vi) Asparagine

(vii) Serine

(viii) Cysteine

(ix) Tyrosine

(x)

Proline

Exercise Problem 12.


Define the following as related to proteins
(i)

Peptide linkage

(ii) Primary structure

(iii) Denaturation.
Strategy.
(i)

Peptide linka ge:- Peptide linkage is simply the amide


linkage formed when COOH group of one amino acid
reacts with NH2 group of another amino acid.

H O
H O
H2 N
C OH + H N
COH
R
H R'
Amino acid(I)
Amino acid(II)

H O
H O
H 2N
CN
COH
R
H R'
Peptide linkage

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(ii) Primary structure:- Every polypeptide in a protein has
amino acids linked with each other in a specific sequence
and this sequence of amino a cid is called as prima ry
structure of that perticular protein. Any change in primary
structure of protein creates different protein.
(iii) De na turation:- When a protein in its native form is
subjected to physica l cha nge such a s cha nge in
temperature, or some chemical change such as change in
pH, the hydrogen bond present in the secondary structure
of protein get disturbed. Due to this change the protein
globules gets unfold and helix get uncoiled and protein
loses its biological activity. This loss of biological activity
of protein is called as denaturation of protein.
In this denaturation, secondary & tertiary structures of protein
gets destroyed but the primary structure of protein remains as
such.
Some common examples of denaturation of protein is the
coagulation of egg on heating & curdling of milk.
Exercise Problem 13.
What are the common types of secondary structure of proteins?
Strategy.
This

question

is

ba sed

on

understa nding

of

-helix & -pleated sheet. The secondary structure of protein


refers to the shape in which a long polypeptide can exist. The
two common types of secondary structure of proteins are

(i)

:- In a -helix , a polypeptide chain forms a ll

possible
- helix hydrogen bonds by twisting into a right handed
screw i.e. helix with the -NH- group of each amino acid
reside hydrogen bonded to CO of an adjacent turn of
the helix.

(ii) - pleated sheet:- In -pleated sheet structure of protein,


all peptide chains are stretched out to nearly maximum
extension and then aid side by side which are held together
by intermolecular hydrogen bonds.

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Biomolecules
This structure resembles the pleated fold of drapery, so is called
as -pleated sheet.
Exercise Problem 14.
What type of bonding helps in stabilising the -helix structure
of proteins?
Strategy.
The -helix structure of protein is stabilized by intramolecular
hydrogen bonding between CO & NH group of different
peptide bonds.

O
...

...

...

H O

..

N
C

...
O

..

N
..
.
HO
.. C.
.. O..
C N
H
O
...
N
..
H
N
..
C

-Helix structure of protein

Exercise Problem 15.


Differentiate between globular and fibrous proteins.

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Strategy.
Differentiation between globular proteins & Fibrous proteins
are as follows:
SN.

Globular proteins

Fibrous proteins

1. In th i s pr ote in s , po ly
pe pt ide s chains are
arranged as a coils.
2. Globula r protei ns h ave
spherical shape.

In this proteins, polypeptides


chains are parallel to each
other.
Fibrous proteins have thread
like structure.

They are water insoluble.


3. They are water soluble.
4. E x a m p l e o f g l o b u l a r Example of fibrous proteins
p ro te i n s a r e - i n s ul i n , are- Keratin, Myosin etc.
albumins etc.

Exercise Problem 16.


How do you explain the amphoteric behaviour of amino acids?
Strategy.
As amino acid have amino group (NH2), which is basic in
nature & carboxylic acid group (COOH), which is acidic in
nature. So in aqueous medium, NH2 group abstract proton
from COOH group and form a dipolar ion, which is called as
Zwitter ion. In this form, amino acids can behave as both as
acid as well as base so are considered as amphoteric in nature.
O

COH

..

NH 2
H

COO
R

NH 3

H
Zwitter ion

Exercise Problem 17.


What are enzymes?
Strategy.
Enzymes are simply the bioca ta lyst which catalysed the

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Biomolecules
reactions occurring in the living organism.
All enzymes are proteins and made up of amino acids only.
On the basis of its functions, it is of 2 types
(A) Endoenzymes- They have intracellular function.
(B) Exoenzymes- They have extracellular function.
Enzymes may be made up of only amino acids but can also be
associated with a non-proteinous part. In that case it is called
as coenzyme.
Exercise Problem 18.
What is the effect of denaturation on the structure of proteins?
Strategy.
During the denaturation of a protein, its secondary & tertiary
structures are destroyed but primary structures remains intact.
During this process, globular proteins are converted into fibrous
protein and biological activity of the protein is lost.
Exercise Problem 19.
How are vitamins classified? Name the vitamin responsible for
the coagulation of blood.
Strategy.
Vitamins are cla ssified into 2 groups on the ba sis of their
solubility in water or fat.
(i)

Water soluble vitamins- These vitamins are soluble in


water and insoluble in fat. Water soluble vitamins are
vitamin B-complex & vitamin C.

