Fatty Acids

Chemistry, Synthesis, and Applications

Moghis U. Ahmad, Moghis U. Ahmad

• Publisher: Academic Press and AOCS Press
• Year: 2017
• ISBN:
  9780128095447
• Topic: Physical Sciences
• Subtopic: Analytic Chemistry

Fatty Acids: Chemistry, Synthesis and Applications is a comprehensive source of information about a wide range of industrially important fatty acids. This practical resource provides key insights into the chemistry, synthesis, industrial applications, derivatives, and analysis of fatty acids, and the chemical modifications that transform them for use in products from biodiesel fuels to pharmaceuticals.

Written by a team of industry experts, Fatty Acids includes detailed descriptions of fatty acid crystallization, enzymatic synthesis, and microbial production. This book focuses heavily on the chemistry of trans fatty acids, with extensive explanations of their synthesis and measurement. Further, the book addresses advances in the analytical methodology, including mass spectrometry, of fatty acids as well as their derivatives.

This book serves as a reference manual to a new generation of lipid scientists and researchers; a useful resource for oleochemical industries; and a valuable teaching aid for undergraduate and graduate students who are interested in fields related to the chemistry of oils, fats, and food.

• Includes recent developments in the synthesis of fatty acid derivatives, as renewable raw materials for the chemical industry
• Presents efficient synthetic methods for the dietary trans fatty acids in multi-gram scale allowing scientists and researchers to study dietary effects of individual trans fatty acids on human health
• Addresses uses of fats and fatty acids in foods and nutrition
• Identifies the roles of fatty acids and derivatives in cosmetic technology

Chapter 1

History of Fatty Acids Chemistry*

Gary R. List¹, James A. Kenar² and Bryan R. Moser², ¹G.R. List Consulting, Washington, IL, United States, ²National Center for Agricultural Utilization Research, Peoria, IL, United States

Abstract

Fatty acids are basic renewable chemical building blocks that can be used as intermediates for a multitude of products. Today the global value of fatty acids exceeds 18 billion dollars and is expected to increase to nearly 26 billion over the period from 2014 to 2019. From its auspicious beginnings, the growth of the fats and oils industry has rested upon the shoulders of those that have gone before and worked tirelessly to understand fatty acids and expand their utilization. Because of the important advances made by these and other researchers, renewable oleochemicals are now an important component of the worldwide chemical industry. This chapter provides a brief general historical perspective of some important developments in the chemistry of fatty acids.

Keywords

History; fatty acids; oleochemistry; fats and oils; lipids

Chapter Outline

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 Summary 17

References 18

1.1 Introduction

The history of fatty acids is a complex one with discoveries often coinciding. However, a number of landmark developments that had significant impact are covered here. The historian is often challenged by who discovered what and when. Fortunately, most of the major events and discoveries surrounding the chemistry of fatty acids are well documented in journal literature. The application of these discoveries in industry is often times difficult to discern because they are mainly documented in the patent literature, which can be time consuming to search, difficult to interpret, and most patents contain references to other patents, which in turn must be examined for prior art. A chronological summary of important discoveries in fatty acid, oleochemical, and triacylglycerol chemistry is shown in Table 1.1. This list is compiled from various sources including the open literature, patents, and chronological compilations from Blank (1942) and the Cyberlipid website (Anonymous, 2016).

Table 1.1

Chronological Summary of Important Discoveries in Fatty Acid, Oleochemical, and Triacylglycerol Chemistry

