The acid catalysed formation of peracids from ω-phenyl and ω-phenoxy fatty acids (benzoic (I), phenylacetic (II), β-phenylpropionic (III), γ-phenylbutyric (IV), δ-phenylvaleric (V), phenoxyacetic (VI) and β-phenoxypropionic (VII) acids) has been studied kinetically in dioxane. The comparison of the second order rate constants indicated the rapid formation of the peracids from II, III, IV and VII. Plots of logarithms of the rate constants vs Taft's steric substituent constants show that the reaction is controlled by steric rather than polar effects. The activation parameters suggest the effect of benzene ring on the carboxyl group of II, which increases freedom of the transition state for the peracid formation.
As part of investigation of the triglyceride structure of hydrogenated fats, a series of standard positional isomers of triglycerides has been synthesized from palmitic and elaidic acids, and the possible extension of the von Rudloff procedure to hydrogenated fats has been studied. The purities of the tri and partial glycerides were checked by melting point, infrared spectrometry, and thin-layer chromatography, and a comparison of their polymorphic forms with those reported in the literatures was made. The standard triglyceride mixtures were oxidized according to the Youngs' modification and esterified with diazomethane in the presence of methanol. After removal of the volatile esters, the oxidized methylated glycerides were fractionated into four glyceride types, S3, S2U, SU2, and U3, by preparative thin-layer chromatography. The fractions were recovered quantitatively with ether, weighed, and the resultant methyl esters were analyzed by gas-liquid chromatography. No evidence of hydrolysis of acyl groups was observed, besides a little overoxidation and formation of the polar by-products. The final triglyceride composition, however, appeared to be reliable to within plus or minus one unit per cent. This method provides a new basis for the determination of the triglyceride structure of hydrogenated fats.
Rate constants were determined for the thermal dimerization of methyl 9-trans, 11-trans-octade-cadienoate at 230, 250, 270 and 290°C. The activation energy of this reaction was also determined is 22.5 kcal/mol. Furthermore, an attempt was made to see whether the octadecenoate would react with methyl octadecenoate (oleate and elaidate) to form addition compounds. When an equimolar mixture of the octadecadienoate and methyl oleate was heated, the octadecadienoate was dimerized but did not form scarcely any addition compound with oleate. Therefore, the oleate has little dienophlilic activity. Similar results were obtained when an equimolar mixture of the octadecadienoate and methyl elaidate was heated. In this latter case, however, the amount of cis, trans-conjugated octadecadienoate increased. This suggests that, in heat treatment in the presence of methyl elaidate, the trans, trans-conjugated octadecadienoate undergoes geometrical isomerization besides dimerization.
Oil stain on mild steel induced by rust preventive oil was studied to elucidate a mechanism of its formation. Modified oil stain testing method of Rock Island Arsenal Laboratory Illinois, U.S.A. was used. Oil stain was slightly observed in the system (liquid paraffine+rust inhibitor) at 75±3°C, while the addition of unsaturated fatty acid (oleic acid, linolic acid) to this system induced a markeddegree of oil stain. In this mixed system (liquid paraffine+rust inhibitor+unsaturated fatty acid) effect of severaladditives known as antioxidants or radical scavengers was investigated. The formation of oil stainwas retarded by adding these agents, the ability of retardation of radical scavengers being stronger than that of antioxidants. A possible mechanism is proposed on the basis of these results.
The aerobic biodegradabilities of C15 alkenyl sulfonate, C14 hydroxy alkane sulfonate, and n-α-olefim sulfonates (AOS) were measured in comparison with those of linear alkylate sulfonate (LAS), tetrapropyl benzene sulfonate (ABS), and dodecyl sulfate (DAS) by use of the Japanese Industrial Standard method for testing the biodegradability of anionic detergents (now only applicable to LAS-ABS), after good reproducibility of a Methylene Blue colorimetric method was confirmed in the determination of these surfactants. It was found that biodegradabilities of alkenyl sulfonate, hydroxy alkane sulfonate, and AOS were above 99%.