As a part of serial studies on differential thermal analysis of edible oils, similar analyses were carried out on hardened fish oil and rape-seed oil, having a longer chain than the usual edible oils, and on fish oil blended in various ratios with coconut oil having an extremly different molecular chain. 1) The differential thermal analysis (DTA) curve of hardened fish oil (I.V. 52.7), allowed to stand at 0°C and 20°C, showed one large and broad endothermic peak at 34°C and an indistinct and gentle peak was present in the low temperature side. When left at 30°C, the curve showed a great difference, and a peak of broad melting range appeared on both sides. 2) The DTA curve of hardened rape-seed oil (I.V. 69.9), allowed to stand at 0°C, showed a large, broad peak at 2127°C. When left at 20°C, a small but gentle peak appeared in the low temperature side as well. When left at 30°C, two endothermic peaks appeared and the peak in the low temperature side increased in size with lapse of time. 3) Addition of 10% of coconut oil to hardened fish oil had no effect on its DTA curve but addition of 20% resulted in a broad peak with a broad melting range in the low temperature side. When the amount of coconut oil added was increased to 40 and 60%, the large peak in the low temperature side, corresponding to that of coconut oil, increased in size, and this peak became larger and clearer with higher temperature and longer time of standing. 4) When coconut oil was added to hardened fish oil in 80 or 90%, DTA curve of the samples shovcted a characteristic curve of the coconut oil and the melting range became narrower.
The addition reactions of methyl acrylate to conjugated octadecadienoic acid methyl esters were studied by a kinetic method. The study shows that the addition is based on the Diels-Alder reaction between conjugated double bond with methyl acrylate. The rate constants as second order were determined in Table-3 for the addition reactions of methyl acrylate to trans-9, trans-11- and cis-9, trans-11-octadecadienoate at various temperature, respectively. The activation energy of the reactions was also determined in Table-3. From the results of the differences of rate constants, it has been found that trans, trans-conjugated octadecadienoate has about one hundred times greater activity as diene than cis, trans-conjugated octadecadienoate at 160°C. Futhermore, the adducts separated by column chromatograpy was observed to have a cyclohexene ring structure by IR, NMR, and Mass spectral analysis.
Selectivity of the transalkylation of tertiary amine and alcohol was studied. The transalkylation reaction of tertiary amine with alcohol was examined by use of various metals and metal oxides as catalyst, but the reaction was only catalyzed by cobalt, nickel, iron, or ruthenium. The metal oxides did not catalyze the reaction without hydrogen pressure, but the metal powders catalyzed it in nitrogen atmosphere. The best yield and selectivity of the transalkylated tertiary amine was obtained by using cobalt powder, ruthenium powder or copper chromite modified with manganese dioxide or barium oxide. By increasing the temperature (250→300°C), decreasing the reaction time (3→2hrs), increasing the initial hydrogen pressure (0→20kg/cm2) and by increasing the amount of tertiary amine, the tertiary amine exchanged by one alkyl group was increased. By the use of cobalt powder or ruthenium powder, the tertiary amine exchanged by one alkyl group was formed in best yield, and formation of the tertiary amine exchanged by two alkyl groups decreased.
The reaction conditions for the synthesis of lauryl mercaptan (RSH) from lauryl chloride (RCl) and sodium hydrogensulfide (NaSH, flakes, 68% purity) were investigated in alcoholic solvents (mainly in n-butanol). There was no definite relation between the yields of RSH and the dielectric constants or solvent polarity parameters of the alcooholic (hydroxylic) solvents used; methanol, ethanol, propanols, butanols and n-amyl alchol. The yield of RSH in dimethylformamide (a dipolar aprotic solvent) was higher (by 25.1, 21.2, and 28.9%) than in ethanol, n-propanol and n-butanol, respectively. Accordingly, from a viewpoint of reaction mechanism, it was suggested as necessary that the reaction of RCl with NaSH in alcoholic solvents should be investigated in detail. The reactions in n-butanol were markedly influenced by reaction temperature and amount of water, and it was suggested that a side reaction, namely the formation of di-n-dodecyl sulfide (RSR), occurred as follows; 1) 2NaSH _??_ Na2S+H2S Na2S+2RCl→RSR+2NaCl and/or 2) RSH+NaSH _??_ RSNa+H2S RSNa+RCl→RSR+NaCl. Moreover, the effects of some reaction conditions on the yields of RSH and the formations of RSR were investigated, and the results were discussed based on the reaction mechanism previously proposed.