(ii) Fat soluble vitamins- These vitamins are soluble in fats &
insoluble in water. Fat soluble vitamins are vitamins A, D,
E & K.
The vitamin responsible for the coagula tion of blood is
vitamin K.
Exercise Problem 20.
Why are vitamin A and vitamin C essential to us? Give their
important sources.

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Strategy.
All vitamins are essential for us as they protect us from different
diseases. Every vitamin is specific in it function.
Deficiency of vitamin A cause Xerophthalmia or nightblindness while deficiency of vitamin C cause scurry or
bleeding of gums.
The main source of vitamin A is fish liver oil, carrots,
butter & milk while main source of vitamin C is citrus
fruits, amla & green leafy vegetables.
Exercise Problem 21.
What are nucleic acids? Mention their two important functions.
Strategy.
Nucleic acids are the biomolecules which are found in the nuclei
of living orga nisms in the form of nucleoproteins or
chromosomes.
Nucleic acids are of 2 types.
(A) DNA (Deoxyribonucleic acid)
(B) RNA (Ribonucleic acid)
The two important functions of nucleic acids are
(i) DNA, due to its replica tion property, tra nsmits
hereditary cha ra cteristics from one genera tion to
another.
(ii) DNA & RNA help in the protein synthesis in the cell.
RNA synthesises the protein and DNA has the message
for this synthesis.
Exercise Problem 22.
What is the difference between a nucleoside and a nucleotide?
Strategy.
The main difference between nucleoside and a nucleotide are
as follows:

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Biomolecules

Nucleoside
SN.
1. Nucleoside is combination
of nitrogenous base & sugar
unit.
2. 4 nucleosides are
(A) Adenosine =
Adenine + ribose
(B) Guanosine =
Guanine + ribose
(C) Cytidine =
Cytosine + ribose
(D) Deoxythymide =
Thymine + Deoxyribose
3. The structure of nucleoside
is
HOH 2 C O Base
H
H

H
OH OH

Nucleotide
Nucleotide is combination of
nitrogenous base, sugar unit
& phosphoric acid.
4 nucleotides are
(A) Adenylic acid =
Adenosine + H3PO4
(B) Guanylic acid =
Guanosine + H3PO4
(C) Cytidylic acid =
Cytidine + H3PO4
(D) Uridylic acid =
Uridine + H3PO4
The structure of nucleotide is
O

OPOCH 2 O Base

O
H H
H
H
OH OH

Exercise Problem 23.


The two stra nds in DNA a re not identica l but a re
complementary. Explain.
Strategy.
The two strands of DNA molecules are held together by
hydrogen bonding with a specific rule i.e. Adenine is bounded
with thymine & guanine is bounded with cytosine.
Due to this base pairing principle, the sequence of bases in one
strand is autometically fixed with the sequence of base in the
other strand. So the two stra nds a re not identical but are
complimentary.

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Double stand helix of DNA

Exercise Problem 24.


Write the important structural and functiona l differences
between DNA and RNA.
Strategy.
The important structural and functional differences between
DNA & RNA is as follows:

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Biomolecules
SN.

DNA

RNA

Structural difference
1. The pentose sugar present in
The pentose sugar present
DNA is deoxyribose.
in RNA is ribose
2. Pyrimidine base present in
DNA is cytosine & thymine.

Pyrimidine base present in


RNA is Cytosine & Uracil.

3. DNA has a double-standed


ccchelix
structure.

RNA has single stranded


helix structure.

4.

RNA molecule is relatively


short with low mol. mass.

with high molecular mass.

Functional difference
1. It has a unique property of
replication.

It has no property of
replication.

2. It controls the transmission of


hereditary charactors.

It controls protein
synthesis.

Exercise Problem 25.


What are the different types of RNA found in the cell?
Strategy.
There are mainly 3 different types of RNA found in the cell.
(A) Ribosomal RNA ( r-RNA)
(B) Messenger RNA (m-RNA)
(C) Transfer RNA (t-RNA)

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Polymers

Unit

Polymers

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Polymers

Objective
This unit give you an understanding of Polymers and
covers following topics:

284

Classification of polymers.
Types of polymerization reactions.
Molecular mass of polymers.
Biodegradable polymers.
Polymers of commercial importance.

