MORISSON   Organic Chemistry

MORISSON Organic Chemistry


DisciplinaQuímica Orgânica I15.015 materiais276.788 seguidores
Pré-visualização50 páginas
Stability of free radicals 11 I
\.is Ease offormation of free radicals 113
1,.-ZS Transition state for halogenation 113
3:.ti orientation and reactivity 114
3.Zg Reactivity and selectivity 115.
3.2g Non-rearran;;;;"i of fiee radicals' Isotopic tracers 116
3.30 Combustion 118
l.lf The greenhouse effect 119
3.32 PlrolYsis: cracking 120
3: 3, Determination of structure 121
3.34 AnalYsis of alkanes 122
4 Stereochemistry I' Stereoisomers
4.1 Stereochemistry and stereoisomerism 125
4.2 Isomer numbei and tetrahedral carbon 126
4., Optical activity' Plane-polarized light 128
4.4 The Polarimeter 128
4.5 SPecific rotation 129
q.A Enantiomerism: the discovery 130
4: .1 Enantiomerism and tetrahedral. carbon I 31
+.g Enantiomerism and optical activity 133 ' ^
4:.g Prediction ofenantiomerism' Chirality 13i
4.10 The chiral center 135
4.11 Enantiomers 136
4.12 The racemic modifieation 138
Ltl Optical activity: a closer look 139
4.14 Configuration 140
+.iS Speci[cxion of configuration: R and S 140
4.16 Sequence rules 141
4.17 Diastereomers 144
4. 18 Meso structures 146
4. 19 Specincalio*i oi toong"'"tion:^more than one chiral center 
148
I l0 ionformational isomers 149
..ii Reactions involving stereoisomers . 150
: ll Generation of u tiiitJ *nter' Synthesis and optical activity
1 5 1
vtu CONTENTS
4.23 Reactions of chiral molecules. Bond-breaking IS34.24 Reactions of chiral molecules. Relating confiiurations Is44.25 Optical purity 156
4.26 Reactions of chiral molecures. Generation of a second chiral
center 156
4.27 Reactions of chiral molecures with optically active reagents.
Resolution 158
4.28 Reactions of chiral molecules. Mechanism of free-radicar
chlorination 160
Alkyl Halides Nucleophilic Aliphatic Sabstitution
5.1 Homolytic and heterolytic chemistry 165
5.2 Relative ralesof competing reactions 166
5.3 Structure. The functional group 167
5.4 Classification and nomenclature 16g
5.5 Physical properties 169
5.6 Preparation 170
5.7 Reactions. Nucleophilic aliphatic substitution 172
5.8 Nucleophilic aliphatic substitution. Nucleophiles and leavinggroups 175
5.9 Rate of reaction: effect of concentration. Kinetics lZ7
5.10 Kinetics of nucleophilic aliphatic substitution. second-order and
first-orderreactions 178
5.1 I Nucleophilic aliphatic substitution: duality of mechanism s 179
5.12 The S"2 reaction: mechanism and kinetici lgl
5.13 The Sng2 reaction: stereochemistry. Inversion of
configuration /,82
5.14 The S"2 reaction: reactivity. Steric hindrance Ig5
5.15 The $*1 reaction: mechanism and kinetics. Rate-determining
step 188
5.16 Carbocations 191
5.17 Structure of carbocations 193
5.18 The S"l reaction: stereochemistry Ig4
5. I 9 Relative stabilities of carbocations I 96
5.20 Stabilization of carbocations. Accommodation of charge. polar
effects 199
5.21 The Snnl reaction: reactivity. Ease of formation of
carbocations 200
5.22 Rearrangement of carbocations 203
5.23 $or2 as. S"l 208
5.24 Analysis of alkyl halides 2I I
6 Alcohols and Ethers
Introduction 213
Structure of alcohols 214
Classification of alcohols 214
Nomenclature of alcohols 2ls
Physical properties ofalcohols 2ls
6.1
6.2
6.3
6.4
6.5
l
: l
- i
CONTENTS i:
Industrial source 218
Fermentation of carbohydrates 219
Fuel from carbohydrates. Carbon dioxide balance 219
Ethanol 221
Preparation ofalcohols 222
Reactions of alcohols 224
Alcohols as acids andbases 227
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 ofethers 238
Industrial sources of ethers. Dehydration of alcohols 238
Preparationofethers 240
Preparation of ethers. Williamson synthesis 241
