The seeds of Ilex integra were extracted with petroleum ether. The fatty acid mixture obtained on saponification of the crude fats was esterified with methanol and concentrated sulfuric acid and then analyzed by GLC. The main component was octadecadienoic acid (linoleic acid). As minor components, the presence of eicosanoic, and octadecadienoic acids was confirmed by using the GC-MS method and ECL-value. Moreover, by the same means, the presence of some odd numer acids, such as heptadecanoic, and nonadecadienoic acids-which are seldom found in natural fatty acids-were identified. Authors believe that the combined use of the GC-MS method and ECL-value is an effective procedure for the determination of small amounts of fatty acids in natural compounds.
Triolein was hydrogenated under various operating conditions. Five types of catalysts were employed. Platinum and palladium catalysts were used at 50°C and each of three types of nickel catalyst was used at 160°, 180°, 200° and 220°C. The hydrogenated products were subjected to lipase hydrolysis (lipolysis) to remove a portion of the acyl groups on the α, α'-positions. The hydrogenated products and fatty acids liberated by lipolysis were analyzed for fatty acid compositions and for content of the trans isomers. In case of nickel boride catalyst, the results showed that the oleoyl groups on α, α'-positions of triolein molecule are hydrogenated slightly faster than that on β-position. The other catalysts have not shown the selectivity of hydrogenation toward the position of acyl groups. There was no relation to be discussed between the position of acyl groups and the formation of trans isomers during hydrogenation with each nickel catalyst. Upon comparison at the same iodine value, trans isomer content in hydrogenated products was the most in case of nickel boride catalyst.
Various kinds of phosphates are widely used as additives for gasolines and lubricating oils. This paper deals with the separation and identification of trialkyl phosphates having carbon atoms up to eight in the alkyl group and triaryl phosphates having methyl substituted radicals up to two in the aryl group by partition paper chromatography. It has been found that the solvent systems of chlorinated paraffin (40% Cl) (stationary phase) -100% ethyl alcohol (mobile phase) and chlorinated paraffin (40% Cl) or alkyl naphthalene (stationary phase) -80% ethyl alcohol (mobile phase) are suitable for partition paper chromatography of these phosphates. The Rf values of these phosphates become smaller with increase in the number of carbon atoms in the alkyl group or methyl substituted radicals in the aryl group. The Rf values of triaryl phosphates are smaller than those of trialkyl phosphates in the solvent system of chlorinated paraffin (40% Cl) -100% ethyl alcohol, therefore, it is possible to discriminate triaryl phosphates from trialkyl phosphates. For the identification of each phosphate, the solvent system of chlorinated paraffin (40% Cl) or alkyl naphthalene-80% ethyl alcohol is suitable. Phosphates in lubricating oils can be applied to partition paper chromatography through concentrating there of by silica gel adsorption chromatography.
Liquid-phase oxidation of acrolein into acrylic acid by oxygen in the presence of metal catalyst of cobalt laurate has been studied. There are several papers which reported on the formation of a considerable amount of polymer during the oxidation, but the discussions were not enough in detail. Authors made clear quantitatively the effect of oxygen, acrolein and concentration of catalyst affecting the formation of the polymer. When oxygen was dissolved enough in the solution no polymer formed. The formation of polymer is expressed by the following equation; 1/IP (P) =K (AL) 1.75 (O2) -1 where, IP (P) is induction period (min.) of polymer formation given by the time for formation of a turbid solution, and AL is concentration of acrolein (M). IP (P) increased with increase of concentration of catalyst. Elementary, functional and thermal analyses of the polymers were carried out as well as IR measurement. The contents of -CHO and -C=C- were high, and -COOH increased with increase of oxygen concentration though the content was low. Approximately, an amount of 86% of the polymers was formed by radical polymerization via acyl radical, and not via peracid radical. The above equation well explains the initiation of the oxidation and the mechanism of the polymerization.
In the course of the studies on thiiranes, the authors have synthesized the lower homologues of 1-alkoxy-3-chloropropane-2-sulfochloride by the reaction of 2-alkoxymethylthiirane and chlorine under presence of water. The present study is for the preparation of some higher homologues of 1, 3-bisalkoxypropane-2-sulfonates (C number of alkyl; 4, 6 and 8) and for clearification of properties of these sulfonates as surfactant. Above cmc, the surface tension of aq. solution of n-octylhomologue of the sulfonate (I) was 24.9dyne/cm at 40°C, lower than that of Na-dioctylsulfosuccinate (II) by about three dynes. The cmc value of (I), 2.5×10-4mol/l, was lower than that of (II), 4.3×10-3mol/l. The wettability and foam-stability of (I) were superior than those of (II). These properties can be explained in terms of the difference of the effective hydrophobic chain length and the state of adsorption, owing to the difference of hydrophilic property between the ether group in (I) and the ester group in (II).
Some higher homologues of 1, 3-bisalkylthio-2-propanol (I) and 1-alkoxy-3-alkylthio-2-propanol (II) were synthesized from epichlorohydrin, 1-alkanthiols and 1-alkanols, then converted by polyaddition of ethylene oxide (E0) into a series of new nonionics respectively, (RSCH2) 2CHO (C2H4O) nH (S type) and RSCH2 ROCH2 CHO (C2H4O) nH (OS type) where R=C4C8, n=7.546.
The stabilities of aqueous suspension of azo-type ahd anthraquinone-type disperse dyes dispersed with various types of surfactants at high temperature have been examined. The stability highly depends on the ionic nature and chemical structure of surfactants. With ionic surfactants, stable suspensoins are obtained when a surfactant has a polynuclear aromatic ring (or benzene rings more than 2) and a phenolic hydroxyl group in the molecule. With nonionic surfactants, suspensions are stable when a surfactant has benzene rings more than 2 and a cloud point of 2040°C. This suggests that there exists an optimum hydrophilic-lipophilic balance for the suspensions of disperse dyes when they are dispersed with nonionic surfactants. The results have been discussed in connection with the affinity of surfactants for disperse dyes and the difference in change of dissolution state with increasing temperature between ionic and nonionic surfactants.