(1) It was observed in the reaction of organic chloride with silver nitrate that the irregular catalytic action can be avoided by carrying experiments in a dark room. (2) Silver nitrate was interacted with several organic chlorides which were highly reactive in SN2 type reaction and the kinetic data obtained were fully discussed. (3) Some organic polychlorides were reacted with silver nitrate and with potassium iodide and rates obtained in these reactions were discussed.
By studying the reactions of protein with the aid of monolayer technique, Rothen found that antigen and antibody, and also enzyme and substrate molecules, can react in despite of being apparently separated by some inert screen. He assumed from these results, that the specific long range forces operate in immunologic and enzymatic reactions. We have found that similar phenomena occurred in the following systems: monolayer of hapten-conjugated protein as antigen and antibody directed specifically against the hapten, azo-ovalbumin and ovalbumin, and even cholestanol and digitonin. Therefore, it leaves some room for consideration to assume specific long range forces in immunologic and enzymatic reaction alone. Besides, we suggested that there was required an almost constant thickness (about 150 Å.) of barium stearate to inhibit completely the combination of antibody with antigen in transferred film, independent of the variety of the systems. We have also noticed, from the data of the contact angle towards water, those of surface potential and of static friction coefficient of stearic acid multilayers on glass or metal surface, that the multilayers of stearic acid must have a thickness over about 150 Å. (same as the result of antigen-antibody reaction) to interrupt the effect of underlying substance, regardless of the phenomena concerned. These facts appear to suggest the fragile nature of screen film which is thinner than the certain thickness which we call the “critical thickness.” Such a thin film may conceivably be such as the net-work structure loose enough to permit the diffusion and the penetration of large molecules. Such a physical state of screen film may primarily be responsible for the results of the experiments of Rothen, Singer and the present authors.
The dipole moments of tropolone (cycloheptatriene-2,4,6-ol-2-one-1) and related compounds were measured in benzene solution. The values obtained are:— tropolone, 3.71 D (25°) and 3.64 D (35°) ; tribromotropolone (3,5,7-tribromo-), 1.84D(25°); hinokitiol(4-isopropylcycloheptatriene-2,4,6-ol-2-one-1), 4.04 D (33°); α-monobromohinokitiol (7-bromo-), 4.32 D (33°); α-dibromohinokitiol (3,7-dibromo-), 4.27 D (33°); β-dibromohinokitiol (5,7-dibromo-), 3.14 D (20°); α-mononitrohinokitiol (3- or 7-nitro-), 6.19 D (25°); dinitrohinokitiol (3,5- or 3,7-dinitro-), 4.63 D (20°). The high dipole moments of tropolone and hinokitiol were explained adequately by taking into consideration the contribution of various resonance structures with a formal positive charge at the ring C-atoms. The resonance was supposed to give a certain amount of double bond character to each bond in the ring, causing plane cycloheptatrienolone ring. The position of substituents in the substituted tropolone and hinokitiols were determined and are given immediately after each name of these compounds in parentheses.
The molecular orbital treatment was carried out on tropolone. The π -electron distribution, interatomic distances, free valence indices and dipole moment were derived. It was found that the dipole moment is very high (second approximation value of π -electron moment = 4.4 D) owing to resonance and lies along a line from the center of the ring to the middle point between two O-atoms with its positive end at the ring and that the resonance energy amounts to about 1.5 times that of benzene in general agreement with experimental results. It was shown that the substitution by electrophilic atoms and groups are most liable to occur at C-atoms 7, 3 and 5.
Cation exchange resins in H-form each having only one kind of exchange group were titrated with sodium hydroxide solution conductometrically. The results were analysed, and exchange capacity and tendency of each exchange group were determined. A mixture of two resins, each having one kind of exchange group was titrated. The analysis of the results gave adsorption values which agree well with that expected from the determination for the separate resin. From the titration results for more complex cation exchange resins the number of the sorts of exchange groups was estimated and each group was identified.
The reactivity of various kinds of carbon to the solution of potassium dichromate in phosphoric acid was examined. The samples investigated contained carbon blacks, graphite, pitch cokes, and charcoals. The rate of the reaction varied depending on the types of carbon, and the order of the reactivity was found to be in the order shown above. This is attributed to the modes of aggregation of crystallites. It was assumed that, in carbon blacks the crystallites are mobile individually for dispersing or swelling, on the other hand, in pitch cokes as well as charcoals there are some linkages to bridge the micelles with each other. This is supported by the results of the X-ray examination which was carried out following the steps of the wet oxidation.
Details of the methods of measuring the relative intensity of the fluorescence were described, in which the photographic spectral photometry and the visual observation method were related. Several examples of uranium contents in rocks and sinter deposits determined by this method are treated from the geochemical interest.
Coast and ocean water sample were analysed on their uranium contents by the fluorometric method. The variation to the depth of 4000 m. was also examined in the ocean water sample. The content is likely to be constant even to the deep, though a little decrease appears in the surface water. The obtained values in the deeper layer (average 2.8×10−6 g.U/l.) are somewhat higher than those by foreign investigators.
Differential heat of adsorption of carbon dioxide on reduced nickel, cobalt or iron catalyst was determined by the indirect method at the lower degree of adsorption with particular precaution for securing thermodynamical equilibrium, being found at 22, 14 and 15,5 kcal./mole respectively. Using the heat of adsorption derived adsorption isotherms were investigated statistical mechanically with reference to the adsorbed state of carbon dioxide molecule, leading to the conclusion that the molecule dissociates into three statistically independent atoms in any case of the catalysts.
(1) 2-Arylimino-3-aryl-4-keto-tetrahydro-thiazoles were prepared by condensation of di-arylthioureas with monochloroacetic acid in the presence of anhydrous sodium acetate and absolute alcohol. (2) The formation of semicarbazones of 2-arylimino-3-aryl-4-keto-tetrahydrothiazoles has revealed the presence of a keto-group.