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SIXTH EDITION Organic Chemistry Robert Thornton Morrison Robert Neilson Boyd New York University Prentice Hall, Englewood Clzffs,New Jersey 0 7632 Contents Preface xxiii Acknowledgments xxvii PART ONE The Fundamentals l Structure and Properties Organic chemistry 1 The structural theory 3 The chemical bond before 1926 4 Quantum mechanics 5 Atomic orbitals 6 Electronic configuration. Pauli exclusion principle 8 Molecular orbitals 9 The covalent bond 9 Hybrid orbitals: sp l l Hybrid orbitals: sp 13 Hybrid orbitals: sp3 15 Unshared pairs of electrons 17 Intramolecular forces 20 Bond dissociation energy. Homolysis and heterolysis 21 Polarity of bonds 23 Polarity of molecules 23 Structure and physical properties 26 Melting point 2 7 Intermolecular forces 28 Boiling point 30 Solubility 31 vi CONTENTS 1.22 Acids and bases 33 1.23 Isomerism 36 2 Methane Energy of Activation. Transition State Hydrocarbons 39 Structure of methane 40 Physical properties 41 Source 41 Reactions 42 Oxidation. Heat of combustion 42 Chlorination: a substitution reaction 43 Control of chlorination 44 Reaction with other halogens: halogenation 44 Relative reactivity 45 Reaction mechanisms 45 Mechanism of chlorination. Free radicals 46 Chain reactions 48 Inhibitors 49 Heat of reaction 50 Energy of activation 51 Progress of reaction: energy changes 52 Rate of reaction 55 Relative rates of reaction 58 Relative reactivities of halogens toward methane 59 An alternative mechanism for halogenation 61 Structure of the methyl radical. sp2Hybridization 64 Transition state 65 Reactiyity and development of the transition state 67 Chlorofluorocarbons and the ozone shield 69 Molecular formula: its hndamental importance 72 Qualitative elemental analysis 72 . Quantitative elemental analysis: carbon, hydrogen, and halogen 73 Empirical formula 74 Molecular weight. Molecular formula 74 3 Alkanes Free-Radical Substitution Classification by structure: the family 77 Structure of ethane 78 Free rotation about the carbon-carbon single bond. Conformations. Torsional strain 79 Propane and the butanes 83 conformations of n-butane. Van der Waals repulsion 85 Higher alkanes. The homologous series 86 Nomenclature 87 Alkyl groups 88 Common names of alkanes 90 IUPAC names of alkanes 90 CONTENTS vii Classes of carbon atoms and hydrogen atoms 92 Physical properties 92 Industrial source 94 Industrial source vs. laboratory preparation 96 Preparation 97 The Grignard reagent: an organometallic compound 99 Coupling of alkyl halides with organometallic compounds 101 d Reactions 102 Halogenation 104 Mechanism of halogenation 106 Orientation of halogenation 107 Relative reactivities of alkanes toward halogenation 109 Ease of abstraction of hydrogen atoms. Energy of activation 110 Stability of free radicals l l l Ease of formation of free radicals 113 Transition state for halogenation 113 Orientation and reactivity 114 Reactivity and selectivity 115 Non-rearrangement of free radicals. Isotopic tracers 116 Combustion 118 The greenhouse effect 119 Pyrolysis: cracking 120 Determination of structure 121 Analysis of allcanes 122 4 Stereochemistry I. Stereoisomers Stereochemistry and stereoisomerism 125 Isomer number and tetrahedral carbon 126 Optical activity. Plane-polarized light 128 The polarimeter 128 Specific rotation 129 Enantiomerism: the discovery 130 Enantiomerism and tetrahedral carbon 131 Enantiomerism and optical activity 133 Prediction of enantiomerism. Chirality 133 The chiral center 135 Enantiomers 136 The racemic modification 138 Optical activity: a closer look 139 Configuration 140 Specification of configuration: R and S 140 Sequence rules 141 Diastereomers 144 Meso structures 146 Specification of configuration: more than one chiral center 148 Conformational isomers 149 Reactions involving stereoisomers 150 Generation of a chiral center. Synthesis and optical activity 151 viii CONTENTS 4.23 Reactions of chiral molecules. Bond-breaking 153 4.24 Reactions of chiral molecules. Relating configurations 154 4.25 Optical purity 156 4.26 Reactions of chiral molecules. Generation of a second chiral center 156 4.27 Reactions of chiral molecules with optically active reagents. Resolution 158 4.28 Reactions of chiral molecules. Mechanism of free-radical chlorination 160 5 Alkyl Halides Nucleophilic Aliphatic Substitution Homolytic and heterolytic chemistry 165 Relative rates of competing reactions 166 Structure. The functional group 167 Classification and nomenclature 168 Physical properties 169 Preparation 170 Reactions. Nucleophilic aliphatic substitution 172 Nucleophilic aliphatic substitution. Nucleophiles and leaving groups 175 Rate of reaction: effect of concentration. Kinetics 177 Kinetics of nucleophilic aliphatic substitution. Second-order and first-order reactions 178 Nucleophilic