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Showing papers in "Bulletin of the Chemical Society of Japan in 1953"


Journal ArticleDOI
TL;DR: In this article, the magnetic susceptibilities of condensed polynuclear aromatic compounds with higher molecular weights (ten hydrocarbons and twelve quinones) have been measured by the Gouy method and the diamagnetic anisotropies have been approximately evaluated.
Abstract: The magnetic susceptibilities of condensed polynuclear aromatic compounds with higher molecular weights (ten hydrocarbons and twelve quinones) have been measured by the Gouy method, and the diamagnetic anisotropies have been approximately evaluated. The diamagnetic anisotropy becomes progressively large as the number of rings increases, when the aromatic condensation takes place in the manner of the closely compact arrangement of rings; while, when it is not the case, it depends strikingly upon the molecular structure. When the diamagnetic anisotropy has a smaller value, notwithstanding the molecule is made of a large number of rings, the localization of the π-electrons or some other excited states must be assumed. Such a case is found, when a molecule is not made of the aromatically conjugated system as a whole but separated into two predominant nuclei, as meso-naphthodianthrene and violanthrone, or when a molecule is made of a long shaped structure as pyranthrene or violanthrene.

71 citations




Journal ArticleDOI
TL;DR: In this paper, the molecular structures of acetamide and N-methylacetamide were determined using electron diffraction by gases, and the results were compared with the values obtained from X-ray diffraction.
Abstract: 1) The molecular structures of acetamide and N-methylacetamide were determined using electron diffraction by gases. The results were compared with the values obtained from X-ray diffraction by crystals. 2) C=O distance is longer in the crystalline state than in the gaseous state, while C–N distance is shorter in the crystalline state than in the gaseous state. This is due to the hydrogen bond which is absent in the gaseous state but exists in the crystalline state.

45 citations


Journal ArticleDOI
TL;DR: The dipole moments of tropone, 2-phenyltropone, tropolone methyl ether and their derivatives were measured in benzene solution at 25° as mentioned in this paper, and the agreement between them confirmed the correctness of the position of substituents in these compounds already determined or inferred from the standpoint of organic syntheses.
Abstract: The dipole moments of tropone, 2-phenyltropone, tropolone methyl ether and their derivatives were measured in benzene solution at 25°. The increase of moment of tropone over that of cycloheptanone was adequately explained by mesomeric effect and an additional effect due to the formation of cycloheptatriene ring. The latter effect was supported by the theoretical moment for heptafulvene. The moments of various derivatives were compared with the theoretical data. The agreement between them confirmed the correctness of the position of substituents in these compounds already determined or inferred from the standpoint of organic syntheses. The apparent moment of tropolone methyl ether hydrate indicates that in benzene the hydrate dissociates into three separate molecules.

44 citations


Journal ArticleDOI
TL;DR: In this paper, the von Karman-Pohlhausen method was used to derive the mean diffusion current for the case of amalgam polarography, in which the shielding effect due to the capillary tube was also treated theoretically.
Abstract: In order to integrate the MacGillavry-Rideal differential equation, representing the diffusion process at the dropping mercury electrode, the present author employed the von Karman-Pohlhausen method. Thus the following revised expression of the Ilkovic equation showing the mean diffusion current is derived, in which the shielding effect due to the capillary tube is also treated theoretically. \bari_d=608 n^*CD^1/2m^2/3τ^1/6{1+20.6(D^1/2m^-1/3τ^1/6)+49.0(D^1/2m^-1/3τ^1/6)^2-···} The analogous treatment is also applied to the case of amalgam polarography, and the following equation for the mean diffusion current is obtained. \bari_d=-608 n^*C_MD_M^1/2m^2/3τ^1/6×{1-30.5(D_M^1/2m^-/3τ^1/6)+155(D_M^1/2m^-1/3τ^1/6)^2-···}

42 citations


Journal ArticleDOI
TL;DR: In this paper, a new method for determining 1st CMC from viscosity is experimentally established, and a method of determining 2nd CMC was established by transforming and viscousity in the new variables.
Abstract: (1) Several methods of determining CMC are compared and criticised. (2) A new method of determining 1st CMC from viscosity is experimentally established. (3) A new method of determining 2nd CMC from viscosity is established by transforming and viscosity in the new variables. (4) Of each soap, characteristic constants [η1] and [η2] are discovered, and it is shown that a definite relation is concluded between these values and monomer molecular weight. (5) The theoretical explanation of these newly found phenomena has not yet been made.

