Table Of ContentOxidation and Antioxidants
in Organic Chemistry
and Biology
© 2005 by Taylor & Francis Group.
Oxidation and Antioxidants
in Organic Chemistry
and Biology
Evgeny T. Denisov
Igor B. Afanas’ev
Boca Raton London New York Singapore
A CRC title, part of the Taylor & Francis imprint, a member of the
Taylor & Francis Group, the academic division of T&F Informa plc.
© 2005 by Taylor & Francis Group.
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LibraryofCongressCataloging-in-PublicationData
Denisov,E.T.(EvgenyTimofeevich)
Oxidationandantioxidantsinorganicchemistryandbiology/EvgenyT.Denisov,IgorB.
Afanas’ev.
p.cm.
Includesbibliographicalreferencesandindex.
ISBN0-8247-5356-9(alk.paper)
1. Hydrocarbons–Oxidation. 2. Antioxidants. 3. Chemistry, Organic. 4. Biology
I.Afanas’ev,IgorB.,1935-II.Title.
QD305.H5D342004
547’.0104593–dc22 2004059305
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Dedication
We dedicate this book to the memory of pioneers of
Oxidation Chemistry, Aleksey Nikolaevich Bach and
Nikolay Aleksandrovich Shilov
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Table of Contents
Preface
Authors
List of ChemicalSymbols andAbbreviations
List of Physicochemical Symbols
List of Biochemical Abbreviations
Part I
Chemistryand Kinetics of OrganicCompounds Oxidation by Dioxygen
Chapter 1
Molecular Productsand Thermochemistry ofHydrocarbon Oxidation
1.1 Earlier Concepts ofOxidation
1.2 Development of the Chain Theoryof Oxidation of OrganicCompounds
1.3 Hydroperoxides asPrimary Molecular Products ofHydrocarbon Oxidation
1.3.1 Hydroperoxides
1.3.2 Dihydroperoxides
1.3.3 Cyclicand Polymeric Peroxides
1.3.4 Epoxides
1.4 Products of Hydroperoxide Decomposition
1.4.1 Hydroperoxidesas the Intermediates of Hydrocarbon Oxidation
1.4.2 Alcohols
1.4.3 Ketones
1.4.4 Acids
References
Chapter 2
Chain Mechanismof Liquid-Phase Oxidation of Hydrocarbons.
2.1 The Peculiarities ofChain Reactions
2.1.1 Free-Valence Persistence in Reactions ofFreeRadicals withMolecules
2.1.2 Condition ofCyclicityof RadicalConversions
2.1.3 Priority of Chain Propagation Reaction
2.1.4 Generation ofFreeRadicals.
2.1.5 Competition of Chain and Molecular Reactions
2.1.5.1 High Chemical Reactivityof Free Radicals and Atoms
2.1.5.2 Conservation of Orbital Symmetry inChemical Reaction
2.1.5.3 Configuration ofTransition 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 PeroxylRadicals
2.4.2 Reaction RO .þRH ! ROOHþR.
2
2.4.3 Intramolecular HydrogenAtom Transferin Peroxyl Radical
2.4.4 Addition ofPeroxylRadicalto theDoubleBond
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2.5 Chain Termination in Oxidized Hydrocarbons
2.5.1 Tetroxide
2.5.2 Disproportionation ofTertiary Peroxyl Radicals
2.5.3 Disproportionation ofPrimary and Secondary Peroxyl Radicals
2.5.4 Chemiluminescence
2.5.5 Chain Termination viaAlkylRadicals
2.6 Reactionsof AlkoxylRadicals
2.7 DifferentMechanismsof theAliphatic Hydrocarbon Oxidation inGas
and LiquidPhases
References
Chapter 3
Initiation ofLiquid-Phase Oxidation.
3.1 Initiators
3.1.1 Mechanismsof Decomposition of Initiators
3.1.1.1 UnimolecularDecompositionofInitiatorwithOneBondSplitting
3.1.1.2 Concerted Fragmentation of Initiators
3.1.1.3 AnchimericallyAssisted Decomposition ofPeroxides
3.1.2 Decay of Initiatorsto 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 Experimental Evidencesfor 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 CrossoverExperiments
