Atul singhal the pearson guide to organic chemistry for the IIT JEE pearson education (2010)

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Organic Chemistry
for the

IIT-JEE

Atul Singhal

Chandigarh x Chennai xDelhi


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The aim of this publication is to supply information taken from sources believed to be valid and reliable. This is not an
attempt to render any type of professional advice or analysis, nor is it to be treated as such. While much care has been
taken to ensure the veracity and currency of the information presented within, neither the publisher nor its authors bear
any responsibility for any damage arising from inadvertent omissions, negligence or inaccuracies (typographical or factual) that may have found their way into this book.
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To my grandparents,
parents and teachers


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CONTENTS
Preface

vii

Chapter 1

General Organic Chemistry-1
(Nomenclature and Isomerism)

1.1—1.72

Chapter 2

General Organic Chemistry-2
(Concepts of Organic Chemistry)

2.1—2.94

Hydrocarbons

3.1—101

Chapter 4

Organic Compounds Containing Halogens
(Haloalkanes and Haloarenes)

4.1—4.48

Chapter 5

Organic Compounds Containing Oxygen-1
(Alcohols, Phenol and Ether)

5.1—5.79

Chapter 6

Organic Compounds Containing Oxygen-2
(Aldehyde, Ketones)

6.1—6.91

Chapter 7

Acids and Acid Derivatives

7.1—7.69

Chapter 8

Organic Chemistry Based on Functional Group–III
(Nitrogen Containing Compounds)

8.1—8.65

Chapter 9

Polymers And Biomolecules

9.1—9.47

Chapter 10

Practical Organic Chemistry

10.1—10.37

hapter
C
3


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PREFACE
Organic Chemistry for the IIT-JEE is an invaluable book for all the students preparing for the prestigious
engineering entrance examination. It provides class-tested course material and problems that will supplement
any kind of coaching or resource the students might be using. Because of its comprehensive and in-depth
approach, it will be especially helpful for those students who do not have enough time or money to take
classroom course.


A careful scrutiny of previous years’ IIT papers and various other competitive examinations during
the last 10 to 12 years was made before writing this book. It is strictly based on the latest IIT syllabus
(2009–10) recommended by the executive board. It covers the subject in a structured way and familiarizes students with the trends in these examinations. Not many books in the market can stand up to this
material when it comes to the strict alignment with the prescribed syllabus.



It is written in a lucid manner to assist students to understand the concepts without the help of any
guide.



The objective of this book is to provide this vast subject in a structured and useful manner so as to
familiarize the candidates taking the current examinations with the current trends and types of multiplechoice questions asked.



The multiple-choice questions have been arranged in following categories:

Straight Objective Type Questions (Single Choice), Brainteasers Objective Type Questions (Single Choice),
Multiple Correct Answer Type Questions (More than one choice), Linked-Comprehension Type Questions,
Assertion and Reasoning Questions, Matrix-Match Type Questions and the IIT-JEE Corner.
This book is written to pass on to another generation, my fascination with descriptive inorganic chemistry.
Thus, the comments of the readers, both students and instructors, will be sincerely appreciated. Any suggestions for added or updated additional readings would also be welcome.

Atul Singhal



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ACKNOWLEDGEMENTS
The contentment and ecstasy that accompany the successful completion of any work would remain essentially
incomplete if I fail to mention the people whose constant guidance and support has encouraged me.
I am grateful to all my reverend teachers, especially, the late J. K. Mishra, Dr D. K. Rastogi, the late A. K.
Rastogi and my honourable guide, Dr S. K. Agarwala. Their knowledge and wisdom has continued to assist
me to present in this work.
I am thankful to my colleagues and friends, Deepak Bhatia, Er Vikas Kaushik, Er A. R. Khan, Vipul
Agarwal, Er Ankit Arora, Er Wasim, Manoj Singhal, Vijay Arora, (Director, Dronacharya), Mr. Anupam
Shrivastav (Career Point, Kota), Mr Rajiv Jain (MVN, Faridabad), Mr Ashok Kumar, Mr Y.R. Mittra and Mr
N.C. Joshi (Brillant Tutorials).
I am indebted to my father, B. K. Singhal, mother Usha Singhal, brothers, Amit Singhal and Katar Singh,

and sisters, Ambika and Poonam, who have been my motivation at every step. Their never-ending affection
has provided me with moral support and encouragement while writing this book.
Last but not the least, I wish to express my deepest gratitude to my wife Urmila and my little,—but witty
beyond years, daughters Khushi and Shanvi who always supported me during my work.

