For the purpose of establishing a standard method for the determination of total monoacylglycerol (MG), a collaborative study team has carried out analyses of specified samples by three methods ; Method I, II and III. In the Method I, perchloric acid was added simultaneously with periodic acid to a chloroform solution of a sample and then total MG was determined directly. In the Method II, 1-MG and 2-MG were equilibrated by addition of perchloric acid and then only 1-MG was determined by iodometry and the percentage of total MG was calculated with the use of the multiplication factor of 1.15. In the Method III, the amount of perchloric acid and the period of standing differed from them in the Meth d II. When saturated samples were analysed, intra- and interlaboratory scatterings of data obtained by each mothod were almost very small. The analytical values obtained by the Method I agreed very closely with the known values but the values by the Method II and III did not. With unsaturated samples, the analytical values obtained by the Method I, which gave satisfactory result for the saturated MG, were higher than the known values. Since the higher IV of the sample was, the higher the analytical value was, a part of periodic acid added was seemed to be consumed by double bonds present in the sample. It was concluded that with a saturated sample, the Method I was suitable for the determination of total MG.
The catalytic addition reaction of maleic anhydride to camellia fatty acids by flow method was investigated. It was found that the addition of maleic anhydride to camellia fatty acids is carried out by continuously passing the mixed sample of the fatty acids and maleic anhydride at molar ratio of 1 : 1 over the catalyst having 3meq/g of phosphoric acid deposited on the synthetic silica-alumina composed of 70% of SiO2 and 29% of Al2O3 as a carrier. The products formed by the catalytic addition reaction was analyzed to be predominantly consisted of the compounds listed in Table-1. The reaction mechanism for producing the compounds during the addition reaction of maleic anhydride to camellia fatty acids was also discussed.
Optimum reaction conditions for preparing potassium 5, 8-diisopropyl-2-naphthalenesulfonate (KDNS) were investigated. When naphthalene was β-sulfonated with concentrated sulfuric acid for 13h at 160°C and then alkylated with 2-propanol (molar ratio to naphthalene=2 : 1) for 2h at 80°C, KDNS was recovered in a maximum yield (ca. 30%) by neutralizing the sulfonated product with a potassium hydroxide solution. A highly purified KDNS (purity : >99%) was obtained only by recrystallizing the raw KDNS four times from water. On the contrary, the preparation of potassium dibutylnaphthalenesulfonate applying the previous reaction conditions was very difficult. Moreover, the quantitative preparating procedures of 5, 8-diisopropyl-2-naphthalenesulfonyl chloride and methyl 5, 8-diisopropyl-2-naphthalenesulfonate as easily soluble and volatile derivatives of KDNS, were found for determining the purity of KDNS by means of instrumental analyses in approximately 100% yields and conversion ratios.
Effects of concentration of Aerosol OT and amount of solubilized water on degree and rate of removal of water soluble soil from various fabrics in nonaqueous washing were studied. Sodium chloride and thiourea were applied as model of water soluble soil. Wool, cotton, acryl, polyester, and polyester-cotton blend were used as test fabrics. In the nonaqueous solution of Aerosol OT containing solubilized water, the soils are transfered from the soiled fabric to the unsoiled with the aid of the water and the amount of the soil adhering to each fabric becomes equal to reach the equilibrium. Degree of soil removal from the soiled fabrics at equilibrium increases as the amount of the solubilized water increases and also as the concentration of Aerosol OT decreases. Further, the degree of soil removal from the hydrophobic fabric is higher than that from the hydrophilic. Rate of soil removal from fabrics indicated that it was almost of the reaction of the first order. It increases as the amount of the solubilized water increases and as the concentration of Aerosol OT decreases. It was proved, therefore, that removal of the water soluble soil from fabric was mainly due to its dissolving into the solubilized water in the nonaqueous solution of Aerosol OT while the removal as solid dispersion in the solubilized water was partly observed in such cases as the amount of the water was small and the concentration of Aerosol OT was high.
1, 4-Diketones, which are important intermediates for syntheses of jasmones, were prepared from 2-methyl-2-vinyl-1, 3-dioxolane (1) via the radical addition of aldehydes to (1) followed by hydrolysis of ketoacetals. The radical addition reaction of heptanal (2a) to (1) was carried out with benzoyl peroxide or α, α'-azobisisobutyronitrile as an initiator in N2 atomosphere at 8085°C. 2, 2-Ethylenedioxy-5-undecanone (3a) was obtained in 57% yield as a major product by this reaction. The by-products in this reaction were 2-methyl-2-octyl-1, 3-dioxolane (5), 7-tridecanol (6), heptanoic acid (7), 2, 2-ethylenedioxy-3-methyl-4-decanone (8), 3, 3-ethylendioxy-1-phenylbutane (9), and 2- (3, 3-ethylendioxybutyl) heptanal (10). Similarly, 2, 2-ethylenedioxy-cis-8-undecen-5-one (3b), 4, 4-ethylendioxy-1-phenyl-1-pentanone (3c) and 5, 5-ethylenedioxy-2-hexanone (3d) were obtained in 1257% yield. Hydrolysis of (3a) with 20% H2SO4 gave 2, 5-undecanedione (4a) in 95%, yield. Similarly, cis-8-undecene-2, 5-dione (4b), 1-phenyl-1, 4-pentanedione (4c), and 2, 5-hexanedione (4d) were obtained in 9093% yields.