37 citations


Journal ArticleDOI
TL;DR: In this paper, the properties of organovinylsilanes were discussed and the spectral properties of these compounds were obtained using the infrared spectra of the four organovinear-vinyl-silanes.
Abstract: (1) Vinyl chloride and organohalosilanes were shown to react with finely divided metallic sodium in ethyl ether, and trimethyl-, dimethyldi-, triethyl- and dimethylphenyl- vinylsilanes were prepared. Of these, dimethyldi- and dimethylphenyl-vinylsilane are new compounds and their physical constants were given. (2) Infrared spectra of these four organovinylsilanes were obtained and certain characteristic absorption bands were discussed. (3) Trichlorosilane was found to add to these vinylsilanes at the presence of diacetyl peroxide and four new β-trichlorosilylethyl-silanes were prepared and characterized.

31 citations




Journal ArticleDOI
TL;DR: The absolute intensities of the visible absorption spectra and the binding energies of quinhydrone-type molecular compounds have been determined by the measurements of their absorption intensities as discussed by the authors.
Abstract: The absolute intensities of the visible absorption spectra and the binding energies of quinhydrone-type molecular compounds have been determined by the measurements of their absorption intensities ...

Journal ArticleDOI
TL;DR: In this article, the oxygen equilibrium of hemerythrin and its Bohr effect were studied by spectrophotometric method and it was found that the oxygen combining centers in this molecule are not completely independent but the stabilizing effect is weak.
Abstract: The oxygen equilibrium of hemerythrin and its Bohr effect were studied by spectrophotometric method. It was found that the oxygen combining centers in this molecule are not completely independent but the stabilizing effect is weak. The value of n in Hill’s equation is equal to 1.37. The partial pressure of oxygen in equilibrium with the solution of 50 % saturated hemerythrin is 2.9 mm. Hg. Within the pH. range of stable hemerythrin solution, there is no dependence of oxygen equilibrium upon pH, hence no oxygen-linked acid groups are present in hemerythrin molecule.

Journal ArticleDOI
TL;DR: In this paper, the effect of water added to ammonium carbamate on liquid-vapor equilibrium of the CO2-NH3-Urea-H2O system was investigated at 160 °C.
Abstract: (1) The effect of water added to ammonium carbamate on liquid-vapor equilibrium of the CO2-NH3-Urea-H2O system was investigated at 160 °C. and a loading density of ammonium carbamate 0.60 g./cc. an...

Journal ArticleDOI
TL;DR: In this paper, the thickness of the monolayer of synthetic polypeptides at the pressure above and under the transition pressure was determined optically by Langmuir-Blodgett technique.
Abstract: In the force-area curves of the monolayer of synthetic polypeptides of longer side chains, a plateau which is a region of very high compressibility appears. The appearance of the plateau can be attributed to the reorientation of the polymer molecule at the interface. The pressure at which the plateau appears, decreases with the rise of temperature. From the temperature dependence of this pressure, the heat of transformation was evaluated. The polypeptides of shorter side chains of four carbon atoms or less in length scarcely need any energy for reorientation. Accordingly, no plateau was found with these polypeptides. The thickness of the monolayer of these polypeptides at the pressure above and under the transition pressure was determined optically by Langmuir-Blodgett technique. The thickness of the monolayer observed was compared with that calculated by using Stuart model (for the most part.) Our views on the reorientatoin of the film were ascertained.


Journal ArticleDOI
TL;DR: In this article, the molecular structures of monofluorobenzene and monobromobenzenes have been investigated by the electron diffraction method and the C-F and C-Br distances in each molecule have been determined as 1.30±0.03 A and 1.86± 0.02A respectively.
Abstract: The molecular structures of monofluorobenzene and monobromobenzene have been investigated by the electron diffraction method. The C–F and C–Br distances in each molecule have been determined as 1.30±0.03 A and 1.86±0.02A respectively. These distances are shorter than the case in which the bonds have the normal single bond characters. The double bond characters for these bonds have been calculated and obtained 16.9% for C–F and 13.3% for C–Br, in which we have considered the corrected single bond lengths in both cases.