Year	Event
800	Soap produced in Germany
900	Soap produced in France
1600	Soap expands in France
1768	Candles exported to Great Britain
1779	Discovery of glycerol
1801	First oil mill in United States
1811	Bleaching with bone black
1814	Butyric acid discovered
1816	Saponification discovered
1817	Stearic acid discovered
1818	Valeric, caproic, oleic acids isolated
1819	Elaidizination of oleic acid
1823	Chevreul publishes Chemistry of Fats and Oils
1825	Candles patented in France
1825	Distillation of fatty acids
1828	Method for separation of solid and liquid fatty acids
1829	Splitting of tallow with sulfuric acid
1833	Saponification of fats with lime/pressure
1841	Myristic acid discovered
1844	First synthesis of a trigylceride
1844	Linoleic acid discovered
1848	Behenic acid discovered, ricinoleic acid discovered
1849	Lauric acid discovered
1849	Erucic acid discovered
1851	Autoclave for saponification
1852	Polymorphism discovered
1852	Interesterification discovered
1853	Term gylceride first used
1855	Correct structure of glycerol
1855	Margaric acid a mixture
1869	Margarine discovered
1879	Soxhlet extraction
1879	Saponification index
1880	Bleaching patented
1881	Hydroxy myristic acid discovered
1883	Chill roller patented
1884	Iodine value reported
1886	Diene structure of linoleic acid
1886	Tax on margarine
1887	Triene acid in hempseed oil
1889	Death of Chevreul
1892	First acetylenic acid reported
1894	Correct structure of ricinoleic acid
1895	Engine runs on peanut oil
1895	First book on the chemistry of fats and oils
1895	First English book on fats
1895	Lead salts for separation of solid/liquid triglycerides
1897	Discovery of hydrogenation/gas phase
1898	Fat-splitting patented
1898	Correct structure of oleic acid
1898	Liquid chromatography reported
1900	Benzenestearosulphonic acid as fat-splitting catalyst
1903	Hydrogenation in liquid phase
1904	First cyclopentyl acid discovered
1906	Hydrogenation of whale oil
1907	Reagent for splitting of fats
1911	Crisco shortening marketed
1915	Hydrogenation patented
1918	Continuous centrifuge patented
1920	Dimer acids discovered
1921	Separation of solid and liquid fatty acids
1923	Continuous refining patented
1923	Process for lecithin
1924	Industrial interesterification patented
1927	Method for classifying fats
1929	Isomerization during hydrogenation reported
1929	Essential fatty acids discovered
1930	Votator patented
1931	X-ray diffraction used for fatty acids
1931	Continuous fat-splitting patented
1932	Spray shortening
1933	Distillation of fatty acids patented
1933	High-ratio shortenings
1934	Synthesis of oleic acid
1934	First solvent extraction plant in United States
1934	Centrifugal refining introduced
1936	Distillation of fatty acids patented
1936	Primex shortening marketed
1937	Conjugation of linoleic acid by alkali
1937	Synthesis of linoleic acid
1940	Hilditch published Chemical Constitution of Fats
1940	Fatty amines/nitriles patented
1942	DHA from fish oil
1942	Chronology of fats, oils, waxes
1944	Comparison of fat-splitting catalysts
1945	Bailey published Industrial Oil and Fat Products
1945	Displacement analysis for fatty acids reported
1945	Relative rates of fatty acid oxidation reported
1947	Swiftning shortening marketed
1948	Directed interesterification reported
1948	Bailey published cottonseed book
1949	Mechanism of hydrogenation reported
1950	Bailey published melting and solidification of fats
1950	Markley published soybeans and products, 2 volumes
1951	Second edition of Bailey’s book published
1951	Thin-layer chromatography introduced
1952	GC introduced
1953	Death of Bailey
1954	Eckey published third edition of Vegetable Fats and Oils
1954	First soft margarine—Chiffon
1955	Synthesis of mixed acid triglyceride
1955	Golden Fluffo shortening marketed
1956	Stahl advances thin-layer chromatography
1960	Theory of glyceride structures proposed
1961	Hydrogenated winterized soybean oil marketed
1963	Nobel prize for Ziegler-Natta catalyst
1964	Last volume edition of Bailey’s book
1964	Olefin disproportination reported
1964	Markley published five-volume set on fatty acids
1965	Death of Hilditch
1974	Metathesis for synthesis of mono- and dicarboxylic acids
1980	Fatty acids published AOCS Press
1993	First trait modified soybean oil commercialized
2003	Trans fat labeling law
2004	Metathesis reviewed
2004	Metathesis for long-chain dicarboxylic acids
2005	Nobel Prize ...