Table Of Content

Organic Chemistry MMOORRRRMMCCTTOOCC__88113311770044881155__AA..iinndddd ii 88//2255//1100 22::5544::0077 PPMM MMOORRRRMMCCTTOOCC__88113311770044881155__AA..iinndddd iiii 88//2255//1100 22::5544::0077 PPMM SEVENTH EDITION Organic Chemistry Robert Thornton Morrison Robert Neilson Boyd New York University S. K. Bhattacharjee Gauhati University MMOORRRRMMCCTTOOCC__88113311770044881155__AA..iinndddd iiiiii 88//2255//1100 22::5544::0077 PPMM Authorized adaptation from the United States edition, entitled Organic Chemistry 6th Edition, ISBN: 0136436692 by Morrison, Robert Thornton; Boyd, Robert Neilson; published by Pearson Education, Inc., publishing as Prentice Hall © 1992 Indian Subcontinent Adaptation Copyright © 2011 Dorling Kindersley (India) Pvt. Ltd This book is sold subject to the condition that it shall not, by way of trade or otherwise, be lent, resold, hired out, or otherwise circulated without the publisher’s prior written consent in any form of binding or cover other than that in which it is published and without a similar condition including this condition being imposed on the subsequent purchaser and without limiting the rights under copyright reserved above, no part of this publication may be reproduced, stored in or introduced into a retrieval system, or transmitted in any form or by any means (electronic, mechanical, photocopying, recording or otherwise), without the prior written permission of both the copyright owner and the above-mentioned publisher of this book. Pearson Prentice Hall™ is a trademark of Pearson Education, Inc. Pearson® is a registered trademark of Pearson Plc. Prentice Hall® is a registered trademark of Pearson Education, Inc. ISBN 978-81-317-0481-3 10 9 8 7 6 5 4 3 2 1 This edition is manufactured in India and is authorized for sale only in India, Bangladesh, Bhutan, Pakistan, Nepal, Sri Lanka and the Maldives. Published by Dorling Kindersley (India) Pvt. Ltd., licensees of Pearson Education in South Asia. Head Office: 7th Floor, Knowledge Boulevard, A-8(A), Sector – 62, Noida, UP 201309, India. Registered Office: 11 Community Centre, Panchsheel Park, New Delhi 110 017, India. MMOORRRRMMCCTTOOCC__88113311770044881155__AA..iinndddd iivv 88//2255//1100 22::5544::0077 PPMM Contents Preface xxv Acknowledgements xxix List of Reviewers xxxi PART ONE Fundamentals of Organic Chemistry 1 Structures of Organic Compounds 3 1.1 Organic chemistry 3 1.2 Structures and properties of molecules 5 1.3 Isomerism 6 1.4 Nomenclature of organic compounds 8 2 Structural Theory 15 2.1 Introduction 15 2.2 The chemical bond before 1926 16 2.3 Quantum mechanics 17 2.4 Shapes of atomic orbitals 18 2.5 Electronic configuration. Pauli exclusion principle 19 2.6 Molecular orbitals 20 2.7 The covalent bond 20 2.8 Types of MOs 22 2.9 Hybridization of orbitals 23 2.10 Hybridization and overlap 25 2.11 Energies of hybridization 26 2.12 Parameters of molecular geometry 26 MMOORRRRMMCCTTOOCC__88113311770044881155__AA..iinndddd vv 88//2255//1100 22::5544::0077 PPMM vi CONTENTS 2.13 Bond energy and bond dissociation energy 28 2.14 3D-Structure of Csp3 compounds 30 2.15 Intramolecular forces 30 2.16 Polarity of bonds 31 2.17 Polarity of molecules 31 2.18 Structure and physical properties 34 2.19 Melting point 35 2.20 Intermolecular forces 36 2.21 Boiling point 38 2.22 Solubility 40 3 Symmetry of Organic Molecules (Molecular Dissymmetry) 43 3.1 Symmetry elements 43 3.2 Point groups 46 3.3 Determining the point group of organic molecules 47 3.4 Stereogenicity 48 3.5 Achiral stereogenicity 51 3.6 Stereoheterotopicity 