Organic Chemistry, 6th Edition

1282 Pages·2007·57.3 MB·English

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SIXTH EDITION

Organic Chemistry

Robert Thornton Morrison
Robert Neilson Boyd

New York University

Prentice-Hall of India Fcfscts Lfaitied
New Delhi- 110 001
2002
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Contents

Preface ut
Acboomledgments soot

PART ONE
‘The Fundamentals

J Structure and Properties

1 Orunic chemistry 1
‘2. Thestructaral theory

A Thechemical bord bere 19254

“4 Quartum mechanics 5

3 Atomic orbitals 6

{4 —Flecteroic configuration. Pauli cectsion principle §
17 Molecular arbils 9

18 Thecovslent bond 9

19 Hybrid orbials: sp, 12

110 Hybrid orbitals so? 1

LAL Hybrid orbitals spt 15

1I2 Vashare pees of electrons 27

113 Tatrmoeoulse forces 20

1.14 Bond dissociation ence Homolysis and hetertyss 27
11S Polarity ofboads 22

146 Polasity of molecules 27

LY? Structure and physical propenies 26

118 Mebing point 27

1119 Tnlermelecular forces 28

120 Beiting point 10

12LSohabiity 37
conreNTs

122 Acidsand baer 3
123 Teomeniana 36

Methane Energy of Activation. Transition State
ZL Hydrocarbons 39
22 Siroctoreofmmettane 40
23 Physieal properties 47
24 Sou
25° Resclons 4?
2G Oxidation. Fat of combustion 42
2.7 Chlorinstion:asubstition reaction 43
28 Control of chlorination 4
29° Reaction wth ether halogens: alogenation 44
210 Relative activity 45
201 Reaction mechaniams 45
2.12 Mechanism of chlorination. Free radials 46
213 Chain reactions 48

Inkitivor 42
Heat of eaction $0
Energy ofactivation 52
Progress of reaction: energy changes 52
Rate of action 55
Rete ntes ofreacion 58
Relative reactivities af halogens toward methane 59
‘An altematve mechaniam for talogenation 4?
Scuctate ofthe mevhyl radial sp Hsbridieaion 64
‘Tramshion state 65
Reseivty and developnienc ofthe oansition sate 67
‘Chlorofuorocatboas andthe canna shiek! | 69
Molecular formula is fundameatal importance 72
‘Qualiaiveelemenia analysis 72
‘Quantitative elemental anatsss carbon, bydrogen. and
halogen 7
229 Empirical formula 74
230 Molecular weight: Molecular formula 74

Alkenes Free-Radical Substitution

3k Clasication by sructure: the faily 77

32 Structwe ofehane | 78

33 Troe rotation about the carbon-carbon sage bond.
Conformatins, Torsional strain 79

Propane ani ibe butanes $3

(Conformatioas of butane, Van der Waals repulsion 85

Higher alkanes, Tae homologous series 86

Nomencarire #7

Allg groups 38

Comaton eames of alkanes 90

TUPAC aumes af alkanes 90
(Chases of carbon atoms aud hydrogen atoms 92

442 Prysical properties 92

313 industrial source 94

414 eustrialsoutee es: borat preparation 96

B1E Preparation 97

4316 The Grignard reagent: an organometallic compound 99
317 Coupling of sky halides eh organometallic compoueds 107
218 Reactions 102

319 Halogenation 104

3.20. Mechanism of nalogenation 70%

321 Onentation of Ralogeation 107

422 Relaive veartvties of alkanes toward halogenation 109
3.23 Lae of sbarection of hydrogen stome. Energy of activation 170
324 Stability offer radical 1/1

325 ie of formation of free micas 12

4326 Transition ate ar alogmnation 72

A27 Orientation and reasvity 174

428 Renotvinyand setonivay 125

59° Nenzearrangement of fee radicals. ctopic racers 116,

330 Comburtion 118

331 “Thegrenbouse cet 149

232 Pyralic onaling 120

333 Determination of arucure 122

43 Anaysi ofalanes | 122

Stereochemistry I. Stereoisomers
‘Steceocheminty and steecisomeriam 125

Tsomer number and tetabodral carbon 126

(Opies amtivey. Plane polarized ight 12%

‘The polarimeter 124

Specie rotation 129

nantiameriam: the disonvery 724
Enattiomerism and ctahedral bon 231

Enantiomerism and optical activity 133

Predictioa ofensntiomerisr Chirality 127

‘The chiral center 735

Enattiomers 176

‘The racemic modication 138

Optical sctvny closer look 1379

Contiguetion | 140

Spectotion of configuration: Rand S749

Seavence ules 147

Disstteomers 4é

Mosetractuns 146

Specification of configuration: more thin one chiral center 148
Conformational omens 149

Reactions involving stereoisomers 150

Generation of» chin centr. Synthesis and optical activity 152
423 Reactions of chiral molecules, Bond-breaking 252

424 Reseions of chiral molecules, Relating configurations. 154

425 Optical purity 756

426 Reactions of ciel molecles, Generation ofa second chit
center 156

427 Reactions of civ molecoles with optically axtive agents
Revolution 158

428 Reactions of chiral molorles, Mechanism of re-ratical
chlorination 160

Allyl Halides Nucleophilic Aliphatic Substitution

5.1 Homelyicand beterolytic chemicty 165,

52 Relive rate of competing reactions 166

$3 Suucture The functional gun 167

5 Claseation and nomenclature 6H

5.5 Physiul properties 108

58 Preparation 770

53 Reaetions, Nuclophilc aliphatic aubsitution 172

58 Nucleophilic alipbuic substitution, Nuceuptiles und lewving
eros 175

54 ate of action: eect of concentration, Kinetics 177

SLI Kinetics of nucleophile aliphatic substation, Spcond-onder and
firstorderreetions. 178

