Tocopherol and tocotrienol contents in 18 oils extracted from the different rice varieties in different districts in Japan and in 5 commercial rice bran oils were determined by HPLC. α-, β-, and γ-Tocopherols, and α- and γ-tocotrienols were identified. Extracted oils contained 4511, 370μg/g of tocopherols. Tocotrienol contents were about 57% of tocopherols. Tocopherol and tocotrienol contents in commercial oils were about 44% of extracted oils. Tocopherol and tocotrienol contents varied with the same varieties in the different districts and the different varieties in the same districts. Fluctuation of observed value in extracted oil was in the range of 5.410.5%.
The thermogravimetric analyses, changes of ultraviolet spectra by heating, and thermal transitions of several ferulates were investigated. The results of thermogravimetric analyses of cholesteryl ferulate, sitosteryl ferulate, and trimethylysteryl ferulate showed that the thermal stabilities of sitosteryl ferulate and trimethylsteryl ferulate were little inferior to that of cholesteryl ferulate. Although, the thermogravimetric analysis curves of sitosteryl ferulate and trimethylsteryl ferulate were similar to that of cholesteryl ferulate. Under various conditions of heating, the stabilities of ferulates were examined by determining the intensity of absorption at 315nm. Sitosteryl ferulate was more unstable than campesteryl ferulate, stigmasteryl ferulate, and trimethylsteryl ferulate, and cholesteryl ferulate was most stable among the five kinds of ferulates. When the ferulates were heated at 200°C for 4 h in the air atmosphere, the decrease of their absorption by heating was as follows : Cholesteryl ferulate, 35%; sitosteryl ferulate, 65%; campesteryl ferulate, 55%; stigmasteryl ferulate, 50%; and trimethylsteryl ferulate, 55%. The thermal decomposition products of cholesteryl ferulate that was heated at 200°C for 4 h in the air atmosphere were investigated. Cholesterol, vanillin and ferulic acid from the decomposition products were confirmed by TLC, GLC, UV, and mass spectrometry. When a crude rice bran oil containing the ferulates was heated at 180°C for 2 h in the air atmosphere, the absorption maximum of the oil at 291nm was disappeared, and shown newly at 270nm. The heats of transition of four steryl ferulates, trimethylsteryl ferulate and their acetyl derivatives, and oryzanol which is a mixture of ferulates have been evaluated. The order of increase to heats of fusion for steryl ferulates were sitosteryl ferulate, stigmasteryl ferulate, cholesteryl ferulate and campesteryl ferulate, and the result indicates that is in proportion to melting point of each ferulates. The heats of fusion of acetyl derivatives of ferulates were higher than those of corresponding ferulates. There are presence of shoulders in the peak of the melting curves of acetyl derivatives of cholesteryl ferulate and stigmasteryl ferulate, and the melting curves differ from those of corresponding ferulates.
On the analysis of triglyceride by GC-MS, it was commonly assumed that the intensity of some fragment ions (RCO+ and [RCO+128] + ion) were proportional to the quality of corresponding fatty acid. The propriety of the assumption was investigated. Prepared model triglyceride mixture consisted of saturated straight chain fatty acid and had wide molecular distribution. As for total fatty acid composition, GC-MS method was compared with usual hydrolysis-GC method. GC-MS (depend on intensity of RCO+ ion) provided slight excess value at C8 to C14-acid, and less value at C16 to C20-acid. [RCO+128] + ion had same tendency as RCO+ ion, but it was susceptible to obstruction of [RCO+128+14n] + ion series.
