Dioctanoyl peroxide was synthesized from octanoyl chloride and hydrogen peroxide in ether at low temperature, and the reaction of dioctanoyl peroxide with bromine in the presence of nitrogen gas was studied. The reaction products were 1-heptyl bromide, tetradecane, caprilic acid and heptyl caprilate. The yield of 1-heptyl bromide was low and independent to the concentration of bromine. With increase in concentration of bromine, the yield of caprilic acid decreased and tetradecane and heptyl caprilate increased. These results suggest that C7H15COO· produced by the decomposition of dioctanoyl peroxide reacts with bromine to form C7H15COOBr, which is accelerated to decompose into C7H15·, CO2 and Br2 with increase in concentration of bromine, and C7H15· reacts with another C7H15· and C7H15COO· rather than with bromine, and that undecomposed C7H15COOBr reacts with water to form caprilic acid in washing after the reaction.
The hydrogenation of methyl linolenate was carried out in the presence of nickl catalyst at 180°C under a hydrogen pressure of 1 atm and also in the presence of platinum catalyst at 20°C under hydrogen pressures below 40mmHg. The hydrogenation products taken at different stages of reaction were analyzed by spectroscopic and gas chromatographic procedures. The results showed that the amount of isolinoleates formed (i.e. isomers which are formed from methyl linolenate and which do not undergo isomerization upon treatment with alkali) was extremely greater than the total amount of methyl esters of conjugated and normal dienoic acids formed. From the fatty acid compositions of the products obtained employing two types of catalysts, it is considered that the hydrogenation with nickel catalyst is a selective reaction while the hydrogenation with platinum catalyst is a nonselective reaction. A new method involving nuclear magnetic resonance spectral analysis is proposed for the determination of isolinoleates. If the sample consists of unsaturated fatty acids alone, the amount of isolinoleates can readily be determined from the results of nuclear magnetic resonance spectral analysis. However, if the sample contains both saturated and unsaturated acids, the amounts of saturated acids must be determined by gas chromatography before isolinoleates determination.
Stigmasterol and its acetate were epoxdized by perbenzoic acid in dioxane, benzene, diethyl ether, acetone or chloroform. In dioxane or acetone, at 03°C, decomposition (or reaction with the solvent) of perbenzoic acid occured but the rate of epoxidation was slower than in chloroform. In benzene, the rate was slightly slower than in chloroform. In ether, at room temperature, decomposition (or reaction with solvent) of perbenzoic acid also occured but at 03°C, mainly 5, 6-bond out of the two double bonds was epoxidized under the condition of 4 moles perbenzoic acid per 1 mole sterol.
Above mentioned fish were caught in the coldest season. The samples of oils were obtained from these fish. I. Catfish oil. A sample of the catfish (Parosilurus asotus Linne) oil was analyzed, and the following properties have been observed : Body oil Internal Liver oil organs oil Yield% 4.11 0.79 2.33 d154 0.9199 0.9268 - n15D 1.4710 n20D1.4753 n20D1.6730 A.V. 7.6 66.2 36.6 S.V. 191.2 171.2 215.9 I.V. 120.7 166.4 166.0 (Wijs) Unsaponifiable 2.01 16.93 13.37 matter % Color Reddish brown Yellow Dark brown Liver oil value 2.0 (+) 1) (+) 2) *1), 2) : Color reaction with cone H2SO4 The mixed fatty acids of the body oil had the following constants : Yield% N.V. I.V. Color 92.50 201.4 125.3 Yellowish brown The solid and liquid acids separated from the mixed acids had the following data : Solid acids Liquid acids Yield% 25.91 74.09 d204 - 0.9092 n20D - 1.4656 N.V. 209.0 196.8 I.V. 23.5 158.9 mp (°C) 47.248.6 - Color Pale yellow Dark red The above solid and liquid acids of the mixed acids composed of the following acids respectively : (i) Sold acids : Chiefly C16, C18 and minor amounts of C20, C22, C14, C12 acid. (ii) Liquid acid : C18-_??_1, _??_2, _??_3 and minor amounts of C16-_??_ : C22-_??_1, _??_2, _??_3 (_??_4?) acid and C22 unsaturated. Unsaponifiable matter mp (°C) I.V. Color Body oil 110.5117.8 136.9 Yellowish red Internal organs oil 142144 - Colorless Liver oil 141143 - Colorless II. Crucian oil The samples of the crucian oils of the body and internal organs were obtained from the fish by ether extraction and had the following properties : Body oil Internal organs oil Yield% 2.78 1.25 d154 0.9188 0.9188 n15D 1.4724 1.4725 A.V. 15.1 58.2 S.V. 193.4 172.9 I.V. 122.6 150.6 Unsaponifiable matter% 1.85 12.18 Color Reddish brown Yellowish brown Liver oil value 0 0 The mixed fatty acids of the body oil had the following data : Yield% N.V. I.V. Color 92.60 202.9 126.1 Yellowish red The solid and liquid acids separated from the mixed acids had the following properties : Solid acids Liquid acids Yield% 26.26 73.74 d204 - 0.9092 n20D - 1.4660 N.V. 210.0 199.4 V.I. 19.3 158.6 mp (°C) 48.550.6 - Color Pale yellow Dark red The solid and liquid acids composed of the following acids respectively : (i) Solid acids : Chiefly C16, C18 and minor amounts of C14, C20, C12 acid. (ii) Liquid acids : Chiefly C18-_??_1, _??_2 and minor amounts of C16-_??__??_, C20-_??_1, _??_2, _??_3 acid. Unsaponifiable matter mp (°C) I.V. Color Body oil 111.4118.6 125.6 Yellowish red Internall 142146 - Pale yellow organs oil III. Hymenophso curia oil This oil extracted from the only one fish (460g) of “Hymenophso curta” by ether extraction had the following properties : Yield% d154n15D S.V. I.V. 3.46 0.9215 1.4707 198.1 113.7 Unsaponifiable matter % Collor 2.29 Yellowish brown