Quaternary Ammonium Salts (eBook)

Their Use in Phase-Transfer Catalysis

R. Alan Jones (Autor)

eBook Download: PDF

2000 | 1. Auflage
565 Seiten
Elsevier Science (Verlag)
978-0-08-054015-3 (ISBN)

Infos

This text provides experimental methods for a wide range of organic reactions, systematically arranged according to reaction type, and describes the advantages and limitations of the procedures. Traditional methods to speed up organic reactions involve energy-consuming processes and costly and environmentally unfriendly solvents. Additionally, isolation of the product requires energy and time-consuming purification processes. A simple solution, especially for reactions involving anionic reactants, is the use of phase-transfer catalysis. Quaternary ammonium cations have the ability to transfer the anionic reactants as non-solvated ion-pairs from aqueous media into organic media. The resultant effect is to increase the rate of the organic reaction by enhancing the reactivity of the anionic species and increasing the encounter rate with the organic substrate. Side reactions are frequently eliminated so that the overall yield of the desired product is increased.

Quaternary Ammonium Salts presents procedures for reducing reaction times and the need for extreme conditions, which are frequently encountered under standard reaction procedures.

This is the only book to be published on quaternary ammonium salts. Best Synthetic Methods volumes allow the practicing synthetic chemist to choose between all the alternatives and assess their real advantages and limitations. Each volume of the series deals with a particular topic from a practical point of view, giving detailed examples and precise experimental directions and hints. With the emphasis on laboratory use, these volumes represent a comprehensive and practical guide to modern synthetic organic chemistry.

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This text provides experimental methods for a wide range of organic reactions, systematically arranged according to reaction type, and describes the advantages and limitations of the procedures. Traditional methods to speed up organic reactions involve energy-consuming processes and costly and environmentally "e;unfriendly"e; solvents. Additionally, isolation of the product requires energy and time-consuming purification processes. A simple solution, especially for reactions involving anionic reactants, is the use of phase-transfer catalysis. Quaternary ammonium cations have the ability to transfer the anionic reactants as non-solvated ion-pairs from aqueous media into organic media. The resultant effect is to increase the rate of the organic reaction by enhancing the reactivity of the anionic species and increasing the encounter rate with the organic substrate. Side reactions are frequently eliminated so that the overall yield of the desired product is increased.Quaternary Ammonium Salts presents procedures for reducing reaction times and the need for extreme conditions, which are frequently encountered under standard reaction procedures.This is the only book to be published on quaternary ammonium salts. Best Synthetic Methods volumes allow the practicing synthetic chemist to choose between all the alternatives and assess their real advantages and limitations. Each volume of the series deals with a particular topic from a practical point of view, giving detailed examples and precise experimental directions and hints. With the emphasis on laboratory use, these volumes represent a comprehensive and practical guide to modern synthetic organic chemistry.

