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

Front Cover
Springer Science & Business Media, Jun 30, 1994 - Science - 668 pages
1 Review
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.
 

What people are saying - Write a review

User Review - Flag as inappropriate

is one of

Contents

Basic Concepts in PhaseTransfer Catalysis
1
B Basic Steps of PhaseTransfer Catalysis
2
C The PTC Reaction Rate Matrix
5
D Anion Transfer and Anion Activation
6
2 Anion Activation
11
E Effect of Reaction Variables on Transfer and Intrinsic Rates
12
1 Catalyst Structure
13
2 Agitation
14
7 Sulfite Displacement
366
9 Hydroxide Anion Displacements
367
10 Carbonate and Bicarbonate Anion Displacement
368
11 Displacement with Peroxide and Superoxide Anions
369
12 Phosphide and Phosphinite Anion Displacements
370
PhaseTransfer Catalysis Reaction with Strong Bases
383
A CAlkylation
384
2 Aldehydes
391

3 Kind and Concentration of Inorganic Reagent Amount of Water Added
15
4 Amount and Kind of Organic Solvent Used If Any
16
5 Temperature and Microwave Heating
17
F Outline of Compounds Used as PhaseTransfer Catalysts
18
2 Insoluble Catalysts
20
3 Catalysts for VaporPhase Reactions
21
PhaseTransfer Catalysis Fundamentals I
23
B Structural Factors Affecting the Distribution of Anions Between Aqueous and Organic Phases
24
C Structural Factors Affecting the Distribution of PhaseTransfer Catalyst Cations Between the Aqueous and Organic Phases
26
D Effects of the Organic Phase Polarity on the Distribution of Phase Transfer CationAnion Pairs
29
E Effects of Changes in Organic Phase Polarity During Reaction
31
F Factors Affecting the Distribution of PhaseTransfer Catalyst CationAnion Pairs Between an Organic Phase and an Aqueous Phase Containing Hydro...
32
G Effect of Hydration of the Transferred Anion and the Effect of Inorganic Salt andor Hydroxide Concentration in the Aqueous Phase
40
PhaseTransfer Catalysis Fundamentals II
48
B LiquidLiquid PTC
49
2 HydroxidePromoted Reactions of Organic Acids
89
3 Alternative PTC Mechanisms Involving Hydroxide Ion
106
C SolidLiquid PTC
108
1 Complexation and Solubilization of Potassium Salts with 18Crown6
111
2 Simple Displacement Reactions
113
PhaseTransfer Catalysts
123
B Use of Quaternary Salts as PhaseTransfer Catalysts
125
2 Special Quaternary Salts as PhaseTransfer Catalysts
142
C Macrocyclic and Macrobicyclic Ligands
153
2 Croplands
155
3 Special Crowns
156
D PEGs Tris 36dioxaheptylamine TDA1 and Related Ethoxylated Compounds as PhaseTransfer Catalysts
158
2 Phase Distribution Behavior of PEGs
159
3 PEGs and Ethers as PhaseTransfer Catalysts
162
Ethoxylate Derivatives as PTC
165
E Other Soluble Polymers and Related Multifunctional Compounds as PhaseTransfer Catalysts
171
F Use of Dual PTC Catalysts or Use of Cocatalysts in PhaseTransfer Systems
175
1 Use of Dual PTC Catalysts
176
2 Use of Alcohols and Other Weak Acids as Cocatalysts in Hydroxide Transfer Reactions
177
3 Use of Metal Compounds and Salts as PTC Cocatalysts
178
4 Use of Iodide as a Cocatalyst
179
2 Transfer of Acids
183
3 Transfer of Water
184
4 Transfer of Metals and Metal Hydrides
185
6 Transfer of Formaldehyde
186
9 Transfer of Ammonia
187
H Separation and Recovery of PhaseTransfer Catalysts
188
2 Distillation Methods
189
Insoluble PhaseTransfer Catalysts
207
B PTC Catalysts Bound to Insoluble Resins
208
2 Some Examples of Use of ResinBound PTC Catalysts and Comparisons with Soluble Catalysts
210
4 Effects of Reaction and Catalyst Parameters on Triphase Catalyst Effectiveness
221
5 Kinetics of Reactions Catalyzed by ResinBound PTC Groups
247
C PhaseTransfer Catalysts Bound to Inorganic Solid Supports
248
1 PTC Catalysts Adsorbed on Inorganic Supports
249
2 Catalysts with PTC Functions Chemically Bonded to Inorganic Supports
250
D PTC Catalysts Contained in a Separate Liquid Phase ThirdLiquid Phase Catalyst
252
Variables in Reaction Design for Laboratory and Industrial Applications of PhaseTransfer Catalysis
266
1 StructureActivity Relationships of Quaternary Ammonium Catalysts
267
2 StructureActivity RelationshipsOther Catalysts
286
3 Catalyst Stability
288
4 Catalyst Separation and Recycle
292
5 Commercial Catalyst Reference
303
1 Choice of Solvent and the Nature of the Chemical Reaction
