Advances in Physical Organic Chemistry, Volume 33: Cumulative Subject and Author Indexes for Volumes 1-32, Part 1

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Advances in Physical Organic Chemistry Cumulative Title, Author and Cited Author (A-J) Index, Including Table of Contents, Volumes 1-32

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Advances in Physical Organic Chemistry Cumulative Title, Author and Cited Author (A-J) Index, Including Table of Contents, Volumes 1-32

Volume 33

ACADEMIC PRESS A Harcourt Science and Technology Company

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Contents

Table of Contents, Vols. 1-32

1

Cumulative Index of Titles

57

Cumulative Index of Authors

65

Cumulative Index of Cited Authors ( A 4 1

67

This Page Intentionally Left Blank

Advances In Physical Organic Chemistry Volume 1 Edited by V.Gold

.....................

CONTRIBUTOR FOREWORD .... EDITOR’S PREF

....

V

Vii ix

Entropies of Activation and Mechanisms of Reactions in Solution

L. L. Schaleger and F. A. Long A. introduction

1 1

........................

......................... ...................................

.................................... ........,..........................................

..............................

Acknowledgments .................. References .............................................................................. ..

.

2 3 6 7 9 10

10 11 13

14 16 17 17 19 21 23 23 26 27 29 31 31

A Quantitative Treatment of Directive Effects in Aromatic Substitution Leon M.Stock and Herbert C.Brown

...*..................* ..................... 1. Introduction................................................ 11. The Selectivity Relationship ....................................................................................... ....... ._........ ......................................................... A. The Significance of Selectivity ......................... ................* .....,...... B. The Selectivity Relationship ..................

.

..

1

35 44 44 49

2

VOLUME CONTENTS 111. The Data for Aromatic Substitution ............................................................................................

Activated Monosubstituted Benzenes .................................................................................... Polynuclear Aromatic Hydrocarbons ........ ............................. ....... The Alkylbenzenes..... ........... ...................... The Halobenzenes..... E. Deactivated Monosub IV. A Linear Free-Energy Treatment for Aromatic Substitution ...................................................... A. An Approach to the Problem ..... ........... ........... A. B. C. D.

....

V.

tions. .........................................................................

VI . .................................... ........................ VII. VIII. Conclusion References ..............................................................................................................................................

58 59 64 66 73 73 78 78 83 94 94 101 129 132 135 142 146 148

Hydrogen Isotope Exchange Reactions of Organic Compounds in Liquid Ammonia

A. I. Shatenshtein Introduction................................................................................................................................ Liquid Ammonia: A Protophilic Solvent..................................................................................... Method of Studying Hydrogen Exchange in Liquid Ammonia ................................................... Comparison of the Rate of Hydrogen Exchange in Ammonia and in Amphoteric Solvents ....... A. Hydrogen Exchange in Ammonia and in Ethanol ................................................................. B. Catalysis of Hydrogen Exchange in Liquid Ammonia by Potassium Amide .(....................... C. Hydrogen Exchange in Ammonia and in Alcoholic Solutions of Alkoxides .......................... V. Comparison of Hydrogen Exchange Rates in Liquid Ammonia and in other Protophilic Solvents..........,.................,.......................................................................................................... A. Catalysis of Hydrogen Exchange by Alkali Metal Hydroxides and Alkoxides in Protophilic

I. 11. 111. IV.

............................................ . . ................... V1. Unusual Relation Between Hydrogen Exchange Rates in Protophilic and Amphoteric Solvents A. Effect of the Charge of the Substrate on the Hydrogen Exchange Rate ................................ B. Effect of Complex Formation between the Substrateand the Solvent on the Hydrogen Exchange Rate............. ............................... ............................ Liquid Ammonia ................................ VII. The Salt Effect in Hydroge en Exchange in ProtophilicSolvents an VIII. The Kinetic Isotope Effect Metallation Reactions ....... ..................................................... ............................. ............ IX.Hydrocarbons as Acids and Ba....................................... ............................. X. Saturated Hydrocarbons ............................................................................................................. ...,............. ................................ XI. Cyclopropane Hydrocarbons Amines....... ,. ..

I

I

*

*

I

..3

XII. Unsaturated Hydrocarbons ........................................................................................................

A. Aliphatic Olefins.................................................................................................................... B. Hydrocarbons of the Alicyclic Series

....................................

