2, 6, 11, 15-Tetramethylhexadecane (4), 2, 6, 10, 14, 19, 23, 27, 31-octamethyldotriacontane (6) and, 2, 7, 10, 15, 18, 23-hexamethyltetracosane (9) were synthesized by oxidative coupling and subsequent hydrogenolysis from, 3, 7-dimethyl-6-octen-1-yn-3-ol (1), 3, 7, 11, 15-tetramethyl-1-hexadecyn-3-ol (5), and 3, 6, 11-trimethyl-6, 11-dodecadien-1-yn-3-ol (7), respectively. The freezing points of (4), squalane, (9), (6), and 2, 7, 10, 15, 18, 23-hexamethyl-10, 15-tetracosanediol (8), a synthetic intermediate of (9), were found to be -108-110, -92-96, -91-93, -84-86, and -29-30°C, respectively. The density and absolute viscosity of squalane, (9) and (8), were also measured over a wide range of temperature. The specific volume, cubical expansion coefficient, activation energy of fluidity, and dynamic viscosity were deduced from these values, and the relaxation processes of these compounds are discussed. Other physical properties of squalane, (9) and (8) are listed in Table-3.
The composition and content of green pigments in alkali-refined rapeseed oil before and after bleaching were investigated. Pheophytins a and b were detected as major pigments, but chlorophylls a and b could hardly be found, when alkali-refined oil was fractionated by alumina column chromatography. The photofluorometric quantification of the same oil indicated essentially the same results. Bleaching tests of these four authentic pigments with activated clay as an adsorbent indicated the adsorption of each pigment to decrease in the following order: Chl a>Phy a>Chl b>Phy b. However, in experiments using an active carbon, no distinct difference in the adsorbed quantity of each pigments could be observed. The behavior of these pigments during the bleaching of rapeseed oil was analyzed photofluorometrically.
The formation mechanism and stability of low viscous O/W emulsions containing ethanol and having small disperse phase volumes were investigated. Stability against creaming was controlled by the Brownian movement of fine emulsion droplets of submicron order. To obtain such droplets, the effective orientation of surfactant molecules at the oil and water interface through formation of a liquid crystalline phase having a lamellar structure (D2 phase) during emulsification was indispensable. Based on the phase behavior of a ethanol-water-nonionic surfactant-methylphenyl polysiloxane quaternary system, the hydrophil-lipophile-balance of nonionic surfactants was concluded to be greatly influenced by the addition of ethanol. Formation of the D2 phase in the presence of a certain amount of ethanol was found possible only through use of hydrophobic nonionic surfactants having low cloud points.
Phenolic resin base multi-branched high molecular weight nonionic surface active agents were synthesized to evaluate their effects on improving the fluidity of coal-water slurry (CWS). The following results were obtained: 1) Surfactants prepared by addition reactions of ethylene oxide (EO) with phenol resin, parasecondarybutyl phenol resin, nonyl phenolic resin or dodecyl phenol rein improved the fluidity. 2) Nonyl or dodecyl is preferable as a resin alkyl group, and the number of nuclei of either from 12 to 19 is adequate. 3) The number of moles of added EO should be such that each side chain has a molecular weight of about 3, 000. 4) The addition of an agent equal to 0.4% of the coal to meet the above conditions 2) and 3) results in a viscosity of Tatung coal CWS of 1, 200cp at a coal concentration of 70%.
The ring and ball method is not as popular as the capillary melting point method for analysis of fats but is more accurate. It allows for the determination of margarine and shortening without removing moisture and gas. However this method has yet to be standardized. To establish it as a standard method, the methods for filling rings with fat samples and the tempering conditions of the samples in the rings were studied at 10 different laboratories, using the instrument designated as K-2207 by the Japanese Industrial Standard. Under various conditions, tempering at 0°C for 60min gave the best results with standard deviation of less than 0.5 for various fats and fat products.
We have reported that the soap aqueous solution had least frictional coefficient (μ) and the highest-seizure load (ρ) among the various surfactants (Anionics, Cationics, Nonionics & Amphoterics) in J. Jpn. Soc. Lubrication Eng. 29, 839 (1984). The μ and ρ were measured by Soda's 4-b all testing machine under the following condition. (200 r.p.m., step loading velocity 0.5kg/cm2/min, at room temp.) 1% soap solution had less and higher ρ than standard hydrocarbon oil, (100SN, 150SN, 350SN & 600SN) The standard hydrocarbon oil plus 1% of rapeseed oil fatty acids or castor oil fatty acids had the same μ and ρ of 1% soap aqueous solution.
This paper describes the synthesis of menthones (8) from methylheptenone (6-methyl-5-hepten-2-one). The synthetic route is shown in Scheme-1. The pyrolysis and thermocyclization reaction of 4-isopropyl-1-methyl-5-oxohexyl acetate (2), obtained by a radical addition reaction of 1, 5-dimethyl-4-hexenyl acetate (1) with acetaldehyde, gave (8) and isomenthone (9) each in a 28% yield. This reaction was carried out by heating compound (2) in a stainless tube at 350°C. Compounds (8) and (9) were also prepared from 6-bromo-3-isopropyl-2-heptanone (7) by an intramolecular alkylation reaction, in 64% yields. The alkylation reaction was carried out with sodium hydride in the presence of benzo-15-crown-5 as the catalyst in benzene.
光学活性カラムを用いる高速液体クロマトグラフィーによって,モノアシルグリセリンラセミ体の光学分割を検討した。モノアシルグリセリンを3,5-ジニトロフェニルウレタン誘導体に変換し,光学活性カラムスミパックスOA-2100(ν-アミノプロピルシラナイズドシリカに化学結合した(S)-2-(4-クロロフェニル)イソ吉草酸とそのアミド誘導体*,粒径5μm長さ25cm内径4mmのステンレス製カラム)を用いて分析した結果,ラセミ体が完全に分割された。 * (S)-2-(4-chlorophenyl) isovaleric acid and the amide derivatives of this acid chemically bonded to ν-aminopropyl silanized silica.