Free download Undergraduate Organic Chemistry by Dr. Jagdamba Singh

Volume 1

Authors of:  Undergraduate Organic Chemistry by Dr. Jagdamba Singh

Dr. Jagdamba Singh

Dr. L.D.S Yadav

Table of Contents in Undergraduate Organic Chemistry by Dr. Jagdamba Singh

1.1 Localized Chemical Bonding  

1.1.1 Covalent Bonding  

1.1.2 Covalency of Carbon  

1.1.3 Orbital Concept of Bonding  

1.1.4 Atomic Orbitals  

1.1.5 Valence Bond Theory  

1.1.6 Multiple Bonds  

1.1.7 Molecular Orbital Theory  

1.1.8 Comparison between VB and ~O Theories  

1.1.9 Bond Lengths  

1.1.10 Bond Strengths  

1.1.11 Bond Angles  

1.1.12 Hybridisation  

1.1.13 Hybridisation Rules 12

1.1.14 Hybrldisation of Organic Species  

1.1.15 Hybrldisation and Bond Properties  

1.2 Delocalised Chemical Bonding  

1.2.1 Resonance  

1.2.2 Contribution of Resonating Structures to Resonance Hybrid  

1.2.3 Delocalisation in 1, 3-butadiene  

1.2.4 Cross-conjugation  

1.2.5 Resonance Energy 25

1.2.6 Steric Inhibition of Resonance  

1.2.7 Hyperconjugation  

1.2.8 Aromaticity  

1.2.9 Inductive and Field Effects  

1.2.10 Dipole Moment  

1.2.11 Electromeric Effect  

1.3 Intermolecular Forces  

1.3.1 van der Waals Forces  

1.3.2 Dipole-Dipole Interactions  

1.3.3 Hydrogen Bonding  

1.4 Inclusion Compounds  

1.4.1 Cage Compounds  

1.4.2 Channel Compounds  

1.4.3 General Method of Preparation of Inclusion Compounds  

1.4.4 Important use of Inclusion Compounds  

1.4.5 Charge Transfer Complexes  

Very Short Answer Questions  

Problems with Solutions  

Problems for Self Assessment  

Answers to Very Short Answer Questions  

Soluticns of Problems  

MECHANISM OF ORGANIC REACTIONS

2.1 Arrow Notation  

2.2 Breaking of CoveJent Bonds  

2.3 Types of Reagents  

2.3.1 Nucleophiles  

2.3.2 Electrophiles  

2.4 Reaction Intermediates  

2.4.1 Carbocations  

2.4.2 Carbanions  

2.4.3 Free Radicals  

2.4.4 Carbenes  

2.4.5 Nitrenes  

2.4.6 Benzynes  

2.5 Formal Charges  

2.6 Types of Organic Reactions  

2.7 Therodynarnics of Reactions  

2.8 Kinetics of Reactions  

2.9 Reactivity and Rates of Reactions  

2.10 Hammond Postulate  

2.11 Catalysis  

2.12 Kinetic and Thermodynamic control of Reactions  

2.13 Methods of Determination of Reaction Mechanism  

2.13.1 Product Analysis  

2.13.2 Presence of Intermediate  

2.13.3 Isotopic Labelling and Isotope Effects  

2.13.4 Crossover Experiments 105

2.13.5 Stereochemistry 106

2.13.6 Kinetic Evidence 107

2.13.7 Study of Catalysis 108

Very Short Answer Questions 108

Problems with Solutions 109

Problems for Self Assessment 111

Answer to Very Short Answer Questions 112

Solutions of Problems 112

STEREOCHEMISTRY OF ORGANIC COMPOUNDS

3.0 Introduction 114

3.1 Isomerism 114

3.2 Types of Isomerism 114

3.2.1 Constitutional Isomerism 114

3.2.2 Stereoisomerism 115

3.3 Optical Activity 115

3.4 Chirality 116

3.5 Stereogenic Centre 117

3.6 Representation of Three-dimensional Molecules 117

3.6.1 Flying-wedge Representation 118

