Supported Reagents Preparation, Analysis, and Applications

by Clark, James H.; Kybett, Adrian P.; Macquarrie, Duncan J.

• ISBN13: 9780471187790
• ISBN10: 0471187798
• Edition: 1st
• Format: Hardcover
• Copyright: 1996-12-17
• Publisher: Wiley-VCH

Summary

A unique guide written for the chemist who is planning to use or is considering the possible use of supported reagents, an application with great growth potential in the near future. Using practical examples of methods of supported reagent analysis, this comprehensive reference source also contains useful references detailing the best techniques to apply to particular problems. The authors discuss the many choices available in the preparation of supported reagents, including loading, support, method of preparation and activation, as well as covering the various analytical techniques to apply to solids. They also use numerous examples of supported reagents and their use in organic synthesis, emphasizing practical aspects. Chemists in catalysis, organic synthesis, analysis and materials science will obtain enough information to make use of these essentially simple but fascinating materials, which in a little over twenty years have matured from academic curiosities to important industrial materials.

Author Biography

James H. Clark is the author of Supported Reagents: Preparation, Analysis, and Applications, published by Wiley. Adrian P. Kybett is the author of Supported Reagents: Preparation, Analysis, and Applications, published by Wiley.

Table of Contents

1 Introduction to Supported Reagent Chemistry

1.1 Definitions

1.2 The Importance of Supported Reagents

1.3 Choice of Support Material

1.4 Supported Reagents in Organic Synthesis

2 Preparation of Supported Reagents

2.1 Support Pretreatments

2.1.1 Support drying

2.1.2 Hydrolysis of surface groups

2.2 Methods of Preparation

2.2.1 Evaporation

2.2.2 Precipitation

2.2.3 Adsorption from solution

2.2.4 Mixing/grinding

2.2.5 In situ

2.2.6 Ultrasound

2.2.7 Specific syntheses

2.2.8 Substrate adsorption

2.2.9 Ion exchange

2.3 Choice of Loading

2.3.1 Correct loading

2.3.2 Underloading

2.3.3 Overloading

2.4 Choice of Solvent

2.5 Supported Reagent Posttreatment

2.5.1 Further reactions

2.5.2 Thermal posttreatment

3 Analytical Techniques for Studying Supported Reagents

3.1 Introduction

3.2 Infrared Spectroscopy

3.2.1 Direct characterization of surface species

3.2.2 Studies of reagent dispersion

3.2.3 Studies via probe molecules

3.3 Electron Spectroscopy

3.3.1 Ultraviolet--visible spectroscopy

3.3.2 X-Ray Photoelectron and Auger Electron Spectroscopy

3.4 Magnetic Resonance

3.4.1 Nuclear magnetic resonance spectroscopy

3.4.1.1 Direct characterization of surface species

3.4.1.2 Studies of surfaces by probe molecules

3.4.1.3 Other applications of NMR

3.4.2 Electron spin resonance

3.5 Thermal Analysis

3.5.1 Thermogravimetry (TG)

3.5.2 Differential Scanning Calorimetry (DSC)

3.6 X-Ray Techniques

3.6.1 Powder X-ray diffraction

3.6.2 Extended X-ray absorption fine structure (EXAFS)

3.7 Scanning Electron Microscopy

3.8 Mass Spectrometry

3.9 Nonspectroscopic Methods

3.9.1 Acid and base strength and site distribution measurements

3.9.2 Measurement of nonacidic or basic sites

3.9.3 Measurement of surface area, pore volume, and pore diameter

4 Case Studies

4.1 Supported Fluorides

4.2 Supported Thiocyanates

4.2.1 KSCN--SiO2

4.2.2 Optimization of reagents

4.2.3 Effect of exposed surface

4.2.4 Allyl and t-alkyl substrates isomerization

4.2.5 CuSCN--charcoal

4.3 Friedel--Crafts Alkylation and Acylation Using Aluminosilicate-based Catalysts

4.3.1 Disadvantages of conventional Friedel--Crafts catalysts

4.3.2 Alkylation

4.3.3 Acylation

Appendix 1

Organic Synthesis Using Supported Reagents

Oxidation and Reduction

Addition to C--Heteroatom Multiple Bonds

Addition to C--C Multiple Bonds

Intramolecular Rearrangement

Aromatic Substitution

Elimination

Aliphatic Substitution

Index