C. Ethers and Amines ................................................................................................................ XV. Comparison of Regularities in the Protophilic and Electrophilic Substitutionof Hydrogen in Aromatic Compounds.................................... .......................... .,................. A. Partial Rate Factors for Hydrogen Exchange........................................................................

. .....

156 157 158 160 160 162 163

164 164 165 167 167

168 170

172 173 175 176 177 177 179 180 180 182 183 183 185 186 186 187

3

VOLUME CONTENTS B. Application of the Hammett-Brown-Taft Equation to Hydrogen Exchange Reactions in .........* ............................... .................................. Aromatic Compounds ............... f Free Energies of Activation to Reactions C. Application of the Principle of A Involving Protophilic and Electrophilic Hydrogen Exchange ................................................ XVI. Preparation of Deuterated and Tritiated Organic Compo XVII. Conclusions ...................................................................... References .........................................,....................................................................................................

191 193 195 196 197

Planar and Non-Planar Aromatic Systems

George Ferguson and J. Monteath Robertson I. Introduction .......................................... ................................................................................. ..... ....................,............... 11. Theoretical .................. A. Treatment of Planar and Non-Planar Aromatic Molecules ............... B. Causes of Deviations ............................................................................................................. 111. Methods of Observation and their Accuracy B. Quantitative Methods .......

B. C. D. E.

Substituted Benzenes, Naphthalenes, and Anthracenes Phenanthrene and Molecules Containing Similar Angular Ring Systems .............................. 3&Benzophenanthrenes and Skeletally Similar Molecules ................................................... 3,4-5,6-Dibenzophenanthreneand Similarly Constituted Molecules F. Phenanthro[3,4s]phenanthrene (Hexahelicene) ................................... .................................. .................................... G. Examples of Ethylenic Overcrowding VI. Conclusion ............................ References .................................................................... .........................................................................

.

203 205 205 208 212 213 218 224 225 ~~. 225 233 250 263 268 212 213 274 275 ~~

The Identification of Organic Free Radicals by Electron Spin Resonance

M. C. R Symons

....................................

.

ons ........ .............................................................................

........................................... ..................... .......................... ,............................... ......

..............................

.......................................... ............................... ...................... E. The Anion of Tetracyanoethylene .......................................................................................... ....................................... .................................. F. Simple Alkyl Radical G. Theory of Hyperfine H. Theory of Hyperfine V. Radicals in Crystals..... A. a- and p-Proton Int

284 285 287 288 288 289 289 290 29 I 293 300 300 306 308 313 315 316 316 318 321 321

_.

4

VOLUME CONTENTS

B. Substituents in %-Radicals...................................................................................................... D. The g-Tensor in

..........................................

.......................................... .......................... ....................................

g upon Proton Hyperfine Coupling

IX. Radiation Damage ..................................................................................

....................................

......................................................

....................

References .............................

321 329 329 329 333 335 335 336 340 340 345 346 341 341 348 349 349 351 351 352 353 354 355 356 356 356 351 351 359 359

The Structure of Electronically Excited Organic Molecules J. C. D. Brand and D. G. Williamson

.........................................

...............................................

........................

365 366 366 312 380 386 386 390 390 393 396 399 401 41 1 418 418

AUTHOR INDEX ........._.......... ............................................ ................................................................ SUBJECTINDEX ................................................................................................................................

425 439

I. Introduction..

E. Molecular Orbitals.

111. Applications................

A. Free Radicals.........

terocyclic Compounds

5

VOLUME CONTENTS

Advances In Physical Organic Chemistry Volume 2 Edited by V. Gold

CONTRIBUTORS TO VOLUME 2 ................................................................................................... EDITOR'S PREFACE ........................................................ .................................................................

V

vii

Isotopes and Organic Reaction Mechanisms

Clair J. Collins 3 3 1

A. The Isotopic Dilution M

.

........... .................................. ..................... 111. Combined Isotopic-Kinetic Experiments . ition Isomerization of A. Triple-Labeling Experiments on the Is 1,2,2,-Triphenylethyl Acetate ....... B. The Determination of Internal Ret C. The Determination of a Solvolysis D. Exchange Reaction Between Normal and Radioactive Halogens.......................................... E. The Determination of Reaction Rates for Extremely Slow Reactions ...................................

