Fatty Acids: Chemistry, Synthesis, and Applications

617 Pages·2017·14.87 MB·English

by  Moghis U. Ahmad

Fatty Acids
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Fatty Acids
Chemistry, Synthesis, and Applications
Edited by
Moghis U. Ahmad
JinaPharmaceuticals, Inc.,Libertyville, IL,UnitedStates
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Contents
ListofContributors xvii
MeettheEditor xix
Preface xxi
1. History of Fatty Acids Chemistry
GaryR.List,JamesA.KenarandBryanR.Moser
1.1 Introduction 2
1.2 EarlyFattyAcidHistory 2
1.3 MajorDevelopmentsintheOleochemicalIndustry 9
1.3.1 FatSplitting 9
1.3.2 CatalyticHydrogenation 10
1.3.3 FattyAcidDistillation 11
1.3.4 FattyAlcohols 11
1.3.5 Estolides 12
1.3.6 DimerandTrimerCyclicFattyAcids 13
1.3.7 HydroformylationofFattyAcids 14
1.3.8 OzonolysisofFattyAcidsandTriglycerides 14
1.4 ContributionsofAnalyticalChemistrytoFattyAcids 15
1.5 RecentDevelopmentsinFattyAcids 16
1.6 Conclusion 17
References 18
2. Naturally Occurring Fatty Acids: Source,
Chemistry, and Uses
JamesA.Kenar,BryanR.MoserandGaryR.List
2.1 Introduction 24
2.2 ProductionofNaturallyOccurringFattyAcids 28
2.2.1 ChemicalSplitting 29
2.2.2 LipaseSplitting 30
2.3 PurificationofFattyAcids 31
2.3.1 SimpleDistillation 31
2.3.2 FractionalDistillation 32
2.3.3 MolecularDistillation 35
2.3.4 Crystallization 35
2.3.5 UreaFractionation 36
v
vi Contents
2.4 SourcesandTypesofNaturallyOccurringFattyAcids 37
2.4.1 SaturatedFattyAcids 38
2.4.2 UnsaturatedFattyAcids 39
2.4.3 HydroxyFattyAcids 43
2.4.4 AcetylenicFattyAcids 45
2.4.5 AllenicandCumulenicFattyAcids 47
2.5 ChemistryofNaturallyOccurringFattyAcids 49
2.5.1 ReactionsattheCarboxylicAcidGroup 50
2.5.2 ReactionsatUnsaturatedSites 57
2.6 Conclusion 71
References 71
3. Epoxy Fatty Acids: Chemistry and Biological Effects
ArnisKuksisandWaldemarPruzanski
3.1 Introduction 83
3.2 NaturalOccurrenceandStructureofEpoxyFattyAcids 84
3.2.1 OleicandLinoleicAcidMonoepoxidesandHydroxides 84
3.2.2 ArachidonicAcidMonoepoxides 85
3.2.3 EicosapentaenoicAcidandDocosahexaenoicAcid
Monoepoxides 85
3.3 ChemicalSynthesis 88
3.3.1 DirectEpoxidation 88
3.3.2 Chemo-EnzymaticPerhydrolysis 89
3.3.3 OtherChemo-EnzymaticEpoxidations 90
3.4 BiosynthesisofEpoxyFattyAcids 90
3.4.1 OxygenasesandLipoxygenases 91
3.4.2 Peroxygenases 91
3.4.3 CytochromeP450-LikeOxygenases 92
3.5 AnalysisofEpoxyFattyAcids 94
3.5.1 ResolutionofRegioisomers 95
3.5.2 ResolutionofEnantiomers 97
3.5.3 GC/MSandLC/MSIdentificationofLipidEpoxides 103
3.6 BiologicalEffects 104
3.6.1 LipidSignaling 104
3.6.2 CellularEffects 105
3.6.3 SystemicEffects 107
