Table Of ContentOrganic chemistry
a modern approach
Volume-II
A A
bout the uthor
Nimai Tewari is a retired Associate Professor in Department of
Chemistry Katwa College (affiliated to University of Burdwan),
West Bengal. A Ph.D in Organic Chemistry from Calcutta University,
he has taught the subject for a period of more than three decades.
He has published various research papers in national and international
journals. Apart from Organic Chemistry—A Modern Approach,
Volume-II (including Volume-I of this title), Dr Tewari has authored
four more books on Organic Chemistry for undergraduate and
postgraduate students. His research interest includes Organic
Synthesis and Heterocyclic Chemistry.
Organic chemistry
a modern approach
Volume-II
Nimai Tewari
Associate Professor (Retired)
Department of Chemistry
Katwa College
West Bengal
McGraw Hill Education (India) Private Limited
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C
ontents
Preface xiii
1. Addition to Carbon–Carbon Multiple Bond 1.1–1.212
Introduction 1.1
1.1 Electrophilic Addition 1.2
1.1.1 Addition of Hydrogen Halides 1.6
Solved Problems 1.14
Study Problems 1.22
1.1.2 Addition of Water and Alcohol 1.26
Solved Problems 1.32
Study Problems 1.37
1.1.3 Oxymercuration-Demercuration 1.39
Solved Problems 1.42
Study Problems 1.44
1.1.4 Addition of Halogens 1.45
Solved Problems 1.56
Study Problems 1.62
1.1.5 Hydroboration-Oxidation 1.65
Solved Problems 1.75
Study Problems 1.81
1.1.6 Ozonolysis of Alkenes and Alkynes 1.82
Solved Problems 1.93
Study Problems 1.100
1.1.7 Addition of Carbenes and Simons-Smith Reaction 1.102
Solved Problems 1.110
Study Problems 1.115
1.1.8 Hydroxylation of Alkenes 1.117
Solved Problems 1.127
Study Problems 1.131
1.1.9 Hydrogenation 1.134
Solved Problems 1.142
Study Problems 1.147
viii Contents
1.1.10 Diels–Alder Reaction 1.149
Solved Problems 1.163
Study Problems 1.175
1.2 Nucleophilic Addition 1.178
1.2.1 Cyanoethylation 1.178
1.2.2 Direct and Conjugate Addition to a, b-Unsaturated Aldehydes and
Ketones 1.180
1.2.3 Michael Addition or Michael Reaction 1.182
Solved Problems 1.186
Study Problems 1.195
1.3 Addition of Radicals and Radical Substitution of Benzylic and Allylic
Hydrogens 1.199
1.3.1 Radical Addition of Halogens and Hydrogen Halides and Radical
Polymerization 1.200
Solved Problems 1.205
Study Problems 1.206
1.3.2 Allylic Chlorination and Allylic Bromination 1.207
Solved Problems 1.209
Study Problems 1.211
References 1.212
2. Reactions of the Carbonyl Group and Reactions at the a-Carbon
to the Carbonyl Group 2.1–2.346
2.1 Introduction 2.2
2.2 Nucleophilic Addition to Carbon-Oxygen Double Bond 2.5
2.2.1 Structure of the Carbonyl Group 2.5
2.2.2 Effect of Structure on Reactivity 2.5
2.2.3 Stereochemistry of Nucleophilic Addition 2.8
Solved Problems 2.10
2.3 Addition of Oxygen Nucleophiles: Water and Alcohols (ROH) 2.11
2.3.1 Addition of Water (Hydration) and Formation of gem-diols 2.11
2.3.2 Mechanism for Hydrate Formation 2.11
2.3.3 Kinetics of Hydrate Formation 2.11
2.3.4 Thermodynamics of Hydrate Formation 2.13
2.3.5 Formation of Stable and Isolable Hydrates 2.14
2.3.6 Addition of Alcohols and Formation of Hemiacetals and Acetals 2.16
2.3.7 Mechanism for Acid-catalyzed Hemiacetal and Acetal Formation 2.18
2.3.8 Mechanism for Base-catalyzed Hemiacetal Formation (Base-catalyzed
Acetal Formation does not take place) 2.20
2.3.9 Hydrolysis of Acetals 2.20
2.3.10 Acetals as Protecting Groups 2.22
2.3.11 Tetrahydropyranyl Group as a Protecting Group 2.23
Solved Problems 2.24
Study Problems 2.33
Contents ix
