Chlorophosphonations of n-alkyl acetates (CH3COOR; R=C3C8) were carried out and the products were analyzed with GLC, using 3m×3mmφ, Ucon LB 550X column, and identified by comparing their retention times with those of authentic samples synthesized by other methods. The compositions of the products were determined. The results were expressed with relative reactivities per hydrogen at methylene groups to the terminal methyl group as standard, as shown in Table. The substitution of dichlorophosphinyl group on the acetyl group did'nt occur.
Tri-, tetra-, and pentaethyleneglycol ethers of phenol, p-chlorophenol, and 2, 4, 5-trichlorophenol were prepared and tested as the growth inhibiting agents against Staphylococcus aureus 209 P and Escherichia coli in order to study the effect of hydrophilic oxyethylene linkages. They were respectively prepared by the Williamson condensation of potassium salts of phenol, p-chlorophenol, and trichlorophenol with tri-, tetra- and penta-ethyleneglycol-monochlorides. The melting points, elemental analyses and infrared analyses of the products were presented. The inhibiting powers of those ethers against test microorganisms revealed that the introduction of oxyethylene radicals to phenols reduced their antimicrobial activities. Especially the activities of these ethyleneglycol ethers of non-chlorinated phenol were almost lost. The surface tensions of aq. solutions of the pentaethyleneglycol ethers were also determined and it was confirmed that the 2, 4, 5-trichlorophenol ether was surface active as much as the corresponding PCP ether.
Monosodium salt of resorcinol, sodium p-hydroxybenzoate and salicylate were obtained by the reaction of resorcinol or the parent acids with aqueous solution of NaOH or NaHCO3, respectively. These salts were then allowed to react with excess of monochloride of di-, tri- or tetra-ethylene-glycol, which had been prepared from ethylenechlorohydrin and ethylene oxide, and NaCl precipitated was filtered and unchanged monochloride was distilled under reduced pressure from the filtrate. Repeated distillations were employed to obtain di-, tri- and tetra-oxyethylene derivatives from the residues. The compounds thus prepared were identified as expected by elementary analysis, infrared analysis and molecular weight determination. Surface tension of their aqueous solutions was determined by Wilhelmy's meter and those of several solutions were as low as about 40 dyne/cm. The antimicrobial activity of the derivatives was evaluated in terms of minimum inhibitory concentration by agar streak method. Tetraoxyethylene derivatives of p-hydroxybenzoic acid were observed most effective, especially for Escherichia coli, among all compounds in the present work. The activity seemed to increase with the length of oxyethylene chain in the derivatives.
The preparation of etho-anisic acid amide as a nonionic surfactant was studied. The reaction products always contained unreacted amide and polyethyleneoxide as a byproduct. Polyethyleneoxide was separated from the reaction product by gel filtration. Fractionation of the reaction mixture into components was achieved more effectually by column chromatography (silica gel) than by gel filtration (Sephadex), although the former required much longer time. The fractionated samples were examined by thin layer chromatography, infrared spectroscopy and nuclear magnetic resonance. The average chain length of polyoxyethylene in each sample was determined by nuclear magnetic resonance. From the measurements of specific gravity and surface tension in aqueous solution, it was concluded that these samples reduced surface tension only a little and did not form micelles.
Among the water-soluble polymers in which interest has been increasing recently, quaternary ammonium polymer is considered to be most extensively used, but very few kinetic studies have been conducted in the preparation of those polyelectrolytes. In the present work authors made an effort to elucidate the kinetic aspects of quaternization reaction of high polymer. Polystyrene was chloromethylated with chloromethyl ether and quaternization reaction was carried out with tertiary amines including triethylamine, diethyl ethanolamine and pyridine in the media of dimethylformamide (DMF), N-methyl-2-pyrrolidone (NMP), dioxane and tetrahydrofuran (THF). The results of experiments showed that the rate of quaternization had been affected greatly by the basicity of amines and polarity of solvents. Rate constants changed in the order of dielectric constant values of solvents except dioxane as follows : (Values in parenthesis indicate dielectric constants.) DMF (36.7) >NMP (33.0) >Dioxane (2.2) >THF (7.4) This peculiar behavior of dioxane was considered to be attributed to an increase in the micro-dielectric constant value over the bluk value in virtue of the specific solvation of dioxane to the quaternary ammonium salt. Solubility parameter has been found to be used with better correlation to rate constant than dielectric constant. Isokinetic relationship has also been observed between activation energy and entropy in all solvents except dioxane.
Some higher homologues of alkylthioethylamine were synthesized by radical addition of β-aminoethanethiol to α-olefin. From these amines, various cationic surfactants containing -S-, -SO-, -SO2- in the main chains were synthesized. Influences of these sulfurs on surface activities were examined. The orders of their surface activities among the three types of cationics having the same alkyl group were as follows : solubility in water, -SO->-S->>-SO2-; lowering of surface tension of water, -S->-SO-≈-SO2-; foaming, -S->-SO->-SO2-; bacteriostatic action, -S->-SO->>-SO2-.