3.7 PathologicalEffects 108
3.7.1 Toxicity 108
3.7.2 InflammationandPain 108
3.7.3 AngiogenesisandCardiovascularDisease 110
3.7.4 Cancer 111
3.8 Conclusion 112
Abbreviations 112
References 113
Contents vii
4. Acetylenic Epoxy Fatty Acids: Chemistry,
Synthesis, and Their Pharmaceutical Applications
ValeryM.DembitskyandDmitryV.Kuklev
4.1 Introduction 121
4.2 OccurrenceEpoxyAcetylenicFattyAcidsinNature 122
4.3 LipidsContainingEpoxyAcetylenicFattyAcids 125
4.4 EpoxyAcetylenicFuranoidandThiopheneFattyAcidand
Derivatives 128
4.5 PyranoneandMacrocyclicEpoxides 129
4.6 AcetylenicCyclohexanoidEpoxyFattyAcids 130
4.7 DeterminationorEpoxyAcetylenicLipids 131
4.8 SynthesisofEpoxyAcetylenicLipids 136
4.9 ConcludingRemarks 141
References 142
FurtherReading 146
5. Carbocyclic Fatty Acids: Chemistry and Biological
Properties
MoghisU.Ahmad,ShoukathM.Ali,AteeqAhmad,
SaifuddinSheikhandImranAhmad
5.1 Introduction 148
5.2 NaturallyOccurringCyclopropeneFattyAcids 150
5.2.1 TheHalphenTest 151
5.2.2 IsolationofCyclopropeneFattyAcidsFromSeedOils 152
5.2.3 ChemicalCharacterization 152
5.3 SynthesisandCharacterizationofSterculicAcid 156
5.3.1 CharacterizationofDihydrosterculicAcid 158
5.3.2 TotalSynthesisofcis-CyclopropaneFattyAcids 160
5.3.3 DeuteratedCyclopropeneFattyAcids 161
5.4 BiosynthesisofCyclopropaneandCyclopropeneFattyAcids 163
5.5 MassSpectrometryofCyclopropeneFattyAcids 165
5.5.1 GasChromatography-MassSpectrometryAnalysisof
CyclopropeneFattyAcids 166
5.5.2 GasChromatography-MassSpectrometryAnalysisof
CyclopropaneFattyAcids 171
5.6 PhysiologicalPropertiesofCyclopropeneFattyAcids 171
5.7 CyclopropaneoctanoicAcid2-HexylinHumanAdipose
TissueandSerum 173
5.7.1 CyclopropaneoctanoicAcid2-HexylinPatientsWith
Hypertriglyceridemia 175
5.8 LeishmaniaCyclopropaneFattyAcidSynthetase 176
5.8.1 Leishmania:AFungalInfection 177
5.9 Conclusion 178
References 179
FurtherReading 185
viii Contents
6. Modification of Oil Crops to Produce Fatty
Acids for Industrial Applications
JohnL.Harwood,HelenK.Woodfield,GuanqunChen
andRandallJ.Weselake
6.1 Introduction 188
6.2 KeyAspectsofPlantOilBiosynthesis 189
6.3 MajorOilCrops 194
6.3.1 OilPalm(Elaeisguineensis) 194
6.3.2 Soybean(Glycinemax) 197
6.3.3 BrassicaOilseedSpecies(Brassicanapus,Brassicarapa,
Brassicaoleracea,Brassicacarinata) 201
6.3.4 Sunflower(Helianthusannuus) 206
6.4 MinorOilCrops 208
6.4.1 Alfalfa(Medicagosativa,Medicagofalcata) 209
6.4.2 Almond(Prunusdulcis,Prunusamygdalus,Amygdalus
communis) 209
6.4.3 Avocado(Perseaamericana,Perseagratissima) 209
6.4.4 Blackcurrant(Ribesniger) 209
6.4.5 Borage(Boragoofficinalis) 209