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Polymers

Solved Example:
Example 1.
CHCH(C 6 H 5 ) is a homopolymer or a copolymer?
n

Strategy.
CHCH(C 6 H 5 ) is a homopolymer of styrene.
n

Homopolymer is that polymer in which a single type of


monomer unit polymerise to form polymer while copolymer is
that polymer in which two or more than two monomer units
polymerises to form polymer such as buna-S, buna-N etc.
CN
CH 2 CH=CHCH2 CH2 CH
n
Buna-N
Ph
CH 2 CH=CHCH 2 CH2 CH
n
Buna-S

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Polymers

Intext Problem:
Intext Question 1.
What are polymers ?
Strategy.
Polymer is a compound of la rge molecules ha ving high
molecular mass. It is formed by joining small repeating units of
small basic unit, monomer by the process of polymerization.
Ex- Polythene, Polystyrene etc.
Intext Question 2.
How are polymers classified on the basis of structure?
Strategy.
On the basis of structures, polymers are classified into 3 classes.
(A) Line ar polymer- They a re high density polythenes,
polyvinyl chloride etc.
(B) Bra nche d cha in polyme r- They ha ve low density
polythene.
(C) Cross-linked or network polymers- bakelite & melamines
etc.
Intext Question 3.
Write the names of monomers of the following polymers:
H

(i)

(ii)

N(CH2 )6 N
O

C(CH 2 )4 C
n

C (CH 2 )5 N
n

(iii) CF CF
2
2
n
Strategy.
To solve such question look over the linkage & then make the
monomer unit.

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Polymers
(i)

As it has amide linkage with 6 carbon is both side of amide


bond. So it is a polymer of diamine having 6 C atom &
diacid having 6 C atoms which we get by breaking amide
linkage.
H

N(CH 2 )6 N
H

O
H 2O

C(CH 2 )4 C
OH
n

H2 N(CH 2 )6 NH 2+
Hexane-1,6-diamine

HOOC (CH 2 )4 COOH


Adipic acid
O

(ii)

C (CH 2 )5 N a lso conta ins a mide linka ge but


n
between the same molecule. So we get its monomer unit
by adding water molecule.

C (CH 2 )5 N
n

O
H2 O

HO C (CH 2 )5 NH2
6-Aminohexanoic acid

(iii) CF2 CF2 contains the same monomer unit, so it is a


n
addition polymer of a monomer unit containg a double
bond.
CF2 CF2
n
Teflon

CF2 =CF2
(Tetrafluoroethene)

Intext Question 4.
Classify the following as addition and condensation polymers:
Terylene, Bakelite, Polyvinyl chloride, Polythene.
Strategy.
Addition polymers are obta ined from polymerisa tion of
unsaturated monomers while condensation polymers a re
obtained from condensing the monomer units conta ining

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Polymers
functional group by removing some neutral molecules such as
H2O, CH3OH etc.
Addition polymer- Polyvinyl chloride & Polythenes
Condensation polymer- Terylene, Bakelite
Intext Question 5.
Explain the difference between Buna-N and Buna-S.
Strategy.
Buna-N & Buna-S are synthetic rubber & are copolymer formed
by adding 2 monomer units. The difference in both these
copolymer lies in their composition.
Buna-N is formed by polymerisa tion of Buta-1 ,3-diene &
acrylonitrile while Buna-S are formed by polymerisation of Buta1,3-diene & styrene.
CN
n CH2 =CHCH=CH 2 + n CH 2 =CH
CN
CH 2 CH=CHCH 2 CH2 CH
n
Buna-N

Ph
n CH2 =CHCH=CH 2 + n CH 2 =CH
Ph

Intext Question 6.

CH 2 CH=CHCH 2 CH2 CH
n
Buna-S

Arrange the following polymers in increasing order of their


intermolecular forces.
(i)

Nylon 6,6, Buna-S, Polythene.

(ii) Nylon 6, Neoprene, Polyvinyl chloride.


Strategy.
To solve such question, first look over the order of intermolecular
force in different polymers which follows the order.

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Polymers
Eastomer < Plastics > Fibres.
So first classify the given polymer into the above classes & then
arrange them in increasing order of force. So increasing order
of their intermolecular forces follow.
(i)

Buna-S < Polythene < Nylon-6,6

(ii) Neoprene < Polyvinyl chloride < Nylon-6

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Polymers

Exercise Problems:
Exercise Problem 1.
Explain the terms polymer and monomer.
Strategy.
Polymers are the compound of large molecules having high
molecular mass. They are formed by joining small repeating
units of small units which are called as monomers, by the
process called as polymerization.
n CH 2 =CH 2 Polymerisation
Ethene
(Monomer unit)

CH 2 CH2
n
Polythene
(Polymer)

Exercise Problem 2.
What are natural and synthetic polymers? Give two examples
of each type.
Strategy.
Natural polymer- They are those polymers which are found
in anima ls & plants. They are also called as bio-polymers.
Examples are- Starch, Cellulose, Proteins etc.
Synthe tic polyme r- They are those polymers which are
synthesized with the help of chemicals in industries. They are
also called as men-made polymer. Examples are- Polythenes,
Nylon-6,6, Nylon-6 etc.
Exercise Problem 3.
Distinguish between the terms homopolymer and copolymer
and give an example of each.
Strategy.
Homopolymer- They are those polymer in which a single type
of monomer is used. Example- Polythene, Polystyrene etc.
Copolymer- They are those polymer in which more than on
monomers are used. Example- Buna-N, Buna-S etc.