.......................

.

21 21 35 36

36 36 38 39 40 40 41 46 56 60 60 62 87

Use of Volumes of Activation for Determining Reaction Mechanisms E. Whalley

............................ ................................... ....................... 1. Introduction.. ................................. ... 11. Experimental Techniques..................... .......... 111. Theorv of Effect of Pressure on Reaction Rates..................................... A. The Transition-State Theory .................................... ......................... ......................... .................................. . B. Effectof Electrolytes on Volume of Activation C. Molecular Components of Volumes of Activat IV. Determination of Mechanisms A. Unimolecular Decomposition or Bimolecular Attack of Solvent on Ions ..............................

.

93 95

LOO

101

106 108 114 1 I5

VOLUME CONTENTS

6

B. Acidcatalyzed Reactions........................................................................................... C. Hydrolysis of Esters and Amides........................................................................................... D. Mechanisms of Specific Acid Catalysis in Solvents other than Water ................................... E. Some Rearrangements ........................................................................................................... F. Diels-Alder Reactions ............................................................................................................ G . Radical Polymerizations........................................................................................................ References ..............................................................................................................................................

.

120 i36

147 147 151 155 158

Hydrogen Isdtope Effects In Aromatic Substitution Reactions

H. Zollinger 1. Introduction ................................................................................................................................ ..................................................................... I1. Electrophilic Aromatic Substitutio A. Differentiation between SE2-and SE3-Mechanisms................................................................ .................................................................. < ...... B. Types of S, 2-Mechanisms.......... ......a .............................................................. C. Structural Characteristics of In D Isotope Effect Studies in the Benzidine Rearrangement ........................................................ 111. Nucleophilic Aromatic Substitution ............................................................................................ A . Benzyne Mechanism ......................................................................... B. Bimolecular Mechanism ........................................................................................................ IV. Homolytic Aromatic Substitution ............................................................................................... References ..............................................................................................................................................

.

163 164 164

I67 179 185 187 187 188 192 196

The Reactions of Energetic Tritium and Carbon Atoms With Organic Compounds

Arfred P. Worf

.

1 Introduction................................................................................................................................ II . The Hot-Atom Procem................................................................................................................ A. General Aspects and Product Formation .............................................................................. B Recoil Energy ........................................................................................................................ C. Bond Rupture Following the Nuclear Event ......................................................................... D. Charge State of the Recoil Atom After "Birth" ..................................................................... E. Slowing-Down Process ofthe Hot-Atom............................................................................... F. Reaction Models............................................................................................... I .......... G . Theoretical Approaches .......................................................... ,............................................. H Criteria for Differentiating Hot from Thermal Reactions ..................................................... I11. The Chemical System.................................................................................................................. A Annealing .............................................................................................................................. B Radiation Effects ................................................................................................................... C. Impurities .............................................................................................................................. D Isolation and Assay of Products............................................................................................ IV General Considerations in the Reactions of Tritium Atoms Produced by Nuclear Recoil .......... A. Production ofTritium ........................................................................................................... B. Assay of Tritiated Compounds .............................................................................................. C Radiation Damage to the System .......................................................................................... D . Charge State.......................................................................................................................... E. Radiochemical Yields and Product Distribution ................................................................... V . Major Reactions of "Hot" Tritium Atoms.................................................................................. A. Hydrogen Abstraction and Substitution................................................................................ B . ExcitationXkmnposition in Substitution ............................................................................. C Alkyl Group Substitution ...................................................................................................... D . "Hot" Radical Formation..................................................................................................... E. Double-Bond Addition Reactions ................................................. F . Heavy Atom or Group Substitution......................................................................................

.

.

. . . . .

.

202 204 204 206 207 207 208 209 211 214 217 217 218 219 220 221 ~~

~

221 222 222 225 225 227 221 227 228 229 229 229

1

VOLUME CONTENTS VI . Geometric and Stereochemical Results of the Substitution Reactions......................................... VII . Mechanisms of Formation of Hot Products in the Gas Phase.... ............................ ............................................................ A. General Considerations ... .................................... B. Mechanisms in Alkanes ......... .................................... C. Excitation-Decomposition Mechanisms .................... D. Inertial Effects........................................................... .................................... E Hot Free Radicals.................................................................................................................. F . Summary on Gas Phase Model .................................. G. Mechanisms of Hot Reactions in Gaseous Alkencs............................................................... ...................................................................... VIII . Mechanisms in Condensed Phases .............. A. Alkanes Alkenes and Alkynes ....................................... .............................................. B. Aromatic Compounds ........................................ ,.................................................................. ........................ C. Substitution of Heavy Atoms and Groups in Aromatic Molecules ........................ ............................ D. Summary................. IX. General Considerations ............................ A . Production of Energetic Carbon Atoms .............

