SYNTHESIS OF THE GLYCERIDES 175 



isfactorily used by a large number of workers for the preparation of mixed 

 triglycerides .^ '^^ ~" 



(4) Sijnthesis of Fats from Petroleum 



The shortage of natural fats in Germany prior to and during World War 

 II afforded a stimulus to the development of the sjoithetic fat industry. 

 The background information necessary for establishing such commercial 

 production of food fats had been available for many years. Gessner/^ 

 as early as 1865, had demonstrated the oxidation of hydrocarbons by air, 

 and SchaaP^ had patented a similar process in 1885. Much additional in- 

 formation was obtained shortly after World War I in the laboratories of 

 Lever Brothers and Unilever in England, by Francis and co-workers.^~^'^ 

 These investigators studied the relative activity of a variety of oxidizing 

 agents and catalysts. They came to the conclusion that the most economi- 

 cal and efficient sjaithesis of fatty acids was brought about by the oxidation 

 of the paraffins at a high temperature with air. However, little was done 

 with this information in England, because the low cost of natural fats pre- 

 cluded the commercial production of the more expensive synthetic prod- 

 ucts. 



Interest in this field was revived in 1935 in Germany by the demonstra- 

 tion that the by-product, ''gatsch," could serve as a source of fatty acids. 

 This Fischer ''gatsch" originated, to the extent of 5 to 12%, in the synthe- 

 sis of petroleum products by the treatment of carbon monoxide with hy- 

 drogen at a high temperature under a pressure of 10 atmospheres, by the 

 so-called Fischer-Tropsch process. It could readily be separated from the 

 hydrocarbons, gasoline, Diesel oil, and "macroparaffins" by distillation. 

 It consisted of soft waxy hydrocarbons melting in the 340-450°C. range. 



The process, started in 1937 by Deutsche Fettsaure Werke in Witten, 

 Germany, involves the following main steps : After oxidation in an alumi- 



" H, C. Black and C. A. Overley, /. Am. Chem. Soc, 61, 3051-3052 (1939). 



" G. F. Converse and E. H. Shaw, Proc. S. Dakota Acad. Set., 17, 31-33 (1937). 



" C. Amberger and K. Bromig, Biochem. Z., ISO, 252-266 (1922). 



« O. E. McElroy and C. G. King, J. Am. Chem. Soc, 56, 1191-1192 (1934). 



»« H. E. Robinson, J. N. Roche, and C. G. ICing, /. Am. Chem. Soc, 54, 705-710 

 (1932). 



" P. E. Verkade and J. van der Lee, Proc Acad. Set. Amsterdam, 37, 812-818 (1934). 



** O. Gessner, Practical Treatise on Coal, Petroleum, and Other Distilled Oils (1865). 

 Cited by F. A. O. Report, Synthetic Fats, Their Potential Contribution to World Food Re- 

 quirements, Washington, D. C, Nov. 3, 1948, p. 1. 



*' E. Schaal, "Verfahrung zur Oxidation von Petroleum und ahnlichen Kohlenwasser- 

 stoffen zu Sauren und zur Herstellung von Seifen und Estern dieser Sauren," Patent- 

 schrift, 32, 705 (1885). Cited by F. A. O. Report, Synthetic Fats, Washington, D. C, 

 Nov. 3, 1948, p. 1. 



^ F. Francis, J. Chem. Soc, 121, 496-505 (1922). 



" F. Francis and J. C. Pope, /. Chem. Soc, 121, 506-511 (1922). 



« F. Francis and R. H. Coysh, J. Chem. Soc, 121, 511-513 (1922). 