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Exercise Problem 4.
How do you explain the functionality of a monomer?
Strategy.
Functionality of a monomer means the number of bonding sites
present in it. i.e. functionality of ethene, Propene, Styrene is
one and that of ethylene glycol, adipic acid & hexamethylene
diamine is two.
CH 2 =CH 2

H 2 NCH 2 CH 2 CH 2 CH 2 CH 2 CH 2 NH2

(one)

(two)

Exercise Problem 5.
Define the term polymerisation.
Strategy.
Polymeriz ation is the process of formation of polymers by
joining several monomer units by covalent bond.
n CH 2 =CH 2 Polymerization
Ethene
(Monomer)

CH 2 CH2
n
Polythene
(Polymer)

Exercise Problem 6.
Is (NH-CHR-CO)n , a homopolymer or copolymer?
Strategy.
NHCHRCO is a homopolymer as it has single monomer
n

unit of H 2 NCHRCOOH
R

NCHC
H
n
(Polymer)

R
H2 O

H2 NCHCOOH
(monomer)
Amino acid

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Exercise Problem 7.
In which classes, the polymers are classified on the basis of
molecular forces?
Strategy.
On the basis of intermolecular forces, polymers are classified
into mainly four classes.
(A) Elastomers

(B) Fibres

(C) Thermoplastic polymer

(D) Thermosetting polymer

Exercise Problem 8.
How can you differentiate between addition and condensation
polymerisation?
Strategy.
The differentiation between a ddition & condensa tion
polymerisation are as follows.
SN. Addition polymerization Condensation polymerization
1. In this polymerization,
monomer units have a
double bond or triple bond
in their molecule. These
re pre sent s t he ir
functionality.
2. Addition polymerization
is generally chain growth
poly meri za tio n a s
monomer units combines
c o n t i n o u s l y w i t h o ut
loosing anything.

In t h is po l ym eri z a tio n ,
monomer units have specific
fun c tio n al g rou p wh ic h
represent their functionality.

Condensation polymerization
is generally step growth
p olym eri za tio n as so me
molecules such as water,
alcohol continously removes
at each step of growth of
poymer.

3. E x a mp l e o f a dd i t i on Example of condensation
p o l y m e r i z a t i o n i s polymerization is terylene,
polythenes, polystyrenes nylon-6 etc.
etc.

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Exercise Problem 9.
Explain the term copolymerisation and give two examples.
Strategy.
Copolymerization- It is the polymerization reaction in which
more than one monomer units polymerize to form a copolymer.
The two most common examples are
(A) Buna-N:- It is a copolymer formed by the copolymerization
of two monomers- Buta-1,3-diene & acrylonitrile.
CN
CH 2 =CHCH=CH 2 + CH 2 =CH
Buta-1,3-diene Acrylonitrile
CN
CH 2 CH=CHCH 2 CH2 CH
n
Buna-N
(B) Buna-S:- It is a copolymer formed by the copolymerization
of two monomers- Buta-1,3-diene & styrene.
Ph
CH 2 =CHCH=CH 2 + CH 2 =CH
Buta-1,3-diene
Styrene
Ph
CH 2 CH=CHCH 2 CH2 CH
n
Buna-S

Exercise Problem 10.


Write the free radical mechanism for the polymerisation of
ethene.
Strategy.
Free radical mechanism for the polymerization is similar to
other free radical mechanism, i.e. follows 3 steps.
(A) Chain initiation step

(B) Chain propagation step

(C) Chain termination step

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Polymers
General reaction:
CH 2 =CH2
ethene

(PhCO)2O 2

CH2 =CH 2
Polythene

Mechanism:
(A) Chain initia tion ste p- In this step free radicals are
generated from benzoyl peroxide.
O

..

PhCO

. . .

OCPh

2 Ph

CO

2 Ph + 2 CO 2

(B) Chain propagation step- In this step phenyl free radical


formed in chain initiation step attacks over alkene to
propage the reaction.

Ph + CH 2 =CH 2

PhCH 2 CH 2

PhCH 2 CH 2 + CH 2 =CH 2

PhCH2 CH 2 CH2 CH 2

(C) Chain termination step- In this step, all the free radicals
formed, combines together to form neutral molecules.

. .
.

Ph + Ph

Ph Ph

PhCH 2 CH 2 + PhCH2 CH 2

PhCH 2 CH 2 CH2 CH 2 Ph

Exercise Problem 11.


Define thermoplastics and thermosetting polymers with two
examples of each.
Strategy.
Thermoplastic polymers- Those polymers which are capable
of softening on heating and hardening on cooling are called
thermoplastic polymer.
These polymers possess intermolecular forces of attraction
intermediate between elastomers & fibres.

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Examples are polythenes, polyvinyl chloride, polystyrene etc.
Thermosetting polymers- Those polymers which on heating
do not soften and can not be remoulded are called thermosetting
polymers.
On heating they undergo extensive cross-linking in moulds and
becomes infusible.
Examples are bakelite, Urea-formaldehyde resins etc.
Exercise Problem 12.
Write the monomers used for getting the following polymers.
(i)

Polyvinyl chloride

(ii) Teflon

(iii) Bakelite

Strategy.
(i)

Monomer of polyvinyl chloride is vinyl chloride.

