Preparative Chemistry Using Supported Reagents - 1st Edition - ISBN: 9780124371057, 9780323146067

Preparative Chemistry Using Supported Reagents

1st Edition

Editors: Pierre Laszlo
eBook ISBN: 9780323146067
Imprint: Academic Press
Published Date: 3rd December 1987
Page Count: 560
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Preparative Chemistry Using Supported Reagents explains a certain dimension in the methodology of organic reactions.

This book discusses the physical methods for study that characterizes surfaces and their adsorbates and chemical reactivity at interfaces. The polymer-supported reagents, shape-selectivity within zeolites, and graphite intercalates are also described. Other topics include the metal oxides and their physico-chemical properties in catalysis and synthesis; photochemistry of adsorbed molecules; and magnetic spin resonance methods and applications to oxide surfaces. The physico-chemical characterization of supported reagents; polymer-supported oxidations; and alumina and alumina-supported reagents are likewise deliberated. This text also covers the novel aluminophosphate-based molecular sieves, clay-activated isomerization reactions, anionic activation, and cationic reactions.

This publication is beneficial to chemists and researchers conducting work on supported reagents.

Table of Contents


Part I Supported Reagents: General Principles

1 Homogeneous and Heterogeneous Reaction Conditions

I. The Alchemical Heritage

II. The Example of Industrial Chemistry

III. The Lessons from Chromatography

IV. The Lead from Biochemistry

V. Shifting Habits

VI. Easier Work Up

VII. Faster Reactions under Milder Conditions

VIII. Improved Selectivity

IX. Safer Reagents

X. Surface Chemistry as a New Frontier in Chemistry


2 Characterization of Surface Irregularity

I. Introduction

II. Notion of Fractal Dimension

III. Experimental Methods of Fractal Surface Analysis

IV. Restricted Diffusion on a Surface and Encounter of Reagents: The Effects of Dimensionality

V. Diffusion of Reagents in Pore Space

VI. Conclusions and Strategies for Supported Reactions


3. Metal Oxides and Their Physico-Chemical Properties In Catalysis and Synthesis

I. Structural Aspects of Metal Oxides

II. Chemisorption Processes on Metal Oxides

III. Important Catalytic Processes on Metal Oxides

IV. Metal Oxides as Synthetic Reagents

V. Conclusions


4. The Photochemistry of Adsorbed Molecules

I. Introduction

II. Photophysics

III. Photochemistry

IV. Conclusions


5. Electrochemistry at Modified Electrode Surfaces

I. Introduction

II. Methods of Preparation

III. Methods of Characterization of Modified Electrodes

IV. Applications


6. Practical Considerations: How to Set Up a Supported Reagent

I. Introduction

II. Setting Up a Supported Reagent

III. Representative Experimental Procedures

IV. Glossary of Terms, in the Form of Practical Hints

V. Sonication: A Tool for the Near Future?

VI. Conclusion


Part II Phsico-Chemical Studies of the Structure of the Solid Supports

7 New Tools for the Study of Surfaces

I. Introduction

II. Description of Methods

III. General Conclusions


8 Magnetic Spin Resonance Methods and Applications to Oxide Surfaces

I. Introduction

II. Physical Parameters Measurable by Electron Spin Resonance

III. Applications to Zeolites

IV. Applications to Silica


9 Magnetic Resonance Methods

I. Nuclear Magnetic Resonance Methods

II. Nuclear Magnetic Resonance Studies of Porous Solids

III. Nuclear Magnetic Resonance Studies of Hydroxyl Groups on Surfaces

IV. Nuclear Magnetic Resonance Studies of Surface Compounds (Chemisorbed Molecules)


10 Physico-Chemical Characterization of Supported Reagents

I. Introduction

II. Molybdenum on Silica

III. Copper Ammine Complexes in Zeolites

IV. Ruthenium Bipyridine Complexes in Zeolites and Clays

V. Cobalt Bipyridine-Terpyridine Complexes in Zeolites

VI. Future Prospects


11 X-Ray Studies

I. Introduction

II. The Nature and Definition of Clays

III. X-Ray Diffraction Studies of Clay-Organic Complexes

IV. A Philosophic Approach of Clay Sciences: The Clay Integron

V. The Advantages of the XRD Method

VI. Concluding Remarks


