OxidationandAntioxidantsinOrganicChemistryandBiology(2005).PDF

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Oxidation and Antioxidants in Organic Chemistry and Biology(2005).PDF
Denisov/Oxidation and Antioxidants in Organic Chemistry and Biology dKl l62 prelims Final Proof page iv 25.2.2005 l1: llam Published in 2005 by RC Press Taylor francis Group 6000 Broken Sound Parkway Nw Boca raton. FL 33487-2742 c 2005 by Taylor Francis Group CRC Press is an imprint of Taylor Francis Group No claim to original U.S. Government works Printed in the United States of America on acid-free paper 10987654321 International Standard Book Number-10: 0-8247-5356-9(Hardcover) International Standard Book Number-13: 978-0-8247-5356-6(Hardcover) Library of Congress card Number 2004059305 This book contains information obtaincd from authentic and highly regarded sources. Reprinted matcrial is quoted with permission, and sources are indicated. A wide variety of references are listed Reasonable efforts have been made to publish reliable data and information. but the author and the publisher cannot assume responsibility for the alidity of all materials or for the consequences of their use No part of this book may be reprinted, reproduced transmitted, or utilized in any form by any electronic, mechanical or other means, now known or hereafter invented, including photocopying, microfilming, and recording, or in any information storage or retrieval system, without written permission from the publishers Forpermissiontophotocopyorusematerialelectronicallyfromthisworkpleaseaccesswww.copyright.com(httpi/ www.copyright.com/)orcontacttheCopyrightClearanceCenterInc.(ccc)222RosewoodDrive,Danvers,Ma 01923, 978-750-8400. CCC is a not-for-profit organization that provides licenses and registration for a variety of users For organizations that have been granted a photocopy license by the CCC, a separate system of payment has been arrange Trademark Notice: Product or corporate names may be trademarks or registered trademarks, and are used only for idcntification and cxplanation without intent to infringe Library of Congress Cataloging-in-Publication Data Denisov, E. T(Evgeny Timofeevich) Oxidation and antioxidants in organic chemistry and biology! Evgeny T Denisov, Igor B Afanase m clue IsBN 0-8247-5356-9(alk. paper) 1. Hydrocarbons-Oxidation. 2. Antioxidants. 3. Chemistry, Organic. 4. Biology L. Afanas'ev, igor B.1935-Il. Title QD305HSD342004 547.0104593dc22 2004059305 INforma Visit the taylor francis web site at http://www.taylorandfrancis.com Taylor Francis Group and the crc press web site at is the Academic Division of T&F Informa plc. http://www.crcpress.com Denisov Oxidation and Antioxidants in Organic Chemistry and Biology dKll62 prelims Final Proof page v 25.2.2005 11: 1 lam Dedication we dedicate this book to the memory of pioneers of Oxidation Chemistry, Aleksey nikolaevich Bach and Nikolay aleksandrovich shilov Den: sov/ Ox: dation and Antioxidants in Organic Chemistry and Biology DKl 162 prelims Final Proof page vii 25 2.2005 11: llam Table of contents Pre Authors List of chemical symbols and Abbreviations List of physicochemical symbols List of Bio chemical Abbreviations Part i Chemistry and Kinetics of Organic Compounds Oxidation by Dioxygen Chapter 1 Molecular products and thermochemistry of Hydrocarbon Oxidation 1 Earlier Concepts of Oxidation 1.2 Development of the Chain Theory of Oxidation of Organic Compounds 1.3 Hydroperoxides as Primary Molecular Products of Hydrocarbon Oxidation 1.3.1 Hydroperoxides 1.3.2 Dihydroperoxides 1. 3. 