The solution behavior of five α-monoalkyl glyceryl ethers with different chemical structures in water was investigated by a polarizing microscopic technique, differential scanning calorimetry, and electric conductivity measurements and binary phase diagrams of these alkyl glyceryl ethers and water were obtained. α-Monoalkyl glyceryl ethers comprised mainly of linear alkyl chains as the hydrophobic moiety formed liquid crystalline phases including neat and reversed middle phases for a wider range of concentrations of water and temperature. α-Monoalkyl glyceryl ethers with sterically bulky hydrophobic parts such as branched alkyl chains which hinder aggregation of molecules formed no mesomorphic phases and no mutual interaction between water and glyceryl ether was observed. The solution behavior of α-monoalkyl glyceryl ether differed from that of 1-monoalkyl glyceride, although they have similar molecular structures. This difference was observed in the liquid crystalline phases possibly attributable to the greater hydrophobicity of the α-monoalkyl glyceryl ether.
The effects of tri-n-octylamine (TOA) on the oxidative decomposition and dimerization of γ-and δ-tocopherol (Toc) during the thermal oxidation of trilinolein (Tri-Li) containing a small amount of tri-n-butylphosphate (TBP) was investigated. After Toc (5%) and TBP (0.1%) were dissolved in Tri-Li and an aliquot of TOA was added to the solution, the solution was oxidized with air at 180°C for a fixed period of time. The determination of the concentration of Tocs and their dimers was carried out by HPLC. The stability of Tocs increased by the addition of TBP in Tri-Li, while TOA had no influence on the stability. (Fig.-1) When TOA was added to Tri-Li containing TBP at a concentration of 0.1%, the stability increased (Figs.-2 and 4), indicating the phosphate ester and amine to act synergistically to suppress the thermal oxidation of Tocs in Tri-Li. On the other hand, small influences due to TOA and TBP appeared on the formation of Toc's dimers. (Fig.-3 and 5)
The reaction of 1, 2-epithiodecane with diethylamine in a glass ampoule gave 1- (N, N-diethylamine) -2-decanethiol. The ratio of yield vs. conversion, (Y) / (C), was about 50% for equal molar reaction. Excess amine raised (Y) / (C) to 60%. Though higher temperature promote the reaction, (Y) / (C) decreased. Polar solvents, particularly alcohols, promoted the reaction. The addition of a small amount of alcohol, water or acetic acid promoted the reaction in a glass tube at 80°C and increased (Y) / (C). Though the reaction of 1, 2-epithiodecane with pyperidine or molpholine gave 1-amino-2-decanethiols in good yield, the expected product could not be obtained without methanol for the reaction with N-methylaniline. The reaction mechanism was considered to be a nucleophilic attack of the amine on the terminal methylene of 1, 2-epithiodecane, activated by ammonium ions.
A method for identifying the surfactant components of commercial heavy duty liquid laundry detergents was devised using two-dimensional thin layer chromatography. For the chromatography, Silica Gel G was used as the stationary phase and solvent system consisting of ethyl methyl ketone-benzene-ethanol-water in the first direction and 4-methyl-2-pentanone-1-propanol-acetic acid-acetonitrile in the second direction. The chromatographic patterns obtained from the two-dimensional thin layer chromatography of the commercial heavy duty liquid laundry detergents showed two series of spots in the upper and central areas. These spots were identified respectively as nonionic and anionic surfactants on the basis of Rf values and indicators. The ethanol extracts of these spots were examined by UV, IR and NMR spectroscopy, and the results were compared with the spectra of standard surfactants. The nonionic surfactnt was thus identified as alkyl poly (oxyethylene) ether, and anionic surfactants were detected as being only linear alkylbenzenesulfonate in one case and as both linear alkylbenzeneselfonate and alkylethoxylated sulfate in other case. The above data indicate that the two-dimensional thin layer chromatography technique is an effective method for detecting the surfactant components of a detergent consisting of anionic and nonionic surfactants.
Zeolite has been partly substituted for sodium tripolyphosphate (STPP) since 1980 and possibly over 85% of commercially available synthetic detergents have excluded STPP since the end of 1983. In this study, the contribution of Zeolite to detergent washing capacity was studied to gain an understanding of anti-redeposition effects. Anti-redeposition effects were studied by examining under various conditions the action of suds containing Fe2O3 on soiling polyester fabrics at different calcium ion concentrations. The anti-redeposition effects of Zeolites were found to be rather low, compared to STPP or a binary system of STPP and Zeolite. The effects of Zeolite became gradually higher with an increase in sud concentration. Anti-redeposition effects became more pronounced as the Ca binding capacity increased.
This paper describes a convenient method for the synthesis of 4-alkyl-4-butanolides (3). Methyl 3-oxoundecanoate (1f) was converted to methyl 4-oxoundecanoate (2f) in good yield by the alkylation of (1f) with methyl bromoacetate and subsequent demethoxycarbonylation of the alkylated product. The reduction of (2f) with sodium borohydride gave 4-octyl-4-butanolide (3f), a flavor component of apricot and the pheromone of the rove beetle. A lower homolog of (3f) could also be prepared from methyl-3-oxoalkanecarboxylates (1) by the same method.