Methyl octadecenoates are formed by thermal reaction of methyl linoleate in the presence of iodine. For the purpose of clarification of hydrogen source required for the formation of octadecenoates, quantitative relationship of reaction products was studied by the methods of fractional distillation, mass spectral and GLC analyses, and of the measurement of UV spectra of the reaction products after hydrogenation. The results showed that hydrogen iodide evolved by the action of iodine on Diels-Alder adduct type dimers makes an important role as hydrogen source for the formation of octadecenoates.
Oxygen was blown into a stirred mixture of α-cedrene (1) or β-cedrene (2) in a polar aprotic solvent (DMSO, DMF or HMPA) for 258O h at 80100°C. The oxidation of (1) in DMSO at 80°C took place to give 5-isocedranone (5), 6 (13) -cedren-5-one (6), and 5-cedren-4-one (7), while a similar oxidation of (2) yielded (5), (6), and 5-cedren-13-al (8) as major products. In DMF at 100±5°C, the oxidation of (1) gave 5α, 6α- epoxycedrane (3) that was a precursor of (5), (7), and (8), and the oxidation of (2) gave 6α, 13-epoxycedrane (4) that was a precursor of (8), (6), and 5-cedren-13-ol (9). When the oxidation of (1) was conducted in HMPA at 100±5°C, (1) was obtained selectively (68%).
Oxygen was blown into a mixture of β-elemene (1) and γ-elemene (2), α-selinene (3) and β-selinene (4) or α-humulene (5) in a polar aprotic solvent (DMAc or DMSO) for 516 h at 100120°C. Oxidation of (1) and (2) took place to give 3-isopropenyl-4-methyl-4-vinyl-1-cyclohexanone (6) and 1-acetyl-3-isopropenyl-4-methyl-4-vinylcyclohexane (7), while (3) and (4) yielded mainly 11-eudesmen-3-one (8), 2-acetyl-4a, 8-dimethyl-1, 2, 3, 4, 4a, 5, 6, 8a-octahydronaphthalene (9) and 2-acetyl-4a-methyl-8-methylenedecahydronaphthalene (10). A similar oxidation of (5) was found to afford two products; humulene epoxide-II (11) and humulenol-II (12). The compounds (9) and (10) are new sesquiterpenoids.
Polystyrene particles and basic iron sulfate [Fe3 (OH) 5 (SO4) 2·2 H2O] particles adhered to a glass plate, and cellulose, polyester and polystyrene films were removed in a washing device which was designed to produce a laminar flow between two cylinders of 5 mm gap at various rotation speed. The relationship between the separating force and the removal percentage, and the adhesive force between particles and substrate were estimated. The following results were obtained. 1) The results obtained in the new device were superior in accuracy than those in the device eqipped with a turn table which was reported in Part 1. 2) Under all washing conditions, the removal percentage of basic iron sulfate particles was lower than that of polystyrene particles. 3) The relationship between the separating force and removal percentage in each washing condition was similar to that in Part 1. 4) The adhesive force to several substrates of polystyrene particles in water was in the order; cellulose<glass<polyester, and was estimated at the range of 3.86 to 5.32×10-7 dyn, and that of basic iron sulfate particles was; cellulose<glasspolystyrene<polyester, and was estimated at the range of 11.5 to 15.8×10-7 dyn.
Aminolysis of p-nitrophenyl acetate (PNPA), p-nitrophenyl laurate (PNPL), phenyl acetate (PA), methyl acetylsalicylate (AMS), and ethyl benzoate (EB) catalyzed by dodecylammonium propionate (DAP) and monoethanolammonium dodecanoate (EAD) was studied in various apolar solvents. The dependence of pseoud-first order rate constants (κobs) on the concentration of surfactants in the micellarsystems differed markedly by the combination of the kinds of esters and the surfactants, while all kobsincreased linearly up to the cmc of surfactants in particular slopes. The extent of rate-enhancement was order of PNPA>>PNPL>PA≈AMS>EB in DAP/cyclohexane systems and of heptane>cyclohexane>benzene in PNPA/DAP systems. Further, the thermodynamic quantities of activation in both the monomer and micellar systems were evaluated from the temperature dependence of the rate constants. Remarkable decrease in the entropy of activation was observed and the results were compared with that in the hydrolysis of PNPA by aqueous micellar catalyst or that in the deacetylation of acetyl-enzyme (α-chymotrypsine) by α-chymotrypsine.
The anionic surfactants developed recently, alkanamide poly (oxyethylene) sulfates, are supposed to be more mild in the skin irritating action than the surfactants such as alkyl poly (oxyethylene) sulfates used conventionally in practice as a principal constituent of the household liquid detergents, shampoos and so on. In the present work, with the intention of investigating the practicability of these new surfactants the solution viscosities have been measured to depict the isoviscous curves on the triangular diagrams for the ternary systems, sodium alkanamide poly (oxyethylene) sulfate/N, N-diethanoldodecanamide (thickener) /water. Consequently, the following informations were obtained. (1) While, with increase in number of oxyethylene unit in the surfactant molecule, the high viscosity region extends toward the water corner, it is shifted to higher concentration of thickener and the highest viscosity falls down. In other words, the thickening effect of N, N-diethanoldodecanamidelowers. (2) Among three samples of different alkane chain lengths, dodecan-, tetradecan- and hexadecanamide poly (oxyethylene) sulfates, in the case of tetradecanamide the thicking effect is most remarkable and the solution of the utmost viscosity is obtainable. (3) In the case of sodium dodecyl poly (oxyethylene) sulfates, with increase in number of oxyethylene unit the highest viscosity falls down in a simillar manner, but the high viscosity region is shifted to lower concentration of thickener contrary to above.
High-boiling fraction of China gum terpentine have been investigated with GC-MS. The following compounds were shown to be present; dihydro-5-caryophyllen-one (13), isodihydro-5-caryophyllen-one (19), longicamphene hydrate (21), longicamphenilone (27), longi-β-camphenilanaldehyde (30), longi-β-fenchyl alcohol (31), longiverbenone (32), T-cadinol (33), 5-cloven-ol (36), α-cadinol (3i), 4 (12), 8 (13) -caryophylladien-5α-ol (43), longi-α-nojigiku alcohol (44), longicyclenyl alcohol (45), 3, 8 (13) -caryophylladien-5α-ol (46), and 3, 8 (13) -caryophylladien-5 β-ol (50). Three sesquiterpenoid compounds (19, 21, and 36) had not previously been found in natural products.