Iron, copper, zinc, and magnesium combined with poly L-Glu (poly L-glutamic acid) in metal concentration of 100ppm at 50°C for 20hr. Iron combined almost with poly L-Glu. In the metal concentration of 1000ppm, Cu-poly L-Glu and Zn-poly L-Glu complexes formed the precipitate, but Fe-poly L-Glu complex did not form the apparent precipitate. In the mixture of Mg and poly L-Glu, no precipitate was formed. Cu-poly L-Glu mixture gave the absorbance of 250 and 700nm. In IR spectra, the absorbance of 1580cm-1 decreased in order of Mg-poly L-Glu mixture, Fe-poly L-Glu, Cu-poly L-Glu, and Zn-poly L-Glu complex. On the contrary, the absorbance of 1540cm-1 increased in above order. Iron did not combine almost with poly L-Lys, but copper and zinc combined. Cu-poly L-Lys and Mg-poly L-Lys mixtures gave new absorbance at 1120cm-1.
The alkali-fusion reactions of six sodium alkanesulfonates were studied. The reaction of sodium 2- (p-substituted phenyl) ethanesulfonates and sodium 1-hexanesulfonate with sodium deuteroxide afforded p-substituted styrenes and 1-hexene respectively, which contained one or two deuterium atoms on the terminal olefinic carbons, whereas the reaction of 1-phenylethanesulfonate with sodium deuteroxide afforded styrene which contained one deuterium atom on the α-carbon and also one to three deuterium atoms on the phenyl carbons. Furthermore, the reaction of sodium 2, 2-d2-2-phenylethanesulfonate with sodium hydroxide afforded mainly α-d-styrene. From these results, it was suggested that the alkalifusion reaction of sodium alkanesulfonates to produce olefins is E2 elimination accompanied with the hydrogen exchange on the α-carbon to the sulfonyl group, prior to the elimination.
In the homogeneous metathesis of 2-heptene catalyzed by WCl6-Et3Al and WCl6-R4Sn systems, the influence of the reaction medium on the conversion was investigated. Many kinds of halogenated hydrocarbon were found to be the more excellent medium than benzene and chlorobenzene. The polychlorinated aliphatic hydrocarbons, and polyhalogenated benzenes such as trichloroethylene, tetrachloroethylene, hexachloro-1, 3-butadiene, hexachlorocyclopentadiene, 1, 1, 2, 2-tetrachloroethane, o- and m-dichlorobenzene and 1, 2, 4-trichlorobenzene gave the good conversions without the formation of the undesirable Friedel-Crafts products. The optimum range of the ratio Et3Al/WCl6 and Olefin/WCl6 shifted depending upon the medium used. In the binary solvent systems of benzene-trichloroethylene, -1, 2, 4-trichlorobenzene and -m-dichlorobenzene, the best conversions were observed at 4045 volume% of the halogenated solvent. The metathesis was significantly inhibited by the addition of the compounds containing oxygen, sulfur, nitrogen and phosphorus atoms to the reaction medium. The mechanisms of the medium effects were discussed.
The surface activities of amino acid ester hydrochlorides were determined. Among these esters, amino acid lauryl ester hydrochlorides showed the best performance, with respect to lowering power of surface tension, foaming power and wetting power. The lowering power of surface tension decreased with increasing the carbon number of the amino acid residue, that is, in the following order, glycine, alanine and valine. On the contrary the wetting power gradually increased. The cmc values of L-forms were smaller than those of DL-forms. But there were no notable differences in the solubility, lowering power of surface tension, foaming power and wetting power.
The relationship between the molecular structure of nonionic surfactants and their adsorptivities on activated carbons was investigated. The adsorption isotherms for all water-soluble nonionic surfactants used in this study were Langmuir type and the adsorptivities were higher than ordinary organic compounds. With the increase in the length of polyoxyethylene chain of polyoxyethylene nonylphenyl ether (NP), activated carbons were saturated by NP in lower concentrations, and both the adsorption rate and the amount of adsorbed NP at saturation decreased. For the surfactants with a fixed length of polyoxyethylene chain, the adsorption was favored by the increase in the length of the alkyl chain. An unsaturated bond in the alkyl chain depressed the adsorption. The carbon activated with zinc chloride had large surface area and pores, and was effective for the adsorption of nonionic surfactants. When an aqueous solution of NP was passed through the column of activated carbon under certain conditions, the adsorption efficiency was 90.6%. These results suggest that the use of activated carbon may be very effective for the treatment of wastewater containing nonionic surfactants.
The effect of coexisting salts for adsorption of nonionic surfactants on activated carbon in aqueous solution was investigated. Inorganic salts which reduced the cloud point of polyoxyethylene nonylphenyl ether (NP-10) increased the adsorption of NP-10 on activated carbon, while inorganic salts which raised the cloud point disturbed the adsorption. In the case of organic salts, the adsorption of NP-10 on activated carbon was disturbed because of the competing adsorption between NP-10 and organic salts. The amount of adsorption of NP-10 decreased with increasing the hydrophobicity of organic salts. Sodium sulfate, sodium perchlorate and sodium citrate aggregated NP-10 molecules. The aggregation was influenced by temperature. The amount of adsorption of NP-14 on activated carbon was unaffected by the changes of pH in the range of 2 to 12.
Sodium silicate and sodium tripolyphosphate in detergents were determined automatically by using Technicon Auto Analyzer. Detergents were fused with alkali carbonates to form soluble silicate and orthophosphate from sodium silicate and tripolyphosphate. Then, the alkali fused sample solution was neutralized and determined colorimetrically. Silicate is measured at 420nm based on silicomolybdate method, and phosphate is measured at 660nm based on molybdenumblue method. Both compounds were determined using the same sample solution without interference and also determined simultaneously. The range of determination for silicate was from 10 to 100mg/l, and for phosphate from 50 to 300mg/l. Forty samples could be determined within one hour.
The stereochemistry of allylic oxidation of trans-β-terpinyl acetate (1) and cis-β-terpinyl acetate (2) by selenium dioxide were studied. In each case, both the methine group at C4 and the methyl group at C9 of (1) and (2) were oxidized, and the reactivity sequence was CH>CH3. The trans- and cis-8-p-menthene-1-acetoxy-4-ols ((1c) and (1d)) were obtained by the oxidation of (1) and (2), respectively. The acetoxy group at C1, has no steric hindrance toward the oxidation of the methine group at C4, and so there is little stereoselectivity observed in the tertiary alcohols (1c) and (1d). The reaction path of the oxidation of (1) and (2) was also elucidated by Bhalerao's mechanism described in the previous papers.
The study on homogeneous hydrogen transfer from indoline, 2-propanol, and L- (+) -ascorbic acid to methyl linoleate was made. Metal complexes, RuH2 (PPh3) 4, RuCl2 (PPh3) 3, RhH (PPh3) 4, and RhCl3·2H2O were used as homogeneous catalysts. Even under mild conditions, the hydrogenation of the diene proceeded easily. In the hydrogen transfer from L- (+) -ascorbic acid catalyzed by any catalyst shown above, and that from 2-propanol catalyzed by RuCl2 (PPh3) 3 or RhCl3·2H2O, the reduction of linoleate was selective and no stearate was produced. In the cases of the hydrogenation with 2-propanol and L- (+) -ascorbic acid, the formation of isolated trans double bonds was insignificant.