Reactions of ethers. Cleavage by acids 242
Analysis of alcohols 243
Analvsis of ethers 244
I r U
f ; i
6 t 7
f . l J
6 . l 4
6 . l 5
6 . l 6
6 . t 7
6 . 1 8
6 . t 9
6.20
6.2r
6.22
6.23
7 Role of the Solvent Second'ary Bonding
7 . 1
7.2
7.3
7.4
7.5
7.6
7.7
7.8
7.9
'1 . t0
Role of the solvent 249
Secondarybonding 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 S,*2 reaction: role of the solvent. Protic and aprotic
solvents 261
The S,*2 reaction: phase-transfer catalysis 264
$.2 us. Snl: effect ofthe solvent 267
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 276
Hybridization and orbital size 276
The butylenes 277
Geometricisomerism 279
Higher alkenes 282
Names of alkenes 282
Physicalproperties 283
The oryanic chemistry of vision 285
Industrial source 287
Preparation 287
Dehydrohalogenation ofalkyl halides: l,2-elimination 290
Kinetics of dehydrohalogenation. Duality of mechanism 293
8 . 1
8.2
8 .3
8.4
8 .5
8 .6
8 . 7
8 . 8
i 9
r
i
i
i
CONTENTS
8.15 The E2 mechanism 294
8,16 Evidence for the E2 mechanism. Kinetics and absencr of
rearrangements 294
8.17 Evidence fior the E2 mechanism. Isotope effects 295
8.18 Evidence for the E2 mechanism. Absence of hydrogen
exchange 297
8.19 Evidence for the E2 mechanism. The element effect 299
8.20 The E2 reaction: orientation and reactivity 300
8.21 The El mechanism' 303
8.22 Evidence for the El mechanism 304
8.23 The El reaction: orientation 306
8.24 Elimination:E2 us.El 308
8.25 'Elinoination us. substitution 308
8.26 Dehydration of alcohols 310
Alkenes II. Reactions of the Carbon-Carbon Double Bond
Electrophilic end Free-Rodical Addition
9.1 Reactions of alkenes 317
9.2 Reactions at the carbon-carbon double bond. Addition 317
9.3 Hydrogenation. Heat of hydrogenation 323
9.4 .Ileat of hydrogenation and stability of alkenes 326
9.5 Addition of hydrogen hahdes. Markovnikov's rule. Regioselective
reactions 327
9.6 Addition of hydrogen bromide. Peroxide effect 330
9.7 Addition of sulfuric acid 331
9.8 Addition of water. Hydration 332
9.9 Electrophilic addition: mechanism 332
9.10 Electrophilicaddition:rearrangements 334
9.11 Electrophilic addition: orientation and reactivity 335
9.12 Addition of halogens 339
9.13 Mechanism of addition of halogens 340
9.14 Halohydrin formation: addition of the elements of hypohalous.
acids 342
9.15 Addition of alkenes. Dimerization 343
9.16 Addition of alkanes. Alkylation 344
9.17 Oxymercuration-demercuration 346
9.18 Hydroboration-oxidation 347
9.19 Orientation of hydroboration -148
9.20 Mechanism of hydroboration 349 -
9.21 Free-radical addition. Mechanism of the peroxide-initiated
addition of HBr 35/,
9.22 Orientation of free-radical addition 352
9.23 Other free-radical additions J55
9.24 Free-radical polymerization of alkenes 356
9.25 Hydroxylation. Formation of l,2diols 357
?.26 Cleavage: determination of structure by degradation.
Ozonolysis 358
9.27 Analysis of alkenes 360
I ( t
CONTENTS xl
stereochemistry II. Stereoselective and Stereospecific
Reactions
I0.I Organic chemistry in three dimensions 367
10.2 Stereochemistry of addition of halogens to alkenes. syt?- and anti-
addition 368
10.3 Mechanism of addition of halogens to alkenes 372
10.4 StereochemistryoftheE2reaction. syn-andantl-elimination 377
10.5 StereosPecific reactions 381
10.6 Stereoselectivityus.stereospecificity 382
10.7 A look ahead 383
Conjugation and Resonance Dienes
1 l.t The carbon-carbon double bond as a substituent 387
ll.2 Free-radical halogenation of alkenes: substitution us.
addition 388
I 1.3 Free-radical substitution in alkenes: orientation and
reactivity 390
ll.4 Free-radical substitution in alkenes: allylic rearrangement 392
t 1.5 Symmetry of the allyl radical 393
1 1.6 The theory ofresonance