3.6.2 Fischer Projection Formula 118

3.6.3 Sawhorse Formula 120

3.6.4 Newman Projection 120

3.6.5 Interconversions of projection and perspective formulae 121

3.6.6 Simple method for converting wedge formula into Fischer project 121

3.6.7 Simple method for converting Fischer projection formula

into flying wedge formula 122

3.7 Elements of Symmetry 123

3.7.1 Plane of Symmetry 123

3.7.2 Centre of Symmetry 123

3.7.3 Alternating Axis of Symmetry 123

3.8 Nomenclature 124

3.8.1 D, L Nomenclature 124

3.8.2 R, S Nomenclature 125

3.8.3 Sequence Rule 127

3.8.4 Comparison between D, Land R, S Nomenclature 130

3.8.5 Erythro and Threo Nomenclature 130

3.9 Molecules with one Chiral Centre 131

3.9.1 Properties of Enantiomers 131

3.9.2 Racemic Modification 131

3.10 Molecule with Two Chiral Centres 132

3.10.1 Molecule with Two Nonidentical Chiral Centres 132

3.10.2 Molecules with Two Identical Chiral Centres 133

3.10.3 Calculation of Number of Optical Isomers 134

3.11 Resolution of Racemic Modifications 135

3.12 Racemisation 138

3.13 Inversion, Retention and Racemisation 139

3.13.1 Inversion of Configuration 139

3.13.2 Racemisation 140

3.13.3 Retention of Configuration 141

3.14 Geometrical (cis-trans) Isomerism 142

3.14.1 Geometrical isomerism due to C=C Bond 143

3.14.2 Nomenclature of Geometrical Isomers 143

3.14.3 Number of Geometrical Isomers in Polyenes 144

3.14.4 Determination of the Configuration of Geometrical Isomers 145

3.15 Geometrical Isomers of Oximes 146

3.16 Geometrical Isomerism of Alicyclic Compounds 148

3.17 Conformational Analysis 148

3.17.1 Conformation of Acyclic Systems 149

3.17.2 Conformation of Cyclohexane 151

3.17.3 Axial and Equatorial Bonds 154

3.17.4 Conformation of Monosubstituted Cyclohexanes 155

3.18 Difference Between Conformation and configuration 158

Very Short Answer Questions 158

Problems with Solutions 159

Problems for Self Assessment 162

Answer to Very Short Answer Questions 164

Solutions of Problems 165

ALKANES AND CYCLOALKANES

4.0 Alkanes 170

4.1 Isomerism in Alkanes 171

4.2 The Alkyl Group 172

4.3 Classification of Carbon Atoms in Alkanes 173

4.4 IUPAC Nomendature of Alkanes 173

4.4.1 IUPAC Nomenclature of Unbranched Alkanes 173

4.4.2 Nomenclature of Branched-Chain Alkanes 173

4.5 Skeletal Structures 176

4.6 General Methods of Preparation of Alkanes 177

4.7 Physical Properties of Alkanes 180

4.8 Reactions of Alkanes 182

4.8.1 Halogenation 182

4.8.2 Nitration 188

4.8.3 Sulphonation 189

4.8.4 Oxidation 189

4.8.5 Cracking 189

4.8.6 Reforming 190

4.9 Cycloalkanes 191

4.9.1 Nomenclature of Cycloalkanes 192

4.9.2 Bicyclic Compounds 193

4.9.3 Nomenclature of Bicyclic Compounds 193

4.9.4 Synthesis of Cycloalkanes 194

4.9.5 Physical Properties of Cycloalkanes 197

4.9.6 Reaction of Cycloalkanes 198

4.10 Cyclopropane: Bent or Banana Bonds 198

4.11 Cycloalkanes: Ring Strain 199

4.12 Baeyer-Strain Theory 201

Very Short Answer Questions 202

