AdministratorText BoxRef. 547.21 OLA V.2 Pt.1-Pt.2

xiv Contents-Volume I1

b. a-Methylstyrenes . c. Unconjugated aryl-substituted olefins d. Polyaryl-substituted olefins .

K. Alkylation with Cyclooleha . a. Unbranched cycloolefins . b. Branched cycloolefins .

L. Telomerization . 2. Halogenated and Nitrated Benzenes .

A. Halogenated Benzenes . B. Nitrated Benzenes .

3. Polycyclic Aromatic Hydrocarbons . A. Naphthalenes . B. Tetralin and Indane . C. Tricyclics . D. Polyphenyl Derivatives .

111. Alkylation of Phenols and Derivatives . 1. Theory . 2. Phenols, Cresols and Dimethylphenols . .

A. Thermal Alkylation . B. Alkylation with n-Olefins .

a. Ethylene . b. Propene . c. n-Butene and higher .

C. Alkylation with Isoolefins . a. Phenol. b. Cresols and dimethylphenols .

D. Alkylation with Olefin Polymers . . a. Diisobutylene . b. Triisobutylene and tetraisobutylene c. Polypropenee .

E. Alkylation with Cyclic Olefins . 3. Halogenated and Nitrated Phenols .

A. Halogenated Phenols . B. Nitrophenols .

4. Higher Phenols. . 5. Polyhydric Phenols and Bisphenols . 6. Aromatic Ethers . 7. Methoxyphenols . 8. Halogenated asd Nitrated Aromatic Ethers 9. Phenoxide Catalysts .

IV. Alkylation of Thiophenols and their Ethers . V. Alkyhtion of Aromatic Amines .

VI. Alkylation of Furans and Thiophenes . 1. Furass . 2. Thiophenes ,

VII. Alkylation of Aromatic Acids . VIII. Alkylation with Alkanes and Cycloalkanes . .

1. Alkanes . 2. Cycloalkanes .

IX. Appendix . .

XV. Alkylation of Allcenes by Robe~t I. Introduction . 11. Dienea . .

3. Summary.

Alkylation of: Benzene (Tables 1-8). . . 116 Toluene (Tables 9-14) . . 147 C8 Aromatics (Tables 15-19) . . 159 Co Aromatics and higher (Tables 20-23) . . 170 Indanes (Table 24) . . 180 Naphthalene and derivatives (Tables 25-29) . . 181 Tetralins and halogenated tetralins (Table 30) . . 187 Polyphenyl hydrocarbons (Table 31) . . 188 Tricyclic hydrocarbons (Table 32) . . 190 Halogenated and nitrated benzenes and homologs (Tables 33, 34) . . 192 Phenol (Tables 36-41) . . 196 Cresols (Tables 42, 43) . . 211 Higher phenol homologs (Table 44) . . 219 Indanols and naphthols (Table 45) . . 222 Halogenated phenols and nitrophenols (Tables 46, 47) . 223 Anisole (Table 48) . . 226 Higher ethers (Table 49) . . 228 Halogenated anisoles (Table 50) . . 231 Polyhydric phenols and bisphenols (Table 51) . . 232 Methoxyphenols and dimethoxybenzenes (Table 52) . 235 Thiophenol (Table 53) . . 236 Thiophenol homologs and ethers (Table 5 3 ~ ) . . 237 Aniline (Tables 54, 55) . . 238 Aniline homologs and derivatives and phenylenediamine (Table 56) . . 240 Heterocyclic amines (Table 57) . . 243 Aromatic acids (Table 58) . . 245 Thiophene (Tables 59-63) . . 247 Thiophene derivatives (Table 64) . . 252 Fur-, pyrrole, and phenthiazine (Table 65) . . 253 Aromatics with alkanes (Table 66) . . 254 Aromatics with cycloalkanes (Table 67) . . 257