230 231 231 . .

X. Reaction Mechanisms of Energetic Carbon Atoms in Hydrocarbons ......................................... ....................... A. Carbon-Atom Inscrtion .............................................. B. Methyne Formation ............................................................................................................... C. Methylene Formation ........................................................................................................... ........................... D. Methyl-Radical Formation .......... E. Reactions in Olefins ............................................................................................................... F . Phase Dependence ................................................................................................................. XI, Reactions of Energetic Carbon Atoms in Some Other Systems................................................... A. Reactions in Ammonia and Methylamine ............................................................................. B. Effect of Oxygen Concentration on Yields of Carbon.11 Products ........................................ C. Deuterium Isotope-Effects in Acetylene-"C and Ethylene-"C Production ............................. D Use of Accelerated Ion Beams in Studying Reactions at High Kinetic Energies.......... XI1. General Mechanism ..................................................... ........................................................ XI11. Conclusion ........................................................................................... Ackn~wledgment ................................................... References .,...........................................................

232 238 239 240 240 241 242 242 243 244 245 245 245 248 252 253 255 259 26 I 262 263 264 264 266 267 261 269 213 213 213

AUTHOR INDEX ................................................................................................................................ CUMULATIVE INDEX OF AUTHORS ......................................................................... CUMULATIVE INDEX OF TITLES ..............................................................................

219 289 289

.

.

............................

.

.

Advances In Physical Organic Chemistry Volume 3 Edited by V . Gold

CONTRIBUTORS TO VOLUME 3

....................................................................................................

Molecular Refractivity and Polarizability

R J. W. Le FPvre

v

VOLUME CONTENTS

8

1. Introduction ................................................................................................................................

...................,,.............

1 3 41 53 68 73 75 79

Gas-Phase Heterolysis

Allan Maccoll

........................

................................ ........

ys1s ......................

esults ....................................... .............................. ,..................................... V. Regularities in the Experimental Data ........................................................................................ VI. Homogeneous Catalysis of Gas-Phase Eliminations VII. General Conclusions................................................................................................................... References .........................................................,......,..,....,,,.......,......................................._. ..................

91 92 96 100 103 117 119 120

Oxygen Isotope Exchange Reactions of Organic Compounds

David Samuel and Brian L. Silver 1. Introduction ................................................................................................................................ 11. Experimental Methods

References ..............................................................................................................................................

123 125 128 147 168 174 181 182 183

N.M.R. Measurements of Reaction Velocities and Equilibrium Constants as a Function of Temperature

L. W . Reeves 1. Introduction and Scope 11. The Bloch Equations wi

References ..............................................................................................................................................

187 193 228 233 259 265

AUTHOR INDEX CUMULATIVE IN CUMULATIVE IN

27 1 28 I 28 1

..........................

...................................................... ............. ................................... ................................

VOLUME CONTENTS

9

Advances In Ph sical Organic Chemistry L m e4 Edited by V. Gold

CONTRIBUTORS TO VOLUME 4

....................................................................................................

v

The Reversible Hydration of Carbonyl Compounds

R P. Bell I. Introdu 11. Hydrati 111. Acidity of Carbonyl IV. Kinetics of Hydration and Dehydration Reactions ............................................... References .............................. .............................................................

21

Ionization Potentials

D. W; Turner 1. Introduction........... 11. The Measurement 111. Molecular Structu References ..............................

....................

.............................................................

31

.............................................................

69

Reactivity Indices in Conjugated Molecules: The Present Position

H. H.Greenwood and R Mc Weeney 11. Some Applications of the Indices ................................................... 111. Properties of the Secular Equatio IV. The Isolated Molecule Method ...................................... V. The Localization Method .................................................................................................. ......................................... VI. Relationship between the Indices .......