(ii) Monomer of teflon is tetrafluoro ethene.


(iii) Monomer of bakelite is phenol & formaldehyde.
Exercise Problem 13.
Write the name and structure of one of the common initiators
used in free radical addition polymerisation.
Strategy.
The common initia tor used in free ra dica l a ddition
polymerisation is benzoyl peroxide.
O

COOC
(Benzoyl peroxide)
Exercise Problem 14.

How does the presence of double bonds in rubber molecules


influence their structure and reactivity?
Strategy.
Na tura l rubber is polymer of 2 -Methylbuta-1,3 -diene i.e.
isoprene. It is obtained by polymerization of isoprene unit of
1,4-position.

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Polymers
CH3

CH 3

CH 2 =CCH=CH 2 + CH 2 =CCH=CH 2
1
2 3
4
(2-Methylbuta-1,3-diene)

CH 3
CH2 C=CHCH 2
n
1
2 3 4
(Natural rubber)

In rubber molecule, double bonds are located between C2 & C3


of each isoprene unit and therefore creats a geometrical centre.
These cis-double bonds do not allow the polymer chain to come
closer and hence only weak Vander waal force are observed in
the molecule.
Since the chain is not linear, they can be stretched like springs
& exhibit elastic properties.
Exercise Problem 15.
Discuss the main purpose of vulcanisation of rubber.
Strategy.
Vulca niz ation of rubber is done to develop some specific
qualities in natural rubber. These qualities are as below
(A) It make rubber quite resistant to the action of organic acids.
(B) It makes rubber resistant to wear & tear.
(C) It increases the elasticity of rubber due to which it remains
uneffected over a wide range of temperature.
(D) It makes rubber resistant to the attack of air.
Exercise Problem 16.
What are the monomeric repeating units of Nylon-6 and Nylon6,6?
Strategy.
Monomeric repeating unit of Nylon-6 is Caprolactum a nd
Nylon-6,6 is hexanethylene diamine & adipic acid.
Exercise Problem 17.
Write the names a nd sturctures of the monomers of the
following polymers:
(i)

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Buna-S (ii) Buna-N (iii) Dacron (iv) Neoprene

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Strategy.
(i)

The monomer of Buna-S are 1,3-Butadiene & Styrene.


CH=CH 2
CH 2 = CH CH = CH 2
1,3-Butadiene

Styrene

(ii) The monomer of Buna -N a re 1 ,3 -Buta die ne &


acrylonitrile.
CH 2 = CH CH = CH2
1,3-Butadiene

CH2 = CH CN
Acrylonitrile

(iii) The monomer of Da cron a re Ethyle ne glycol &


Terephthalic acid.
O

CH 2 CH2

HOC

OH OH
Ethylene glycol

O
COH

Terephthalic acid

(iv) The monomer of Neoprene is 2-Chlorobuta-1,3-diene or


Chloroprene.
Cl
CH 2 =CCH=CH 2
2-Chlorobuta-1,3-diene
(Chloroprene)

Exercise Problem 18.


Identify the monomer in the following polymeric structures.
O

(i)

C(CH 2 )8 C

NH(CH 2 )6 NH
n

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Polymers
NH

(ii)

NH CH 2

N
NH

Strategy.
(i)

To solve such question add water molecule over amide


bond to get monomer where acid & amines are present.

O
O

C(CH 2 )8 C
NH(CH2 )6 NH
n
HO H
Polymer

HO C(CH 2 )8 COH
+
H2 N(CH 2 )6 NH 2

(ii) Here again, add water molecule over secondary amine to


get monomer unit.

NH

H OH
N NH CH 2
N N

H 2O

NH

O
H 2 N N NH 2
+ HCH
N N
NH (Formaldehyde)
2

(Melamine)

Exercise Problem 19.


How is dacron obtained from ethylene glycol and terephthalic
acid ?

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Polymers
Strategy.
Dacron is formed by the condensation polymerization of glycol
& terephthalic acid. During this condensation, a molecule of
water goes out at each step growth of polymer.
This polymeriz a tion rea ction ta ke pla ce a t 4 2 0 -4 6 0 K
temperature in presence of Zinc acetate antimony trioxide as a
catalyst.
O

COH
n HOCH2 CH 2 OH + HOC
Ethylene glycol
Terephthalic acid
420460 K
(CH 3COO)2 Zn/Sb 2O 3

O
OCH 2 CH2 OC
Dacron

O
C + H2 O
n

Exercise Problem 20.