XV. Alkylation of Aromatics with Dienes and Substituted Alkenes by Robert Koncos and B. S. Friedman . . 289

I. Introduction . . 289 11. Dienes . . 290

1. Side-chain Structure . . 290 2. The Effect of Catalysts and Conditions on the Alkenyla-

tion Reaction . . 298 3. Summary. . 300

111. Unsaturated Halides . . 300 1. Vinyl Halides . . 300

A. Monohalides . . 300 B. Polyhalides . . 303 C. Side Reactions . . 305

xvi Contents-Volume I1

2. Ally1 Halides . . 307 A. Monohalides . . 307 B. Polyhalides . . 312

3. Miscellaneous Halides . . 313 4. Summary. . . 313

IV. Unsaturated Alcohols and Ethers . . 313 1. Unsaturated Alcohols . . 313 2. Unsaturated Ethers . . 316 3. Summary. . . 318

V. Unsaturated Acids . . 318 1. Addition . . 319 2. Rearrangement. . . 323 3. Replacement . . 324 4. Hydrogen Transfer . . 327 5. Summary. . . 327

VI. Unsaturated Esters. . 328 1.Summary. . . 331

VII. Unsaturated Aldehydes . . 331 VIII. Unsaturated Ketones . . 332

1. Addition . . 332 2. Replacement . . 339 3. Hydrogen Transfer . . 340 4. Miscellaneous Reactions . . 341 5. Summary. . . 342

IX. Unsaturated Acid Chlorides . . 342 X. Unsaturated Nitriles . . 344

XI. Miscellaneous Unsaturated Alkylating Agents . . 345 XII. Appendix . . 347

Alkylation with dienes (Tables I-VIII) . . 347 Alkylation with unsaturated halides (Tables IX-XIV) . 368 Alkylation with unsaturated alcohols and ethers (Tables XV-XVII) . . 368 Alkylation with unsaturated acids (Tables XVIII-XXII) 373 Alkylation with unsaturated esters (Tables XXIII- XXVIII) . 381 Alkylation with unsaturated ketones and aldehydes (Tables XXIX-XXXIV) . . 389 Alkylation with unsaturated nitriles (Table XXXV) . 400 Alkylation with miscellaneous unsaturated compounds (Tables XXXVI-XXXVIII) . . 401

Con

XVII. Alkylation of Aromatias Drahowzal . I. Introduction .

11. Catalysts and Solvents

10. Aqueous Metal

B. Zinc . .

V. Mechanism . . 1

1 XVIII. Alkylation of Aro

XVI. Alkylation of Aromatics with Alkynes by V. Franzen . . 413 AhSch&heim . I. Alkylation with Acetylene . . 413 4 I. Introduction .

IT. Alkylation with Haloalkynes . . 415 11. Consideration of

<

C

xviii Contents-Volume I1

1. Carbonium-ion Reactions . . 480 2. Aromatic Substitution . . 481

A. Alkylation, Isomerization, and Disproportionation 482 B. Conclusions . . 485

111. Alkylation using Alcohols as Alkylating Agents . . 486 1. Friedel-Crafts Halides . . 486

A. Alkylation by Alcohols, using Boron Fluoride . . 486 a. Alkylation of benzene and phenol and their

homologs . . 488 b. Alkylation of naphthalene and other poly-

cyclic aromatics. . . 494 c. Alkylation of esters . . 495 d. Miscellaneous . . 496

B. Alkylation by Alcohols using AlC1, . . 497 a. Alkylation of benzene and phenol and their

homologs . . 497 b. Miscellaneous . . 506

C. Other Halides as Alcohol Alkylation Catalysts . 508 a. Zinc chloride . . 508 b. Ferric chloride . . 513 c. Stannic chloride and titanium tetrachloride . 513

2. Proton-donating Acids . . 514 A. Alkylation by Alcohols using Sulfuric Acid . 617 B. Alkylation by Alcohols using Phosphoric Acid . 622

3. Metal Oxides . . 624 A. Alkylation of Benzene and Phenols by Alcohols 525 B. Alkylation of Naphthalene by Alcohols . . 527 C. Alkylation of Ammonia by Alcohols . . 528 D. Alkylation of Arnines by Alcohols . . 631 E. Alkylation of Heterocyclics by Alcohols . . 533 F. Alkylation of Mercaptans and Hydrogen Sulfide

by Alcohols . . 534 IV. Alkylation using Acyclic Ethers as Alkylating Agents . 534