Inhalt

Front Cover 1
Quaternary Ammonium Salts: Their Use in Phase-Transfer Catalysed Reactions 4
Copyright Page 5
Contents 6
Preface 24
Abbreviations 25
Chapter 1. General Principles 26
1.1 Introduction 26
1.2 Mechanism for phase-transfer catalysis 33
1.3 Choicc of catalyst 42
1.4 Supported catalysts 44
Chapter 2. Simple Nucleophilic Exchange Reactions and Aromatic Substitution Reactions 48
2.1 Simple aliphatic SN reactions 48
2.2 Nucleophilic aromatic reactions 55
2.3 Electrophilic halogenation and related reactions 73
Chapter 3. Formation of C–O Bonds 94
3.1 Alkylation of alcohols and related compounds 94
3.2 Alkylation of phenols and enols 105
3.3 Ester formation and related reactions 111
3.4 Phosphoric, sulphonic and other esters 133
3.5 Miscellaneous reactions 141
Chapter 4. Formation of C–S Bonds and Related Reactions 144
4.1 Synthesis of thiols, thioethers, thioacetals and S-alkyl thiocarboxylic esters 144
4.2 Michael-type reactions of thiols with electron-deficient C=C and C=C bonds 169
4.3 Synthesis of thioamides and related compounds 173
4.4 Synthesis of sulphones and sulphoxides 176
4.5 S-Alkylation of dialkyl-and diarylthiophosphinates 180
4.6 S–N bond formation 181
Chapter 5. Formation of C–N Bonds and Related Reactions 184
5.1 Alkylation and acylation of amines and related compounds 184
5.2 Alkylation of amides and related compounds 197
5.3 Alkylation and acylation of heteroarenes 220
5.4 Miscellaneous reactions 242
Chapter 6. Formation of C–C Bonds 254
6.1 Introduction 254
6.2 Alkylation and acylition of activated methylene groups 258
6.3 Aldol and related reactions 285
6.4 Michael reactions and other related reactions 299
6.5 Other C–C bonding reactions 313
Chapter 7. Preparation and Synthetic Applications of Carbenes 328
7.1 Introduction 328
7.2 Insertion of dihalocarbenes into C–H bonds 338
7.3 Insertion of carbenes into C=C bonds 341
7.4 Reactions of the chloroform/base system with carbonyl compounds 360
7.5 Reactions with alcohols, phenols and epoxides 364
7.6 Reactions of dihalocarbenes with amines, imines, amides and related compounds 369
7.7 Reactions with heteroaromatic compounds 382
Chapter 8 Carbonylation and Other Reactions 390
8.1 Introduction 390
8.2 Carbonylation reactions leading to aliphatic carboxylic acids, esters, lactones and carboxamides 393
8.3 Carbonylation of aryl and vinyl halides leading to carboxylic acids and related compounds 406
8.4 Carbonylation reactions leading to ketones and aldehydes 410
Chapter 9. Elimination Reactions, Cleavage and Rearrangement Reactions, Isomerism and H/D Exchange Reactions 416
9.1 Elimination reactions 416
9.2 Cleavage reactions 424
9.3 Rearrangement reactions 432
9.4 Hydrogen isotope exchange reactions 436
Chapter 10. Oxidation of Organic Compounds 440
10.1 Introduction 440
10.2 Permanganate oxidations 440
10.3 Chromate and dichromate mediated oxidations 450
10.4 Oxidation using hypochlorite and chlorite anions 456
10.5 Iron(III) and cerium(IV) oxidations 464
10.6 Peroxy acid oxidations 468
10.7 Autoxidation reactions and oxidation with hydrogen peroxide 482
10.8 Miscellaneous oxidation reactions 492
Chapter 11 Reduction of Organic Compounds 500
11.1 Introduction 500
11.2 The use of quaternary ammonium aluminium hydrides 501
11.3 The use of quaternary ammonium borohydrides 502
11.4 ‘Modified’ quaternary ammonium borohydrides 514
11.5 Reductions using diborane 518
11.6 Phase-transfer catalysed reductions with sodium dithionite 520
11.7 Hydridometal carbonyl reductions and related reactions 523
11.8 Miscellaneous reduction procedures 530
11.9 Catalytic hydrogenation under phase-transfer catalytic conditions 535
Chapter 12. Stereoselective Control in Phase-transfer Catalysed Reactions 540
12.1 Introduction 540
12.2 Chiral quaternary ammonium catalysts 543
12.3 Carbon–carbon bond formation 550
12.4 Carbon–nitrogen, carbon–oxygen, carbon–sulphur and carbon–halogen bond formation 558
12.5 oxidation reactions 562
12.6 Reduction 566
Index 570

Produkt-Details

• Erscheint lt. Verlag: 1.11.2001
• Sprache: englisch
• Themenwelt: Naturwissenschaften ► Biologie ► Biochemie
• Themenwelt: Naturwissenschaften ► Chemie ► Analytische Chemie
• Themenwelt: Naturwissenschaften ► Chemie ► Organische Chemie
• Themenwelt: Naturwissenschaften ► Chemie ► Physikalische Chemie
• Themenwelt: Naturwissenschaften ► Chemie ► Technische Chemie
• Themenwelt: Naturwissenschaften ► Geowissenschaften ► Mineralogie / Paläontologie
• Themenwelt: Technik
• Themenwelt: Weitere Fachgebiete ► Land- / Forstwirtschaft / Fischerei
• ISBN-10: 0-08-054015-5 / 0080540155
• ISBN-13: 978-0-08-054015-3 / 9780080540153