Polymorphism, temperature of phase transition, enthalpy and entropy of trans-monounsaturated monoglycerols were investigated, and correlation between trans- and cis-monounsaturated monoglycerols was examined. 1) Trans-monounsaturated monoglycerols have β, α, and Sub-α type polymorphism, but Sub-α2 was not observed even in monobrassidoylglycerol. Consequently, the acyl groups of monoglycerols capable of forming Sub-α2 are restricted by the structure having saturated hydrocarbon longer than 18 carbon atoms. Trans-monounsaturated monoglycerols showed similar transition behavior to cis-monounsaturated monoglycerols, and easily transformed from metastable to stable state at room temperature. 2) Temperature of phase transition, enthalpy and entropy of trans-monounsaturated monoglycerols were listed in the Table. It was characteristic that enthalpy and entropy of monobrassidoylglycerol for Sub-α→α transition were larger than those of monoelaidoylglycerol. 3) Temperature of phase transition, enthalpy and entropy of trans-monounsaturated monoglycerols were larger than those of cis-monounsaturated monoglycerols at each phase. These differences between cis- and trans-monounsaturated monoglycerols were larger at metastable than stable state, and became larger in the monoglycerols having shorter acyl groups.
Oxygen was blown into a mixture of cumene (1), m- and p-diisopropylbenzenes [(2) and (3)], p-cymene (4), 1-isopropenyl-4-methylbenzene (5), stylene (6), isosafrole (7), anethole (8) or isoeugenole (9) in a polar aprotic solvents (DMSO, DMI, DMAc or DMF) for 3200h at 100120°C. The oxidation of (1) (5) with isopropyl or isopropenyl group in DMSO at 100120°C took place to give acetylbenzene (10), 1-acetyl-3-isopropylbenzene (12), 1-acetyl-4-isopropylbenzene (14), and 1-acetyl-4-methylbenzene (16) in high selectivity (100%), while a similar oxidation in DMF or DMI yielded 2-phenyl-2-propanol (11), 2- (m-isopropylphenyl) -2-propanol (13), 2- (p-isopropylphenyl) -2-propanol (15), and 2- (p-methylphenyl) -2-propanol (17). In the case of (6) (8) with vinyl or allyl group, in DMSO at 100120°C gave benzaldehyde (18), piperonylacetone (22), and (p-methoxyphenyl) acetone (23) as major products. In DMI, DMAc or DMF at 100120°C, the oxidation of (6) (9) gave (18), 1-phenyl-1, 2-epoxyethane (19) that was a precurser of (10), piperonal (20), anisaldehyde (22), (23), 1- (p-methoxyphenyl) -1, 2-epoxypropane (24) that was a precurser of (23), and vaniline (25).
A homologous series of 3-alkoxypropylamines (II) with various alkoxyhydrocarbon chain lengths was synthesized as follows : ROH+CH2=CHCN_??_ROCH2CH2CN (I) (I) +2H2→ROCH2CH2CH2NH2 (II) (II) is characterized by the existence of one oxygen atom in the hydrocarbon chain. Nonionic surfactants derived from (II) were more hydrophilic than those from alkylamines with the corresponding carbon number; the effect of an addition of one oxygen atom in the molecule on surface activity corresponded to that of the decrease of approximately 3 to 4 carbon atoms. This fact was confirmed from the results obtained by the measurements of the surface tension, the wetting, the foam height and the solubilization.
Synthesis of cis-Jasmone (6) from readily available starting materials are described. The synthetic route is shown in Scheme-1. The Michael addition of acrolein to nitromethane catalyzed by tributyl phosphine in benzene followed in situ by the acetalization gave 1, 1-ethylenedioxy-4-nitrobutane (1). The Michael addition of (1) to 3-buten-2-one gave 1, 1-ethylenedioxy-4-nitro-7-octanone (2) in 95% yield. 1, 1-Ethylenedioxy-4, 7-octanedione (3) was obtained from (2) with H2O2-K2CO3 in 85% yield. Hydrolysis of (3) with 1% H2SO4 gave 4, 7-dioxooctanal (4) in 90% yield. The Wittig reaction between (4) and propylidene triphenylphosphorane in benzene gave cis-8-undecene-2, 5-dione (5) in 60% yield. cis-Jasmone (6) was formed from (5) under basic conditions in 83% yield. Similarly, cis-Jasmone (6) was prepared from (7) which was obtained by cyclization of (3).