52 4 Types of Reactions of Organic Compounds 55 4.1 Reaction mechanism 55 4.2 Electron delocalization 59 4.3 Formation of reaction intermediates 64 4.4 Transition state 89 4.5 Types of reagents 90 4.6 Types of organic reactions 90 4.7 Acids and bases 91 4.8 Hard and soft acids and bases (HSAB concept) 94 4.9 Thermodynamics of organic reactions 95 4.10 Kinetics of organic reactions 96 4.11 Thermodynamic and kinetic control of reactions 97 4.12 Effect of catalyst on the kinetics of a reaction 97 4.13 Linear free energy relationships (the Hammett equation) 98 4.14 Curved Hammett diagrams 101 4.15 Separation of polar, resonance, and steric effects of substituent constants (s(cid:2) and s(cid:3)) values 102 4.16 The Taft equation 103 4.17 Secondary bonding and role of solvent 103 5 Alkanes, Cycloalkanes and Aromatic Hydrocarbons 120 5AI. Introduction to Alkanes 5AI.1 Classification of hydrocarbons 120 5AI.2 Alkanes: structure of methane 120 5AI.3 Classification by structure: the family 121 5AI.4 Structure of ethane 122 MMOORRRRMMCCTTOOCC__88113311770044881155__AA..iinndddd vvii 88//2255//1100 22::5544::0077 PPMM CONTENTS vii 5AI.5 Free rotation about the carbon–carbon single bond. Conformations. Torsional strain 123 5AI.6 Propane and the butanes 127 5AI.7 Conformations of n-butane. Van der Waals repulsion 129 5AI.8 Higher alkanes. The homologous series 131 5AI.9 Nomenclature 132 5AI.10 Alkyl groups 132 5AI.11 Common names of alkanes 134 5AI.12 IUPAC names of alkanes 134 5AI.13 Classes of carbon atoms and hydrogen atoms 136 5AI.14 Physical properties 136 5AI.15 Industrial source 138 5AI.16 Industrial source vs. laboratory preparation 140 5AI.17 Preparation 141 5AI.18 The Grignard reagent: an organometallic compound 143 5AI.19 Coupling of alkyl halides with organometallic compounds 145 5AI.20 Reactions 147 5AI.21 Halogenation 148 5AI.22 Mechanism of halogenation 150 5AI.23 Orientation of halogenation 151 5AI.24 Relative reactivities of alkanes toward halogenation 154 5AI.25 Ease of abstraction of hydrogen atoms. Energy of activation 155 5AI.26 Stability of free radicals 156 5AI.27 Ease of formation of free radicals 157 5AI.28 Transition state for halogenation 158 5AI.29 Orientation and reactivity 159 5AI.30 Reactivity and selectivity 160 5AI.31 Non-rearrangement of free radicals. Isotopic tracers 161 5AI.32 Combustion 163 5AI.33 The greenhouse effect 164 5AI.34 Pyrolysis: cracking 165 5AI.35 Determination of structure 166 5AII. Stereoisomerism 5AII.1 Stereoisomerism 169 5AII.2 Enantiomerism 169 5AII.3 Plane-polarized light 169 5AII.4 Polarimeter 170 5AII.5 Specific rotation 171 5AII.6 Optical activity: how does it arise? 172 5AII.7 Projection structures of stereoisomers 173 5AII.8 Properties of enantiomers 177 5AII.9 Racemic modification and resolution 179 5AII.10 Optical activity: a closer look 181 5AII.11 Assignment of configuration 182 5AII.12 Specification of configuration: R and S 183 5AII.13 Sequence rules 184 5AII.14 Diastereomers 186 5AII.15 Meso structures 188 MMOORRRRMMCCTTOOCC__88113311770044881155__AA..iinndddd vviiii 88//2255//1100 22::5544::0077 PPMM viii CONTENTS 5AII.16 Specification of configuration: more than one chiral center 190 5AII.17 Conformational isomers 191 5AII.18 Reactions involving stereoisomers 193 5AII.19 Generation of a chiral center. Synthesis and optical activity 193 5AII.20 Reactions of chiral molecules. Bond-breaking 195 5AII.21 Reactions of chiral molecules. Relating configurations 196 5AII.22 Optical purity 199 5AII.23 Reactions of chiral molecules. Generation of a second chiral center 199 5AII.24 