Fundamentals of
Organic Chemistry
for
[Second Year B.Sc. (Main) Students of M.G. University, Kerala]
III Semester
(This Book is an outcome of “Modern Organic Chemistry” by M.K. Jain &
S.C. Sharma duly recommended by M.G. University.)
M.K. JAIN
S.C. SHARMA
M.Sc., Ph. D. (Glasgow)
Former, Professor,
National Dairy Research Institute
(Deemed University), KARNAL (Haryana)
M.Sc., Ph.D.
Former-Head Deptt. of Chemistry
V.B.R.I. P.G. College,
UDAIPUR (Rajasthan)
VISHAL PUBLISHING CO.
Future for WINNERS
JALANDHAR – DELHI
CONTENTS
Chapter No.
Title
1. CLASSIFICATION
NOMENCLATURE
COMPOUNDS*
Page No.
Chapter No.
&
IUPAC
OF
ORGANIC
1-22
1.0. Classification
1
1.1. IUPAC or Geneva names
3
Title
Page No.
2.2. Types of reagents
24
1. Nucleophiles
24
2. Electrophiles
25
3. Free radicals
25
2.3. Types of organic reactions
25
1.2. Rules of IUPAC system of nomenclature for
acyclic compounds
3
[A] Substitution reactions
25
[B] Addition reactions
26
1.3. IUPAC system of nomenclature for
substituted alkanes
4
[C] Elimination reactions
27
[D] Rearrangement reactions
27
1.4. Alkenes, alkynes and substituents
9
1.5. IUpac nomenclature of cycloalkanes and
its derivatives
10
1.6. IUPAC nomenclature of bicycloalkanes and
related compounds
11
1.7. IUPAC nomenclature of bicyclic spiro
compounds
12
2.4. Homolytic and Heterolytic Cleavage of a
covalent bond (formation of reactive
intermediates)
28
1. Carbocations / Carbonium ions
28
2. Carbanions
30
3. Free Radicals
32
2.5. Electron Displacement effects
33
1.8. IUPAC nomenclature of alkyl halides
12
1.9. IUPAC nomenclature of alcohols
13
1. Inductive or inductometric Effect
34
13
2. Electromeric Effect
37
1.11. IUPAC nomenclature of aldehydes and
ketones
14
3. Resonance and Resonance Effect
39
4. Resonance theory
41
1.12. IUPAC nomenclature of acids
14
5. Mesomeric effect
46
1.13. IUPAC nomenclature of acid derivatives 15
6. Hyperconjugation
46
1.14. IUPAC nomenclature of amines
7. Steric effects / Inhibition / Hindrance 49
1.10. IUPAC nomenclature of phenols
16
1.15. IUPAC nomenclature of nitro compounds17
1.16. Procedure for writing the structure of a
compound with a given IUPAC name
18
Questions
2. FUNDAMENTALS
OF
REACTION MECHANISM-I
2.0. Introduction
19
ORGANIC
23-54
23
2.1. Notations used to show Electron Migration
23
1. Curved arrow notation
23
2. Double Headed Arrow(s).
24
3. Half-headed Arrow (Fish hook arrow) 24
Questions
3. FUNDAMENTALS
OF
REACTION MECHANISM-II
52
ORGANIC
55-79
3.0. Introduction
55
3.1. Addition Reactions
55
1. Electrophilic Additions to double bond 55
3.2. Polymerisation
60
1. Types of Polymerisation Reactions 61
3.3. Aliphatic Substitution Reactions
66
1. Detailed Mechanisms Of aliphatic
Nucleophilic Substitution Reactions 66
Chapter No.
Title
Page No.
Chapter No.
3.4. Elimination Reactions
4.9. Properties of Diastereomers
71
2. Orientation In Elimination Reactions
(hofmann & saytzeff elimination)
74
95
97
4.9.1. Distinction Between Diastereomers
And Enantiomers
97
72
1. Mechanisms Of Elimination Reactions
72
Page No.
