Ozonation in Organic Chemistry V2

Preface

Acknowledgments

Contents of Volume I

Chapter I Introduction

Chapter II Ozonation of Acetylenic Compounds

I. Historical Overview

A. Products

B. Early Mechanistic Concepts

II. Present-Day Mechanistic Concepts

A. The Criegee Mechanism

B. The Initial Ozone Attack, Adduct, and Subsequent Intermediates

III. Vapor-Phase Ozonation of Acetylenes

IV. Miscellaneous Synthetic Applications and Novel or "Anomalous" Results

Chapter III Ozonation of Aromatic Compounds: Benzene and Substituted Benzenes

I. General Overview

A. Historical Background

Β. Comparison with Other Systems

C. Nonperoxidic Ozonolysis Products

II. Mechanism of Ozonation of Benzenoid Compounds

A. General Mechanistic Scheme

B. Peroxidic Ozonolysis Products

C. Initial Ozone Attack

D. Summation and Conclusions

III. Vapor-Phase Ozonations

IV. Ozonation of Phenols

V. Practical Applications

VI. Alkenylferrocenes

Chapter IV Ozonation of Aromatic Compounds: Bond Attack on Benz-Fused Carbocyclics

I. Introduction

II. Naphthalenes

A. Historical General Overview

B. Peroxidic Ozonolysis Products and Mechanism

C. Nonperoxidic Ozonolysis Products. Utility of Ozonolysis of Naphthalenes

III. Triphenylene and Perylene

IV. Phenanthrenes

A. General Overview

B. Peroxidic Ozonolysis Products. Mechanism

C. Nonperoxidic Ozonolysis Products. Utility

D. 4,5-Methylenephenanthrene

E. Miscellaneous

V. Phenanthrene-Like Poly cyclic Aromatic Hydrocarbons

A. Chrysene

B. Benzo[c]phenanthrene

C. Picene

D. Benzo[g]chrysene

E. Dibenzo[c,g]phenanthrene and Coronene

F. Dibenzo[g,p]chrysene

VI. Summation

Chapter V Ozonation of Aromatic Compounds: Bond Attack versus Atom Attack on Benz-Fused Carbocyclics