2.4 Addition of Sulphur Nucleophiles: Thiols (RSH) and Sodium Bisulphite
(NaHSO ) 2.38
3
2.4.1 Addition of Thiols 2.38
2.4.2 Mechanism for Thioacetal Formation 2.38
2.4.3 Thermodynamics for Thioacetal Formation 2.39
2.4.4 Importance of Thioacetals in Organic Synthesis 2.39
2.4.5 Addition of Sodium Bisulphite (NaHSO ) 2.40
3
2.4.6 Mechanism for Bisulphite Additions 2.40
2.4.7 Applications of Bisulphite Addition Reaction 2.41
Solved Problems 2.42
Study Problems 2.45
①
2.5 Addition of Hydride Ion (:H ) and addition of electrons 2.46
2.5.1 Reduction of carbonyl compounds by lithium aluminium hydride
(LiAlH ) 2.47
4
2.5.2 Mechanism for the reduction of carbonyl compounds by lithium aluminium
hydride (LiAlH ) 2.47
4
2.5.3 Reduction of aldehydes and ketones by sodium borohydride (NaBH ) to
4
form primary and secondary alcohols, respectively 2.50
2.5.4 Mechanism for the reduction of an aldehyde or a ketone by sodium
borohydride (NaBH ) 2.51
4
2.5.5 Reduction of carboxylic acids, amides and nitriles by borane (BH ) 2.51
3
2.5.6 Reduction of Acid Chlorides to the Corresponding Aldehydes by Lithium
tri-tert-butoxyaluminium Hydride [LiAlH(O-t-Bu) ] and Reduction of Esters
3
and Nitriles to the Corresponding Aldehydes by Diisobutylaluminum
Hydride (i–Bu AlH or DIBAL–H): 2.53
2
2.5.7 Meerwein–Ponndorf–Verley (MPV) reduction 2.55
2.5.8 Cannizzaro Reaction 2.57
2.5.9 Tishchenko Reaction 2.64
2.5.10 Bouveault-Blanc Reduction 2.65
2.5.11 Pinacolization of Ketones 2.67
2.5.12 Clemmensen Reduction 2.68
Solved Problems 2.69
Study Problems 2.81
2.6 Addition of Nitrogen Nucleophiles 2.84
2.6.1 Addition of Primary Amines and Formation of Imines 2.84
2.6.2 Addition of Compounds like Hydroxylamine, Hydrazine and Substituted
Hydrazines (Similar to Primary Amines and Formation of Imine
Derivatives) 2.86
2.6.3 Reductive Amination 2.88
2.6.4 Wolff-Kishner Reduction 2.89
2.6.5 Important uses of the Imine-Forming Reaction 2.91
2.6.6 Addition of Secondary Amines and Formation of Enamines 2.91
Solved Problems 2.96
Study Problems 2.104
x Contents
2.7 Addition of Carbon Nucleophiles 2.106
2.7.1 Addition of Hydrogen Cyanide (HCN) 2.106
2.7.2 Addition of Grignard and Other Organometallic Compounds 2.109
2.7.3 Addition of Acetylides 2.116
2.7.4 Addition of Diazomethane (CH N ) 2.116
2 2
2.7.5 Addition of Ylides 2.118
Solved Problems 2.127
Study Problems 2.142
2.8 Addition of Enolate Ions 2.145
2.8.1 Aldol Reactions 2.145
2.8.2 Stobbe Condensation 2.157
2.8.3 Darzenes Condensation 2.160
2.8.4 Benzoin Condensation 2.164
2.8.5 Reformatsky Reaction 2.169
2.8.6 Perkin Reaction 2.172
2.8.7 Knoevenagel Condensation 2.175
2.8.8 Mannich Reaction 2.180
Solved Problems 2.182
Study Problems 2.203
2.9 Reactions at the a-carbon of Carbonyl Compounds of Aldehydes and
Ketones 2.208
2.9.1 Halogenation at the a-carbon of Aldehydes and Ketones 2.208
2.9.2 Alkylation at the a-carbon of Aldehydes and Ketones 2.214
2.9.3 The Claisen Condensation (Addition of Acid Derivatives to the a-carbon of
Carbonyl Compounds) 2.227
Solved Problems 2.236
Study Problems 2.273
2.9.4 Green Chemistry 2.279
Solved Problems 2.283
Study Problems 2.285
2.10 Acyl Substitution 2.286
2.10.1 Mechanism of Nucleophilic Addition–Elimination at the Acyl Carbon or
Nucleophilic Acyl Substitution 2.286
2.10.2 Reactions of Carboxylic Acids 2.290
2.10.3 Reactions of Acid Chlorides 2.311
2.10.4 Reactions of Esters 2.313
2.10.5 Reactions of Amides 2.317
2.10.6 Reactions of Carboxylic Acid Anhydrides 2.319
2.10.7 Reactions of Nitriles 2.320
Solved Problems 2.321
Study Problems 2.341
References 1.346
