The selectivity of the hydrogenation of linseed oil
We have invest igated the se lec t iv i ty of the hydrogenat ion of l inseed oil, which is a mix tu re of t r i g l y c e r ides of fatty acids of different degrees of unsaturat ion linolenic, l inoleic, and ole ic and sa tura ted fatty acids . Depending on the conditions of hydrogenat ing oils and fats , the p roce s s may go according to the following scheme , given in the l i t e r a tu re [1]:
Some additional notes on the kinetics and theory of fatty oil hydrogenation
Summary1.Equations are given for estimating from the composition of oil samples the relative reaction rates of the different unsaturated fatty acids in an oil subjected to catalytic hydrogenation.2.Application of the equations to data from the hydrogenation of cottonseed oil reveals that the ratio of reaction rates, linoleic acid to oleic acid, varies from about 4 to 1 in very non-selective to about 50 to 1 in very selective hydrogenation. Re-examination of analytical data on two series of linseed oils hydrogenated selectively and non-selectively showed the following relative reaction rates for oleic, isolinoleic (9: 10, 15: 16 octadecadienoic), linoleic, and linolenic acids, respectively: non-selective, 1, 2.5, 7.5, 12.5; selective, 1, 3.85, 31, 77. In the non-selective hydrogenation of the oil, 24% of the linolenic acid reacting went to linoleic acid, 65% to isolinoleic acid, and 11% directly to oleic acid. In the selective reaction the corresponding figures were none to linoleic acid, 54% to isolinoleic acid, and 46% to oleic acid. The behavior of soybean oil hydrogenated selectively was quite similar to that of linseed oil.3.The results are discussed in relation to the theory of catalytic hydrogenation. They indicate that the solution of hydrogen in the oil and the adsorption of unsaturated oil on the catalyst are the two steps which are controlling with respect to the reaction rate. It is suggested that the hydrogen pressure, the degree of hydrogen dispersion through the oil, the catalyst concentration, and the temperature all affect the selectivity of the reaction through their influence on the concentration of hydrogen in the reaction zone, with selectivity being favored by a low concentration.
Sterol metabolism. XLI. Cholesterol A-ring autoxidations
Abstract Chromatographic and spectral evidence is adduced for the presence of cholest-5-en-3-one, cholest-4-en-3-one, and cholest-4-ene-3,6-dione in samples of cholesterol aged naturally in air or subjected to irradiation in air by 60 Co gamma radiation. These findings establish an additional mode of air oxidation of cholesterol to A-ring 3-ketones. Moreover, the oxidation by air of cholest-5-en-3-one induced by 60 Co gamma radiation yielded cholest-4-en-3-one, cholest-4-ene-3,6-dione, and the epimeric 3-oxocholest-4-ene-6-hydroperoxides. Cholest-4-en-3-one was not altered by irradiation in air, nor was cholesterol isomerized to cholest-4-en-3β-ol upon irradiation. From these observations it is deduced that the radiation-induced A-ring dehydrogenation of cholesterol yields initially cholest-5-en-3-one which upon isomerization yields cholest-4-en-3-one not further oxidized and which by a second oxidation yields the epimeric 3-oxocholest-4-ene-6-hydroperoxides which decompose to cholest-4-ene-3,6-dione.