Phase-Transfer Catalysis: Fundamentals, Applications, and Industrial PerspectivesSpringer 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. |
Inhalt
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 |
637 | |
639 | |
Andere Ausgaben - Alle anzeigen
Phase-Transfer Catalysis: Fundamentals, Applications, and Industrial ... C.M. Starks,M. Halper Eingeschränkte Leseprobe - 2012 |
Phase-Transfer Catalysis: Fundamentals, Applications, and Industrial ... C.M. Starks,M. Halper Keine Leseprobe verfügbar - 2013 |
Häufige Begriffe und Wortgruppen
1-bromooctane acetate alcohols aldehydes Aliquat 336 alkyl halides anion aqueous phase aqueous sodium hydroxide benzene benzyl chloride C-alkylation carboxylic acids CH3 CH3 Chapter Chem chemical chiral cocatalyst compounds concentration crosslinking crown ethers cryptands cyanide displacement deprotonation displacement reactions effect enantiomeric excess epoxidation esters example Figure formation groups hydration hydroxide ion increase insoluble iodide ion pair ketones Khim kinetics Landini Makosza methyl methylene chloride NaOH nucleophilic olefins organic phase organophilic oxidation Phase Transfer phase-transfer catalysts phosphonium salts polar Polym polymer-bound polymerization potassium presence PTC catalysts PTC conditions PTC reactions PTC systems PTC/OH quaternary ammonium cation quaternary ammonium salts quaternary cation quaternary salts rate constants rate limited reactant reacted reaction rate reactivity resin resin-bound Sasson sodium hydroxide soluble solvent substrate sulfate sulfide Synth Synthesis Table temperature tetrabutylammonium bromide Tetrahedron Lett toluene transfer catalysts transfer rate two-phase system U.S. Patent yield