Topicity of ligands (prochirality) 200 5BI. Cyclic Aliphatic Compounds (Carbocyclic Compounds) 5BI.1 Open-chain and cyclic compounds 206 5BI.2 Nomenclature 206 5BI.3 Industrial source 208 5BI.4 Preparation 209 5BI.5 Reactions 210 5BI.6 Reactions of small-ring compounds. Cyclopropane and cyclobutane 211 5BI.7 Baeyer strain theory 212 5BI.8 Heats of combustion and relative stabilities of the cycloalkanes 213 5BI.9 Orbital picture of angle strain 215 5BI.10 Factors affecting stability of conformations 216 5BI.11 Conformations of cycloalkanes 217 5BI.12 Equatorial and axial bonds in cyclohexane 222 5BI.13 Preparation of cyclopropane rings by (cid:4)-insertion reaction of carbenes 225 5BII. Stereoisomerism 5BII.1 Stereoisomerism of cycloalkanes and their derivatives: configurational isomerism of cyclic compounds 228 5BII.2 Geometric isomerism of alkenes 230 5BII.3 Conformational analysis 233 5C. Aromatic Hydrocarbons and Aromaticity 5C.1 Aliphatic and aromatic compounds 243 5C.2 Structure of benzene 244 5C.3 Molecular formula. Isomer number. Kekulé structure 244 5C.4 Stability of the benzene ring. Reactions of benzene 246 5C.5 Stability of the benzene ring. Heats of hydrogenation and combustion 247 5C.6 Carbon–carbon bond lengths in benzene 248 5C.7 Resonance structure of benzene 249 5C.8 Orbital picture of benzene 250 5C.9 Representation of the benzene ring 252 5C.10 Aromatic character. The Hückel 4n (cid:2) 2 rule 253 5C.11 Nomenclature of benzene derivatives 257 5C.12 Polynuclear aromatic hydrocarbons. Naphthalene 259 5C.13 Electrophilic aromatic substitution 262 5C.14 Effect of substituent groups 265 MMOORRRRMMCCTTOOCC__88113311770044881155__AA..iinndddd vviiiiii 88//2255//1100 22::5544::0077 PPMM CONTENTS ix 5C.15 Determination of orientation 265 5C.16 Regioselectivity of electrophilic aromatic substitutions: relative reactivity of monosubstituted benzenes 266 5C.17 Classification of substituent groups 267 5C.18 Orientation in disubstituted benzenes 268 5C.19 Mechanism of electrophilic aromatic substitution: the two steps 270 5C.20 Reactivity and orientation 273 5C.21 Theory of reactivity 274 5C.22 Theory of orientation 276 5C.23 Electron release via resonance 278 5C.24 Effect of halogen on electrophilic aromatic substitution 280 5C.25 Electrophilic substitution in naphthalene 283 PART TWO Chemistry of Functional Groups 6 Alkenes 291 6A. Structure and Preparation (Elimination) 6A.1 Classes of organic compounds having one or more functional group(s) 291 6A.2 Unsaturated hydrocarbons 291 6A.3 Structure of ethylene. The carbon–carbon double bond 291 6A.4 Propylene 294 6A.5 Hybridization and orbital size 294 6A.6 The butylenes 295 6A.7 Higher alkenes 297 6A.8 Names of alkenes 297 6A.9 Physical properties 298 6A.10 The organic chemistry of vision 300 6A.11 Industrial source 302 6A.12 Preparation 302 6A.13 Dehydrohalogenation of alkyl halides: 1,2-elimination 305 6A.14 Kinetics of dehydrohalogenation. Duality of mechanism 309 6A.15 The E2 mechanism 309 6A.16 Evidence for the E2 mechanism. Kinetics and absence of rearrangements 310 6A.17 Evidence for the E2 mechanism. Isotope effects 311 6A.18 Evidence for the E2 mechanism. Absence of hydrogen exchange 313 6A.19 Evidence for the E2 mechanism. The element effect 315 6A.20 The E2 reaction: orientation and reactivity 316 6A.21 The E1 mechanism 319 6A.22 Evidence for the E1 mechanism 320 6A.23 The E1 reaction: orientation 322 6A.24 Stereochemistry of elimination from alicyclic compounds 324 MMOORRRRMMCCTTOOCC__88113311770044881155__AA..iinndddd iixx 88//2255//1100 22::5544::0077 PPMM