Atul Singhal



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GENERAL ORGANIC
CHEMISTRY-1
(NOMENCLATURE AND ISOMERISM)

CHAPTER

1

CHAPTER CONTENTS
Classification of organic compounds; IUPAC nomenclature of simple organic compounds (only hydrocarbons, mono-functional and bi- functional compounds); Conformations of ethane and butane
(Newmann projections). Structural and geometrical isomerism; Optical isomerism of compounds
containing upto two asymmetric centres, (R, S and E, Z nomenclature excluded); Determination of
empirical and molecular formula of simple compounds (only combustion method) and various levels
of multiple-choice questions.

INTRODUCTION
The word ‘organic’ means ‘pertaining of life’. The compounds like sugars, fats, oils, dyes, proteins, vitamins
etc., which were isolated directly or indirectly from the living organisms like animals and plants were called
organic compounds and their study is called Organic Chemistry. The compounds like common salt, alum,
nitre, blue and green vitriol etc., which were isolated from the non-living sources such as rocks and minerals
were called inorganic compounds. CO , CO2, CO3–2, HCO3–, HCN etc., not organic compounds.

VITAL FORCE THEORY OR BERZELIUS HYPOTHESIS
According to it the organic compounds cannot be synthesized in the laboratory because they require the presence of a mysterious force that is, vital force which exists only in the living organisms.

FALL OF VITAL FORCE THEORY OR WOHLER’S SYNTHESIS
According to Wohler when ammonium cyanate (obtained by double decomposition of ammonium chloride
and potassium cyanate) is heated, urea is formed. Urea was the ¿rst organic compound to be prepared in
lab.
NH4Cl + KCNO

NH4CNO

heat
Rearrangement

NH4CNO + KCl
Amm. cyanate
O
║
NH2 – C – NH2
Urea

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General Organic Chemistry-1 (Nomenclature and Isomerism)

MODERN DEFINITION OF ORGANIC CHEMISTRY
Organic compounds may be de¿ned as hydrocarbons and their derivatives and the study of hydrocarbons and
their derivatives is called organic chemistry.
For example, CH3OH, CH3CN etc.

LARGE NUMBER OF ORGANIC COMPOUNDS
The main reasons for the large number of organic compounds are:
(i) Catenation The property of self-linking of carbon atoms through covalent bonds to form long straight or branched
chains and rings of different sizes is called catenation. Carbon shows maximum catenation in the periodic table and
this property is primarily due to its small size, electronic con¿guration and maximum bond energy or strength of
carbon-carbon bonds for catenation.

C > Si > S > P > …..
(ii) Electronegativity and Strength of Bonds The electronegativity of carbon (2.5) is close to a number of
other elements like Hydrogen (2.1), Nitrogen (3.0), Phosphorous (2.1), Chlorine (3.0), Oxygen (3.5) so it can form
strong covalent bonds with these elements.

(iii) Tendency to Form Multiple Bonds Due to its small size, carbon atom has a strong tendency to form multiple
bonds with Carbon, Oxygen and Nitrogen atoms.

(iv) Isomerism Many organic compounds show the phenomenon of isomerism by virtue of which a single molecular
formula may represent two or more structures.