or two asymmetric/chiral carbon
2. Factors Influencing Rates Of aliphatic
Nucleophilic Substitution Reactions 70
3. SN1 vs. SN2 Mechanisms
Title
4.10. Fischer projections
97
4.10.1. Specifying R–S Configurations on
Fischer Projection
100
3. Substitution vs. Elimination
77
4.11. Erythro and threo nomenclature (notation)
of configurations
101
Questions
77
4.12. Resolution
4. STEREOCHEMISTRY-I
80-106
4.0. Introduction
80
4.1. Stereoisomerism
80
4.2. Types of Stereoisomers
80
4.3. General Stereochemistry
80
4.3.1. Concept of Chirality
80
4.3.2. Tetrahedral Carbon
81
4.3.3. Chirality and Enantiomerism
81
4.3.4. Wedge and Dashed Bond Drawing of
Organic Molecules (Perspective
Drawings)
82
4.3.5. Asymmetric Carbon Atom and Related
Terms
82
4.3.6. Elements of symmetry
83
4.3.7. The Asymmetric Carbon Atoms And
Molecular Chirality
85
4.4. Optical activity
86
4.5. Acyclic molecules with one asymmetric/chiral
carbon or stereogenic centre
87
4.6. Enantiomers And Related Aspects
89
4.6.2. The Racemic Modification
90
4.7. Configuration
4.13. Asymmetric (Stereogenic Centre) Synthesis
104
4.14. Walden Inversion
104
4.15. Retention and racemisation
105
5.
STEREOCHEMISTRY-II
90
4.7.1. Relative Specification of Configuration
‘D’ and ‘L’* Notation
91
4.7.2. Specification of Configuration R and
S notation
93
4.8. Compounds with two Stereogenic Centres
107-128
5.0. Geometric isomerism (cis-trans isomerism)
107
1.
Concept of Hindered Rotation About
a Carbon-Carbon Double Bond and
Geometric Isomerism
107
2.
Geometric Isomers as Diastereomers
108
3.
Structure of Alkenes and Geometric
Isomerism
108
4.
Extended
Isomerism
5.
Assigning Configuration to Geometric
Isomers
110
Scope
of
Geometric
109
5.1. E-Z System of Nomenclature for Cis-trans
Isomers
110
1.
88
4.6.1. Properties of Enantiomers
102
Relative Stabilities of cis-trans Isomers
114
5.2 Conformation Of Alkanes (conformational
analysis)
114
5.3. Factors Influencing Conformational Stability
118
5.4. Conformational Analysis Of Cyclohexane
120
1.
Axial And Equatorial Bonds* In
Cyclohexane
122
Chapter No.
2.
Title
Page No.
1,
3-Diaxial
Interactions
In
Cyclohexane Derivatives
122
5.5. Conformational Isomers vs Configurational
Isomers
123
Questions
Chapter No.
Title
7.3.1. Bimolecular
Mechanism
Page No.
Displacement
158
7.3.2. Benzyne Intermediate Mechanism
(Elimination Addition Mechanism)
160
123
Questions
6. ARENES AND AROMATICITY
129-147
6.0. Introduction
129
6.1. Structure Of Benzene
129
6.2. Aromatic Sextet And Orbital Picture
133
6.3. Resonance And Molecular Orbital Structure
Of Naphthalene
133
I. Resonance Structure
6.4. Resonance
Anthracene
and
M.O.
134
Structure
of
135
(1) Resonance Structure.
135
(2) Molecular Orbital Structure.
135
6.5. Concept Of Aromaticity
136
6.6. Aromaticity/Aromatic Character
136
6.7. Hückel Theory Of Aromaticity
136
(1) Benzenoids
(2)
137
Non-Benzenoid Aromatic Compounds/
Ions
137
6.8. Electrophilic Aromatic Substitution Reactions
140
6.9. General Pattern Of Electrophilic Aromatic
Substitution
142
6.10. Reactivity Of Naphthalene
143
Questions
145
7. ORIENTATION OF SUBSTITUTION IN
ARENES
148-164
7.0. Introduction
7.1. Orientation
Electrophilic
Substitution Reactions.
148
Aromatic
148
7.1.1. Effect Of Activating Groups
149
7.1.2. Effect Of Deactivating Groups
152
7.2. Nucleophilic Aromatic Substitution
155
7.3. Mechanisms
157
8. PERICYCLIC REACTIONS
162
165-173
8.0 Introduction
165
8.1 Salient features of Pericyclic reactions 165
8.2 Classification of Pericyclic reactions
165
8.2.1
Electrocyclic reactions
8.2.2
Cycloaddition reactions (Diels-Alder
reaction)
170
8.2.3
Sigmatropic rearrangements
8.3 The Frontier orbital method
Questions
Model Question Papers
University Question Paper
166
171
172
173
175-180
181-184