Chemistry, Synthesis, and Applications Edited by · 2020. 1. 31. · 1.3.5 Estolides 12 1.3.6...
12
Fatty Acids Chemistry, Synthesis, and Applications Edited by Moghis U. Ahmad Jina Pharmaceuticals, Inc., Libertyville, IL, United States & ADCS PRESS ACADEMIC PRESS An imprint of Elsevier
Transcript of Chemistry, Synthesis, and Applications Edited by · 2020. 1. 31. · 1.3.5 Estolides 12 1.3.6...
Fatty Acids
Chemistry, Synthesis, and Applications
Edited by
Moghis U. Ahmad
Jina Pharmaceuticals, Inc., Libertyville, IL, United States
&ADCSPRESS
ACADEMIC PRESS
An imprint of Elsevier
Contents
List of Contributors xvii
Meet the Editor xix
Preface xxi
1. History of Fatty Acids ChemistryGary R. List, James A. Kenar and Bryan R. Moser
1.1 Introduction 2
1.2 Early Fatty Acid History 2
1.3 Major Developments in the Oleochemical Industry 9
1.3.1 Fat Splitting 9
1.3.2 Catalytic Hydrogenation 10
1.3.3 Fatty Acid Distillation 11
1.3.4 Fatty Alcohols 11
1.3.5 Estolides 12
1.3.6 Dimer and Trimer Cyclic Fatty Acids 13
1.3.7 Hydroformylation of Fatty Acids 14
1.3.8 Ozonolysis of Fatty Acids and Triglycerides 14
1.4 Contributions of Analytical Chemistry to Fatty Acids 15
1.5 Recent Developments in Fatty Acids 16
1.6 Conclusion 17
References 18
2. Naturally Occurring Fatty Acids: Source,
Chemistry, and Uses
James A. Kenar, Bryan R. Moser and Gary R. List
2.1 Introduction 24
2.2 Production of Naturally Occurring Fatty Acids 28
2.2.1 Chemical Splitting 29
2.2.2 Lipase Splitting 30
2.3 Purification of Fatty Acids 31
2.3.1 Simple Distillation 31
2.3.2 Fractional Distillation 32
2.3.3 Molecular Distillation 35
2.3.4 Crystallization 35
2.3.5 Urea Fractionation 36
v
vi Contents
2.4 Sources and Types of Naturally Occurring Fatty Acids 37
2.4.1 Saturated Fatty Acids 38
2.4.2 Unsaturated Fatty Acids 39
2.4.3 Hydroxy Fatty Acids 43
2.4.4 Acetylenic Fatty Acids 45
2.4.5 Allenic and Cumulenic Fatty Acids 47
2.5 Chemistry of Naturally Occurring Fatty Acids 49
2.5.1 Reactions at the Carboxylic Acid Group 50
2.5.2 Reactions at Unsaturated Sites 57
2.6 Conclusion 71
References 71
3. Epoxy Fatty Acids: Chemistry and Biological Effects
Amis Kuksis and Waldemar Pruzanski
3.1 Introduction 83
3.2 Natural Occurrence and Structure of Epoxy Fatty Acids 84
3.2.1 Oleic and Linoleic Acid Monoepoxides and Hydroxides 84
3.2.2 Arachidonic Acid Monoepoxides 85
3.2.3 Eicosapentaenoic Acid and Docosahexaenoic Acid
Monoepoxides 85
3.3 Chemical Synthesis 88
3.3.1 Direct Epoxidation 88
3.3.2 Chemo-Enzymatic Perhydrolysis 89
3.3.3 Other Chemo-Enzymatic Epoxidations 90
3.4 Biosynthesis of Epoxy Fatty Acids 90
3.4.1 Oxygenases and Lipoxygenases 91
3.4.2 Peroxygenases91
3.4.3 Cytochrome P450-Like Oxygenases 92
3.5 Analysis of Epoxy Fatty Acids 94
3.5.1 Resolution of Regioisomers 95
3.5.2 Resolution of Enantiomers 97
3.5.3 GC/MS and LC/MS Identification of Lipid Epoxides 103
