Iodine-methyl oleate-heptane solutions were heated in sealed tubes at 140°C. It was found that experimental data satisfy the following rate equation : -d [C] /dt=kcis [C] -ktrans [T] /√1+Kcis [C] +Ktrans [T] kcis= (const) × [I2] 1/2, ktrans= (const) '× [I2] 1/2 where [C] and [T] are the concentrations of cis and trans isomers, respectively. Kcis and Ktrans denote the iodine molecule-corresponding isomer charge transfer equilibrium constants.
Structural analysis was studied for nonaromatic poly (oxyethylene) quaternary ammonium compounds. It became possible to discriminate between mono and dialkyl types of these compounds by TLC with solvent systems consisting of hexane-chloroform-methanol-sodium perchlorate (10 : 10 : 10 : 0.05). On the other hand, these compounds were converted to tertiary amines by hydroiodic acid cleavage and successive Hofmann degradation, and the amines were analyzed by GC with 10% apiezon grease L containing potassium hydroxide packed in a 0.25m column. These amines were identified by IR, NMR, and MS spectra, and the relationships between original compounds and the types of these amines were clearified. These two methods were used to structural analysis of these compounds in household detergents or toiletaries that were separated by ion exchanger.
Quaternary ammonium salts of poly [2- (N, N-dimethylamino) ethyl methacrylate] (cationic polymer) were prepared by the reaction of poly [2- (N, N- dimethylamino) ethyl methacrylate] (PAEM) with various alkyl bromides with a view of obtaining good flocculants. The flocculating ability for aqueous suspensions of kaolin was investigated with respect to the structure of quaternary ammonium salt polymers by measuring the sedimentation velocity, sedimentation volume, and residual turbidity. The results obtained are as follows. 1) The sedimentation velocity of cationic polymer (QPC2X) prepared from PAEM and ethyl bromide was independent of the degree of quaternization and maximum sedimentation velocity showed 3.03.2 cm/min. Of other cationic polymers (QPC6X, QPC12X, QPC18X) obtained from PAEM and higher alkyl bromides (hexyl bromide, dodecyl bromide, and stearyl bromide), cationic polymers of the lower degree of quaternization displayed the larger rate of sedimentation and the maximum rate of sedimentation showed 2.33.2 cm/min at the optimum dosage of 610 ppm. 2) The bulky precipitation was obtained with cationic polymer of the medium degree of quaternization (5070%). 3) The clearest supernatant gave 2550 ppm turbidity at the dosage of 810 ppm. 4) Cationic polymers were most effective for flocculation with the increase of acidity. 5) The sedimentation velocity decreased rapidly at the concentration of 2.55.0% of kaolin suspension. 6) Cationic polymers derived from PAEM and various alkyl bromides were more effective with the commercial flocculants such as Sumifloc-FC, Himoloc-Neo 600, and PAS-A.
Phosphate which has been formulated in synthetic detergents for many years, is now often considered to accerelate eutrofication. In this connection, an intensive search is being made by the detergent industries for phosphate substitutes. Japan Oil Chemists' Society has been entrusted in regard to the method of reducing phosphates in detergents by the Ministry of International Trade and Industry. In order to obtain more reliable soil removal data, it was decided to incorporate bundle testing into our detergency evaluation scheme. Bundle testing, compaing four laundry detergents, A : (STPP 10% as P2O5), B : (STPP 5% as P2O5), C : (STPP 0 % as P2O5), D : (STPP 5 % as P2O5, Zeolite 8.5%), and using naturally soiled family items such as dress shirts, shirts, socks etc., under controlled conditions, has been performed. For over ten months, 14 oil and surface chemists, 40 research assistants and 48 families (192 panelers) were engaged in this project. In our laborious experience, it was concluded that phosphate has proved useful and detergency lowered with decreasing phosphate in detergents, while certain amount of sodium almino silicate “Zeolite” may be used as a substitute to reduce the total amount of phosphate.
Some aldehydes are widely used as an artificial perfume. However, little has been known on the optically active aldehydes. In order to obtaine the optically active aldehydes, enamines were synthesized from racemic aldehydes and optically active amines which were derived from natural amino acids. The optically active aldehydes were recovered from the hydrolysis of the enamines under various conditions. The aldehydes employed were 3-p-cumenyl-2-methylpropionaldehyde (CPA) and 2-methyl-3-phenylpropionaldehyde (MPA), which had similar structure to CPA. CPA is employed as an artificial perfume (Cyclamenaldehyde). The acids employed for the hydrolysis were hydrochloric acid or cation exchange resin. When the amine components of the enamines were (S) -3-isopropylmorpholine (1a) and (S) -3-isobutylmorpholine (1b), (+) -aldehyde was recovered. However, in the case where (S) -3-benzylmorpholine (5) was employed, (-) -aldehyde was recovered. In order to evaluate the optical purity of recovered aldehydes, the aldehydes were converted to corresponding alcohols, the optical rotation of which were compared with those values for the optically pure alcohol synthesized from the corresponding optically pure acid. The specific rotations of the optically pure MPA and CPA were determined as follows ; [(S) -MPA [α] 25435=+9.10° (c=6.21 in benzene)] [(S) -CPA [α] 25435=+13.9° (c=6.87 in benzene)] The odor of (+) -CPA was compared with that of (-) -CPA, and there was clear difference between the odors of (+) -and (-) -CPA.