............................................................. VIII. The Physical Basis of Reactivity Indices .................................... IX. Reactivity Indices in Many-Electron Th X. Conclusions and Future Prospects ..........................................................

................................................................................

13 81 88 95 102 101 112 118 129 141 143

VOLUME CONTENTS

10

The Gas Phase Pyrolyses of Some Small Ring Hydrocarbons

H. M.Frey

................................... ning CyclobuteneRings

.................................................................

...............................

148 148 151 155 165 165 169 170 170 175 180 183 183 188 189 190 191

The Basicity of Unsaturated Compounds

H . 4 Perkampus

......................................

195 200 232 262 284 297 300

Spectroscopic Observation of Aikylcarbonium Ions in Strong Acid Solutions

George A. Olah and Charles U.Pittman. Jr. I. Introduction ...................................

V. Cyclopropylcarbonium Ions...........,........................................................ VI. Alkylarylcarbonium Ions References .................................................

305 307 307 324 333 338 345 349 357 357

11

VOLUME CONTENTS

Advances In Physical Organic Chemistry Volume 5 Edited by V. Gold

CONTRIBUTORS TO VOLUME 5

....................................................................................................

V

Polarography and Reaction Kinetics

P.Zuman

.....................

1

4 5 16 30

30 ..

35 31 50 50

.......................................

Electron-spin Resonance Studies of Short-lived Organic Radicals

R 0,C. Norman and B. C. Gilbert

....................,. E. Priming Reactions ..................................................

....................

..................... .....................

111. Results: Reaction Mechanisms......................................................... A. Oxidation .....................

*

......................

B. Reduction ..................... IV. Results: Structures and Rates .......................................

References ................

....................

..........................................

I..

...................

53 54 55 64 64 65 66 61 12 13 13 93 98 98 108 1 I3

VOLUME CONTENTS

12

Heat Capacities of Activation and their use6 in Mechanistic Studies G. Kohnstam 1. Introduction ................................................................................................................................ 11. Determination of Activation Parameters .....,...................((..............I..........................................

A. Rate Measurements...............................................

,............

............................................................. IV. Solvolytic Reactions A. Mechanism ........................... B. Activation Parameters ......................................................... C. The Interpretation of Heat Capacities and Entropies of Act D. Mechanistic Information ..................................................... V. Non-Solvolytic Reactions ........................... ...,... A, Rate-determining Proton Transfer Processes

.............,...................... ......................

.................

121 125 125 125 130 136 139 139 140 142 151

......................................,...................,......................................

162 162 163 165 165 167 169

Rates of Bimolecular Substitution Reactions in Protic and Dipolar Aprotic Solvents

A. J. Parker

................................... ......................................

..................... ...................... 1..

.I...

,.................................,....................

C. Nucleophilic Tendencies ....... VII. Finkelstein Reactions in DMF ............................................................................. ................,..... VIII. Some Linear Free Energy Relationships ..................................................................................... .....,..... References .............................,...............

173 177 177 180 181 184 191 191 20 1 204 208 209 209 213 213 216 217 22 1 225 228 232

General Base and Nucleophilic Catalysis of Ester Hydrolysis and Related Reactions S. L. Johnson I. Introduction .............................................................................. 11. The Tetrahedral Addition Intermediate .............................. ............................ ............. A. General Considerations

VOLUME CONTENTS

13 246 262 267 27 1 271 278 284 294 299 312 318 321 325

C. NucleophilicReactivity ..

The Reactions of Aliphatic Diazocompoundswith Acids

R. A. More O'Ferrall I. The Rate-Determining Steps A. Hydroxylic Solvents ....... .................................... ......................... B. Aprotic Solvents ................... 11. The Product-Determining Steps A. Ion Pair Phenomena .............................................................................................................. ............... B. Substitution,Rearrangement and Elimination ........ C. Carbonium Ions from Diazonium Ions ...... ..............I......

.................................... Acknowledgements References .......................................................................................................... AUTHOR INDEX CUMULATIVE IN CUMULATIVE INDEX OF TITLES ..................................................................................................

331 332 353 355 357 374 384 387 394 395 401

415 417

Advances In Physical Organic Chemistry Volume 6 Edited by V.Gold

CONTRIBUTORS TO VOLUME 6

....................................................................................................

v

Mechanisms of Formation and Reactions of Arynes at High Temperatures

E. K. Fields and S. Meyerson I. Introduction ................................................................................................................................ 11. Arynes from Aromatic Anhydrides .............................................................................................