3 Cyclic and polymeric peroxides 1.3.4 Epoxides 1. 4 Products of Hydroperoxide decomposition 1. 4.1 Ilydroperoxides as the Intermediates of llydrocarbon Oxidation 1. 4.2 Alcohols 1. 4.3 Ketones 4.4 Acids References Chapter 2 Chain Mechanism of Liquid-Phase Oxidation of Ilydrocarbons 2.1 The peculiarities of chain reactions 2.1.1 Free-Valence persistence in reactions of free radicals with molecules 2. 1.2 Condition of Cyclicity of Radical conversions 2.1.3 Priority of Chain Propagation Reaction 2.1. 4 Generation of free Radicals 2.1.5 Competition of Chain and molecular Reactions 2.1.5.1 High Chemical Reactivity of Free Radicals and Atoms 2.1.5.2 Conservation of Orbital symmetry in Chemical reaction 2.1.5.3 Configuration of Transition State 2.2 Chain Mechanism of Hydrocarbon Oxidation 2.3 Reaction of Alkyl Radicals with Dioxygen 2. 4 Reactions of Peroxyl radicals 2.4.1 Structure and thermochemistry of peroxyl radicals 2.4.2 Reaction ro,+RH-Rooh+R 2.4.3 Intramolecular Hydrogen Atom Transfer in Peroxyl Radical 2.4.4 Addition of Peroxyl Radical to the double bond Denisov/Oxidation and Antioxidants in Organic Chemistry and Biology dKl162 prelims Final Proof page vill 25.2.2005 11: 1 lam 2.5 Chain Termination in Oxidized Hydrocarbons 2.5.1 Tetroxide 2.5.2 Disproportionation of Tertiary Peroxyl Radicals 2.5.3 Disproportionation of Primary and Secondary peroxyl radicals 2.5.4 Chemiluminescence 2.5.5 Chain Termination via Alkyl Radicals 2.6 Reactions of Alkoxyl Radicals 2. 7 Different Mechanisms of the Aliphatic hydrocarbon Oxidation in gas and Liquid Phases References Chapter 3 Initiation of Liquid-Phase Oxidation 3.1 Initiators 3.1.1 Mechanisms of Decomposition of Initiators 3.1.1.1 Unimolecular Decomposition of Initiator with One Bond Splitting 3. 1.1.2 Concerted Fragmentation of Initiators 3.1.1.3 Anchimerically Assisted Decomposition of Peroxides 3.1.2 Decay of Initiators to Molecular Produ 3.1.3 Chain Decomposition of Initiators 3. 1. 4 Peroxides 3.1.5 Azo-Compounds 3.2 Cage Effect 3. 2. 1 Expcrimental Evidences for Cage Effect 3.2.1.1 Quantum Yield 3.2.1.2 Products of radical pair Combination 3.2.1.3 Oxygen-18 Scrambling and racemization 3.2.1.4 Crossover Experimen ts 3. 2.1.5 Racemization 3.2.1.6 Influence of viscosity 3.2.1.7 Influence of Pressure 3.2.1. 8 Spin Multiplicity Effects 3.2.2 Mechanistic Schemes of the Cage effect 3. 3 Initiation of Oxidation by Chemically Active Gases 3.3.1 Ozone 3.3.2 Nitrogen Dioxide 3.3.3 Halogens 3. 4 Photoinitiation 3. 4. 1 Intramolecular and Intermolecular Photophysical Processes 3. 4.2 Photosensitizers 3.4.3 Photoinitiators 3.4.3.1 Azo-compounds 3.4.3.2 Peroxides 3.4.3.3 Carbonyl Compound 3.44 Nonchain photooxidation 3.5 Generation of Radicals by Ionizing radiation 3.5.1 Primary radiation-Chemical Processes 3.5.2 Radiolytic Initiation of llydrocarbon Oxidation Re eferences Denisov /Oxidation and Antioxidants in Organic Chemistry and Biology dKl 162 prelims Final Proof page ix 25.2.2005 11: llam Chapter 4 Oxidation as an autoinitiated chain reaction 4.1 Chain Generation by Reaction of Hydrocarbon with Dioxygen 4.1.1 Bimolecular Reaction of Dioxygen with the C H Bond of the Hydrocarbon 4.1.2 Trimolecular Reaction of Hydrocarbon with Dioxygen 4.1.3 Bimolecular and Trimolecular Reactions of Dioxygen with the Double Bond of olefin 4.2 Hydroperoxides 4.2. 1 Analysis 4.2.2 Structure of Hydroperoxides 4.2.3 Thermochemistry of Hydroperoxides 4. 2. 4 Hydrogen Bonding between Hydroperoxides 4.3.1 Unimolecular Decomposition of Hydroperoxide y 4.3 Reactions of Free Radical Generation by Hydroperoxide 4.3.2 Bimolecular Decomposition of hydroperoxides 4.3. 