Tetravalency of Carbon

C

109°28’

The tetravalent nature and tetrahedral structure of carbon was introduced by Liebel and Van’t Hoff. The carbon atom is tetravalent, that is, one carbon atom can combine with four monovalent atoms or groups or with
an equivalent number of atoms or groups having other valencies, thus,
H
│
H–C–H
│
H
Methane
H
│
H–C=O
Formaldehyde

H
│
H – C –OH
│
H
Methyl alcohol
OH
│
H–C=O
Formic acid

Equivalence of Four Carbon Valencies

All the four valencies of carbon are alike and symmetrical with respect to the atom that is, equal and equivalent to each other. It is obvious from the fact that methane forms only one mono-substituted isomer, that is,
monochloromethane on chlorination.


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General Organic Chemistry-1 (Nomenclature and Isomerism)



Catenation Property of Carbon


Carbon atoms possesses a great tendency to link with one another. The linking is possible through a
single, double or triple bond as follows:
│ │
–C –C
│ │
Single bond

│ │
C=C
│ │
double bond

–C≡C–
Triple bond

Carbon atoms may link to from
(a) an open chain which may be straight or branched

(b) a closed chain
Both are as follows:
(a) Open Chain
│ │ │
│ │ │
│
– C – C – C – , – C – C = C – , –C – C ≡ C
│ │ │
│
Straight chain
C
│ │ │
–C–C–C–
│
│
Branched chain
(a) Closed Chain

CLASSIFICATION OF ORGANIC COMPOUNDS
All the known organic compounds have been divided into following two classes:


Acyclic compounds (Aliphatic compounds)



Cyclic compounds (Aromatic compounds)

ACYCLIC OR OPEN CHAIN OR ALIPHATIC COMPOUNDS
The organic compounds in which all the carbon atoms are linked to one another to form open chains either

straight or branched are called acyclic or open chain or aliphatic compounds.
For example,

CH3CH2CH2CH3
Butane

CH3
│
CH3 – CH – CH3
Isobutane

CH3CH2CH2OH Propanol

Cyclic Compounds The compounds which have at least one ring or closed chain of atoms are called cyclic compounds.


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General Organic Chemistry-1 (Nomenclature and Isomerism)

Types of Cyclic Compounds These are of two types:
(a) Homocyclic Compounds Such compounds contain rings which are made up of only one kind of
atoms.


Carbocyclic Compounds If all the atoms in the ring are carbon atoms, they are called carbocyclic
compounds.
These are of following two types:

(i) Alicyclic Compounds These are carbocyclic compounds which resemble aliphatic compounds
in their properties.
For example,

Cyclopropane

cyclobutane

cyclopentane

Cyclohexane

(ii) Aromatic Compounds The compounds containing one or more fused or isolated benzene rings
are called Aromatic or Benzoid compounds.
For example,
OH

Benzene

Naphthalene

Phenol

(b) Heterocyclic Compounds The cyclic compounds having one or more heteroatoms (other than
C-atom) (For example, O, N, S etc.) in the ring are called heterocyclic compounds.
These are of following two types:
(i) Alicyclic Heterocyclic Compounds Such compounds resemble with aliphatic compounds in their
properties.
For example,
N

H

O

Tetrahydrofuran (THF)

Piperidine

(ii) Aromatic Heterocyclic Compounds Those compounds which resemble benzene and other aromatic compounds in most of their properties are called aromatic heterocyclic compounds.
For example,
N
H

O

Furan

Pyrrole

N

Pyridine


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General Organic Chemistry-1 (Nomenclature and Isomerism)



)XQFWLRQDO*URXS: It is an atom or a group of atoms present in a molecule which determines its chemical
properties, that is, site of chemical activity.
For example, −OH (hydroxy), −CHO (aldehydic)
COOH (carboxylic) etc.
CLASSES OF CARBON ATOMS



3ULPDU\&DUERQ$WRPV: A carbon atom either alone or attached to not more than one other carbon
atom is called a primary carbon atom and it is represented by 1o or p.
For example,
CH3 – CH3
p
p



6HFRQGDU\&DUERQ$WRP:A carbon atom which is attached to two other carbon atoms (2o or s).
For example,
CH3 – CH2 – CH3
s