1 5

VOLUME CONTENTS

14

A. Reactions of Benzyne with Benzene ...................................................................................... B. Reactions of Benzyne with Deuteriated Benzenes.................................................................. C. Arynes from Aromatic Anhydrides Other Than Phthalic ...................................................... D. Reactions with Chlorinated Benzenes ....................................................... E. Reactions with Pyridine ............................................................................. F. Reactions with Thiophene and Benzothiophene........................................ G. Reactions of Tetraphenylbenzynefrom Tetraphenylphthalic Anhydride .. 111. Benzyne from 0-Sulfobenzoic Anhydride ............................................................................. ......

.

V.

...................................... *.......................... Conclusion ............................................,..,.................,................................................................ ....................................................... ........................

5 8 i5 21 26 32

46 50 54 57 58

Developments in the Study of A-S,2 Reactions in Aqueous Solution . I . M. WiIliams,Jr. and M.M.Kreevoy

.......................................

.......................

>.......I

...................

A. Structureof the St C. Detailed Structure of Intermediates....................................................................................... D. Substituent Effects on Reactivity and the Electronic Structure of the Transition State......... E. Non-Adiabatic Processes....................................................................................................... ...............* .............................. IV. Conclusions, Apologies, and Acknowledgments. ............................ References ...................,........,.........,.....................................

63 64 64 79 83 85 85 88 92 94 95 97 98

Calculations of Conformations of Polypeptides

H. A. Scheraga 11. Conventions 111. Geometrical

................................... D. Hydrogen Bond ........................................... E. Distortion of Geometry ...... F. Role of Crystal Energy Calc

......................................................................... ..........,......................................

103 106 114 118 118 119 124 130 133 137 138

138

.....,.................................................................. ...,....................................,................

141 143 143 143 145

153

.......................................

...................... .,.................,.,

156 156

VOLUME CONTENTS

I5

B. Dipeptides.............................................................................................................................. C. Random Coil; End-tosnd Distance ....................................................................................... D. Helical Structures.......... E. Gramicidin-S........................... F. Oxytocin and Vasopressin ....... X. Conclusions.................................. References .............. ....... ................. . ............(................................................................................ ...

. .

..

...

157 159

I 79

Stereoselection in the Elementary Steps of Organic Reactions

S.I. Miller 1. Introduction ..........................

.....................................................................................................

F. Substitution at Unsaturated Atoms........................ G. Addition and Elimination ..................................................................................................... H. Rearrangements .................................................................................................................... IV. Miscellaneous Factors and Stereoselection .... A. Excited States and Molecular Vibrations............................................................................... B. Magnetic Resonance Data ..................................................................................................... C. Collinearity and Coplanarity of Reacting Centers .................................... D. Principles of Least Motion (PLM) ........................................................... E. Electrical Effects .................................................................................................................... V. Stereoselection Deriving from Steric and Conformational Factors ... A. Steric Effects.................................................. ,........................... ........................................... B. Conformational Analysis................................................................................. ....................... VI. Conclusions............................................................................. ... References .... ...... .................... ..... ......... ... ... ................................... ....... ..................................

185 188 188 191 20 1 202 217 235 243 246 265 272 287 293 293 295 296 30 I 303 308 308 313 32 1 323

AUTHOR INDEX ........,..................... CUMULATIVE INDEX OF AUTHO CUMULATIVE INDEX OF TITLES

333 345 347

,

......................

Ill. Bonding Theory and Stereoselection..

B. Cycloadditions....................................... C. Sigmatropic Migrations,........................ D. Sigma-Sigma and Sigma-Pi Switch........

........... .......................................... ................................. ......I..

I

.. . .

. ..

#.

.

4..

. .

................................ *

.................................

Advances In Physical Organic Chemistry Volume 7 Edited by V. Gold

CONTRIBUTORS TO VOLUME 7

.....................................................................................................

v

VOLUME CONTENTS

16

Nucleophilic Vinylic Substitution

Zvi Rappoport I. scope........................... 11. Introduction ................

.........................

n with Rearrangement (The “Abnormal”Substi

.,....................,

.............................................................................

