Experimental Methods in Organic Fluorine Chemistry

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Format: Hardcover
Pub. Date: 1999-03-08
Publisher(s): CRC Press
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Summary

In the fields of biologically active materials and functional materials, fluorinated organic materials are becoming a focus of significant interest. Over the past decade synthetic methodologies and reagents in fluorine chemistry have been developed, especially stereocontrolled synthetic methods, enzymatic resolution to synthesize enantiomers, fluoromethylated reagents, and fluorination reagents. These methods have contributed to the opening of new pathways for fluorinated materials. However, few fluorinated materials have been put to commercial use. Furthermore, there remain problems to be solved, such as the handling of the materials, availability of reagents and selectivity (stereo-, regio-, and/or chemoselectivity). Research chemists, technical engineers, and graduate students in all branches of chemistry, pharmaceutics, and material science interested in fluorinated materials need to know detailed experimental procedures of how to synthesize the target fluorinated materials.This volume summarizes the chemical and microbial methods for obtaining functionalized fluorinated materials for use as building blocks; detailed experimental methods (reaction conditions, solvent, temperature, handling techniques, etc.); and the stereoview (possible absolute configuration) of the structures with spectral data. Mono-, di-, tri-, and polyfluorinated materials derived from fluorinating agents, fluoromethylated reagents and building blocks are summarized. A chemical name index, molecular formula index, and reagent index are also included. The publication of this monograph will provide access to the enormous possibilities in fluorine chemistry, biological material chemistry, and functionalized material chemistry.

Table of Contents

Preface ix
General Remarks x
Abbreviations xi
Introduction
1(13)
Effect of Fluorine on Physical Properties
1(9)
Mimic and Block Effects
1(2)
Effect of the Electron-withdrawing Nature of Fluorine
3(1)
Deactivation Effect
3(2)
Activation Effect
5(2)
Conformational Preference Including Hydrogen Bonding Ability
7(2)
Steric Size of Fluorine-containing Groups
9(1)
Effect of Fluorine on Chemical Reactivity
10(4)
Stability of Cationic or Anionic Species Next to Fluorine or Fluoroalkyl Groups
10(4)
SN1 and SN2 Reactivity of Fluorinated Materials
14(17)
Preparation of Fluorine-containing Materials
16(4)
Handling Fluorinated Materials
20(1)
References and Notes
21(10)
Preparation of Monofluorinated Materials
31(48)
Fluorination
31(18)
Nucleophilic Fluorination (Substitution)
31(11)
Nucleophilic Fluorination (Addition)
42(2)
Nucleophilic Fluorination (Miscellaneous)
44(1)
Electrophilic Fluorination
45(4)
Carbon-Carbon Bond-forming Reactions
49(19)
Aldol Type Reactions
49(4)
Wittig Type Reactions
53(4)
Rearrangement and Cycloaddition
57(2)
Alkylations
59(3)
Miscellaneous
62(6)
Removal of Fluorine from Difluorinated Materials
68(2)
Optically Active Materials by Bioorganic Methods
70(2)
Substitution Reactions
72(2)
Miscellaneous Reactions
74(5)
Preparation of Difluorinated Materials
79(42)
Fluorination
79(4)
Nucleophilic Fluorination
79(2)
Electrophilic Fluorination
81(1)
Miscellaneous
82(1)
Difluoromethylenation
83(2)
Introduction of Difluoromethyl and Related Groups
85(6)
Carbon-Carbon Bond-forming Reactions
91(15)
Reformatsky Type Reactions
91(4)
Aldol Reactions and Claisen Condensation
95(3)
Diels-Alder Reactions
98(2)
Claisen Rearrangement
100(2)
Alkylations and Acylations
102(4)
Removal of Fluorine from Trifluorinated Materials
106(5)
Reactions of Hemiacetals
111(4)
Oxidations and Reductions
115(3)
Miscellaneous Reactions
118(3)
Preparation of Trifluorinated Materials
121(88)
Introduction of a Trifluoromethyl Group
121(11)
Introduction of a Trifluoromethyl Group (Nucleophilic)
121(6)
Introduction of a Trifluoromethyl Group (Electrophilic, Radical)
127(4)
Introduction of a Trifluoromethyl Group (Miscellaneous)
131(1)
Conversion to a Trifluoromethyl Group
132(3)
Carbon-Carbon Bond-forming Reactions
135(40)
Aldol Type Reactions
135(5)
Michael Reactions
140(6)
Ene Reactions
146(2)
Diels-Alder Reactions and 1,3-Dipolar Cycloadditions
148(4)
Wittig Type Reactions
152(2)
Rearrangements
154(4)
Nucleophilic Additions
158(8)
Electrophilic Additions
166(6)
Miscellaneous
172(3)
Reactions with Hetero Nucleophiles
175(8)
Reactions with Nitrogen Nucleophiles
175(2)
Reactions with Oxygen Nucleophiles
177(4)
Reaction with a Sulfur Nucleophile
181(2)
Dehydrations
183(1)
Oxidations and Reductions
184(10)
Oxidations
184(5)
Reductions
189(5)
Optical Resolutions
194(5)
Bioorganic Methods
194(4)
Chemical Method
198(1)
Miscellaneous Reactions
199(10)
Preparation of Poly- or Perfluorinated Materials
209(24)
Introduction of Poly- or Perfluorinated Groups
209(7)
Introduction of Poly- or Perfluorinated Groups (Nucleophilic)
209(3)
Introduction of Poly- or Perfluorinated Groups (Electrophilic, Radical)
212(4)
Carbon-Carbon Bond-forming Reactions
216(14)
Aldol Type Reactions
216(5)
Wittig Reactions
221(2)
Alkylations
223(2)
Anti-Michael Reactions
225(3)
Miscellaneous
228(2)
Miscellaneous Reactions
230(3)
Appendix Representative Distributors of Fluorochemicals 233(2)
Appendix Availability of Fluorinated Reagents 235(4)
Compound Index 239(4)
Reagent Index 243(4)
Product Index 247(9)
Author Index 256

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