3.6 Biological Effects 104
3.6.1 Lipid Signaling104
3.6.2 Cellular Effects 105
3.6.3 Systemic Effects 107
3.7 Pathological Effects 108
3.7.1 Toxicity108
3.7.2 Inflammation and Pain 108
3.7.3 Angiogenesis and Cardiovascular Disease 110
3.7.4 Cancer 111
3.8 Conclusion 112
Abbreviations 112
References 113
Contents vii
4. Acetylenic Epoxy Fatty Acids: ChemistrySynthesis, and Their Pharmaceutical ApplicationsValery M. Dembitsky and Dmitry V. Kuklev
4.1 Introduction 121
4.2 Occurrence Epoxy Acetylenic Fatty Acids in Nature 122
4.3 Lipids Containing Epoxy Acetylenic Fatty Acids 125
4.4 Epoxy Acetylenic Furanoid and Thiophene Fatty Acid and
Derivatives 128
4.5 Pyranone and Macrocyclic Epoxides 129
4.6 Acetylenic Cyclohexanoid Epoxy Fatty Acids 130
4.7 Determination or Epoxy Acetylenic Lipids 131
4.8 Synthesis of Epoxy Acetylenic Lipids 136
4.9 Concluding Remarks 141
References 142
Further Reading 146
5. Carbocyclic Fatty Acids: Chemistry and BiologicalPropertiesMoghis U. Ahmad, Shoukath M. AH, Ateeq Ahmad,Saifuddin Sheikh and Imran Ahmad
5.1 Introduction 148
5.2 Naturally Occurring Cyclopropene Fatty Acids 150
5.2.1 The Halphen Test 151
5.2.2 Isolation of Cyclopropene Fatty Acids From Seed Oils 152
5.2.3 Chemical Characterization 152
5.3 Synthesis and Characterization of Sterculic Acid 156
5.3.1 Characterization of Dihydrosterculic Acid 158
5.3.2 Total Synthesis of c/s-Cyclopropane Fatty Acids 160
5.3.3 Deuterated Cyclopropene Fatty Acids 161
5.4 Biosynthesis of Cyclopropane and Cyclopropene Fatty Acids 163
5.5 Mass Spectrometry of Cyclopropene Fatty Acids 165
5.5.1 Gas Chromatography-Mass Spectrometry Analysis of
Cyclopropene Fatty Acids 166
5.5.2 Gas Chromatography-Mass Spectrometry Analysis of
Cyclopropane Fatty Acids 171
5.6 Physiological Properties of Cyclopropene Fatty Acids 171
5.7 Cyclopropaneoctanoic Acid 2-Hexyl in Human AdiposeTissue and Serum 173
5.7.1 Cyclopropaneoctanoic Acid 2-Hexyl in Patients With
Hypertriglyceridemia 175
5.8 Leishmania Cyclopropane Fatty Acid Synthetase 176
5.8.1 Leishmania: A Fungal Infection 177
5.9 Conclusion 178
References 179
Further Reading 185
viii Contents
6. Modification of Oil Crops to Produce FattyAcids for Industrial Applications
John L Harwood, Helen K. Woodfield, Guanqun Chen
and Randall J. Weselake
6.1 Introduction 188
6.2 Key Aspects of Plant Oil Biosynthesis 189
6.3 Major Oil Crops 194
6.3.1 Oil Palm {Elaeis guineensis) 194
6.3.2 Soybean {Glycine max) 197
6.3.3 Brassica Oilseed Species (Brassica napus, Brassica rapa,
Brassica oleracea, Brassica carinata) 201
6.3.4 Sunflower {Helianthus annuus) 206
6.4 Minor Oil Crops208
6.4.1 Alfalfa {Medicago sativa, Medicago falcata) 209
6.4.2 Almond (Prunus dulcisf Prunus amygdalus, Amygdaluscommunis) 209
6.4.3 Avocado {Persea americana, Persea gratissima) 209
6.4.4 Blackcurrant (Ribes niger) 209
