Chromium oxidation, well known and widely explored in organic chemistry since the very beginning of this science, is a topic of current interest for the organic chemist as evidenced by the continuous development of new techni ques and procedures reported in the literature. Chromium oxidation is a simple process which can be easily performed in the laboratory and scaled up in industry as well. Although almost every oxidizable organic functional group may undergo chromium oxidation, the most important fields of appli cation are the oxidation of alcohols, allylic and benzylic oxidation, oxidative degradation and oxidation of some organometallic compounds. A high degree of selectivity is often possible by choosing the most suitable reagent among those several ones now available. This book takes account of the various functional groups that undergo oxidation and the entire literature up to 1982. It has been written in the hope to help the synthetic organic chemist in his experimental work. For this purpose a number of tables comprising yields and references have been included; detailed descriptions of typical procedures are meant to show the experimental conditions and the scope of the reactions. We wish to thank Dr. Mario Orena for his valuable scientific and technical assistence and Prof. Bruno Camerino, who read the entire manuscript and corrected many of the errors. Bologna, February 1984 Gianfranco Cainelli Giuliana Cardillo Table of Contents I. Introduction . . . . . . . . . . .

Inhalt
I. Introduction.- 1. The Oxidation States of Chromium.- 2. The Chemistry of Chromium(VI).- 3. Chromium(VI) as Oxidant in Organic Chemistry.- References of Chapter I.- II. Oxidation of Carbon-Hydrogen Bonds.- A. Oxidation of Alkanes.- B. Oxidation of Arylalkanes (Benzylie Oxidation).- C. Allylic Oxidation.- 1. Allylic Oxidation of Olefins With Chromium(VI) in Acetic Acid and Acetic Anhydride.- 2. Allylic Oxidation With Chromium Trioxide-Heterocyclic Bases Addition Compounds.- 3. Allylic Oxidation With Tert-butyl-chrornate.- 4. Mechanism of Allylic Oxidation.- References of Chapter II.- III. Oxidation of Carbon-Carbon Double Bonds.- A. Oxidation of Alkenes.- C. Ring Oxidation of Aromatic Compounds.- 1. Oxidation of Polynuclear Arenes With Chromium(VI) Under Acidic Conditions.- 2. Oxidation of Phenols and Aromatic Amines With Chromium(VI) Under Acidic Conditions.- 3. Oxidation of Phenols With Chromyl Chloride.- 4. Oxidation of Hydroquinone Silyl Ethers With Pyridinium Chlorochromate.- 5. Oxidation of Ortho-Allylphenols With Tetraalkylammonium Dichrornate.- 6. Oxidation of Some Aromatic Heterocyclic Compounds With Chromium(VI).- References of Chapter III.- IV. Oxidation of Alcohols.- A. Oxidation of Alcohols by Chromium(VI) Under Acidic Conditions.- B. Oxidation of Alcohols With Compounds of Chromium(VI) and Heterocyclic Bases.- C. Oxidation of Alcohols With Chromium(VI) Under Neutral Conditions.- D. Oxidation of Alcohols With Supported Chromium(VI) Reagents.- E. Mechanism of Oxidation of Alcohols.- F. Effect of the Structure and Stereochemistry of Secondary Alcohols on the Rate of Oxidation.- References of Chapter IV.- V. Oxidation of Aldehydes and Ketones.- A. Oxidation of Aldehydes.- B. Oxidation of Ketones.- References of Chapter V.- VI. Oxidation of Carbon-Metal Bonds.- A. Oxidation of Organoboron Compounds.- B. Oxidation of Organotin Compounds.- References of Chapter VI.- VII. Oxidation of Halides, Ethers, Acetals, Sulphides, and Some Nitrogen Containing Compounds.- A. Oxidation of Alkyl Halides.- B. Oxidation of Ethers.- C. Oxidation of Acetals.- D. Oxidation of Sulphides.- E. Oxidation of Alkyl Aryl Amines.- F. Oxidation of Oximes.- G. Oxidation of Hydroxylamine.- References of Chapter VII.- VIII. Some Remarks on Selectivity and Synthetic Use of Chromium (VI) Oxidation.- A. Oxidation of Carbon-Hydrogen Bond.- B. Oxidation of Carbon-Carbon Double Bonds.- C. Ring Oxidation of Aromatic Compounds.- D. Oxidation of Alcohols.- E. Oxidation of Aldehydes and Ketones.- F. Oxidation of Carbon-Metal Bonds.