Wha t is a biodegradable polymer ? Give an example of a
biodegradable aliphatic polyester.
Strategy.
Biode gra da ble polyme r- It is tha t polymer which get
decompose over a period of times by itself or by action of microorganisms is called as biodegradable polymer.
Use of such polymer a nd their disposa l does not create
environmental problems. The main examples of biodegradable
polymers are poly - hydroxybutyrate-co- - hydroxy valerate
(PHBV).

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CH 3

CH 2 CH 3

n HOCHCH 2 COOH
3-Hydroxybutanoic acid

+ n HOCHCH 2 COOH
3-Hydroxypentanoic acid
Polymerization

CH3

CH 2 CH3 O

O CH CH2 C O CH CH 2 C + H2 O
PHBV
n

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Chemistry in everyday life

Unit

Chemistry in everyday life

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Chemistry in everyday life

Objective
This unit give you an understanding of Chemistry in
everyday life and covers following topics:

302

Drugs & their classifications.


Drugs-Target interaction.
Therapeutic action of different classes of drugs.
Chemicals in food.
Cleansing agents- Soaps & detergents.

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Intext Problem:
Intext Question 1.
Sleeping pills a re recommended by doctors to the patients
suffering from sleeplessness but it is not advisable to take its
doses without consultation with the doctor. Why ?
Strategy.
Sleeping pills contains drug that may be anti-depressant or may
be transquilizer so they may affect the nervous system of body
or may creat anxiety, stress, irritability or excitement. So they
must strictly used under the supervision of a doctor. If not,
then uncontrolled & over dosage can cause harm to the body
and mind because in higher doses they acts as a poisons for
body.
Intext Question 2.
With reference to which classifica tion has the statement,
ranitidine is an antacid been given?
Strategy.
This statement refers to the classification of drugs according to
pharmacological effect because it may neutralize the acidity of
stomach.
Intext Question 3.
Why do we require artificial sweetening agents ?
Strategy.
Natural sweetners such as sucrose & glucose provides calories
to the body. These extra calories are ha rmful for diabetic
patients, so a artificial sweetener are used to control intake of
calories & act as a substitute of sugar for diabetics.
Intext Question 4.
Write the chemical equation for preparing sodium soap from
glyceryl oleate and glyceryl palmitate. Structural formulae of
these compounds are given below.
(i)

(C 15 H31COO)3 C 3 H 5 Glyceryl palmitate

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(ii) (C 17 H 32 COO)3 C 3 H5 Glyceryl oleate
Strategy.
(i)

CH 2 OCOC 15 H 31

CH2 OH
3 NaOH/

CHOC 15 H 31

CH 2 OCOC 15 H 31
Glyceryl palmitate

(ii)

3 C 15 H 31COONa + CHOH
Sodium palmitate CH OH
2
(soap)
Glycerol

CH 2 OCOC 17 H 33
CHOCOC 17 H 33

CH2 OH
3 NaOH/

CH 2 OCOC 17 H 33

3 C 17 H 33 COONa + CHOH
Sodium oleate CH OH
2
(soap)
Glycerol

Intext Question 5.
Following type of non-ionic detergents are present in liquid
detergents emulsifying agents and wetting agents. Label the
hydrophilic and hydrophobic parts in the molecule. Identify
the functional group(s) present in the molecule.
C 9 H19

O (CH 2 CH 2O )x CH 2 CH 2 OH

(x = 5 to 10)

Strategy.
Hydrophobic part in non-pola r part in the molecule while
hydrophilic part is that which creats polarity and is responsible
for hydrogen bonding with water.
C 9 H19

O (CH 2 CH 2 O)x CH 2 CH 2 OH

Hydrophobic part

Hydrophilic part

The functional groups present in given molecule is ether &


alcohol.

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Chemistry in everyday life

Exercise Problems:
Exercise Problem 1.
Why do we need to classify drugs in different ways ?
Strategy.
Drugs are generally the complex organic molecules so different
types of classification to it is beneficial for the people related to
different fields. Knowing pharmacological effect makes it easy
for doctors to remember their name.
It also makes the correct medicine available to the patient as
first aid such as an antacid, can be used in case of excessive
acidity in stomach.
In the same way, other types of classification helps the scientist,
drug manufacturers, students, chemist etc to remember their
name.
Exercise Problem 2.
Explain the term, target molecules or drug targets as used in
medicinal chemistry.
Strategy.
Targe t mole cule s or drug ta rget- Drugs interact with
biomolecules present in our body such a s proteins,
ca rbohydra tes, lipids & nucleic a cid a nd hence these
biomolecules are called as target molecule or drug target.
Drugs possessing some common structural features may have
the same mechanism of action on target.
Exercise Problem 3.
Name the macromolecules that are chosen as drug targets.
Strategy.
Biomolecules present in the body are the drug targets such as
proteins, carbohydrates, lipids, nucleic acids, enzymes etc.
Exercise Problem 4.
Why should not medicines be taken without consulting doctors ?