6.4.5 Borage {Borago officinalis) 209
6.4.6 Borneo Tallow (Shorea stenoptera) 209
6.4.7 Camelina (Camelina sativa) (Section 6.5 Also) 211
6.4.8 Castor (Ricinus communis) 211
6.4.9 Cocoa (Theobroma cacao) 211
6.4.10 Coconut (Cocos nucifera) 212
6.4.11 Coriander (Coriandrum sativum) 212
6.4.12 Cottonseed (Gossypium hirsutum, Gossypium
barbadense) 212
6.4.13 Crambe (Crambe abyssinica, Crambe hispanica)
(Section 6.5 Also) 212
6.4.14 Cuphea spp.212
6.4.15 Dimorphotheca {Dimorphotheca pluvialis) 213
6.4.16 Echium (Echium plantagineum) 213
6.4.17 Flax {Linum usitatissimum) 213
6.4.18 Hazelnut {Corylus avellana) 213
6.4.19 Jatropha curcas (See Section 6.5) 213
6.4.20 Jojoba (Simmondsia chinensis) 214
6.4.21 Lesquerella {Lesquerella fendleri) (See Section 6.5) 214
6.4.22 Maize (Corn; Zea mays) 215
6.4.23 Meadowfoam (Limnanthes alba) 215
6.4.24 Mustard (Brassica alba, Brassica carinata, Brassica hirta,
Brassica juncea, Brassica nigra) 215
6.4.25 Oats (Avena sativa) 215
6.4.26 Olive {Olea europaea) 215
6.4.27 Peanut (Ground Nut, Arachis hypogaea) 216
6.4.28 Pine Nuts {Pinus spp.) 216
6.4.29 Poppy {Papaver somniferum) 216
Contents ix
6.4.30 Rice (Oryza sativa) Bran Oil 216
6.4.31 Safflower (Carthamus tinctorius) 21 7
6.4.32 Shea {Butyrospermum parkii, Shea Butter, Karate Butter) 21 7
6.4.33 Tall 217
6.4.34 Tung (Aleurites fordii) 217
6.4.35 VernoniaOils 218
6.5 Emerging Industrial Oil Crops 218
6.6 Prospects for Production of Industrial
Oils in Vegetative Tissue 222
Acknowledgments 223
References 223
Further Reading 236
7. Microbial Production of Fatty Acids
Colin Ratledge and Casey Lippmeier
7.1 Introduction 237
7.2 The Process of Lipid Accumulation in OleaginousMicroorganisms 241
7.3 Economic Considerations—Heterotrophic Microorganisms 244
7.4 Economic Considerations—Phototrophic Microorganisms 248
7.5 Production of PUFAs 251
7.5.1 Nutritionally Important Fatty Acids—BackgroundInformation 251
7.5.2 Production of Gamma-Linolenic Acid (GLA 18:3 n-6) 255
7.5.3 Production of Arachidonic Acid (ARA 20:4 n-6) 258
7.5.4 Production of Docosahexaenoic Acid (DHA 22:6 n-3) 259
7.5.5 Production of Eicosapentaenoic Acid (EPA 20:5 n-3) 260
7.5.6 Production of EPA/DHA Mixtures as Alternatives to Fish
Oils 264
7.6 Safety Aspects 266
7.7 Future Prospects 268
References 270
8. Chemical Derivatization of Castor
Oil and Their Industrial Utilization
Rachapudi B.N. Prasad and Bhamidipati V.S.K. Rao
8.1 Introduction 280
8.2 Derivatives of Castor Oil Based on Unsaturation
of Ricinoleic Acid 282
8.2.1 Hydrogenated Castor Oil 282
8.2.2 Epoxy Castor Oil 282
8.2.3 Ozonolysis of Castor Oil 284
8.2.4 Preparation of 9,10,12-Trihydroxy Octadecanoic Acid 285
8.2.5 Halogenated Derivatives of Castor Oil 285
8.2.6 Novel Derivatives of Ricinoleic Acid EmployingMetathesis Reaction 285
x Contents
8.3 Derivatives of Castor Oil Based on Hydroxy Functionality