3.2.1.5 Racemization
3.2.1.6 Influence ofViscosity
3.2.1.7 Influence ofPressure.
3.2.1.8 Spin Multiplicity Effects
3.2.2 Mechanistic Schemes ofthe Cage Effect
3.3 Initiation ofOxidation by Chemically Active Gases
3.3.1 Ozone
3.3.2 Nitrogen Dioxide
3.3.3 Halogens
3.4 Photoinitiation
3.4.1 Intramolecularand 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 CarbonylCompounds
3.4.4 Nonchain Photooxidation
3.5 Generation ofRadicals by Ionizing Radiation
3.5.1 Primary Radiation–Chemical Processes
3.5.2 Radiolytic Initiation ofHydrocarbon Oxidation
References
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Chapter 4
Oxidation as an Autoinitiated Chain Reaction
4.1 Chain Generation by Reaction of Hydrocarbon with Dioxygen
4.1.1 Bimolecular Reaction of Dioxygenwiththe C HBond of the
Hydrocarbon
4.1.2 Trimolecular Reaction ofHydrocarbon with Dioxygen
4.1.3 Bimolecular and Trimolecular Reactionsof Dioxygen with theDouble
Bond of Olefin
4.2 Hydroperoxides
4.2.1 Analysis
4.2.2 Structure ofHydroperoxides
4.2.3 Thermochemistry ofHydroperoxides
4.2.4 HydrogenBonding between Hydroperoxides
4.3 Reactions of Free Radical Generation by Hydroperoxides
4.3.1 UnimolecularDecomposition of Hydroperoxides
4.3.2 Bimolecular Decomposition of Hydroperoxides
4.3.3 Bimolecular Reactions ofHydroperoxideswithp-Bonds of Olefins
4.3.4 Bimolecular Reactions ofHydroperoxideswithC H, N H, and
O(cid:1)(cid:1)H Bonds ofOrganicCompounds
4.4 Parabolic Model ofBimolecular Homolytic Reaction
4.4.1 MainEquationsof IPM
4.4.2 Calculation of E and kof aBimolecular Reaction
4.4.3 Bimolecular Reactions ofRadical 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 Hydrocarbons
4.4.3.4 Reaction of Hydroperoxides with Alcoholsand Acids
4.5 Initiationby Reaction ofHydroperoxides withKetones
4.6 Chain Decomposition ofHydroperoxides
4.7 Kinetics ofAutoinitiated Hydrocarbon Oxidation
4.7.1 Initial Stage ofAutoxidation
4.7.2 Autoxidation withBimolecular Hydroperoxide Decay
4.7.3 Initiation by Reactions of Hydroperoxide with Products ofOxidation
4.7.4 Hydroperoxide as the Intermediate Product of Autoxidation
4.7.5 Self-Inhibition of Hydrocarbon Oxidation
References
Chapter 5
Co-Oxidation ofHydrocarbons
5.1 Theory of Hydrocarbon Co-oxidation
5.2 Hydrocarbon Oxidation withHydroperoxide
5.3 Co-oxidation ofHydrocarbons and AlcoholswithSelectiveInhibitor
5.4 Cross-disproportionation of PeroxylRadicals
5.5 Cross-propagation Reactions of Peroxyl Radicals
5.6 High Reactivity ofHaloidalkylperoxyl Radicals
5.7 Co-oxidation ofHydrocarbon and its Oxidation Intermediates
5.8 Catalysisby Nitroxyl Radicals inHydrocarbon Oxidation
References
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Chapter 6
Reactivity ofthe Hydrocarbons in Reactions with Peroxyl, Alkoxyl,
and AlkylRadicals
6.1 Semiempirical Model ofRadicalReaction asan Intersection of Two Parabolic
PotentialCurves
6.1.1 Introduction
6.1.2 IntersectingParabolas Model(IPM)
6.1.3 Calculation of theActivation Energy
6.2 Factors Influencingthe Activation Energ
6.2.1 Reaction Enthalpy
6.2.2 Force Constants ofthe Reacting Bonds
6.2.3 Triplet Repulsionin theTransition State
6.2.4 Electron Affinityof Atomsof Reaction Center
6.2.5 Radii ofAtomsof Reaction Center
6.2.6 Influence of Adjacentp-Bonds
6.2.7 PolarEffec
6.2.8 Influence of Solvation
6.3 Geometryof the Transition State of RadicalAbstraction Reaction
6.4 Intramolecular Hydrogen Transfer Reactions in Peroxyl, Alkoxyl,
and AlkylRadicals.
6.4.1 PeroxylRadicals
6.4.2 Alkoxyl Radicals
6.4.3 Alkyl Radicals
6.5 Free RadicalAdditionReactions
6.5.1 Enthalpy ofFreeRadicalAddition.
6.5.2 Parabolic Modelof RadicalAdditionReaction
6.5.3 Triplet Repulsionin RadicalAddition Reactions
6.5.4 Influence of theNeighboringp-Bonds on the Activation Energy
of RadicalAddition
6.5.5 Role ofthe Radius ofthe Atom Bearing a Free Valence
6.5.6 Interaction ofPolarGroups
6.5.7 Steric Hindrance
6.6 Free RadicalSubstitution and Hydrogen Atom Transfer Reactions
6.6.1 Free Radical Substitution Reactions
6.6.2 Reaction ofPeroxides withKetylRadicals
References
Chapter 7
Oxidation of Alcoholsand Ethers
7.1 Oxidation of Alcohols
7.1.1 Introduction
7.1.2 Chain Mechanism ofAlcohol Oxidation
7.1.2.1 Kinetics ofOxidation
7.1.2.2 Reactionsof Ketyl Radicals with Dioxygen
7.1.2.3 Reactionsof Alkylhydroxyperoxyland Hydroperoxyl
Radicals
7.1.2.4 Chain Termination in Oxidized Alcohols
7.1.3 Co-Oxidation of Alcoholsand Hydrocarbons
7.1.4 Reactivity ofAlcohols inReaction with Peroxyl Radicals
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7.1.5 Chain Generation in Autoxidation of Alcohols