Problems with Solution 203

Problems for Self Assessment 203

Answer to Very Short Answer Questions 205

Solutions of Problems 206

ALKENES, CYCLOALKENES, DIENES AND ALKYNES

5.0 Alkenes 208

5.1 The Alkenyl Group 208

5.2 Nomenclature of Alkenes 208

5.2.1 Common or Trivial Nomenclature 208

5.2.2 IUPAC Nomenclature of Alkenes 209

5.3 Methods of Preparation of Alkenes 210

5.3.1 Elimination Reactions 210

5.3.2 Thermal Elimination Reactions 211

5.3.3 Addition Reaction 212

5.3.4 Wittig Reaction 212

5.3.5 Kolbe Hydrocarbon Synthesis 212

5.4 Elimination Reactions 213

5.4.1 Types of Elimination Reactions 213

5.4.2 ,Types of p-elimination Reactions 213

5.4.3 EI Reactions 213

5.4.4 Characteristics of El Reactions 215

Factors Influencing El Reaction Rate 216

E2 Reactions 216

Stereochemistry of E2 Reactions 218

Factors Influencing E2 Reaction Rate 218

Competition Between E2 and E1 Reactions

E1cb Reactions 220

5.4.11 Comparison Between El. E2 and Elcb Pathways 221

5.4.12 Number of Products in ~-elimination Reactions 221

5.5 Orientation in Eliminaton Reactions 222

5.5.1 Saytzeff Rule 222

5.5.2 Hofman Rule 222

5.5.3 Theoretical Explanation of Saytzeff Rule 224

5.5.4 Theoretical Explanation of Hofmann Rule 224

5.6 Types of El and E2 Reactions 227

5.6.1 Dehydrohalogenation 227

5.6.2 Dehydration of Alcohols 228

5.6.3 Dehalogenation 231

5.6.4 Peterson Reaction 233

5.6.5 Thermal Eliminations 233

5.7 Physical Properties and Relative Stabilities of Alkenes 234

5.8 Addition Reactions of Alkenes 235

208-336

5.9 Electrophilic Addition Reactions 235

5.9.1 Addition of Hydrogen Halides 237

Addition of Concentrated Sulphuric Acid

Addition of Water 241

Oxymercuration-demercuration 241

Addition of Halogens 243

Addition of Nitrosyl Chloride 245

Addition of Borane 245

Addition of Divalent Carbon Compounds

Friedel-Crafts Reaction 250

5.9.10 Hydrocarbonylation Reaction 250

5.9.11 HYdroformylation 251

5.9.12 Addition with Aldehydes 251

5.9.13 Mixed addition 252

5.9.14 Halolactonisation 252

5.10 Free Radical Addition 253

5.11 Nucleophilic Additions 255

5.11.1 Addition to Acrylonitrile 255

5.11.2 Addition to a, J3-unsaturated Carbonyl Compounds 255

5.12 Addition of Hydrogen (Catalytic Hydrogenation) 256

5.13 Oxidation of Alkenes 259

5.13.1 Oxidation without Cleavage 259

5.13.2 Oxidation with Cleavage: Oxidative Cleavage 262

5.14 Addition of Ozone and Ozonolysis 263

5.14.1 Reductive Ozonolysis 264

5.14.2 Oxidative Ozonolysis 266

5.15 Isomerisation 266

5.16 Alkylation of Alkenes 267

5.17 Substitution Reactions 267

5.17.1 Allylic Substitution 267

5.17.2 Substitution at Vinylic Position 269

5.18 Polymerisation Reaction 269

5.19 Summary of Key Reactions of Alkenes 270

5.20 Industrial Applications of Ethylene and Propene 271

5.21 Cycloalkenes 272

5.21.1 Methods of Preparation of Cycloalkenes 272

5.21.2 Conformation of Cycloalkenes 273

5.21.3 Chemical Reactions of Cycloalkenes 273

5.22 Dienes 276