1. Friedel-Crafts Halides . . 536 A. Alkylation of Benzene and its Homologs by

Ethers using Boron Fluoride . . 636 B. Alkylation of Naphthalene by Ethers using

Boron Fluoride . . 638 C. Alkylation of Phenols by Ethers using Boron

Fluoride . . 639 D. Alkylation of Active Methylene Groups by

Ethers using Boron Fluoride . . 539 2. Metal Oxides . . 541

A. Alkylation of Benzene and its Homologs by Ethers using Metal Oxides . . 541

B. Alkylation of Naphthalenes by Ethers using Metal Oxides. . 542

C. Alkylation of Phenols by Ethers using Metal Oxides . . 542

V. Alkylation using

I. Introduction . 1. General Mech

11. Addition of Ketene

2. Reactions

IV. Condensation of

2. Reactions of

V. Miscellaneous Addi VI. Appendix . .

I. Introduction . 11. .Alkyl Sulfates, S

111. Alkyl Borates . IV. Alkyl Chlorofomtea,

V. Akyl Benzen

VI. Akyl p-Toluen

VII. Alkyl Perchlorates

VIII. Akyl Nitrates .

XXI. Haloalkylations by I. Introduction

xx Contents-Volume I1

c. Indan . d. Naphthalene and derivativee . e. Anthracene and phenanthrene . f. Miscellaneous hydrocarborn . g. Polymeric hydrocarborn (polystyrenes) .

B. Heterocyclic Compounds . a. Furan derivatives . b. Thiophene and derivativee . c. Selenophene derivatives . d. Pyrazoles and isoxazoles . e. Benzofuram and benzopyram . f. Benzothiophenes . g. Quinolines . h. Pyrimidines . i. Miscellaneous heterocyclic compounds .

C. Haloaromatic Compounds . a. Haloarenes . b. Haloaralkanes .

D. Phenols and Phenol Ethers . E. Aldehydes and Ketones . F. Nitrogen Compounds .

a. Nitroaromatics . b. Amines, amides, imines, and imides . c. Azo compounds .

G. Acids and Esters . H. Sulfur Compounds .

a. Thiophenol ethers (sulfides) . b. Sultones and sultams .

I. Silicon Compounds . 4. Bromomethylation . 6. Iodomethylation . 6. Fluoromethylation . 7. Haloethylations, Halopropylatiom, and Halobutyla-

tiorn . A. With Aldehydes and Haloalkyl Ethers . B. With Haloalkenes . C. With Di- and Polyhaloalkanes . D. With Haloalcohols . E. With Di(chloroalky1) Sulfates, Haloalkyl Chloro-

sulfonates, and Haloalkyl-p-tosylates . 8. Mechanism .

A. Aldehydes and Hydrogen Halides or Haloalkyl Ethers . a. Orientation . b. Rates . c. General aspects of mechanism .

B. Haloalkenes . C. Dihaloalkanes . D. Haloalcohols E. Haloalkyl Esters .

Con

111. Haloakylation of Alip 1. Alkanes . 2. Alkenes . 3. Ketones and A1

XXII. Cyclialkylation of A ~ O

I. Introduction . 11. Intramolecular Ring Cl

1. Intramolecular

xxii Contents-Volume I1

B. Aromatic Cyclodehydration . a. Cyclodehydrations yielding polycyclic aro-

matic hydrocarbons: naphthalene, phenan- threne, mthracene, and derivatives .

b. Cyclodehydratione yielding heterocyclic system .

111. Cyclialkylation by Di- and Polyfunctional Alkylating Agents .

1. Cyclialkylations with Dihalides . 2. Cyclialkylations with Diols and Derivatives and with

Tetrahydrofuram . 3. Cyclization involving Acylation-Alkylation .

IV. Cyclialkylation of Aromatic Hydrocarbons with Olefins . 1. Cyclialkylation of Styrene Compounds with 0leh.e

to yield Indam . 2. Cyclialkylations of Aromatic Hydrocarbons involving

Hydride-ion Tramfer Proceases .