305
2 Stabilization of the Transition State and Solvation of the Anion
306
3 Solubility of the CatalystAnion PairComplex in the Organic Phase
307
5 Solvent and the Nature of the Two Phases
310
6 Examples of Effect of Solvent
311
7 SolventFree PTC
314
8 Choice of Solvent and Process Aspects
315
C Presence of Water
318
D Agitation
319
E Choice of Anion Leaving Group and Counteranion
322
F Choice of Base
325
G Guidelines for Exploring New PTC Applications
326
PhaseTransfer Catalysis Displacement Reactions with Simple Anions
339
1 Important Factors in PTC Displacement Reactions
340
2 Characteristics of Various Anions for Simple PTC Displacement Reactions
342
B Behavior of Various Anions in PTC Displacement Reactions
343
2 Halide Displacement and Exchange Reactions
347
3 Displacement with Carboxylate Anions
355
4 Azide Displacements
358
5 Sulfide and Disulfide Displacements
362
6 Thiocyanate Displacement
364
3 Esters and Carboxylic Acids
392
5 Nitriles
395
6 Sulfones
398
B NAlkylation
400
2 Amides
406
3 Amines
408
C OAlkylationEtherification
410
2 Etherification of Phenoxides
413
D SAlkylationThioetherification
418
E Dehydrohalogenation
420
F Carbene Reactions
424
2 Dibromocarbene Addition
426
3 Mixed Dihalocarbene Addition
427
G Condensation Reactions
430
2 Aldol Condensation
431
3 Wittig
433
4 Darzens
435
5 Other Condensations
437
H Deuterium Exchange Isomerization and Oxidation
438
PhaseTransfer Catalysis Polymerization and Polymer Modification
452
2 Anionic Polymerizations
479
3 RadicalInitiated Polymerizations
481
C Chemical Modification of Polymers
484
2 Chemical Modification of Polymer Terminal Positions
489
3 Chemical Modification of Pendant Groups Attached to Polymer Backbone
490
PhaseTransferCatalyzed Oxidations
500
2 Transfer of Permanganate into Organic Phases
501
3 PTC Permanganate Oxidations
503
C Oxidations with Hypochlorite and Hypobromite
508
3 Oxidation of Amines Amides Thioamides and Related Compounds
512
4 Oxidation of Sulfides and Related Compounds
514
6 Oxidation of Nonoleftnic Hydrocarbons
518
D PTC Oxidations with Hydrogen Peroxide
521
2 Hydrogen Peroxide Oxidations
522
E PTC Air or Oxygen Oxidations
534
2 PTC Involvement in FreeRadical Oxidations
538
4 PTC with Singlet Oxygen Generation
539
5 TransitionMetalMediated Oxidations Involving PTC
540
2 Electrochemical Regeneration of Chromium Oxidants in Combination with PTC Systems
547
I PTC Carbon TetrachlorideSodium Hydroxide Oxidations
548
J PTC Oxidations with Periodate and Related Oxidizing Anions
549
2 Ruthenium as Cocatalyst
550
M PTC Oxidations with Superoxide
551
O PTC Oxidations with Other Oxidants
552
PhaseTransferCatalyzed Reductions
565
2 Azide Reductions
566
3 Other PTC Borohydride Reductions
567
B Lithium Aluminum Hydride Reductions
568
D Reductions with SulfurContaining Anions
569
E Hydrogenation
570
F Reductions with Formaldehyde
571
H Photochemical Reduction
572
PhaseTransfer Catalysis Chiral PhaseTransfer Catalyzed Formation of CarbonCarbon Bonds
576
B Alkylation Reactions
577
2 Alkylation of 23Dichloro5methoxy2npropyllindanone with 13Dichloro2butene in Toluene50 Aqueous Sodium Hydroxide
584
3 Asymmetric Alkylation of Oxindoles
586
4 Synthesis of Chiral Amino Acids
587
5 Michael Addition Reactions 5p
589
PhaseTransfer CatalysisTransition Metal Cocatalyzed Reactions
594
B Carbonylation and Reactions with Carbon Monoxide
595
3 Carbonylation of Olefins
600
4 Carbonylation of Acetylenes
602
5 Carbonylation of Aziridines and Azobenzenes
604
6 Carbonylation of Thiiranes
605
2 Reduction of Acid Chloride Groups to Aldehydes
609
4 Reduction of Nitrogen Compounds
610
5 Other Reductions and Hydrogenations
613
2 Acetylene and Olefin Coupling Reactions
616
D Other Reactions
617
PhaseTransfer Catalysis in Analytical Chemistry
622
C NonNucleophilic PTC Reactions Used in Analytical Chemistry
623
PhaseTransfer Catalysis Industrial Perspective
626
2 Advantages of PTCIndustrial Viewpoint
627
3 Limitations of PTC and Barriers to Commercialization
631
4 Identifying Future Opportunities for Making Economic Impact Using PTC
635
5 Conclusion
637
Index
639
Copyright

Other editions - View all

Common terms and phrases

References to this book

All Book Search results »

Bibliographic information