5.22.1 Nomenclature and Classification 276

5.22.2 Methods of Preparation of Conjugated Dienes 277

5.22.3 Structure and Stability of 1, 3-butadiene 277

5.22.4 Chemical Reactions of Dienes 278

5.23 Alkynes 284

5.23.1 Nomenclature 284

5.23.2 Methods of Preparation of Alkynes 285

5.23.3 Acidity of Alkynes 286

5.23.4 Chemical Reactions 287

5.24 Reactions Due to Acidic Hydrogen of Alkynes 287

5.24.1 Salt Formation 287

5.24.2 Formation of Metal Alkynide 288

5.24.3 Reaction with Grignard Reagent arW Alkyllithium 288

5.24.4 Electrophilic Substitution with X2/0R or NaOX 289

5.25 Reactions Due to pi Bonds 289

5.26 Electrophilic Addition Reactions of Alkynes 289

5.26.1 Addition of Halogens 289

5.26.2 Addition of Hydrogen Halides 290

5.26.3 Addition of Water 291

5.26.4 Addition of HOX 293

5.26.5 Addition of Acetic Acid 293

5.26.6 Hydroboration 293

5.26.7 Addition of Carbenes 295

5.27 Addition of Hydrogen 295

5.28 Nucleophilic Addition Reactions 297

5.29 Oxidation of Alkynes 297

5.29.1 Oxidation without Cleavage 297

5.29.2 Oxidative Cleavage 298

5.30 Addition of Ozone-Ozonisation 298

5.31 Isomerisation 299

5.32 Coupling of Alkynes 299

5.33 Polymerisation of Acet~’lene 300

5.34 Summary of Key Reactions of Alkynes 301

5.35 Individual member of alkynes (Acetylene) 302

Very Short Answer Questions 304

Problems with Solutions 304

Problems for Self Assessment 311

Answers to Very Short Answer Questions 317

Solutions of Problems 318

ARENES AND AROMATICITY 337-417

6.0 Aromatic Hydrocarbons (Arenes) 337

6.1 Nomenclature of Benzene Derivatives 338

6.2 The Aryl Group 340

6.3 Aromatic Nucleus and Side Chain 340

6.4 Structure of Benzene 340

6.4.1 Molecular Formula and Kekule’ Structure 340

6.4.2 Present Day Position of the Structure of Benzene 342

6.5 Stability of Benzene 344

6.6 Aromaticity: The Hiickel Rule 345

6.6.1 Application of Hiickel Rule to Simple Annulenes 345

6.6.2 Aromatic ions 346

6.7 Chemical Reactions of Benzene 348

6.7.1 Addition Reactions 348

6.7.2 Oxidation Reactions 349

6.7.3 Condensation with Carbonyl Compounds 349

6.7.4 Substitution Reactions 350

6.8 Electrophilic Aromatic Substitution Reactions 350

6.8.1 General Pattern of the Mechanism 350

6.8.2 Role of (J and 1t Complexes in Aromatic Electrophilic Substitution 351

6.8.3 Evidence for the Formation of (J and 1t Complexes 353

6.9 Mechanism of Some Important Aromatic Substitution Reactions 353

6.9.1 Halogenation of Benzene 353

6.9.2 Nitration of Benzene 354

6.9.3 Sulphonation of Benzene 355

6.9.4 Friedel-Crafts Alkylation 356

6.9.5 Friedel-Crafts Acylation 358

6.9.6 Mercuration 362

6.10 Summary of Different Electrophilic Substitution Reactions of Benzene 3M

6.11 Orientation of Substitution 365

6.11.1 Activating and Deactivating Groups 366

6.12 Theory of Substituent Effects on Electrophilic Aromatic Substitution 367

6.12.1 Theory of the Effect of Substituents on Reactivity 367

6.12.2 Theory of the Effect of Substituents on Orientation 369