7HUWLDU\&DUERQ$WRP:A carbon atom which is attached to three other carbon atoms (3o to t).
For example,
t
CH3 – CH – CH3
│
CH3



4XDWHUQDU\&DUERQ$WRP A carbon atom which is attached to four other carbon atoms (4o or q).
For example,
CH3
│q
CH3 – C – CH3
│
CH3
For example,
o
1

o
1

C
C
o
o
o
│
│
2
3
4
1
C–C–C – C –C
│1o

C
o
1

o


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General Organic Chemistry-1 (Nomenclature and Isomerism)

REMEMBER


Hydrogen atoms attached to primary, secondary or tertiary carbon atoms are called primary, secondary or tertiary hydrogen atoms respectively.



The hydrogen atoms attached to primary, secondary, tertiary and quaternary carbon atoms in alkanes
are respectively three, two, one and zero.



If a carbon atom is unsaturated it is not indicated as p, s, t carbon atom however it is counted for
other atoms.
For example,
CH2 = CH – CH2 – CH3
s

p

For example,
(1)

po

po

so
to
so

to

po

C-atom
po
so
to

H-atoms
4
12
2
4
2
2

C-atom
po
so
to
qo

H-atoms
3
9
1
2
3
3
1
0

po

(2)

po
to

po
to

qo
po

so

to

HOMOLOGOUS SERIES
It is a series of structurally similar compounds having same functional group in the increasing number of
carbon atoms.

CHARACTERISTICS OF HOMOLOGOUS SERIES


Any two successive members of a homologous series differ in their molecular formula by CH2 group
and their molecular weights differ by 14.



All the members can be prepared by a number of general methods.



The members have many similar chemical properties.



The physical properties of the members show a regular gradation with increase molecular weight.



The IUPAC names of all homologues have the same ending, as -ane in alkanes, -ene in alkenes, -ol in
alkanols etc.

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General Organic Chemistry-1 (Nomenclature and Isomerism)



For example,
CH4 (Methane )
C2H6 (Ethane)
C3H8 (Propane)
C4H10 (Butane)

Hydrocarbon Radicals
Parent hydrocarbon (R–H)
Alkane

–H

–H

For example, CH4
Methane
C2H6
Ethane

–H

Hydrocarbon group (R –)
Alkyl

–CH3
Methyl
–C2H5
Ethyl

IUPAC SYSTEM “International Union of Pure and Applied Chemists”.

Basic Rules of nomenclature
Carbon chain length Root word ( Alk.) Carbon chain

Root word

C1
C2
C3
C4
C5
C6
C7
C8

NonDecUn decDo dec-

MethEthPropButPentHexHeptOct-

C9
C10
C11
C12

Selection of the longest chain of C-atoms
To write the IUPAC name, the ¿rst step is to select the longest chain, that is parent or main chain.
For example,
CH3

CH3

CH CH CH2 CH3
|
CH2 CH3

CH

CH2

CH3

CH

CH3

CH2

CH3

CH2

CH3

6C-atom chain [Longest here]
5C-atom chain
6C-atom chain [longest here]


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General Organic Chemistry-1 (Nomenclature and Isomerism)

REMEMBER
Prefer the chain having maximum or all possible functional groups, or (=) or (≡) bonds and for it longest
chain rule can be neglected. For example (1)
CH2— COOH
│
CH —COOH
│
CH2—COOH
3 C-atom chain [ since, it includes all the three functional groups so it is prefered here]

For example, (2)
CH3

CH2

C

CH2

CH2

CH3

6C-atom[longest possible chain]
5C-atom chain including (=) bond so it is preferred

CH2



If in a given compound there are two or more chains having similar number of C-atoms than a chain
with maximum side chains is preferred.
For example,
CH3

CH2

CH

CH2

H 3C

C

CH3

5C-atom chain with one-side chain

CH3

5C-atom chain with 3-side chains so it is
preferred

CH3
CH3
CH3

CH

CH3
CH
CH2

CH

CH2

CH3

6 ‘C’-atom chain only two-side chains

6 ‘C’-atom chain with 3-side so it is preferred here.