5.11 Nocleophie aliphatic aihtiation: dua of meckaninms 279
“The Sy2 renetion: mechanism and kinetics 78?
‘The 52 reactiom: sterenchemisry, Inversion of
onlignraion 782

5.14 The §,2 reaction: reactivity Serc hindrance 185

58 The Spl ceaction: mechanioan and hinrlce, Ratesetermining
sep 188

5.16 Carboeations 192

517 Structure of abucutions 123

518 The Sct rewction: stereochemistry 9¢

5.19 Relativesmiltes af carmocutions 195

5.20. Suhlizaiom of earbnoations, Acommodsion of charge, Polar
ots 798

521 The Sy seacion: reactivity. Ease formation of
carbocations 200

5:22 Rearrangement of earocations 203

523 Sho St 208

S24 Shalsis OF al halides 277

Alcohols and Ethers

641 Iettodveton 273
82 Strucureot alcohol 214

83 Clasuication af aleohols 244
G4 Nomenclature of aleahola 275
65 Physical properties ofsleobole 2/5
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Iedunial source 208
Feroeatation ofcarbohiydraes 219

Fuel from carbohydrates, Carbon dioxide bulinee 210
Ethanal 277

Preparation ofaleohels 222,

Reactions of alohols | 224

‘Alcohnlt.a acide and bases. 227

Reaction of alohols with hydrogen halides, Acid catysis 220
Formation of alll solfonsies 237

Gridaton of ateohols 235,

Structure and nomenclature of ethers 237

Phesical proper of ethers 234

Industrial sources of ethers Dehydration of akoobols 238
Propacatin ofethers 240

Preparation of ether, Wiliarason synthesin 247
Reactions of ethers. Cleavage by acids | 242

Analysis ofelcobols 243

Analysis of ethers 244

Role of the Solvent Secondary Bonding

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Role of the solvent 249
Seeondary handing, 250

Soluble: nanaonic soiutes 252

Solubiity:inicsolmes. Proticandapraticsotvenis lonpaira 254
“The Syl reaction: ole ofthe slvent.lon-aipole hands | 25
“The Su? reaction: ole ofthe alvent. Prove and aprati

solvents 257

‘The Syd reaction: phasesransier catalais 264

Sy 18 Syl eee af the solvent 267

Solvolyi- Nacloophilicasstance by th solvent 269

Tee medium: 2 mesags 272

Alkeoes 1 Siructure and Preparation Elimination

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Unsaturated bydeonarboas 272
Strucure of ethylene. The carbun-carbun Uuble bund 272
Prupylene 276

Hiybadization and orbital size 276

The bubjleaes 277

Geometric itomeriam 279

Tigher alkenes 282

Names ofulkenes 282

Physical propentis °289

The organic chemistry of vision 285

Tedustcial source 287

Preparation 287

[Dehydrobalogenation of ally hides | 2elimination 260
‘Kinelics of dehydrobalogeration, Duality af mechatism 293
S45 The BZ mechanism 296

816 Evidence for the E? mechauism. Kiaetics and abeence of
eamangements 294

SAT Evidence forthe F2 mochariam, Wotope eects 295

BAB Evidence for the F2 mochanisin, Absehoe af hydrogen
exchange | 207

8.19. Fvidonee for che E2 mechanism, The element efect 209

820 The EZ weaction: ventaton and reactivity | 300

821 The Et mechanism’ 303

822 Evidence forche Fl mechanism 300

823 The Bt easton: evientation 306

824 Elimination: R25, F108

825. Flimination xs substcation 30

$26 Detiydmation af alcohols 320

Alkenes IL. Rescticus of the Carhon—Carboa Double Band
Electrophilic.and Free- Radical Addition

9.4 Readions of alkenes $17

5'2 Reoctions a the carbon-carbon double boii. Addition 347

93 Hydrogenation. Heat af hy¢rogenation, 225

34 Heat of Ryerogenatinn and sabi of kenns 32

93 Ain oftydoge bales Mankavaiors ul, Regscive

9.6 Addon of hydcagen bromide, Peroxide elect 130

9.7 Addition of sulfuric acid 337

98 Addition of water. Hydration 322

99 Hlectrophilic addition: mechanism 332

9.10 Hletrophiie addition: rearrangements 374

941 Eletrophiic addition orientation and reacivity 235

9.12 Addition of halogens 370

3.13 Mechanic of aaition of halogens 240

14 Halohysrin fosmation: addition of the elements of hypahslous
acids 342

9.15 Addition of alkenes, Dimerizution 143

9.16 Addition of alkanes. alkylation 244

9.17 Onymercuration-demercuration 346

9.18 Hydroborstion-onidation 347

9115 Onematon af hydrobormtion 248

920 Mechanism of tirboration 349

9.21 Freesadical addition. Mechanism ofthe peroxideinitated
addition oF HRC 38

9.22 Orientation of free-radical abition 352

9.23 Other free-radical addons 355

928 Feesradical polimerzation ofalkesee 356

9.25 Hydroxylation, Formation of (Qetiols 337

9.26 Cleavage: determination of structure by degradation
Oranolysis 388

9.27 Anais of alkenes 360