Phase-Transfer Catalysis: Fundamentals, Applications, and Industrial Perspectives

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Springer Science & Business Media, 30.06.1994 - 668 Seiten
Since 1971 when useful working concepts for the technique of phase-transfer catalysis (PTC) were introduced, the understanding, development, and applica tions of this method for conducting organic reactions has expanded exponentially. PTC has brought vast new dimensions and options to chemists and chemical engineers. From its use in less than ten commercial processes in 1975, PTC use has increased so that in the early 1990s it is involved in more than 600 industrial applications to manufacture products valued at between 10 and 20 billion U.S. dollars. PTC is widely used for simple organic reactions, steps in synthesis of pharmaceuticals, agricultural chemicals, perfumes, ftavorants, and dyes; for specialty polymerization reactions, polymer modifications, and monomer synthe sis; for pollution and environmental control processes; for analysis oftrace organic and inorganic compounds; and for many other applications. Often, PTC offers the best (and sometimes only) practical technique to obtain certain products. The authors experience in teaching a short course on phase-transfer catalysis has shown to us that a newcomer to PTC can easily be frustrated and confused by the large amount of information available in the literature and in patents. The purpose of this book, therefore, was to bring this information together in a logical and user-friendly way, without sacrificing matters of scholarly and fundamental importance.
 

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Inhalt

Basic Concepts in PhaseTransfer Catalysis
xiii
B Basic Steps of PhaseTransfer Catalysis
xiv
C The PTC Reaction Rate Matrix
3
D Anion Transfer and Anion Activation
4
2 Anion Activation
9
E Effect of Reaction Variables on Transfer and Intrinsic Rates
10
1 Catalyst Structure
11
2 Agitation
12
7 Sulfite Displacement
364
9 Hydroxide Anion Displacements
365
10 Carbonate and Bicarbonate Anion Displacement
366
11 Displacement with Peroxide and Superoxide Anions
367
12 Phosphide and Phosphinite Anion Displacements
368
PhaseTransfer Catalysis Reaction with Strong Bases
381
A CAlkylation
382
2 Aldehydes
389

