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

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6A.25 Elimination: E2 vs. E1 326

6A.26 Dehydration of alcohols 327
6A.27 Conversion of aldehydes and ketones to alkenes 331
6A.28 Reactions of the carbon–carbon double bond of alkenes 334
6A.29 Addition reactions: electrophilic additions 335
6A.30 Hydrogenation. Heat of hydrogenation 341
6A.31 Heat of hydrogenation and stability of alkenes 344
6A.32 Addition of hydrogen halides. Markovnikov’s rule.
Regioselective reactions 345
6A.33 Addition of hydrogen bromide. Peroxide effect 347
6A.34 Addition of sulfuric acid 348
6A.35 Addition of water. Hydration 350
6A.36 Mechanism of electrophilic addition reactions 350
6A.37 Electrophilic 1,2-shift during electrophilic additions 352
6A.38 Reactivity and regioselectivity in electrophilic additions 353
6A.39 Addition of halogens 357
6A.40 Mechanism of addition of halogens (stereoselectivity
of the reaction) 358
6A.41 Halohydrin formation: addition of the elements
of hypohalous acids 360
6A.42 Addition of alkenes. Dimerization 361
6A.43 Addition of alkanes. Alkylation 362
6A.44 Oxymercuration–demercuration 364
6A.45 Hydroboration–oxidation 365
6A.46 Mechanism of hydroboration (regio- and stereoselectivity
of the reaction) 366
6A.47 Free-radical addition. Mechanism of the peroxide-initiated
addition of HBr 368
6A.48 Regioselectivity of free-radical addition 369
6A.49 Free-radical polymerization of alkenes 372
6A.50 Hydroxylation. Formation of 1,2-diols 374
6A.51 Cleavage: determination of structure by degradation.
Ozonolysis (1,3-dipolar cycloaddition) 375
6B. Dienes (Conjugation and Resonance)
6B.1 The carbon–carbon double bond as a substituent 382
6B.2 Free-radical halogenation of alkenes: substitution vs. addition 382
6B.3 Free-radical substitution in alkenes: orientation and reactivity 385
6B.4 Free-radical substitution in alkenes: allylic rearrangement 387
6B.5 The theory of resonance 388
6B.6 The allyl radical as a resonance hybrid 388
6B.7 Stability of the allyl radical 391
6B.8 Orbital picture of the allyl radical 391
6B.9 Using the resonance theory 393
6B.10 Resonance stabilization of alkyl radicals. Hyperconjugation 395
6B.11 The allyl cation as a resonance hybrid 396
6B.12 Dienes: structure and properties 397
6B.13 Stability of conjugated dienes 398
6B.14 Resonance in conjugated dienes 399

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 CONTENTS xi

6B.15 Ease of formation of conjugated dienes: orientation

of elimination 401
6B.16 Electrophilic addition to conjugated dienes. 1,4-Addition 401
6B.17 1,2- vs. 1,4-Addition. Rate vs. equilibrium(kinetically and
thermodynamically controlled reactions) 404
6B.18 Free-radical polymerization of dienes. Rubber
and rubber substitutes 406

7 Alkynes 411
7.1 Introduction 411
7.2 Structure of acetylene. The carbon–carbon triple bond 411
7.3 Higher alkynes. Nomenclature 414
7.4 Physical properties of alkynes 414
7.5 Industrial source of acetylene 415
7.6 Preparation of alkynes 415
7.7 Reactions of alkynes 416
7.8 Reduction to alkenes 419
7.9 Mechanism of electrophilic addition to alkynes 420
7.10 Acidity of alkynes. Very weak acids 421
7.11 Reactions of metal acetylides. Synthesis of alkynes 423
7.12 Analysis of alkynes 423

8 Alkyl Halides Nucleophilic Substitutions,

SN Reactions 426
8.1 Functional groups 426
8.2 Classification and nomenclature 427
8.3 Physical properties 427
8.4 Preparation 428
8.5 Reactions. Nucleophilic aliphatic substitution 430
8.6 Nucleophilic aliphatic substitution. Nucleophiles
and leaving groups in SN reactions 433
8.7 Kinetics of SN reactions 435
8.8 Kinetics of nucleophilic aliphatic substitution. Second-order and
first-order reactions 436
8.9 Nucleophilic aliphatic substitution: duality of mechanism 437
8.10 Mechanism of SN2 reactions 439
8.11 Stereochemistry of SN2 reactions: Walden inversion 440
8.12 The SN2 reaction: structure of the substrate and reactivity 442
8.13 Mechanism of SN1 reactions 446
8.14 Carbocations 448
8.15 Stabilization of carbocations. Accommodation of charge.
Polar effects 448
8.16 Stability of carbocation and its ease of formation:
SN1 reactivity 450
8.17 Stereochemistry of SN1 reactions 451
8.18 Rearrangement of carbocations 455

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