7.1.5.1 Chain Generation by Reaction with Dioxygen
7.1.5.2 Decomposition of Hydrogen Peroxideinto Free Radicals
7.1.5.3 Chain Generation by Reaction of Hydrogen Peroxide with
CarbonylCompound
7.2 Oxidation of Ethers
7.2.1 Introduction
7.2.2 Chain Oxidation ofEthers
7.2.3 Co-Oxidation of Ethers and Hydrocarbons
7.2.4 Reactivity ofEthersin Reactions with Peroxyl Radicals
References
Chapter 8
Oxidation of CarbonylCompounds and Decarboxylation of Acids
8.1 Oxidation of Aldehydes
8.1.1 Introduction
8.1.2 Chain Mechanism ofAldehyde Oxidation
8.1.3 Co-Oxidation of Aldehydeswith Hydrocarbons,Alcohols,
andAldehydes
8.1.4 Reactivity ofAldehydes in Reactions with Peroxyl Radicals
8.2 Chemistryof Peracids
8.3 Oxidation of Ketones.
8.3.1 Chain Mechanism ofKetone Oxidation
8.3.2 Reactivity ofKetones inReactions withPeroxylRadicals
8.3.3 Interactionof Ketones with Hydroperoxides
8.3.4 Chemistry ofKetone Oxidation
8.4 Oxidative Decarboxylation of Carboxylic Acids
8.4.1 Attack of PeroxylRadicals on C(cid:1)(cid:1)H Bond
8.4.2 Oxidative Decarboxylation ofAcids
References
Chapter 9
Oxidation of Amines, Amides, andEsters
9.1 Oxidation of Aliphatic Amines
9.1.1 Introduction
9.1.2 Chain Mechanism ofAlkylamine Oxidation
9.1.3 Reactivity ofAminesin Reaction with PeroxylRadicals
9.2 Oxidation of Amides
9.2.1 Introduction
9.2.2 Chain Mechanism ofAmideOxidatio
9.2.3 Decomposition ofHydroperoxides
9.3 Oxidation of Esters
9.3.1 Introduction
9.3.2 Chain Mechanism ofEster Oxidation
9.3.3 Reactivity ofEsters inReactionswithPeroxylRadicals
9.3.4 Effect of Multidipole Interaction inReactionsof
PolyfunctionalEsters
References
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Chapter 10
Catalysisin Liquid-Phase Hydrocarbon Oxidation
10.1 Catalysisby Transition Metal Ions and Complexes in Hydrocarbon
Oxidation by Dioxygen
10.1.1 Introduction
10.1.2 Catalytic Decomposition of Hydrogen Peroxideby FerrousIons
10.1.3 Catalysis by Transition Metal Ionsand Complexes in
Liquid-Phase Oxidation of Hydrocarbons and Aldehydes
by Dioxygen
10.1.4 Competitionbetween Homolytic and Heterolytic Catalytic
Decompositions of Hydroperoxides
10.1.5 Reactions ofTransition Metalswith Free Radicals
10.1.6 Reactions ofTransition Metal Ionswith Dioxygen
10.1.7 Catalytic Oxidation ofKetones
10.2 CobaltBromide Catalysis
10.3 Oscillating Oxidation Reactions
10.4 Acid Catalysis inLiquid-PhaseOxidation ofHydrocarbons
and Alcohols
10.5 CatalyticEpoxidation of Olefins by Hydroperoxides
10.6 CatalyticOxidation of Olefins toAldehydes
10.6.1 Catalysis by PalladiumSalts
10.6.2 Kinetics and Mechanismof Reaction
10.7 Heterogeneous Catalysisin Liquid-Phase Oxidation
10.7.1 Introduction
10.7.2 Decomposition of Hydroperoxides on CatalystSurface
10.7.3 Activation of Dioxygen
10.7.4 Critical Phenomenain Heterogeneous Catalysis.
10.7.5 Selectivityof Catalytic Oxidation
10.8 Oxidation in Basic Solutions
References
Chapter 11
Oxidation of Hydrocarbonsin MicroheterogeneousSystems
11.1 Emulsion Oxidation of Hydrocarbons
11.2 HydrocarbonOxidation inMicroheterogeneous Systems
References
Chapter 12
Sulfoxidation ofHydrocarbons
12.1 Introduction
12.2 Chain Mechanismof Sulfoxidation
12.3 Elementary Steps of Sulfoxidation
12.4 Decomposition ofAlkylsulfonyl Peracids
12.5 Oxidation by Alkylsulfonic Peracids
12.5.1 Oxidation ofAromatic Hydrocarbons
12.5.2 Oxidation ofOlefins..
12.5.3 Oxidation ofKetones
References
© 2005 by Taylor & Francis Group.
Description:Providing a comprehensive review of reactions of oxidation for different classes of organic compounds and polymers, and biological processes mediated by free radicals, Oxidation and Antioxidants in Organic Chemistry and Biology puts the data and bibliographical information you need into one easy-to-