XXI11. Dehydrogenation Condensation of Aromatics (Scholl and Related Reactions) by A. T. Balaban and C. D. Nenitzescu 979

I. Introduction . . 979 11. Inter- and Intramolecular Scholl Reaction . . 979

1. Definition of the Scholl Reaction . . 979 2. Historical . . 980 3. Scope and Limitations . . 982 4. Reaction Mechanism . . 983

A. The First Stage, Protolytic Reaction . . 987 B. The Second Stage, Electrophilic Substitution . 989 C. The Third Stage, Dehydrogenation . . 993

6. Thermodynamic Aspects . . 997 6. Technique of the Reaction . . 998 7. Allied Reactions . . 1000

A. General Considerations . . 1000 Table I. General scheme of Friedel-Crafts reactions . . 1001

B. Cyclialkylations . . 1001 C. Alkaline Fusion . . 1002 D. Oxidation . . 1003

8. Classification and Review of Scholl Reactions . . 1004 Table 11. Intermolecular: Hydrocarbons . 1006 Table 111. Intermolecular: Miscellaneous . 1008 Table IT. Intramolecular: Fluorene . . 1010 Table V. Intramolecular : Carbazole . . 10 1 1 Table VI. Intramolecular: {1,5) . . 1012 Table VII Intramolecular: { I ,2,5) . . 1014 Table VIII. Intramolecular: {1,3,5) . . 1020 Table IX. Intramolecular: {1,2,4,5) . . 1020 Table X. Intramolecular: {1,2,3,5) . . 1022

111. Related Reactions

2. Reaction of

XXIV. Isomerization of McCaulay . .

I . Introduction . 11. Measurement of Re

111. Nature of Arene

V. Concluaion . .

XXV. Alkylation of S

I. Introduction . 11. Thermal Alkylation

b.

>v

xxiv Contents-Volume I1

4. Nitroalkane Solutions of Aluminum Chloride . . 1087 6. Aluminum Chloride Double Salts . . 1098 6. Aluminum Bromide . . 1098 7. Boron Fluoride . . 1099 8. Zirconium Chloride . . 1100 9. Hydrogen Fluoride . . 1100

A. Propene . . 1101 B. n-Butylenes . . 1102 C. Isobutylene . . 1104 D. Higher Olefins . . 1104

10. Sulfuric Acid . . 1104 A. Propene . . 1105 B. n-Butylenes . . 1105 C. Isobutylene . . 1106 D. Higher Olefins . . 1106 E. Cyclohexene . . 1108

V. Catalytic Alkylation of Isopentane with Olefins . . 1109 1. Boron Fluoride . . 1109 2. Hydrogen Fluoride . . 1109 3. Sulfuric Acid . . 1110

VI. Catalytic Alkylation of Hexanes wit11 Olefins . . 1110 VII. Reaction of Isoalkmes with Alkyl Halides . . 1111

1. With Alkyl Chlorides . . 1111 A. Aluminum Chloride . . 1111 B. Nitromethane Solutions of Aluminum Chloride . 1112 C. Sulfuric Acid . . 1112 D. Dichloroaluminum Acid Sulfate . . 1113

2. With Alkyl Bromides . . 1114 3. With Alkyl Fluorides . . 1114

A. Boron Fluoride . . 1114 B. Hydrogen Fluoride . . 1118

VIII. Reaction of Isoalkmes with Alcohols . . 1119 1. Hydrogen Fluoride . . 1119 2. Sulfuric Acid . . 1120

IX. Condensetion of Isobutme with Chloroolefins . . 1121 X. Catalytic Alkylation of Cycloparaffins . . 1123

1. Aluminum Chloride . . 1123 A. Methylcyclohexane . . 1123 B. Cyclohexane . . 1124 C. Methylcyclopentane with t-Butyl Chloride . 1126

2. Aluminum Bromide . . 1126 3. Hydrogen Fluoride . . 1127 4. Sulfurio Acid . . 1128

A. Methylcyclopentene . . 1128 B. Alkyloyolohexanes . 1129

XXVI. Condensation of alkenes by Louis S

I. Condensation of Alkyl

3. Butenes . 4. Cyclohexene 5. Alkadienes .

11. Condensation of Cyc

111. Condensation of Alkyl

XXVII. Alkylation of

I. Introduction .

xxvi Contents-Volume I1

IV.

v. VI.

VII.

VIII.

IX.