Part III Polymer-Supported Reagents

12 Polymer-Supported Reagents, Polymer-Supported Catalysts, and Polymer-Supported Coupling Reactions

I. The Chemistry of Polymer Supports

II. Stoichiometric Reactions

III. Polymer-Supported Catalysts

IV. Conclusions


13 Polymer-Supported Oxidations

I. Introduction

II. Covalently Bound Reagents

III. Ionic Species on Ion Exchange Resins

IV. Prospective Considerations


14 Polymer-Supported Reductions

I. Introduction

II. Polymer-Supported Reduction versus Soluble Reduction

III. Polymeric Materials Used for Polymer-Supported Reductions

IV. Polymer-Bound Reducing Reagents

V. Polymer-Bound Catalysts

VI. Prospects


Part IV Graphite Intercalated

15 Intercalation Compounds of Graphite and Their Reactions

I. General Features of the Graphite Intercalation Compounds

II. The Graphite Intercalation Compounds as a Reagent

III. The Graphite Intercalation Compounds as a Catalyst


Part V Alumina-Supported Reagents

16 Alumina and Alumina-Supported Reagents

I. Introduction

II. Addition Reactions

III. Redox Reactions

IV. Substitution Reactions

V. Elimination Reactions

VI. Rearrangement Reactions

VII. Conclusions


17 Anionic Activation, Reactions in Dry Media

I. Introduction

II. Anionic Activation on Alumina

III. Alumina-Supported Alkali Metal Hydroxides and Alkoxides

IV. Alumina-Supported Alkali Metal Fluorides

V. Alumina-Supported Potassium

VI. Onium Salts Immobilized on Alumina

VII. Conclusions


Part VI Silica-Supported and Silica Gel-Supported Reagents

18 Reductions, Oxidations, and Anionic Activations: Catalytic Reductions and Oxidations

I. Introduction

II. Oxidations and Catalytic Oxidations

III. Reductions and Catalytic Reductions

IV. Anionic Activation

V. Conclusions


19 Silica-Supported Reagents: Polymerizations

I. Introduction

II. Polymerization Reactions Involving SiO2

III. Polymerization Reactions Involving SiO2-Supported Main Group Species

IV. Reactions Involving SiOj-Supported Transition Metals


20 Silica-Supported Reagents: Reactions In Dry Media

I. Why Dry-Media Reactions?

II. Oxidation Reactions

III. Reduction Reactions

IV. Anionic Condensations

V. Other Reactions

VI. Conclusions


Part VII use of Zeolites as Supports

21 Use of Molecular Sieves as Supports: Novel Aluminophosphate-Based Molecular Sieves

I. Introduction

II. Aluminophosphate Molecular Sieves

III. Silicoaluminophosphate Molecular Sieves

IV. Metal Aluminophosphate Molecular Sieves

V. Summary



22 Shape-Selective Catalysis

I. Introduction

II. Description of Molecular Sieves and Other Shape-Selective Materials

III. Shape Selectivity: Reactant and Product Type

IV. Restricted Transition-State-Type Selectivity

V. Molecular Traffic Control

VI. Para-Selective Alkylation of Toluene

VII. Control of Shape Selectivity

VIII. Erionite as an Example of Selectivity

IX. The Cage (or Window) Effect

X. Quantitative Measure of Shape Selectivity

XI. Selected Examples of Shape-Selectivity Catalysis

XII. Applications of Shape-Selective Molecular Sieve Catalysis

XIII. Conclusion


Part VIII Clay-Activated Organic Reactions

23 Clay-Activated Isomerization Reactions

I. Introduction

II. Acidic Properties of Clays

III. Methods of Catalyst Preparation

IV. Isomerization Reactions

V. Conclusions


24 Oxidations and Catalytic Oxidations

I. Introduction

II. Clay-Supported Postassium Permanganate

III. Clay-Supported Thallium(III) Nitrate

IV. Clay-Supported Copper(II) and Iron(III) Nitrates


25 Clay-Activated Catalytic Hydrogenations: Catalyst Synthesis and Factors Influencing Selectivity

I. Introduction

II. Synthesis of Intercalated Clay Catalyst

III. Catalytic Reactions


26 Anionic Activation

I. Introduction

II. Nucleophilic Properties of Smectites

III. Quaternary Ammonium Clays as Phase-Transfer Catalysts

IV. Clay-Supported Reagents


27 Cationic Reactions

I. Introduction

II. Reactivity

III. Reactions and Conditions




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© Academic Press 1987
Academic Press
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About the Editor

Pierre Laszlo

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