of Ricinoleic Acid 286
8.3.1 Dehydrated Castor Oil and Dehydrated Castor
Oil Fatty Acids 286
8.3.2 Sulfated Castor Oil (Turkey Red Oil) 288
8.3.3 Acetylated Castor Oil 288
8.3.4 Castor Oil-Based Estolides 289
8.3.5 Castor Oil—Based Polymer Products 289
8.3.6 Potent Hydroxy Derivatives of Ricinoleic Acid 291
8.4 Derivatives Based on Ester Functionality of Castor Oil 291
8.4.1 Hydroxy Fatty Acid Esters 291
8.4.2 Castor Oil-Based Biodiesel 292
8.4.3 Preparation of Ricinoleyl Alcohol 293
8.4.4 Ricinoleic Acid—Based Amides 293
8.4.5 Ethanolamides of Castor Oil Fatty Acids 293
8.5 Unique Derivatives of Castor Oil 293
8.5.1 Castor Oil—Based Dimer Acids 293
8.5.2 10-Undecenoic Acid and Heptaldehyde 294
8.5.3 Sebacic Acid and 2-Octanol 295
References 296
Chemical Modification of High Free FattyAcid Oils for Biodiesel Production
Godlisten G. Kombe
9.1 Introduction 305
9.2 Production of Biodiesel 306
9.2.1 Types of Feedstocks 306
9.2.2 The Potential of High FFA Feedstocks in Biodiesel
Production 307
9.2.3 Challenges of Processing High FFA Feedstocks 308
9.3 Chemical Modification of High FFA Feedstocks for
Biodiesel 309
9.3.1 Potential Processes for Modification of High FFA
Feedstocks 309
9.4 Conclusion and Recommendations 321
References 323
Further Reading327
Synthesis of Sugar Fatty Acid Esters
and Their Industrial Utilizations
Bianca Perez, Sampson Anankanbil and Zheng Guo
10.1 Introduction 329
10.2 Synthesis of Sugar Fatty Acid Esters 331
10.2.1 Chemical Synthesis of Sugar Fatty Acid Esters 331
10.2.2 Enzymatic Synthesis of Sugar Fatty Acid Esters 333
Contents xi
10.3 Physicochemical Properties of Sugar Fatty Acid Esters 343
10.3.1 Emulsifying Stability and Foaming Ability 344
10.3.2 Toxicity and BiodegradabiIity 345
10.4 Industrial Applications of Sugar Fatty Acid Esters 346
10.5 Conclusion 347
Acknowledgment 348
Abbreviations 348
References 348
Further Reading 354
11. Fatty Acids-Based Surfactants and Their Uses
Douglas C. Hayes
11.1 Introduction 355
11.1.1 Biobased Surfactants: A Growing Market 355
11.2 Biobased Surfactants Are a Robust Product for an
Oleochemical-Based Biorefinery 359
11.3 Oleochemical Feedstocks for Surfactant Synthesis 361
11.4 Sustainability of Oleochemical-Based Surfactants:
Truths and Myths 367
11.5 Green Manufacturing of Biobased Surfactants 368
11.6 Ionic Surfactants 369
11.6.1 Methyl Ester Sulfonates 369
11.6.2 Esterquats 369
11.6.3 Amino Acid—Based Surfactants 370
11.6.4 Others 371
11.7 Ester-Based Nonionic Surfactants 372
11.7.1 Glyceride Esters 372
11.7.2 Ethoxylates of Fatty Acids and Partial Glycerides 372
11.7.3 Sugar Esters 372
11.7.4 Polyol Esters 373
11.8 Ether and Amide-Based Nonionic Surfactants 373
11.8.1 Alkyl Polyglucosides 373
11.8.2 N-Alkyl N-Methyl Glucamine 374
11.8.3 Others 374
11.9 Zwitterionic (Amphoteric) Surfactants 374
11.9.1 Phospholipids 374