3 Kind and Concentration of Inorganic Reagent Amount of Water Added
13
4 Amount and Kind of Organic Solvent Used If Any
14
5 Temperature and Microwave Heating
15
F Outline of Compounds Used as PhaseTransfer Catalysts
16
2 Insoluble Catalysts
18
3 Catalysts for VaporPhase Reactions
19
PhaseTransfer Catalysis Fundamentals I
21
B Structural Factors Affecting the Distribution of Anions Between Aqueous and Organic Phases
22
C Structural Factors Affecting the Distribution of PhaseTransfer Catalyst Cations Between the Aqueous and Organic Phases
24
D Effects of the Organic Phase Polarity on the Distribution of Phase Transfer CationAnion Pairs
27
E Effects of Changes in Organic Phase Polarity During Reaction
29
F Factors Affecting the Distribution of PhaseTransfer Catalyst CationAnion Pairs Between an Organic Phase and an Aqueous Phase Containing Hydro...
30
G Effect of Hydration of the Transferred Anion and the Effect of Inorganic Salt andor Hydroxide Concentration in the Aqueous Phase
38
PhaseTransfer Catalysis Fundamentals II
46
B LiquidLiquid PTC
47
2 HydroxidePromoted Reactions of Organic Acids
87
3 Alternative PTC Mechanisms Involving Hydroxide Ion
104
C SolidLiquid PTC
106
1 Complexation and Solubilization of Potassium Salts with 18Crown6
109
2 Simple Displacement Reactions
111
PhaseTransfer Catalysts
121
B Use of Quaternary Salts as PhaseTransfer Catalysts
123
2 Special Quaternary Salts as PhaseTransfer Catalysts
140
C Macrocyclic and Macrobicyclic Ligands
151
2 Croplands
153
3 Special Crowns
154
D PEGs Tris 36dioxaheptylamine TDA1 and Related Ethoxylated Compounds as PhaseTransfer Catalysts
156
2 Phase Distribution Behavior of PEGs
157
3 PEGs and Ethers as PhaseTransfer Catalysts
160
Ethoxylate Derivatives as PTC
163
E Other Soluble Polymers and Related Multifunctional Compounds as PhaseTransfer Catalysts
169
F Use of Dual PTC Catalysts or Use of Cocatalysts in PhaseTransfer Systems
173
1 Use of Dual PTC Catalysts
174
2 Use of Alcohols and Other Weak Acids as Cocatalysts in Hydroxide Transfer Reactions
175
3 Use of Metal Compounds and Salts as PTC Cocatalysts
176
4 Use of Iodide as a Cocatalyst
177
2 Transfer of Acids
181
3 Transfer of Water
182
4 Transfer of Metals and Metal Hydrides
183
6 Transfer of Formaldehyde
184
9 Transfer of Ammonia
185
H Separation and Recovery of PhaseTransfer Catalysts
186
2 Distillation Methods
187
Insoluble PhaseTransfer Catalysts
205
B PTC Catalysts Bound to Insoluble Resins
206
2 Some Examples of Use of ResinBound PTC Catalysts and Comparisons with Soluble Catalysts
208
4 Effects of Reaction and Catalyst Parameters on Triphase Catalyst Effectiveness
219
5 Kinetics of Reactions Catalyzed by ResinBound PTC Groups
245
C PhaseTransfer Catalysts Bound to Inorganic Solid Supports
246
1 PTC Catalysts Adsorbed on Inorganic Supports
247
2 Catalysts with PTC Functions Chemically Bonded to Inorganic Supports
248
D PTC Catalysts Contained in a Separate Liquid Phase ThirdLiquid Phase Catalyst
250
Variables in Reaction Design for Laboratory and Industrial Applications of PhaseTransfer Catalysis
264
1 StructureActivity Relationships of Quaternary Ammonium Catalysts
265
2 StructureActivity RelationshipsOther Catalysts
284
3 Catalyst Stability
286
4 Catalyst Separation and Recycle
290
5 Commercial Catalyst Reference
301
1 Choice of Solvent and the Nature of the Chemical Reaction
303
2 Stabilization of the Transition State and Solvation of the Anion
304
3 Solubility of the CatalystAnion PairComplex in the Organic Phase
305
5 Solvent and the Nature of the Two Phases
308
6 Examples of Effect of Solvent
309
7 SolventFree PTC
312
8 Choice of Solvent and Process Aspects
313
C Presence of Water
316
D Agitation
317
E Choice of Anion Leaving Group and Counteranion
320
F Choice of Base
323
G Guidelines for Exploring New PTC Applications
324
PhaseTransfer Catalysis Displacement Reactions with Simple Anions
337
1 Important Factors in PTC Displacement Reactions
338
2 Characteristics of Various Anions for Simple PTC Displacement Reactions
340
B Behavior of Various Anions in PTC Displacement Reactions
341
2 Halide Displacement and Exchange Reactions
345
3 Displacement with Carboxylate Anions
353
4 Azide Displacements
356
5 Sulfide and Disulfide Displacements
360
6 Thiocyanate Displacement
362
3 Esters and Carboxylic Acids
390
5 Nitriles
393
6 Sulfones
396
B NAlkylation
398
2 Amides
404
3 Amines
406
C OAlkylationEtherification
408
2 Etherification of Phenoxides
411
D SAlkylationThioetherification
416
E Dehydrohalogenation
418
F Carbene Reactions
422
2 Dibromocarbene Addition
424
3 Mixed Dihalocarbene Addition
425
G Condensation Reactions
428
2 Aldol Condensation
429
3 Wittig
431
4 Darzens
433
5 Other Condensations
435
H Deuterium Exchange Isomerization and Oxidation
436
PhaseTransfer Catalysis Polymerization and Polymer Modification
450
2 Anionic Polymerizations
477
3 RadicalInitiated Polymerizations
479
C Chemical Modification of Polymers
482
2 Chemical Modification of Polymer Terminal Positions
487
3 Chemical Modification of Pendant Groups Attached to Polymer Backbone
488
PhaseTransferCatalyzed Oxidations
498
2 Transfer of Permanganate into Organic Phases
499
3 PTC Permanganate Oxidations
501
C Oxidations with Hypochlorite and Hypobromite
506
3 Oxidation of Amines Amides Thioamides and Related Compounds
510
4 Oxidation of Sulfides and Related Compounds
512
6 Oxidation of Nonoleftnic Hydrocarbons
516
D PTC Oxidations with Hydrogen Peroxide
519
2 Hydrogen Peroxide Oxidations
520
E PTC Air or Oxygen Oxidations
532
2 PTC Involvement in FreeRadical Oxidations
536
4 PTC with Singlet Oxygen Generation
537
5 TransitionMetalMediated Oxidations Involving PTC
538
2 Electrochemical Regeneration of Chromium Oxidants in Combination with PTC Systems
545
I PTC Carbon TetrachlorideSodium Hydroxide Oxidations
546
J PTC Oxidations with Periodate and Related Oxidizing Anions
547
2 Ruthenium as Cocatalyst
548
M PTC Oxidations with Superoxide
549
O PTC Oxidations with Other Oxidants
550
PhaseTransferCatalyzed Reductions
563
2 Azide Reductions
564
3 Other PTC Borohydride Reductions
565
B Lithium Aluminum Hydride Reductions
566
D Reductions with SulfurContaining Anions
567
E Hydrogenation
568
F Reductions with Formaldehyde
569
H Photochemical Reduction
570
PhaseTransfer Catalysis Chiral PhaseTransfer Catalyzed Formation of CarbonCarbon Bonds
574
B Alkylation Reactions
575
2 Alkylation of 23Dichloro5methoxy2npropyllindanone with 13Dichloro2butene in Toluene50 Aqueous Sodium Hydroxide
582
3 Asymmetric Alkylation of Oxindoles
584
4 Synthesis of Chiral Amino Acids
585
5 Michael Addition Reactions 5p
587
PhaseTransfer CatalysisTransition Metal Cocatalyzed Reactions
592
B Carbonylation and Reactions with Carbon Monoxide
593
3 Carbonylation of Olefins
598
4 Carbonylation of Acetylenes
600
5 Carbonylation of Aziridines and Azobenzenes
602
6 Carbonylation of Thiiranes
603
2 Reduction of Acid Chloride Groups to Aldehydes
607
4 Reduction of Nitrogen Compounds
608
5 Other Reductions and Hydrogenations
611
2 Acetylene and Olefin Coupling Reactions
614
D Other Reactions
615
PhaseTransfer Catalysis in Analytical Chemistry
620
C NonNucleophilic PTC Reactions Used in Analytical Chemistry
621
PhaseTransfer Catalysis Industrial Perspective
624
2 Advantages of PTCIndustrial Viewpoint
625
3 Limitations of PTC and Barriers to Commercialization
629
4 Identifying Future Opportunities for Making Economic Impact Using PTC
633
5 Conclusion
635
Index
637
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