Bulletin of the Chemical Society of Japan

Handa, Takashi

doi: 10.1246/bcsj.36.235pmid: N/A

The chemical resonance structures of the excited states are assumed to correspond to the type of polarization in each state. This theory can explain the absorption energies as the difference in the empirical resonance energies between the ground and excited states by an application of Carter’s empirical equations. Imaginary charges are introduced to estimate the number of resonance structures, thus eliminating the influence of cross-linking atoms; the meaning of the resonance hybride corresponding to each levels is easily interpreted in correlation with Platt’s theory. As a result,, the individual excited state can be represented as a chemical resonance hybride consisting of a group of simple polarized structures; this theory may be said to be adequate from the view-point of absorption energies and of absorption intensities in relation to the direction of electric dipoles.

Araki, Tsuneo

doi: 10.1246/bcsj.36.247pmid: N/A

1. The resistivity of microcrystalline selenium doped with chlorine was changed by heat treatment. The results were in fairly good accord with the measurements obtained by Schweickert. Selenium doped with chlorine had the same characteristics as that doped with iodine or bromine.2. The results of microscopic observation showed that the grain size became smaller with the higher chlorine concentration. This tendency was similar to that found in iodineor bromine-doped selenium.3. The resistivity variation with temperatures below room temperature was affected by the heat treatment of the specimen. The effect was greater for the specimen free from chlorine.4. Carrier concentrations were obtained from the measurement of capacity and also from the thermoelectric power. These two methods gave results which were in agreement with each other. The concentrations were shown to be increased at low temperatures.

Yajima, Seishi; Shiba, Koreyuki; Handa, Muneo

doi: 10.1246/bcsj.36.253pmid: N/A

Yajima, Seishi; Shiba, Koreyuki; Handa, Muneo

doi: 10.1246/bcsj.36.258pmid: N/A

Murakami, Masuo; Chen, Jong-Chen

doi: 10.1246/bcsj.36.263pmid: N/A

Srivastava, Suresh C; Sinha, Surendra Nath; Dey, Arun K

doi: 10.1246/bcsj.36.268pmid: N/A

Tokura, Niichiro; Matsuda, Minoru; Iino, Masashi

doi: 10.1246/bcsj.36.278pmid: N/A

1) The cationic copolymerization of styrene and p-bromostyrene in liquid sulfur dioxide using boron trifluoride etherate as a catalyst has been carried out; the monomer reactivity ratios (MRR) have been found to be r1=0.8 and r2=0.4. The MRR value was independent of the temperature and of the quantity of the catalyst in the copolymerization.2) The effect of added solvents in liquid sulfur dioxide has also been examined. However, the MRR’s have been little affected by the added solvents, the rates of the copolymerization have largely been depressed, and the rates were not dependent on the dielectric constants of the added solvents, the rate in pure liquid sulfur dioxide being the fastest.3) The same cationic copolymerization has been conducted in benzene, carbon tetrachloride, nitrobenzene and ethylene dichloride.The MRR’s were almost equal in all (r1=1.8 and r2=0.3).

Tokiwa, Furnikatsu

doi: 10.1246/bcsj.36.281pmid: N/A

Measurements have been made of the electrical conductivity and the viscosity of mixed solutions of sodium dodecyl sulfate (SDS) and dodecyl alcohol (DA). The addition of DA caused a lowering of the conductance, a phenomenon probably related to the formation of a complex composed of SDS and DA, but it did not essentially alter the form of the Λ−\sqrtc curves up to 0.3 mol. fraction of DA in SDS-DA. The Λ−\sqrtc curves of the mixed solution exhibit a break point which corresponds to a critical concentration of SDS, up to a 0.3 mol. fraction of DA in SDS-DA; the break point becomes obscure when the amount of DA present is larger than this value. The effect of the amount of DA on the critical concentration was not very large in this experiment.The variation of the conductance and viscosity with the temperature was measured on the solution of SDS with varying concentrations of DA. For the solution of SDS without DA, the product of the conductance and the viscosity is almost independent of the temperature, while for the mixed solutions the product is dependent on the temperature, especially in the case of the mixed solution containing a considerable amount of DA.

Takakusa, Michio

doi: 10.1246/bcsj.36.284pmid: N/A

Tricyclohexylbutylsilane, tetracyclohexylsilane and tricyclohexylphenylsilane were prepared by hydrogenation of triphenylbutylsilane and phenyltricyclohexylsilane and partial hydrogenation of tetraphenylsilane, respectively. Preparation of tricyclohexylisopropylsilane and tricyclohexyl-t-butylsilane was unsuccessful due to failure of obtaining corresponding triphenyl derivatives. An attempt to obtain tricyclohexylcyclohexoxysilane by hydrogenating triphenylphenoxysilane was also unsuccessful. In preparation of highlysubstituted cyclohexylsilicon compounds, the steric factor is of less importance in the hydrogenation process, while it is very much enhanced in reactions with organolithium compounds.

Takakusa, Michio

doi: 10.1246/bcsj.36.287pmid: N/A

Discrepancies among reported melting ponints for tetracyclohexylsilane and tricyclohexylbutylsilane were discussed. Tricyclohexylcyclohexoxysilane was obtained in 2∼5% yield in addition to tricyclohexylchlorosilane from the reaction of cyclohexyllithium with silicon tetrachloride. Petrov’s compound melting at 198°C is most likely to be tricyclohexylcyclohexoxysilane and not a stereoisomeric tetracyclohexylsilane. Tricyclohexylbutoxysilane, m. p. 133°C, was prepared by treating sodium butoxide with tricyclohexylchlorosilane, and it was pointed out that Petrov’s “tricyclohexylbutylsilane” is probably tricyclohexylbutoxysilane.