VIII. Substitutionin the Presence of Metal Salts ................................................................................. ................................... Acknowledgments ..................

i 2 5 5 10 31 62 13 74 74 75 91 92 98 102 107 107 108 108

The Reactions of Hydrated Electrons with Organic Compounds

M. Anbar 1. Reactions of Hydrated Electrons with Different

A. Saturated Hydrocarbons, Alcohols, Ethers a B. Alkenes ......................................................... C. Carbonylic Compounds..................................................

.....................

............................................* ..........

...........................

.............

......................... .....................

y Acids and Steroids ..... ptides ............................

...................................

IV. Conclusion............................................................................................. References ...................... ........................................................................................................................

117 117 118 119 I 24 126 128 131 134 135 136 138 139 139 140 141 142 143 144 148 148

Structure and Mechanism in Carbene Chemistry

D. Bethell I. Introduction ................................................................................................................................

153

VOLUME CONTENTS A. Definitions and Scope ........................................................................................................... B. Nomenclature and Formalism ...............................................................................................

IV. Mechanisms of Reaction of Carbenes in Solution A . Excitation, Multiplicity and Reactivity.................................................................................. B. Insertion .................... C. Addition to Olefins ....

17 i53 i57

I57 157 160 169 169 I70 177 184 187 187 190 194 200 202 202

Meisenheimer Complexes

M . R Crampton 1. Introduction .................................................................

A . Historical Aspects ................................................................................................................. B. Survey of the Reaction0 of Aromatic Nitro-Compounds with Bases ..................................... I1 Structural Studies of the Adducts................................................................................................ A. Adducts from Picryl Ethers ................................................................................................... B. Adducts from 1.3. 5-Trinitrobenzene C Products from Picramides (2,4,6-Trinitroan D . Adducts from Other Substituted Trinitrobe E. Adducts from mera-Dinitrobenzenes.......... F. Adducts with Other Compounds ........................................................................................... I11. Equilibrium and Kinetics Studies................................................................................................ A. Variation of Reactivity with Substrate Structure ...... B. Variation of Reactivity with the Attacking Nucleophile ........................................................ C. Effects of Solvent on the Stabilities of the Adducts ............................................................... References ..............................................................................................................................................

.

.

...........

211 211 212 214 215 219 227 233 234 239 241 242 250 252 254

Protolytic Processes in H.0-D. 0 Mixtures

V. Gold I . Introduction................................................................................................................................ A. General Background ............................................................................................................. B. List of Important Symbols............................ ............................................. I1 . “Simple” Equilibrium Theory for Reactions Inv ydrogen Ions ....................... A. Assumptions................................................ ............................................ B. Acid Dissociation as a Function of n ........... ............................................ C. Extension of Simple Equilibrium Theory to Acid Catalysis................................................... D. Acid Catalysis by Species other than H,0’............................................................................ I11. Solvent Isotope Effects in Relation to the Brmsted Catalysis Law ............................................. A. Acidity Constants of Hydrogen Ions ................................................... B. Application of the Catalysis Law ........................................................................................... IV . Critique and Possible Improvements of Simple Theory ............................................................... A. The Formula of the Hydrogen Ion and the Value of the Fractionation Parameter I .............. B. The Rule of the Geometric Mean ..........................................................................................

259 259 263 265 265 268 271 277 217 277 279 281 281 284

18

VOLUME CONTENTS 287 294 295 291 312 312 316 319 322 322 323 325 321

A. Summary of Availab B. Some Case Studies VI. Catalysis by Species ot A. Carboxylic Acids ..

AUTHOR INDEX CUMULATIVE INDEX OF TITLES ...................................................................................................

333 347 349

Advances In Physical Organic Chemistry Volume 8 Edited by V. Gold

CONTRIBUTORS TO VOLUME 8

....................................................................................................

v

The Study of Free Radicals and Their Reactions at Low Temperature Using a Rotating Cryostat J. E. Bennett, B. Mile, A. Thomas and B. Ward 1. 11.

111. Specific Free Radicals

..............................

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D. Substituted Ally1 Radicals E. Unsuccessful Preparations IV. Specific Radical Ions.............. B. Ketone Radical Anions V. Solvated Electrons.............

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VOLUME CONTENTS

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B. Trapped Electrons in Alcohols....