6.4.6 BorneoTallow(Shoreastenoptera) 209
6.4.7 Camelina(Camelinasativa)(Section6.5Also) 211
6.4.8 Castor(Ricinuscommunis) 211
6.4.9 Cocoa(Theobromacacao) 211
6.4.10 Coconut(Cocosnucifera) 212
6.4.11 Coriander(Coriandrumsativum) 212
6.4.12 Cottonseed(Gossypiumhirsutum,Gossypium
barbadense) 212
6.4.13 Crambe(Crambeabyssinica,Crambehispanica)
(Section6.5Also) 212
6.4.14 Cupheaspp. 212
6.4.15 Dimorphotheca(Dimorphothecapluvialis) 213
6.4.16 Echium(Echiumplantagineum) 213
6.4.17 Flax(Linumusitatissimum) 213
6.4.18 Hazelnut(Corylusavellana) 213
6.4.19 Jatrophacurcas(SeeSection6.5) 213
6.4.20 Jojoba(Simmondsiachinensis) 214
6.4.21 Lesquerella(Lesquerellafendleri)(SeeSection6.5) 214
6.4.22 Maize(Corn;Zeamays) 215
6.4.23 Meadowfoam(Limnanthesalba) 215
6.4.24 Mustard(Brassicaalba,Brassicacarinata,Brassicahirta,
Brassicajuncea,Brassicanigra) 215
6.4.25 Oats(Avenasativa) 215
6.4.26 Olive(Oleaeuropaea) 215
6.4.27 Peanut(GroundNut,Arachishypogaea) 216
6.4.28 PineNuts(Pinusspp.) 216
6.4.29 Poppy(Papaversomniferum) 216
Contents ix
6.4.30 Rice(Oryzasativa)BranOil 216
6.4.31 Safflower(Carthamustinctorius) 217
6.4.32 Shea(Butyrospermumparkii,SheaButter,KarateButter) 217
6.4.33 Tall 217
6.4.34 Tung(Aleuritesfordii) 217
6.4.35 VernoniaOils 218
6.5 EmergingIndustrialOilCrops 218
6.6 ProspectsforProductionofIndustrial
OilsinVegetativeTissue 222
Acknowledgments 223
References 223
FurtherReading 236
7. Microbial Production of Fatty Acids
ColinRatledgeandCaseyLippmeier
7.1 Introduction 237
7.2 TheProcessofLipidAccumulationinOleaginous
Microorganisms 241
7.3 EconomicConsiderations—HeterotrophicMicroorganisms 244
7.4 EconomicConsiderations—PhototrophicMicroorganisms 248
7.5 ProductionofPUFAs 251
7.5.1 NutritionallyImportantFattyAcids—Background
Information 251
7.5.2 ProductionofGamma-LinolenicAcid(GLA18:3n-6) 255
7.5.3 ProductionofArachidonicAcid(ARA20:4n-6) 258
7.5.4 ProductionofDocosahexaenoicAcid(DHA22:6n-3) 259
7.5.5 ProductionofEicosapentaenoicAcid(EPA20:5n-3) 260
7.5.6 ProductionofEPA/DHAMixturesasAlternativestoFish
Oils 264
7.6 SafetyAspects 266
7.7 FutureProspects 268
References 270
8. Chemical Derivatization of Castor
Oil and Their Industrial Utilization
RachapudiB.N.PrasadandBhamidipatiV.S.K.Rao
8.1 Introduction 280
8.2 DerivativesofCastorOilBasedonUnsaturation
ofRicinoleicAcid 282
8.2.1 HydrogenatedCastorOil 282
8.2.2 EpoxyCastorOil 282
8.2.3 OzonolysisofCastorOil 284
8.2.4 Preparationof9,10,12-TrihydroxyOctadecanoicAcid 285
8.2.5 HalogenatedDerivativesofCastorOil 285
8.2.6 NovelDerivativesofRicinoleicAcidEmploying
MetathesisReaction 285