Ozonation in Organic Chemistry V1

Ozonation in Organic chemistry, Volume I: Olefinic Compounds covers the historical background of ozone reactions with organic substances and the mechanisms of these reactions. Composed of 12 chapters, this book first deals with the development of the available theory of all ozone reactions, such as the Harries and Staudinger theories, particularly the Criegee mechanism of ozonolysis. This text then describes the step-by-step mechanism of the classical ozonolysis reaction of olefins and how it evolved. Considerable chapters are devoted to the reactions that compete with ozonolysis, such as epoxidation and other partial cleavage reactions. Both liquid- and gas-phase ozone reactions are explored in other chapters. This volume will appeal to those who are interested in exploring the frontiers of ozone-organic chemistry.

Preface

Acknowledgments

Tentative Contents of Volume II

Chapter I Introduction

I. Importance of Ozone Chemistry

II. Historical

A. Discovery: The Schönbein Period, 1840-1902

B. Development: The Harries Period, 1903-1948

C. Understanding and Utilization: The Criegee Period, 1949 to Present

III. Scope and Terminology

Chapter II The Ozone Molecule

I. Resonance and Molecular Orbital Descriptions

II. The Singlet Diradical Description

III. Types of Ozone Attack

Chapter III Ozonolysis of Olefins: Introduction

I. Historical Perspective

A. Contributions of Harries

B. The Staudinger Mechanism

C. The Criegee Mechanism

II. Chronological Mechanistic Description

Chapter IV Ozonolysis of Olefins: Initial Ozone Attack and Adduct

I. The Primary Ozonide

II. 1,3-Dipolar Cycloaddition

A. Electrophilic Nature of Ozone in 1,3-Dipolar Cycloaddition

B. Other Evidence for 1,3-Dipolar Cycloaddition

Chapter V Ozonolysis of Olefins: The Peroxidic Products

I. Ozonides

A. Formation: Properties

B. Spectral Properties: Identification

II. Ketone and Aldehyde Diperoxides

III. Polymeric Ozonides and Peroxides. Oligomers

IV. α-Oxyalkyl Hydroperoxides

Chapter VI Ozonolysis of Olefins: Routes to Peroxidic Products

I. Evidence for Criegee Mechanism

II. Stereochemistry. Flaws in Simple Criegee Mechanism

III. The SMY Mechanism

IV. Refinements of Criegee Mechanism

A. Bauld-Bailey Scheme. SYN and Anti Carbonyl Oxides

B. Kuczkowski Scheme

C. Symmetrical and Unsymmetrical Olefins with Small Substituents at Double Bond

D. Further Comparisons

V. The "Unified Concept"

VI. Weighing the Evidence: Criegee Carbonyl Oxide Confirmed

A. 18O Studies

B. Criegee's Last Contribution

Chapter VII Ozonolysis of Olefins: Competitions in Peroxidic Product Formation

I. Competitions in Nonparticipating Solvents

A. Ozonide vs. Diperoxide and Oligomer Formation

B. Effects of Various Experimental Conditions on Ozonide Formation

C. Peroxy Epoxides

D. Summation

II. Competitions in Participating Solvents

A. α-Oxyalkyl Hydroperoxide Formation

B. Amozonolysis, Cyanozonolysis

C. Ozonide Formation in Participating Solvents

D. Intramolecular Interactions

III. Direction of Cleavage of Primary Ozonides of Unsymmetrical Olefins

IV. Summary of Routes to Peroxidic Products

Chapter VIII Ozonolysis of Olefins: Routes from Peroxidic to Nonperoxidic Products

I. Reductive. Nucleophilic Displacement at Oxygen

II. Other Reductive Methods

A. Borane

B. Glyoxalic Acid

C. Tetracyanoethylene

D. Catalytic

III. Acid-Catalyzed Decompositions. Solvolysis

A. "Acidolysis"

B. Hydrolysis of α-Oxyalkyl Hydroperoxides

IV. Base-Catalyzed Decompositions

V. Pyrolysis and Photolysis

VI. Miscellaneous

Chapter IX "Anomalous" Ozonolysis of Olefins

I. Introduction and General Theory

II. Allylic Compounds

III. α,β-Unsaturated Carbonyl Compounds

IV. 1,4-Naphthoquinones

V. Cinnamic Esters

VI. Miscellaneous Types

A. Camphene and Other Cyclic Systems

B. Simple Olefins

C. Miscellaneous

D. Feist's Acid

VII. Thermal and Photochemical

Chapter X "Special" Liquid-Phase Ozonolyses

I. Haloethylenes

II. Unsaturated Oxyphosphoranes

III. Alienes

IV. Miscellaneous

A. Cycloheptatrienes and Cyclooctatetraene

B. Benzvalene

Chapter XI Electrophilic Ozone Attack on Olefins. Epoxides and Other "Partial Cleavage" Products

I. Introduction

II. Examples

III. Theory of Competition between Ozonolysis and "Partial Cleavage"

A. Hindered Olefins

B. Unhindered Olefins

IV. Low-Temperature Studies, π Complexes

V. Highly Hindered Olefins. Radical Formation with Vinyl Alcohols

Chapter XII Gas-Phase Ozonation of Olefins

I. Kinetics

II. Products

III. Mechanisms

A. The Initial Ozone Attack. The Criegee Mechanism

B. The O'Neal-Blumstein Mechanism

IV. Special Types

A. 1,3-Butadiene and Aliene

B. Haloethylenes

V. Solid-Gas Phase Ozonolyses

Epilogue

Overview and New Developments

Bibliography

Index