I. Pyrene-Type Benz-Fused Carbocyclics

A Pyrene

B. Benzo[a]pyrene

C. Benzo[r,s,t]pentaphene

D. Summation

II. Anthracene and Substituted Anthracenes

A. General Overview

B. Mechanism of Ozonation of Anthracene

C. 9,10-Dimethylanthracene and Related Compounds

D. 9,10-Dihaloanthracenes

E. Other Substituted Anthracenes—A Summary

III. Benz[a]anthracene and Derivatives

A. General Overview

B. Mechanism of Ozonation of Benz[a]anthracene

C. 7,12-Dimethylbenz[a]anthracene

D. 3-Methylcholanthrene

IV. Other Anthracene-Type Benz-Fused Aromatics

A. Naphthacene

B. Dibenz[a,h]anthracene

C. Dibenz[a,j]anthracene

D. Pentaphene

V. Summation and Conclusions

Chapter VI Ozonation of Aromatic Compounds: Heterocyclics

I. Introduction

II. Furans

A. Alkylfurans

B. Arylfurans and Mechanism of Ozonation of Furans

C. Practical Aspects

III. Pyrroles

A. General

B. Mechanism of Ozonation of Pyrroles

IV. Thiophenes

V. Other Five-Membered Ring Heterocycles

A. Pyrazoles

B. Isoxazoles

C. Furoxans and Osotriazole Oxides

D. Arsenic Heterocycle

VI. Indoles and Other Benz-Fused Five-Membered Ring Heterocycles

A. Introduction

B. Mechanism of Ozonation of Indoles

C. Miscellaneous Applications of Ozonation of Indoles

D. Benzofurans, Benzothiophenes, and Similar Heterocycles

VII. Pyridine and Other Six-Membered Ring Heterocycles

A. Pyridine and Homologs

B. 4-Pyrones

VIII. Quinoline and Other Benz-Fused Six-Membered Ring Heterocycles

A. Quinolines

B. Isoquinolines

C. Benzoquinoline Types

D. Benzopyrylium Salts

IX. Purines and Pyrimidines

Chapter VII Ozonation of Nucleophiles

I. Introduction

II. Electrophilic Ozone Attack on Nitrogen

A. Historical Background

B. Reactivity of Amines with Ozone

C. Amine Oxide Formation versus Side-Chain Oxidation: Tertiary Amines

D. Ammonia

E. Primary Amines

F. Secondary Amines

G. Hydroxylamines and Nitrosoalkanes

H. Miscellaneous

I. Summation of Reactions of Amines with Ozone

III. Electrophilic Ozone Attack on Other Elements of Group V: Phosphites

IV. Electrophilic Ozone Attack on Sulfur

A. Thioethers: Liquid Phase

Β. Di and Tetrasulfides: Liquid Phase

C. Miscellaneous Sulfur Compounds: Liquid Phase

D. Vapor-Phase Ozonations

E. Miscellaneous Applications

V. Electrophilic Ozone Attack on Other Elements of Groups VI and VII

A. Selenium

B. Oxygen

C. Iodine

Chapter VIII Ozonation of Hetero Multiple Bonds

I. Carbon-Nitrogen Double Bonds

A. Introduction and Survey

B. Mechanisms of Ozonation of Carbon-Nitrogen Double Bonds

C. Special Examples

II. Carbon-Sulfur Double Bonds

III. Carbon-Oxygen Double Bonds

IV. Miscellaneous

Chapter IX Ozone Attack at sp3 Carbon Centers: Ozonation of Carbon-Hydrogen Bonds

I. Introduction

II. General Survey

A. Alkanes

B. Cycloalkanes

C. Alkyl-Substituted Aromatics

D. Other Unactivated Methylene and Methyne Groups

III. The Mechanistic Spectrum

IV. Unactivated Carbon-Hydrogen Bonds

A. Mechanism of Liquid-Phase Ozonation

B. Further Rationalizations

C. Vapor-Phase Ozonation

D. Alkyl-Substituted Aromatics

E. Ozonation of Unactivated Carbon-Hydrogen Bonds: A Summary

V. Activated Carbon-Hydrogen Bonds

A. Ozonation of Alcohols: General Overview

B. Ozonation of Ethers: General Overview

C. Mechanism of Ozonation of Alcohols and Ethers

D. Ozonation of Acetals and Glycosides

E. Ozonation of Aldehydes

VI. Deactivated Carbon-Hydrogen Bonds

A. Ozonation of Ketones

B. Ozonation of Carboxylic Acids

C. Miscellaneous

VII. Ozonation of Polymers and Miscellaneous Substrates

A. Polymers

B. Miscellaneous

VIII. Special Techniques and Applications

A. Dry Ozonation

B. Ozonations in "Superacid" Solutions

C. Miscellaneous

Chapter X Ozonation of Miscellaneous Organic Species

I. Introduction

II. Ozonation of Organic Heteroatom Compounds of Group IVA: Organometallics

A. Organosilicon Compounds

B. Other Organic Heteroatom Compounds of Group IVA

C. Other Organometallic Compounds

III. Ozonolysis of the Cyclopropane Ring

IV. Cleavage of sp3 Carbon-Carbon Bonds by Ozone

V. Ozone as a Nucleophile: Ozonation of Carbocations

VI. Radical Reactions of Ozone

A. Introduction

B. Hydroperoxides

C. Aromatic Substitutions and Oxidations

D. Ozonation in Aqueous Solution: Hydroxyl Radicals

E. Freons

F. Miscellaneous

Chapter XI The Practical Side

I. Introduction

II. Techniques

III. Synthesis

IV. Analysis and Proof of Structure

V. Water, Wastewater, and Sewage Purification

VI. Pulping and Bleaching of Wood

VII. Miscellaneous Uses

VIII. The Ozone Layer Controversy

IX. The Negative Side of Ozone Organic Chemistry

A. Ozone in Air Pollution

B. Effects of Ozone on Biological Systems: Toxicity

C. Degradation of Rubber: Antiozonants

Chapter XII Ozonation of Olefins Revisited

I. Introduction

II. Ozone

III. Mechanism of Liquid-Phase Ozonolysis of Olefins

A. The Unstable Ozonolysis Intermediates

Β . 1,2,4-Trioxolane (Final Ozonide) Conformations

C. The Mechanistic Steps

D. Other Studies Concerning Routes to Peroxidic Ozonolysis Products

E. Peroxidic Ozonolysis Products

IV. Special and Unusual Ozonolyses and Ozonations

A. Haloolefins

B. Ozonation of Allenes

C. Ozonation of Ketenes

D. Ozonation of Vinylsilanes and Sulfides

E. Epoxidation versus Ozonolysis

F. "Anomalous" Ozonolyses

V. Vapor-Phase Ozonation

A. Mechanisms with Simple Olefins

B. Haloolefins

VI. Summary: Ozonation of Olefins

Epilogue

Overview and Miscellaneous New Developments

Bibliography

Index