Periodate Oxidation of Diol and Other Functional Groups: Analytical and Structural Applications deals with the chemistry of organic periodate oxidations with special reference to the study of carbohydrates, along with their analytical and structural applications. This book explores the mechanistic aspects of the periodate reaction; its historical development; the nature of the so-called anomalous reactions; and some of the synthetic uses of periodate oxidation. This book is comprised of seven chapters and opens with a historical background on periodate oxidation, followed by a discussion on the preparation and properties of periodates. The reader is then introduced to the mechanism of periodate oxidation, with particular reference to 1,2-diols and 1,2-hydroxycarbonyl compounds as well as 1,2-diketones, 1,2-aminoalcohols, and active methylene groups. The remaining chapters consider the structure of carbohydrates and related materials; anomalous periodate oxidations; the analytical aspects and applications of periodate oxidation; and a number of tested and generally well-tried analytical procedures such as the Fleury-Lange method, Malaprade method, ion exchange, and spectrophotometric and polarographic techniques. This monograph will be a useful resource for organic chemists and advanced undergraduate students of chemistry.

PrefaceIntroductionChapter 1. History Literature CitedChapter 2. Preparation and Properties of Periodates Preparation Solubility Stability of Aqueous Solutions Standard Potentials Ionization of Periodic Acid Structure of Periodates Literature CitedChapter 3. Mechanism of Period ate Oxidation 1,2-Diols Kinetics of Periodate Oxidation Further Evidence for a Cyclic Intermediate Alternative Mechanisms Conclusions 1,2-Hydroxycarbonyl Compounds and 1,2-Diketones 1,2-Aminoalcohols Active Methylene Groups Literature CitedChapter 4. Anomalous Periodate Oxidations Overoxidation Sulfur-Containing Compounds Phenols Flavanols Amines Amino Acids Unsaturated Sugars Amino Sugars Proteins Oxidations at Elevated Temperature Oxidations in the Presence of Light Literature CitedChapter 5. Periodate Oxidation in Structural Studies Structure Assignment Based on Periodate Oxidation Information Structure Assignment Based on Periodate Oxidation and Other Information Structure and End-Group Assay of Polysaccharides Nature of the Product of Periodate Oxidation Literature CitedChapter 6. Analytical Methods Conditions of the Oxidation Solvent Oxidant Temperature Light Concentration of Reactants Duration of Reaction pH Buffer Composition Determination of Oxidant Consumption Müller-Friedberger Method Fleury-Lange Method Malaprade Method Discussion of Iodometric Methods Determination of a-Glycerophosphates in the Presence of ß-Glycerophosphates Other Methods for Periodate Determination Spectrophotometric Ion Exchange Polarographic H-Acid Determination of Glycerol Determination of Acid Produced Formic Acid Titration with Alkali Determination of Simple Sugars Influence of Overoxidation Procedure for Minimizing Overoxidation Procedure for Determination of Formic Acid and Formate Ester Potentiometric Titration Iodometric Removal of Formic Acid from Solution before Titration Gasometriç Spectrophotometric Mercuric Chloride Determination of Other Acids Glyoxylic Acid Carbonyl Acids Determination of Formaldehyde Mercuric Chloride Dimedone Chromotropic Acid Phenylhydrazine-Potassium Ferricyanide Acetylacetone Fluorimetric Determination of Acetaldehyde Iodometric Methyl Pentoses in the Presence of Hexoses Spectrophotometric Determination of Carbonyl Compounds with 2,4-Dinitrophenylhydrazine Determination of Ammonia and Amines Determination of Carbon Dioxide Recommended General Methods Oxidation of some Dihydroxy Aminoalkanes Oxidation of Maltotetraose Determination of Mixtures of Glycerol, Ethylene Glycol and 1,2-Propylene Glycol Oxidation on the Microgram Scale Periodate Oxidation of Borohydride-reduced Oligosaccharides Polarographic Determination of Ethylene Glycol and 1,2-Propylene Glycol Conclusions Literature CitedChapter 7. Synthetic and Other Applications of Periodate Oxidations Literature CitedAuthor IndexSubject Index