3 Bimolecular Reactions of Ilydroperoxides with T-Bonds of olefins 4.3. 4 Bimolecular Reactions of Hydroperoxides with C H,N H, and O-H Bonds of Organic Compounds 4.4 Parabolic Model of bimolecular homolvtic Reaction 4.4.1 Main equations of IPM 4.4.2 Calculation of e and k of a bimolecular reaction 4.4. 3 Bimolecular Reactions of radical Generation 4.4.3. 1 Bimolecular Splitting of Hydroperoxides 4.4.3.2 Reaction of Hydroperoxides with Olefins 4.4.3. 3 Reaction of hydroperoxides with h ydrocarbons 4.4.3.4 Reaction of Hydroperoxides with Alcohols and Acids 4.5 Initiation by reaction of Hydroperoxides with Ketones 4.6 Chain Decomposition of ilydroperoxides 4.7 Kinetics of Autoinitiated Hydrocarbon Oxidation 4.7.1 Initial Stage of Autoxidation 4.7.2 Autoxidation with Bimolecular Hydroperoxide decay 4.7.3 Initiation by reactions of Hydroperoxide with Products of Oxidation 4.7.4 Ilydroperoxide as the Intermediate Product of Autoxidation 4.7.5 Self-Inhibition of hydrocarbon oxidation References Co-Oxidation of Hydrocarbons 5.1 The of h bon Co-oxidati 5.2 Hydrocarbon Oxidation with hydr idc 5.3 Co-oxidation of Hydrocarbons and Alcohols with Selective Inhibitor 5.4 Cross-dist nation of peroxyl radicals 5.5 Cross-propagation Reactions of Peroxyl Radicals 5.6 High Reactivity of Haloidalkylperoxyl Radicals 5.7 Co-oxidation of hydrocarbon and its Oxidation Intermediates 5.8 Catalysis by nitroxyl radicals in Hydrocarbon Oxidation Ref Denisov Oxidation and Antioxidants in Organic Chemistry and Biology dKll62 prelims Final Proof page x 25.2.2005 11: 1 lam Chapter 6 Reactivity of the Hydrocarbons in Reactions with Peroxyl, Alkoxyl and Alkyl radicals 6. 1 Semiempirical Model of Radical reaction as an Intersection of Two Parabol Potential curves 6.1.1 Introduction 6. 1.2 Intersecting Parabolas Model (IPM) 6. 1.3 Calculation of the Activation Energy 6.2 Factors Influencing the Activation Energ 6. 2. 1 Rcaction Enthalpy 6.2.2 Force Constants of the Reacting bonds 6.2.3 Triplet Repulsion in the Transition State 6.2.4 Electron Affinity of Atoms of Reaction Center 6.2.5 Radii of atoms of reaction center 6.2.6 Influence of Adjacent T-Bond 6.2 7 Polar effec 6.2. 8 Influence of solvation 6.3 Geometry of the Transition State of Radical abstraction Reaction 6.4 Intramolecular Hydrogen Transfer Reactions in Peroxyl, Alkoxyl, and Alkyl radicals 6.4.1 Peroxyl radicals 6.4.2 Alkoxyl Radicals 6.4.3 Alkyl Radicals 6.5 Free Radical addition reactions 6.5. 1 Enthalpy of Free Radical Addition 6.5.2 Parabolic model of radical addition reaction 6.5. 3 Triplet repulsion in Radical Addition reactions 6.5.4 Influence of the Neighboring T-Bonds on the Activation Energy of radical addition 6.5.5 Role of the Radius of the Atom Bearing a Free valence 6.5.6 Interaction of Polar Groups 6.5.7 Steric hindrance 6.6 Free Radical Substitution and Hydrogen Atom Transfer reactions 6.6.1 Free radical substitution reactions 6.6.2 Reaction of Peroxides with Ketyl Radicals References apter Oxidation of alcohols and ethers 7. 1 Oxidation of alcohols 7. 1.1 Introducti 7. 1. 2 Chain Mechanism of Alcohol Oxidation 7.1.2.1 Kinetics of oxidation 7. 1.2.2 Reactions of Ketyl Radicals with Dioxygen 7.1.2.3 Reactions of Alkylhydroxyperoxyl and Hydroperoxy Radicals 7. 1.2 4 Chain Termination in Oxidized Alcohols 7.1.3 Co-Oxidation of Alcohols and Hydrocarbons 7.1.4 Reactivity of Alcohols in Reaction with Peroxyl Radicals Denisov /Oxidation and Antioxidants in Organic Chemistry and Biology DKI 162 prelims Final Proof page xi 25.2.2005 11: Ilam 7.1.5 Chain Generation in Autoxidation of Alcohol 7.1.5.1 Chain Generation by Reaction with Dioxygen 7. 