11.9.2 Betaines 375
11.10 Glycolipid Biosurfactants 376
11.11 Conclusion 378
References 379
12. The Role of Fatty Acids in Cosmetic Technology
Gary R. Kelm and Randall R. Wickett
12.1 Introduction 385
12.2 Cosmetic and Personal Care Product Formulation Types 386
xii Contents
12.3 Cosmetic and Personal Care Product Categories 388
12.4 Reviewed Fatty Acid Derivatives and Overview of Uses in
Cosmetic and Personal Care Products 391
12.4.1 Fatty Alcohols 392
12.4.2 Anionic and Nonionic Surfactants Based
Upon Fatty Acids 393
12.4.3 Fatty Amines and Quaternary Ammonium
Compounds 393
12.4.4 Esters of Fatty Acids 393
12.5 Cleansing394
12.6 Vehicles/Solvents 395
12.7 Rheological Modification of Suspensions and Sticks 397
12.8 Stabilization of Emulsions 399
12.9 Skin Emollients and Hair Conditioners 401
12.10 Conclusion 402
References402
13. Chemistry of Long-Chain a,(3-Unsaturated FattyAcid and Reactions Thereof
Abdul Rauf and Mohammad F. Hassan
13.1 Introduction
13.2 Synthesis of a,3-Unsaturated Fatty Acids
13.3 Reactions of a,(3-Unsaturated Fatty Acids/Esters
13.3.1 Bromination—Dehydrobromination13.3.2 Cyclopropanation13.3.3 Hypohalogenation13.3.4 Peracid Oxidation
13.3.5 Allylic Halogenations13.3.6 Nitrogen, Oxygen, Sulfur Derivatives of
a,(3-Unsaturated Fatty Acids/Esters
13.3.7 Other Derivatives
13.3.8 a,3-Epoxy Compounds13.4 Applications13.5 Conclusion
AcknowledgmentReferences
Abbreviations
14. Estolides: Synthesis and ApplicationsSteven C. Cermak, Terry A. Isbell, Jakob W. Bredsguardand Travis D. Thompson
14.1 Introduction 432
14.2 Synthesis435
14.2.1 Free-Acid Estolides 436
14.2.2 Estolide 2-Ethylhexyl Esters 438
405
406
407
407
408
409
410
412
414
422
425
425
426
427
427
430
Contents xiii
14.2.3 Coco-Oleic Estolide 2-Ethylhexyl Esters (One-StepProcess) 440
14.2.4 Coco-Oleic Dimer and Coco-Oleic Trimer Plus
Estolides 440
14.2.5 Commercial Estolide 2-Ethylhexyl Ester (SE7B) 443
14.3 Identification 444
14.3.1 GC Analysis 444
14.3.2 Acid Value 447
14.3.3 Nuclear Magnetic Resonance (NMR) Spectroscopy 447
14.4 Basic Physical Properties of Oleic-Based Estolides and Esters 449
14.4.1 Gardner Color 449
14.4.2 Viscosity and Viscosity Index 451
14.4.3 Pour Point and Cloud Point 454
14.4.4 Oxidation Tests 456
14.4.5 NOACK Evaporative Loss 465
14.5 Estolides (SE7B), Base Oil, and Motor Oil
Properties—Applications 466
14.5.1 Performance Properties 467
14.5.2 Estolide Application-Based Motor Oil SE7B—Field
Test 471
14.6 Conclusion 472
References 473
15. An Efficient, Multigram Synthesis of Dietary c/s- and
frans-Octadecenoic (18:1) Fatty Acids
Moghis U. Ahmad
15.1 Introduction 478
15.2 Organic Synthesis of Unsaturated Fatty Acids 480
15.3 Fatty Acids Containing One Acetylene Bond 481
15.3.1 Synthesis of A3-Acetylenic (Octadec-3-Ynoic) Acid 481
15.3.2 Synthesis of A4-Acetylenic (Octadec-4-Ynoic) Acid 482