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Strategy.
If doctors advice is not taken before using medicine then, it
may create some side effects or may cause another ailment. So
the dosage of medicine is also of equal importance which must
be consulted by a doctor.
Exercise Problem 5.
Define the term chemotherapy.
Strategy.
Che motherapy- Chemothera py mea ns the treatment of a
disease with the help of chemicals in the form of medicines.
This chemotherapy ma y involve diagnosis, prevention and
treatment of disease.
Exercise Problem 6.
Which forces are involved in holding the drugs to the active
site of enzymes?
Strategy.
The forces that involved in holding the drugs to the active site
of enzyme are ionic bonding, hydrogen bonding, vander waal
forces of interaction, dipole-dipole interaction etc.
Exercise Problem 7.
While anta cids and antia llergic drugs interfere with the
function of histamines, why do these not interfere with the
function of each other ?
Strategy.
Antacids & Antiallergic drugs do not interfere with the function
of each other because they work on different receptors in the
body. If the side of function of drug is different, then there is
no interference in the action of the two drugs.
Exercise Problem 8.
Low level of noradrenaline is the cause of depression. What
type of drugs are needed to cure this proplem ? Name two
drugs.

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Strategy.
Noradrenaline is a neurotransmitter and plays an important
role in mood changes. Its low level in body leads to depression
so some transquilizer are required by body. The two common
transquilizers are- Iproniazid & Phenylzine.
Exercise Problem 9.
What is meant by the term broad spectrum antibiotics Explain.
Strategy.
Broad spectrum antibiotics- They are those antibiotics which
kills or inhibit a wide range of harmful or desease causing
bacteria. They are equally effective against gram positive and
gram negative bacteria.
The most common broad spectrum antibiotic are ampicillin &
amoxycillin.
Exercise Problem 10.
How do antiseptics differ from disinfectants ? Give one example
of each.
Strategy.
Antiseptics- They are the chemical substance which prevent
the growth of micro-organisms and are capable of killing them
without harming the human tissue. They are generally applied
on wounds, ulcer, cut etc.
The most common examples of antiseptics are dettols, savlon
etc.
Disinfe ctants- They are the chemica l substance which kill
micro-organism but are unsafe for living tissue. They are
generally used to clean toilets, floor etc.
The most common disinfectants are phenol & chlorine.
Exercise Problem 11.
Why are cimetidine and ranitidine better antacids than sodium
hydrogen carbonate or magnesium or aluminium hydroxide ?

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Strategy.
Sodium hydrogen ca rbonate or magnesium or aluminium
hydroxide neutralizes the excess acid produced in the stomach
but their prolong use of it can cause the production of excess
acid in the stomach, which is harmful and may cause ulcer.
Cimetidine & rantidine work without such side effects, as
they prevent interaction of histamine with the receptor of the
stomach wall as histamine stimulate the secretion of acid.
Exercise Problem 12.
Name a substance which can be used as an antiseptic as well
as disinfectant.
Strategy.
0.2% solution of phenol can be used as antiseptic while 1%
solution of phenol can be used as a disinfectant.
Exercise Problem 13.
What are the main constituents of dettol ?
Strategy.
The main constituents of dettol are chloroxylenol & terpineol.
Exercise Problem 14.
What is tincture of iodine ? What is its use ?
Strategy.
Tincture of iodine is the dilute solution of iodine, generally 23% prepared in ethanol.
The main role of it, is its action as powerful antiseptic for wounds.
Exercise Problem 15.
What are food preservatives ?
Strategy.
Food preservatives- They are the chemical substances which
are used to protect food against bacteria, yeasts, moulds etc.
The common food preservatives are sodium meta bisulphate,
sodium benzoate.

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Exercise Problem 16.
Why is use of aspartame limited to cold foods and drinks ?
Strategy.
Aspartame is a chemical, decomposes on heating and may not
work well at high temperature. So its use as a n a rtificial
sweetner is limited to food & drinks at low temperature.
Exercise Problem 17.
What are artificial sweetening agents ? Give two examples.
Strategy.
Artificial sweetening agents- They are the chemical substances
which provides sweetness to the food without increasing the
colories to the body.
The most common examples are saccharin, aspartame.
Exercise Problem 18.
Name the sweetening agent used in the preparation of sweets
for a diabetic patient.
Strategy.
The sweetening agent used in preparation of sweet for a diabetic
patient are saccharin & sucralose.
CH2 OH
OH
Cl
HO
O
O
CH 2 Cl
O
NH
HO
O
S
CH 2 Cl
OH
O O
Sucrolose
Saccharin
Trichloro derivative of sucrose
Exercise Problem 19.
What problem arises in using alitame as artificial sweetener ?
Strategy.
The problem arises in using alitame as artificial sweetener is
that, it is a high potency artificial sweetener. So, it become
difficult to control the level of sweetness while using it.

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O
S

NH 2 O

N
H

Alitame O

OH

Exercise Problem 20.