Reactions of Alkenes end Cycloalkenea with Carbonyl Compounde . . 1177

1. With Formaldehyde . . 1177 2. With Other Carbonyl Compounds . . 1180

Reactions of Simple Hydroxy-substituted Alkenes . . 1180 1. Non-allylic Olefins with Aldehydes and Ketones . 1180 2. Allylic Olefim with Aldehydes and Ketones . . 1182

Halogen-substituted Olefh with Aldehydes . . 1185 Conjugated Olefins with Aldehydes and Ketones . . 1187 Aryl-substituted Olefins . . 1189

1. Styrene and Ring-substituted Styrenes . . 1189 2. Substituted Vinylaromatics . . 1191

A. Halovinylbenzenes . . 1191 B. Miscellaneous Substituted Vinylaromatics . . 1192

3. a-Methylstyrenes . .. 1194 Lewis Acid Catalyzed Reactions of Unsaturated Compounds with Carbonyl Compounds . . 1196 Thermal Reactions of Carbonyl Compounds with Un- saturated Compounds . . 1198 Mechanism of the Prim Reaction . . 1202

XXVIII. Isomerization of Saturated Hydrocarbons by Herman Pines and Norman E. Hoffm.n . . 1211

I. Introduction . 1211 11. Generalized Mechanism . . 1212

111. Carbonium Ions . . 1213 1. Formation of Carbonium Ions . . 1213

A. Addition of Protons to Olefim. . 1213 B. Dissociation of Halides . . 1213 C. Oxidation of Saturated Hydrocarbons . . 1213 D. Protonation of Alcohols . . 1214 E. Other Methods . . 1214

2. Reactions of Carbonium Ions . . 1214 A. Hydride Shift . . 1214 B. Alkide Shift . . 1214 C. Abstraction of a Hydride from a Hydrocarbon

Molecule . . 1215 D. Loss of a Proton . . 1216 E. Addition of a Cmbonium Ion to en O l e h or

Aromatic . . 1216 F. Reduction . . 1216 G. Bete-Scission . . 1217 H. Exchange between Cerbonium-ion Hydrogens

and Acid Hydrogen . . 1217

IV. Lewis Acide .

B. Butmea

VIII. Conclusion . .

r 1.

1 ! [

xxviii Contents-Volume I1

11. The Electrophilic Character of the Reaction . . 1262 1. The Position of Attack in the Aromatic Co~~~pound,

and Exchange Reactivity . . 1262 A. Substituents in the Benzene Nucleus . . 1262 B. Condensed Polycyclic Aromatic Hydrocarbons . 1265 C. Other Systems . . 1268

2. The Interpretation of Quantitative Comparisons of Exchange Reactivity . . 1268

3. The Medium and Catalyst Systern . . 1269 111. Reaction Mechanism . . 1270

1. The Composition of the Transition State. . . 1270 2. The Potential-energy Profile . . 1275 3. Isotope Effects . . 1279

IV. The Application of Hydrogen Exchange to the Study of Complex Catalyst Systems . . 1284

XXX. Polymerization by D. C . Pepper . . 1293 I. Scope . . 1293

11. Introduction . . 1293 111. Initiating Agents and Systems . . 1294

1. Protonic Acids . . 1295 2. Friedel-Crafts Halides . . 1296 3. Carbonium Salts . . 1298 4. Cationogenic Substances . . 1299 5. High-energy Radiations . . 1300

IV. Monomers . . 1300 1. Alkenes . . 1301 2. Vinyl Ethers . . 1302 3. Styrene and Derivatives . . 1303 4. Heterocyclic Monomers. . . 1305 5. Miscellaneous . . 1305

V. Solvents . . 1306 VI. Experimental Conditions . . 1307

VII. Polymer Structure . . 1308 1. Head to Tail Addition: Chain Branching . . 1308 2. Stereoregularity . . 1309

VIII. Mechanisms . . 1310 1. Carboniwn-ion Mechanism (Proton-initiated) . . 1310 2. The Polarized Bond Mechanism . . 1311 3. Water Co-catalyzed (Proton-initiated) Mechanism . 1312 4. Carbonium-ion Initiated (Halide Co-catalyzed)

Mechanim . . . . . 1312 5. Propagation Reactions . . 1315

7. Ions or Ion Pairs

IX. Kinetics . . 3 1. General consider$ 2. Non-stationary 3. Equilibrium Ionic 4

X. Energetics . XI. Solvent Effects . 1

XII. Copolymerization . ;

Index . . .