15.3.3 Synthesis of A5-Acetylenic (Octadec-5-Ynoic) Acid 483
15.3.4 Synthesis of A6-Acetylenic (Octadec-6-Ynoic) Acid 484
15.3.5 Synthesis of A7-Acetylenic (Octadec-7-Ynoic) Acid 486
15.3.6 Synthesis of A8-Acetylenic (Octadec-8-Ynoic) Acid 487
15.3.7 Synthesis of A9-Acetylenic (Octadec-9-Ynoic) Acid 488
15.3.8 Synthesis of A10-Acetylenic (Octadec-10-Ynoic)
Acid 488
15.3.9 Synthesis of A11 -Acetylenic (Octadec-11 -Ynoic)
Acid 490
15.3.10 Synthesis of A12-Acetylenic (Octadec-12-Ynoic)
Acid 490
15.3.11 Synthesis of A13-Acetylenic (Octadec-13-Ynoic)Acid 491
15.3.12 Synthesis of A14-Acetylenic (Octadec-14-Ynoic)
Acid 492
xiv Contents
15.3.13 Synthesis of A15-Acetylenic (Octadec-15-Ynoic)
Acid 494
15.3.14 Synthesis of A16-AcetyIenic (Octadec-16-Ynoic)
Acid 495
15.4 Partial Hydrogenation of Acetylenic Acid and Structure
Determination 495
15.5 Reduction of Acetylenic Acid to c/s-Olefinic Acid 496
15.6 Reduction of Acetylenic Acid to frans-Olefinic Acid 497
15.7 High-Performance Liquid Chromatography Analyses 498
15.8 Conclusion 501
References 502
16. Advancement in Chromatographic and Spectroscopic
Analyses of Dietary Fatty Acids
Magdi M. Mossoba, Sanjeewa R. Karunathilaka,
Jin K. Chung and Cynthia T. Srigley
16.1 Introduction 505
16.2 Gas Chromatography With Flame Ionization Detection 506
16.3 Fourier-Transform Infrared Spectroscopy 510
16.3.1 Infrared Spectroscopy 510
16.3.2 Attenuated Total Reflection Spectroscopy 510
16.3.3 Negative Second Derivative ATR-FT-IR Official
Method 511
16.3.4 Novel Portable ATR- and Transmission-Mode FT-IR
Devices 513
16.4 FT-Near-lnfrared Spectroscopy in ConjunctionWith Partial Least Squares 514
16.5 Conclusion 525
References 525
17. Mass Spectrometry in the Analysis of
Fatty Acids and Derivatives
Yu Lin, Ming Guan, Lin Li, Yangyang Zhang and Zhenwen Zhao
17.1 Introduction 529
17.2 Extraction of Fatty Acids (FAs) and Derivatives 531
17.3 Fatty Acids (FAs) Analysis by Mass Spectrometry 532
17.4 Arachidonic Acid (AA) and Its Derivatives Analysis by Mass
Spectrometry 532
17.5 Triacylglycerols (TAGs) Analysis by Mass Spectrometry 533
17.6 Glycerophospholipids and Sphingolipids Analysis by Mass
Spectrometry 534
17.7 Double Bounds Position Analysis by Mass Spectrometry 535
17.8 Future Perspective 536
Acknowledgment 536
References 536
Contents xv
18. Crystallization of Fats and Fatty Acids in Edible Oils
and Structure Determination
Michael A. Rogers
18.1 Nucleation and Crystal Growth of Fatty Acids & TAGs 541
18.1.1 Super Cooling and Nucleation 542
18.1.2 Crystal Growth 544
18.2 Lipid Polymorphism 546
18.2.1 Lipid Mesophase Polymorphism 546
18.2.2 Crystalline Polymorphism 548
18.3 Nanostructure and Lipid Domains 549
18.4 Microstructure and Fractal Assembly 552
18.5 Modified Fatty Acids and Their Gels 553
18.6 Conclusion 555
Acknowledgments 555
References 555
Index 561
