Treatment of abietic acid with a catalytic amount of iodine at higher temperatures produced several novel resin acids and unsaponifiable matters along with dihydroabietic acid and dehydroabietic acid which were reported previously. These products were separated and the structures were determined on their spectral data. When abietic acid was treated with 0.5 mol% iodine at 250°C for 30 min, the products were secodehydroabietic acid (24%), podocarpatrienoic acid (6%), demethyldehydroabietic acid (10%), octahydroretene (6%), hexahydroretene (1%), and tetrahydroretene (1%). Possible reaction mechanisms were suggested on the basis of results under various reaction conditions.
1-Palmitoyl-3- (3', 4', 5'-trimethoxybenaoyl) glycerol (IV), 1-palmitoyl-3-galloyl glycerol (VII) and 1-galloyl glycerol (X) were prepared according to the method shown in Scheme-1, 2 and 3. The structures were confirmed by means of IR, NMR and chemical analysis. The antioxidation effect of these compounds for the soybean oil has been evaluated by the A.O.M. and the Shaal Oven Tests. The effect of 1-galloyl glycerol was found to be much larger than that of propyl gallate.
The cationic surfactants were determined spectrophotometrically with methyl orange in the presence of nonionic or amphoteric surfactant. The cationic surfactants react with methyl orange to decrease the absorbance of methyl orange solution. The maximum decrease is observed at 462 nm which is the absorption band in alkali region, and the absorbance is constant in the pH range of 6.08.0. The calibration curve for the determination of the cationic surfactants was obtained from the decrease of absorbance at 462 nm in the presence of 3.0×10-5M methyl orange at pH 6.90. Cetyl pyridinium chloride and myristyl benzyl dimethyl ammonium chloride could be determined in the presence of excess amount of polyoxyethylene lauryl ether or N-lauryl betain hydrochloride.
The denaturing action of typical anionic surfactants, alkyl sulfate (AS), alkyl benzene sulfonate (LAS), α-olefin sulfonate (AOS) and sodium alkane sulfonate (SAS), on four different proteins, keratin, albumin, enzyme and lysosome membrane has been investigated by measuring liberation of sulfhydryl group and by enzyme inhibition. The results indicate that in general these surfactants have high denaturing potency for such proteins in the decreasing order of LAS≥AS>AOS≥SAS, although the potency varies considerably with the alkyl-chain length of the surfactants. Moreover, a relationship between the denaturing potency and the skin irritating action of these surfactants has been discussed.
A simple and selective method for the determination of trace amounts of ABS has been developed. It was previously reported that the complexes of Methylene Blue (MB) with methylene blue active substances (MBAS) dissociated into MB and MBAS on silicagel thin-layer chromatography. Based on this phenomenon, ABS contained in MB-MBAS complex could be determined by high performance liquid chromatography (HPLC) under the same conditions as previously reported. The methylene blue active substances in samples were extracted with chloroform in a similar way to MB spectrophotometric method, then concentrated, dissolved in methanol and determined by HPLC. Good recovery and reproducibility were obtained on the determination of ABS in river and waste water. Further, the measured values of ABS agreed well with those obtained by the previously reported method. Therefore, this simple method is applicable to the determination of trace amounts of ABS in river and waste water.
The solubility of alkylpyridinium halides and their interionic charge transfer absorption bands (CT bands) were measured in eight nonaqueous solvents. The influence of counterion on the solubility was also studied. The examination of the CT bands showed that dodecylpyridinium halides dissociate in polar solvents, form ion-pairs in medium polar solvents and probably dissolve as neutral molecules in nonpolar solvents.
Edible oil added with five kinds of organochlorine pesticides and PCB was submitted to deacidification, decolorization and deodorization under a definite laboratory condition, and the amounts of the organochlorine pesticides and PCB in the oil were determined immediately after each process. Results obtained from these experiments are as follows : (1) Concentration of organochlorine pesticides and PCB in the oil remained almost unchanged after deacidification irrespective of the amount of sodium hydroxide used. (2) Dieldrin concentration in the oil decreased markedly by use of activated clay for decolorization, but the concentration of BHC isomers, DDT related substances and PCB hardly decreased. The use of an adsorbent which contains activated carbon gave the result similar to that obtained by the use of activated clay, but the concentration of PCB clearly decreased. (3) The higher the temperature of deodorization treatment, organochlorine pesticides and PCB concentration markedly decreased and deodorization at a temperature usually used in factories would completely remove these chemicals. It was assumed that in this process BHC isomers will be removed from the oil at a lower temperature than DDT related substances. (4) Hydrogenation using nickel catalyst was carried out on some of the oil and this was found to decrease the amount of r-BHC, pp'-DDT and Dieldrin rather than β-BHC and pp'-DDE, but there was almost no decrease in the amount of PCB.
Five kinds of organochlorine pesticides and PCB were added to purified soybean oil and the oil was hydrogenated in a 20l autoclave under 11 different conditions, varying the amount of the catalyst, reaction temperature, and hydrogen gas concentration, but giving oils with almost the same melting points of ca. 35°C. The amounts of residual organochlorine pesticides and PCB were determined and change of the amount of these chemicals by hydrogenation condition was examined. (1) Amounts of these chemicals decreased markedly by hydrogenation but the degree of decrease was not uniform, there being a selectivity between the kind of catalyst used and the kind of organochlorine pesticide removed. The decrease was larger when the catalyst contained copper or chromium. DDT, Dieldrin and r-BHC were removed almost completely. (2) PCB also decreased by hydrogenation like the organochlorine pesticides and this decrease was especially great when the catalyst contained copper or chromium. A high residual rate was found when hydrogenation was carried out under a high pressure, using nickel catalyst alone, showing almost no removal of PCB. (3) Taking the decrease of organochlorine pesticides and PCB as a simple firstorder reaction, reaction rate constants under various hydrogenation conditions were calculated and they were found to be larger under high-pressure than under atomospheric pressure. This result suggested that the decrease of organochlorine pesticide and PCB during hydrogenation was due to the chemical changes such as reduction and dechlorination rather than their evaporation out of the reaction system.
Several higher homologues (R : C4C18) of 3-alkylmercapto-5-chloro-1, 2, 4-thiadiazole (AMCT) were prepared. The nucleophilic substitution reactions of AMCT and other heterocyclic halocompounds with amines were kinetically followed. It was found that AMCT had a high reactivity comparable to that of dimethoxychloro-s-triazine in these reactions and the reactivity of AMCT was almost independent of their alkyl chain length. On applying to cotton cloth treatment, octadecyl homologue of AMCT exhibited a durable water-repellency.