1.5.2 Decomposition of Hydrogen Peroxide into Free Radicals 7. 1.5.3 Chain Generation by reaction of Hydrogen Peroxide with Carbonyl Co nd 7.2 Oxidation of ethers 7.2.1 Introduction 7.2.2 Chain Oxidation of ethers 7. 2.3 Co-Oxidation of Ethers and Hydrocarbons 7. 2.4 Reactivity of Ethers in Rcactions with Peroxyl radicals References Chapter 8 Oxidation of Carbonyl Compounds and Decarboxylation of Acids 8.1 Oxidation of aldehydes 8.1.1 Introduction 8.1.2 Chain Mechanism of Aldehyde oxidation 8.1.3 Co-Oxidation of Aldehydes with Hydrocarbons, Alcohols and aldehydes 8.1.4 Reactivity of Aldehydes in Reactions with Peroxyl radicals 8.2 Chemistry of Peracids 8. 3 Oxidation of ketones 8.3.1 Chain mechanism of Ketone oxidation 8.3.2 Reactivity of Ketones in Rcactions with Peroxyl radicals 8.3.3 Interaction of Ketones with Hydroperoxides 8.3. 4 Chemistry of Ketone Oxidation 8.4 Oxidative Decarboxylation of Carboxylic Acids 8.4.1 Attack of peroxyl r adicals on C-H Bond 8.4.2 Oxidative Decarboxylation of Acids References Chapter g Oxidation of amines. Amides. and esters 9. 1 Oxidation of Aliphatic amines 9.1.1 Introduction 9. 1.2 Chain Mechanism of Alkylamine Oxidation 9. 1.3 Reactivity of Amines in Reaction with Peroxyl radicals 9.2 Oxidation of amides 9.2.1 Introduction 9. 2.2 Chain mechanism of amide oxidatio 9.2.3 Decomposition of Hydroperoxides 9. 3 Oxidation of esters 9.3.1 Introduction 9.3.2 Chain mechanism of ester Oxidation 9.3.4 Effect of Multidipole Interaction in Reactions of icals 9.3.3 Reactivity of Esters in Reactions with Peroxyl Rad Polyfunctional esters References Den: sov/ Ox: dation and Antioxidants in Organic Chemistry and Biology DKl 162 prelims Final Proof page xii 25 2.2005 11: llam 0 Catalysis in Liguid- Phase hydrocarbon Oxidation 10.1 Catalysis by Transition Metal Ions and Complexes in Hydrocarbon Oxidation by Dioxygen 10.1.1 Introductie 10.1.2 Catalytic Decomposition of hydrogen peroxide by ferrous Ions 10.1.3 Catalysis by Transition Metal Ions and Complexes in Liquid-Phase Oxidation of Hydrocarbons and Aldehydes by Dioxyge 10.1. 4 Competition betwcen Homolytic and Heterolytic Catalytic Decompositions of hydroperoxides 10.1.5 Reactions of Transition Metals with Free Radicals 10.1.6 Reactions of Transition Metal lons with Dioxygen 10.1. 7 Catalytic oxidation of Ketones 10.2 Cobalt Bromide catalysis 10.3 Oscillating Oxidation Reactions 10.4 Acid Catalysis in Liquid-Phase Oxidation of llydrocarbons and Alcohols 10.5 Catalytic Epoxidation of Olefins by Hydroperoxides 10.6 Catalytic Oxidation of Olefins to Aldehydes 10.6.1 Catalysis by palladium Salts 10.6.2 Kinctics and mechanism of rcaction 10.7 Heterogeneous Catalysis in Liquid-Phase Oxidation 10.7.1 Introduction 10.7.2 Decomposition of Hydroperoxides on Catalyst Surface 10.7.3 Activation of Dioxygen 10.7.4 Critical Phenomena in Heterogeneous Catalysis. 10.7.5 Selectivity of Catalytic Oxidation 10.8 Oxidation in basic solutions References Chapter ll Oxidation of Hydrocarbons in Microheterogeneous Systems 11.1 Emulsion Oxidation of hydrocarb 11. 2 Hydrocarbon Oxidation in Microheterogeneous Systems Refer Chapter 12 Sulfoxidation of Hydrocarbons 12.1 Introduction 12.2 Chain mechanism of Sulfoxidation 12.3 Elementary Steps of Sulfoxidation 12.4 Dccomposition of Alkylsulfonyl Peracids 12.5 Oxidation by Alkylsulfonic Peracids 12.5. 1 Oxidation of Aromatic Hydrocarbons 12.5.2 Oxidation of olefins 12.5.3 Oxidation of Ketones

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