aliphatic substitution: duality of mechanisms 179 The SN2reaction: mechanism and kinetics 181 The &2 reaction: stereochemistry. Inversion of configuration 182 The SN2reaction: reactivity. Steric hindrance 185 The S,1 reaction: mechanism and kinetics. Rate-determining step 188 Carbocations 191 Structure of carbocations 193 The &l reaction: stereochemistry 194 Relative stabilities of carbocations 196 Stabilization of carbocations. Accommodation of charge. Polar effects 199 The &l reaction: reactivity. Ease of formation of carbocations 200 Rearrangement of carbocations 203 &2 vs. &l 208 Analysis of alkyl halides 21 1 I 6 Alcohols and Ethers !l 6.1 Introduction 213 6.2 Structure of alcohols 214 6.3 Classification of alcohols 214 6.4 Nomenclature of alcohols 215 6.5 Physical properties of alcohols 215 CONTENTS Industrial source 218 Fermentation of carbohydrates 21 9 Fuel from carbohydrates. Carbon dioxide balance 219 Ethanol 221 Preparation of alcohols 222 Reactions of alcohols 224 Alcohols as acids and bases 227 d Reaction of alcohols with hydrogen halides. Acid catalysis 229 Formation of alkyl sulfonates 233 Oxidation of alcohols 235 ETHERS Structure and nomenclature of ethers 237 Physical properties of ethers 238 Industrial sources of ethers. Dehydration of alcohols 238 Preparation of ethers 240 Preparation of ethers. Williamson synthesis 241 Reactions of ethers. Cleavage by acids 242 Analysis of alcohols 243 Analysis of ethers 244 7 Role of the Solvent Secondary Bonding Role of the solvent 249 Secondary bonding 250 Solubility: non-ionic solutes 252 Solubility: ionic solutes. Protic and aprotic solvents. Ion pairs 254 The &l reaction: role of the solvent. Ion-dipole bonds 258 The SN2reaction: role of the solvent. Protic and aprotic solvents 261 The &2 reaction: phase-transfer catalysis 264 &2 vs. & 1: effect of the solvent 26 7 Solvolysis. Nucleophilic assistance by the solvent 268 The medium: a message 271 8 Alkenes I. Structure and Preparation Elimination Unsaturated hydrocarbons 273 Structure of ethylene. The carbon-carbon double bond 273 Propylene 2 76 Hybridization and orbital size 276 The butylenes 277 Geometric isomerism 2 79 Higher alkenes 282 Names of alkenes 282 Physical properties 283 The organic chemistry of vision 285 Industrial source 287 Preparation 287 Dehydrohalogenation of *l halides: 1,2-elimination 290 Kinetics of dehydrohalogenation. Duality of mechanism 293 CONTENTS The E2 mechanism 294 Evidence for the E2 mechanism. Kinetics and absence of rearrangements 294 Evidence for the E2 mechanism. Isotope effects 295 Evidence for the E2 mechanism. Absence of hydrogen exchange 297 Evidence for the E2 mechanism. The element effect 299 The E2 reaction: orientation and reactivity 300 The El mechanism 303 Evidence for the El mechanism 304 8.23 The El reaction: orientation 306 8.24 Elimination: E2 vs. El 308 8.25 Elimination vs. substitution 308 8.26 Dehydration of alcohols 310 9 Alkenes 11. Reactions of the Carbon-Carbon Double Bond Electrophilic and Free-Radical Addition Reactions of alkenes 31 7 Reactions at the carbon-carbon double bond. Addition 31 7 Hydrogenation. Heat of hydrogenation 323 Heat of hydrogenation and stability of alkenes 326 Addition of hydrogen halides. Markovnikov's rule. Regioselective reactions 327 Addition of hydrogen bromide. Peroxide effect 330 Addition of sulhric acid 331 Addition of water. Hydration 332 Electrophilic addition: mechanism 332 Electrophilic addition: rearrangements 334 Electrophilic addition: orientation and reactivity 335 Addition of halogens 339 Mechanism of addition of halogens 340 Halohydrin formation: addition of the elements of hypohalous acids 342 Addition of alkenes. Dimerization 343 Addition of aIkanes. Alkylation 344 Oxymercuration-demercuration 346 Hydroboration-oxidation 347 Orientation of hydroboration 348 Mechanism of hydroboration 349 Free-radical addition. Mechanism of the peroxide-initiated addition of HBr 351 Orientation of free-radical addition 352 Other free-radical additions 355 Free-radical polymerization of alkenes 356 Hydroxylation. Formation of 1'2-diols 35 7 Cleavage: determination of structure by degradation. Ozonolysis 358 Analysis of alkenes 360 CONTENTS 10 Stereochemistry 11. Stereoselective and Stereospecific Reactions 10.1 Organic chemistry in three dimensions 367 10.2 Stereochemistry of addition of halogens to alkenes. syn- and anti- addition 368 10.3 Mechanism of addition of halogens to allcenes 372 10.4 Stereochemistry ofthe E2 reaction. syn- and anti-elimination 377 10.5 Stereospecific reactions 381 10.6 Stereoselectivity vs. stereospecificity 382 10.7 A look ahead 383 11 Conjugation and Resonance Dienes The carbon-carbon double bond as a substituent 387 Free-radical halogenation of alkenes: substitution vs. addition 388 Free-radical
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