How are synthetic detergents better than soaps ?
Strategy.
Synthetic detergents are better than soaps because of following
reasons.
(A) Synthetic detergents can work with hard water too while
soaps can not.
(B) Synthetic detergents can work even in acidic medium
while soap can not.
(C) Synthetic detergents have higher solubility than soaps.
(D) Synthetic detergents are prepared from hydrocarbons,
mainly from petroleum so their use can save the vegetable
oils which are used during preparation of soaps.
Exercise Problem 21.
Explain the following terms with suitable examples
(i)

Cationic detergents

(ii) Anionic detergents and


(iii) Non-ionic detergents.
Strategy.
(i)

Cationic de terge nts- They a re genera lly ca tions of


quaternary ammonium salts of amines with acetate,
chloride or bromides. The most common exa mple of
cationic detergent is cetyltrimethyl ammonium bromide.

(ii) Anionic detergents- They are generally detergents with


large anionic part in their molecules. These are of two types.
(A) Sodium alkyl sulphate
(B)

310

Sodium alkyl benzene sulphonates.

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(iii) Non-ionic detergents- They are generally the esters of high
molecular ma ss. The most common exa mple of this
detergent is polyethylene glycol stearate.
Exercise Problem 22.
What are biodegradable and non-biodegradable detergents ?
Give one example of each.
Strategy.
Biodegradable detergents- They are those detergents which
can be decomposed by microbes. Their molecules ha ve less
branching & they do not create wa ter pollution. The most
common exa mple of it is- sodium-n-dode cyl be nze ne
sulphonate.
Non-biodegradable detergents- They are those detergents
which can not be decomposed by microbes. They have more
branching in their structures and creates water pollution when
go to water sources. The most common example of it is ABS
detergent.
CH 3

CH 3

CH 3 CH CH 2 CH

SO 3Na

ABS detergent

Exercise Problem 23.


Why do soaps not work in hard water ?
Strategy.
Soap do not work with hard wa ter because ca lcium a nd
magnesium salts present in hard water reacts with soap to form
insoluble compounds which form curdy white precipitates and
are difficult to remove from the clothes.
C 17 H35COONa MgCl 2
(C 17 H 35 COO)2 Mg NaCl
(soap)
(in hard water)
(White curdy ppt)

C 17 H35COONa CaCl 2
(C 17 H 35 COO)2 Ca 2 NaCl
(soap) (in hard water)
(White ppt)

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Exercise Problem 24.
Ca n you use soaps and synthetic detergents to check the
hardness of water ?
Strategy.
Yes, we can use soaps & detergents to check the hardness of
water as soaps can form insolube precipitate with hard water
but it is soluble in soft water but detergents are soluble in both
types of water i.e. hard water & soft water.
Exercise Problem 25.
Explain the cleansing action of soaps.
Strategy.
Cle a nsing a ction of soa ps- Soa p molecule ha ve two
components
(A) Hydrophobic part
(B) Hydrophilic part
Hydrophobic part is water repelling while hydrophilic part is
water attracting. When soap is dissolved in water and a dirty
cloth is agitated in the solution, the oily dirt is attached to the
hydrophobic part while water is attached to hydrophilic part.
Due to this attachment, soap molecules arrange themselves in
the form of micelles. As the mixture is agitated more, the more
and more dirt particles leave the cloth and get attached to soap
molecules. The negative charges of micelles prevent the dirt to
form aggregate and thus soap removes the dirt by reducing
the surface tension of water.
Exercise Problem 26.
If water contains dissolved calcium hydrogen carbonate, out
of soaps and synthetic detergents which one will you use for
cleaning clothes ?
Strategy.
Calcium hydrogen carbonate reacts with soap to form white
insoluble precipitate and are difficult to remove from the clothes.

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C 17 H35COONa Ca(HCO 3 )2 (C 17 H 35 COO)Ca NaHCO 3
(soap)
(White ppt)

On the other hand, synthetic detergents do not form such


compounds so they can be used for cleaning clothes with water
containing dissolved calcium hydrogen carbonate.
Exercise Problem 27.
Label the hydrophilic and hydrophobic parts in the following
compounds.
(i)

CH3 (CH 2 )10 CH 2 OSO 3 Na


+

(ii) CH 3 (CH2 )15 N(CH 3 )3 Br


(iii) CH3 (CH2 )16 COO(CH 2 CH 2 O)n CH 2 CH 2 OH
Strategy.
Hydrophilic & hydrophobic part in following compounds are
(i)

CH 3 (CH2 )10 CH 2 OSO 3 Na


Hydrophobic

Hydrophilic

CH 3 (CH 2 )15 N (CH 3 )3 Br

(ii)

Hydrophobic Hydrophilic

CH 3 (CH 2 )16 COO (CH 2 CH2 O)n CH 2 CH 2 OH

(iii)

Hydrophobic

Hydrophilic

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Chemistry in everyday life


You can get free Organic Chemistry video lectures from our
YouTube channel: www.youtube.com/user/Ajnish2081 and
my website: www.OrganicChemistry.co.in
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Organic Chemistry is easy by


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