6.12.3 Orientation Based on sigma Complex Stability 372

6.13 OrtholPara ratio 376

6.13.1 Steric Effect 376

6.13.2 Electronic Effect 377

6.14 Orientation in Disubstituted Benzenes 377

6.15 Side Chain Reactions of Benzene Derivatives 379

6.15.1 Side Chain Oxidation 379

6.15.2 Side Chain Halogenation 379

6.15.3 Nucleophilic Substitution of the Benzylic Position 380

6.15.4 Hydrogenolysis of Benzyl Alcohol 380

6.15.5 Clemmensen reduction 381

6.15.6 Orientation of p-eliminations 381

6.16 Alkyl Benzenes 381

6.16.1 Methods of Formation 381

6.16.2 Chemical Reactions 382

6.17 Alkenyl Benzenes 386

6.17.1 Methods of Formation 386

6.17.2 Chemical Reactions 387

6.18 Alkynyl Benzenes 388

6.19 Biphenyl (Diphenyl) 388

6.19.1 Methods of Formation 388

6.19.2 Properties and Reactions 389

Very Short Answer Questions 392

Problems with Solutions 392

Problems for Self A.ssessment 398

Answers to Very Short Answer Questions 403

Solutions of Problems 405

HALOGEN COMPOUNDS: ALKYL AND ARYL HALIDES 418-492

Introduction 418

Nomenclature of Alkyl halides 418

Classification of Alkyl halides 419

Method of Preparation of Monohaloalkanes 418

Physical Properties of Haloalkanes 422

Chemical Reactions of Alkyl halides  

Nucleophilic Substitution Reactions  

7.6.1 Incoming Nucleophile  

7.6.2 Leaving Nucleophiles  

7.6.3 SN 1 Reaction  

7.6.4 SN2 Reaction  

7.6.5 Competitive Reaction  

7.6.6 Comparison of SNI and SN2 Substitutions  

7.6.7 Inter- and Intramolecular Nucleophilic Substitution Reactions  

7.6.8 Comparison of Factors Governing Substitution and Elimination

Reactions  

7.6.9 Comparison Between SNI and El Reactions  

7.6.10 Comparison Betwen SN2 and E2 Reactions  

7.6.11 Some nucleophilic substitution reactions of alkyl halides  

7.7 . Other Reactions of Alkyl halides  

7.7.1 Oxidation Reaction  

7.7.2 Reduction  

7.7.3 Coupling Reaction  

7.7.4 Reaction with Metals  

7.8 Dihaloalkanes  

7.8.1 Gem Dihalides  

7.8.2 Vicinal Dihalides  

7.8.3 a., ro-Dihalides  

7.9. Polyhaloalkanes  

7.9.1 Trihaloalkanes: Haloform  

7.9.2 Tetrahaloalkanes: Carbon tetrachloride  

7.9.3 Chlorofluorocarbons: Freons  

7.10 Unsaturated Halides  

7.10.1 Vinyl Halides  

7.10.2 Allyl Halides  

7.11 Aryl Halides  

7.11.1 Methods of Preparations  

7.11.2 Physical Properties  

7.11.3 Chemical Reactions of Aryl halides  

(i) Nucleophilic Substitution Reactions  

(ii) Mechanism of Nucleophilic Substitutions  

7.11.4 Relative Reactivity of Vinyl Halides vs Aryl Halides  

7.11.5 Electrophilic Aromatic Substitution Reactions  

7.11.6 Other Reactions of Aryl Halides  

7.12 DDT  

7.13 Benzene Hexachloride  

7.14 Side-chain Halogen Derivatives  

7.14.1 Chemical Reactions of Side-chain Halogen Derivatives  

Very Short Answer Questions  

Problems with Solutions  

Problems for Self Assessment  

Answers to Very Short Answer Questions  

Solution of Problems  

INDEX

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