Oxidation of P4 by O2 in ethyl alcohol was carried out in order to prepare HPO (OEt) 2, obtaining 43% yield. The reaction products were compared with the products obtained by the ethanolysis of P4O6 and with the products obtained by oxidation of P4 in CCl4, and the reaction mechanism was discussed. Reaction rate was affected by temperature. The P4 was oxidized, without detectable intermediate, into P3 and reacted immediately with ethyl alcohol and turned into the products. Alcohol might act the role of suppressing further oxidation of phosphorous derivatives. As products, HPO (OH) 2, HPO (OH) (OEt), HPO (OEt) 2 and condensed phosphorous acid were detected, but no P (OEt) 3 could be detected.
Ionic detergents were added to the human serum and to the egg white, and these protein systems were analyzed by the acrylamide gel electrophoresis. Detergents used were sodium dodecyl sulfate (SDS) and dodecyl trimethylammoniumbromide (DTAB). The zone of the complex AD2n (n=38), which is formed between the serum albumin and SDS, did not exist in the pattern of gel electrophoresis at pH 9.2. This is probably because of loosely bound SDS anions freed from AD2n during the gel electrophoresis to give ADm (m=11). The pre-albumin reacted with SDS and with DTAB to give several zones. In contrast to the serum albumin, the ovalbumin gave the zone of the complex ADn (n≥40), which is formed between ovalbumin and SDS. The effect of DTAB on ovalbumin is simply to precipitate it. The mobility of pre-albumin in egg white was not affected by either SDS or DTAB even at concentration as high as 150200mM. Reactions occurred quantitatively between some minor components and ionic detergents. Only lipoproteins in human serum were affected by nonionic detergent.
Spectroscopic determination has been developed for nonionic surfactants, using ammonium reineckate as precipitant in the presence of sodium ion. It was found that polyethylene glycol (PEG) of average molecular weight 1000 to 20000 react to form the stoichiometrical complex precipitate, polyethylene glycol reineckate (PEG-R) containing 13 moles of ethylene oxide for each mole of reinecke acid. And the combined spectroscopic and ion exchange or gravimetric procedures demonstrated that PEG of average molecular weight 2000 to 20000 react stoichiometrically to form the complexes, Na-PEG-R and Ba-PEG-R, in the presence of sodium ion and barium ion, and these reineckates contain 11 moles of ethylene oxid and 1 mole of sodium, and 10 moles of ethylene oxide and 0.5 moles of barium, respectively, for each mole of reinecke acid. A plot of absorbance at 525mμ against the amount of each PEG reineckates in the aceton solutions was found to be linear, while PEG-R is soluble in water and the aceton solutions of Ba-PEG-R give scattering values in the absorbance. Then, determination of PEG and other nonionic surfactants was studied in the presence of sodium chloride, and PEG and each nonionic surfactant could be determined by using each calibration curve. However, all of surfactants used for the present experiment, were able to be determined with only one calibration curve, by plotting absorbance against the amount of ethylene oxide contained in their surfactanti.
Chelate surfactants were synthesized which having one or two hydrophobic long chained alkyl groups and hydrophilic EDTA-metal chelate ions, and their properties were investigated. N- (1-carboxypentadecyl) ethylenediaminetriacetic acid (C-monotetradecyl EDTA) and N, N'-bis (1-carboxyundecyl) ethylenediaminediacetic acid (C, C'-didecyl FDTA) were used as the chelating agents and they were treated with salts of some transitional metals. The formation of each metal chelate waas observed. It was shown from IR spectra, changes of color and from pH effects that the chelates prepared from C-alkyl EDTA and iron sulfate had octahedral chelating structure. The chelate surfactants thus obtained showed good surface activities. Above all, the chelate surfactant from C, C'-didecyl EDTA and iron sulfate had a particularly superior dipersing power for pigments in coatings.