CH3



RULES FOR NUMBERING OF C-ATOMS OF THE CHAIN



For numbering of C-atoms of the chain priority order is given as follows:
functional group > (=) or (≡) > substituent or alkyl group


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General Organic Chemistry-1 (Nomenclature and Isomerism)



For example,
Br
3
CH
2

2
CH

1
CH3

4
Prefer it (as functional group is at more corner)
CH3
1

Neglect it

OH



In case of (=) or (≡) bond preference for numbering is given to the one which is at corner or has lower
value of locant number.
For example,
1

2

CH2 CH
6

5

3
C
4

4

5

C

CH2

3

2

6
CH3 Prefer it
1

Neglect it

For example,
1
2
3
4
5
6
7
CH ≡ C — CH2—CH=CH—CH2—CH3
7
6
5
4
3
2
1


Prefer it
Neglect it

When both (=) and (≡) bond have same locant numbers prefer (=) bond.
For example,
CH2 = CH — C ≡ CH
1
2
3 4



Similarly, in case of substituent and alkyl groups prefer which has lower locant number value.
For example,
1
2
3
4
5
Prefer it as Cl is on 2nd C-atom
CH3 —CH —CH —CH2 —CH3 that is, locant number is two
5
4│
3│
2
1
Cl
CH3
For example,
1
2
3
4

5
Prefer it as CH3 has lower locant
CH3 — CH —CH —CH2 —CH3 number (2) while in case of Br-atom locant number is 3
5
4│
3│
2
1
CH3 Br



In case any two substituent or alkyl groups have same locant numbers prefer alphabetically.
For example,
1
2
3
4
CH3 — CH —CH — CH3
│
│
Br Cl
2- bromo 3- chloro butane [correct]
3- bromo 2- chloro butane [incorrect]


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General Organic Chemistry-1 (Nomenclature and Isomerism)

For example,
1
2
3
4
5
6
CH3 — CH2 — CH — CH — CH2 — CH3
│
│
CH2 CH3
│
CH3
3-ethyl 4-methyl hexane [correct]
4-ethyl 3-methyl hexane [incorrect]
Lowest Sum Rule
When numbering of a chain is possible from more than one side, prefer numbering of the chain from the side
having lowest sum of all the locant numbers.
For example,
Path (II)
1COOH
OH
Sum of locant numbers
│7
6
5│ 4 3
2
1 [ 1+ 8 + 3 + 5 + 5 + 6 = 28]

Path(I) CH = CH — C — C ≡ C — CH2 — COOH
2
3
4│ 5 6
7
8
Sum of locant numbers
NH2
is
1+ 8 + 2 + 4 + 4 + 5= 24
Since, in path (I) the sum is 24 whereas in path (II) it is 28 hence path (I) is preferred here for numbering.
Naming Of Complex Alkyl Substituents


When a side chain further include another side chain it is numbered and named as,
For example,
1
2
3
4
5
6
CH3 — CH — CH — CH2 — CH2 — CH3
│
│
CH3 1’ CH —Cl
│
2’CH2 — Br
3[ 2’-bromo 1’-chloro] ethyl 2-methyl hexane



Pre¿xes like bis, tris, tetrakis etc., can also be used to indicates the multiplicity of substituted substituent.
For example,
CH2 — Br
│
CH3 — CH2 — C — CH2 — CH2 — CH3
│
CH2 — Br
3, 3-bis [Bromomethyl] hexane



Use pre¿xes like di, tri, tetra etc., in case of simple substituents with same times locant numbers.


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General Organic Chemistry-1 (Nomenclature and Isomerism)



For example,
Cl
Br
│
│
CH — C — CH3
│
│

Cl
Br
2, 2-dobromo 1, 1 dichloro propane


All pre¿xes are written before alk (root word) as in above cases however, -ene, -yne or main functional
group names, that is, suf¿x names are written after root word with their locant numbers are followed.
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