Reaction of 1-methoxy-l-cyclohexylhydroperoxide with 1, 3-butadiene in the presence of iron (II) sulfate gave dimethyl 8, 12-icosadienedioate (6 b) (R=H) and dimethyl 8-vinyl-10-octadecenedioate (5 b) (R=H) in high yield and high selectivity. When 1-methoxy-1-cyclopentyl (or cycloheptyl) hydroperoxide, in stead of 1-methoxy-1-cyclohexyl hydroperoxide, was used, the similar reaction proceeded in the presence of 1, 3-dienes to give the corresponding products (4 a and 4 c, 5 a and 5 c) in the moderated yields.
Seven staple fibers were compared for adhesion to particulate soils. In this study, spherical particles of hydrated iron (III) oxide (Fe2O3·H2O) were prepared, and adhesion to various fibers of Fe2O3·H2O in the dispersion medium was examined after 48 h under weak mechanical oscillation at various temperatures (15, 30, 50°C). The amount of soil per unit external surface area of a fiber (g/m2) was defined as the amount of Fe2O3·H2O adhering to the fiber substrate. Langmuir type adhesion isotherms were obtained for all staple fibers and were exothermic. Affinity parameters of the seven fibers in n-heptane/n-tetradecane mixtures (95 : 5) were of the following order : Vinylon>Cupra rayon > Polyester > Nylon >Acryl >Poly (vinylchloride) > Polypropylene.
The thermal oxidation of thin films of trioleoylglycerol in oxygen and air was investigated by thermogravimetric analysis with dynamic thermal programs. The results obtained are as follows. 1) The thermal oxidation of trioleoylglycerol was affected by film thickness and heating rate. 2) The relationship between the extrapolated value [Y : 100 μg · cm-2] of maximum increased in weight to zero of the heating rate and film thickness [X : μm] of trioleoylglycerol could be expressed as follows; Y=2.4 X [X<110 μm] in oxygen Y=0.98 X+170 [X>110, μm] in oxygen Y=2.0 X [X< 90 μm] in air Y=0.35 X+150 [X> 90, μm] in air 3) The relationship between the thickness [Y : μm] of the thermaly decomposed layer and film thickness [X : μm] of trioleoylglycerol could be expressed as follows; Y=0.85 X [X<80 μm] in oxygen Y=0.45 X+31 [X>80 μm] in oxygen Y=0.85 X [X<60 μm] in air Y=0.37 X+30 [X>60 μm] in air 4) Decrease in weight by heating occured in 23 steps for of thin film and 34 steps for of thick film. The first step appeared to be a thermal oxidation decomposition reaction with an apparent activation energy of 815 kcal/mol. Subsequent steps were possibly various thermal oxidation polymerization reactions with apparent activation energy was 3799 kcal/mol.
Molecular interactions between dipalmitoyl phosphatidylcholine (DFFC) and lipophilic substances in a lipid bilayer were investigated by measurements of the encapusulation efficieny of glucose, micropolarity and microfluidity. The encapusulation efficiency of glucose in liposomes decreased rapidly with an increase in concentrations of polar aliphatic substances such as 1-octanol and octanoic acid, but was almost independent of the non-polar hydrocarbon octane. The micropolarity of the lipid bilayer decreased with increasing concentration of octane (and/or 1-octanol), but was independent of octanoic acid. The microfluidity of the lipid bilayer and rates of glucose leakage for several lipophilic substances varied in the order, 1-octanol>octanoic acid> octane. The permeability of liposomes was found to depend on the position of lipophilic substance in membranes and hydrophobic interactions between lipid and lipophilic substances in the lipid bilayer.
Acetoxylation of alkylfurans with lead tetraacetate in the mixed solution of acetic acid and ether (2 : 1) was studied. It the reaction of 2-butyl-3-methylfuran (8) with lead tetraacetate, 3-methyl-α-propyl-furfuryl acetate (22) was obtained selectively in a 76 % yield. (22) was hydrolyzed in a 78 % yield with aq. NaOH to give 3-methyl-α-propylfurfuryl alcohol (24), and then (24) was treated with hydrogen chloride in ethanol to obtain ethyl 3-methyl-4-oxooctanoate (25) in a 70 % yield. (25) was reducted with sodium borohydride, followed by cyclization to give whisky lacton (26, 27) in a 92 % yield. Menthofuran (28) was also treated with lead tetraacetate to give 3, 6-dimethyl-4, 5, 6, 7-tetra-hydrobenzofuryl acetate (29) in a 41 % yield. (29) was hydrolyzed in a 89 % yield with aq. Na2CO3 to give mintlactone (30).
The solubilization behavior of a poorly water-soluble drug (griseofulvin : GF) was examined using swellable clay minerals. The solubility of GF in pure water markedly increased by complex formation with clay minerals. GF in the complex was completely solubilized in pure water for the samples at a GF/clay mineral ratio less than 10 wt %. The formation of the complex was due to depression of the crystal growth of GF based on strong host-guest interactions between GF and clay minerals. The greatest solubility was achieved by the complex produced for the system GF/synthesized clay mineral.
Bioreactors were developed for water/oil heterogeneous enzymatic bioreactions. Using a cotton fiber disperser, small droplets (0.25 mm) of oil could be efficiently dispersed into an enzymatic water solution. 96 % conversion was achieved when olive oil was fed through the disperser from the bottom of the eight-staged bioreactor into the aqueous solution containing 500 U/mL Candida cylindracea lipase at 37°C.
The identification of sterols obtained from the unsaponifiable lipids of stem extracts of two Lauraceae plants, Neolitsea aciculata and Litsea japonica was carried out based on chromatographic (GLC and HPLC) and mp data. Sterol composition was determined from GLC data. Some minor components were assigned on the basis of MS and NMR spectroscopic data and a comparison with authentic sterols. The major components of the two Lauraceae plants were sitosterol, campesterol and sitostanol, both sterol compositions were essentially the same. These sterol constituents were compared with those of six Lauraceae plants. Neolitsea sericea, Cinnamomum loureirii, Laurus nobilis, Machilus japonica, Lindera umbellata and Lindera obtusiloba.