Journal ArticleDOI
TL;DR: In this article, the authors showed that there exists a kind of mutual interaction between metallic ions through a bridging peroxy-radical and that the interaction between Co (III) and Co (IV) is considerably larger than that between two Co(III) atoms.
Abstract: (1) The dichroisms of decammine-μ-peroxodicobalt (III) nitrate dihydrate, [(NH3)5Co-O2-Co(NH3)5](NO3)4·2H2O, and of decammine-μ-peroxocobalt (III)-cobalt (IV) nitrate, [(NH3)5Co-O2-Co(NH3)5](NO3)5, and the absorption spectrum of the latter in aqueous solution have been quantitatively measured. (2) The empirical rules on the dichroisms of those crystals have been obtained. (3) The considerations on the absorption spectra of the above compounds have led to the conclusions that there exists a kind of mutual interaction between metallic ions through a bridging peroxy-radical and that the interaction between Co (III) and Co (IV) is considerably larger than that between two Co (III) atoms. The interaction of the above type is supposed to be applicable to the explanation of unusually deep colors in the crystals containing the same atoms in different oxidation states.

Journal ArticleDOI
TL;DR: In this paper, the synthesis of N-p-toluenesulfonyl-L-proline was corrected by amination and methylamination at 0° and 100°.
Abstract: (i) Kapfhammer and Eck’s report touching the synthesis of N-p-toluenesulfonyl-L-proline was corrected. (ii) N-p-Toluenesulfonylproline was resulted by the amination and methylamination of [L]-δ-p-toluenesulfonylamino-α- bromovaleric acid. In this case, racemization took place in consequence of amination at 100°, and partial Walden inversions were caused by amination at 0° and methylamination at 0° and 100°.


Journal ArticleDOI
TL;DR: The formation of nucleosides as the final product of hydrolysis was shown from the reducing power measurements and periodate consumption of products and the Preparative method for ribonucleosides from RNA under catalytic effect of lanthanum hydroxide was described.
Abstract: 1. The dephospkorylation reaction of RNA by lanthanum hydroxide gel was further studied. The activation energy of the reaction is 20,200∼20,400 cal. Optimal pH is between 8 and 9. 2. RNA is hydrolysed almost completely into nucleosides and inorganic phosphate at 90° in 40 hours at pH 8. The formation of nucleosides as the final product of hydrolysis was shown from the reducing power measurements and periodate consumption of products. 3. DNA is not dephosphorylated at all under conditions where RNA is almost completely dephosphorylated. This may be related to the structural difference of DNA and RNA. 4. Preparative method for ribonucleosides from RNA under catalytic effect of lanthanum hydroxide was described. Ribonucleosides are obtained in good yields. 5. Desoxyribo-, a-ribo-, b-ribo-, and 5′-ribocytidylic acid are all subject to catalytic dephosphorylation. 5′-Ribocytidylic acid is dephosphorylated most slowly. 6. Cerium hydroxide can be used as catalyst of the reaction in the same way with lanthanum hy...


Journal ArticleDOI
TL;DR: The magnetic susceptibilities of reduced and oxygenated hemerythrin solutions of the same concentration were measured by a Gouy magnetic balance at 25° as mentioned in this paper, indicating a paramagnetic contribution of iron atoms in the reduced molecule with the assumption that the four groups acting as oxygen combining centers in the molecule are equivalent to one another and that they are magnetostatically independent.
Abstract: The magnetic susceptibilities of reduced and oxygenated hemerythrin solutions of the same concentration were measured by a Gouy magnetic balance at 25° The susceptibility of the reduced solution was found to be higher than that of the oxygenated one, indicating a paramagnetic contribution of iron atoms in the reduced molecule With the assumptions that the four groups acting as oxygen combining centers in the molecule are equivalent to one another and that they are magnetostatically independent, the number of unpaired electrons in the group was calculated to be twelve in the reduced state and zero in the oxygenated preparation In the reduced state the bonds of the iron atoms are ionic or ion-dipole type in nature A profound change in the electronic structure takes place when oxygen molecules are combined with the hemerythrin molecule An oxygen molecule not only loses its own paramagnetism, but also affects all three iron atoms in the group in such a way that the bond type is essentially covalent Thes

Journal ArticleDOI
TL;DR: In this article, the dielectric constant of the dispersion has been derived theoretically without employing Wiener's proportionality postulate, where c = 1−4π/9√3.
Abstract: The dielectric constant of the dispersion, in which spherical particles of dielectric constant e1 are dispersed in a medium of dielectric constant e0, has been worked out theoretically without employing Wiener’s proportionality postulate. The following equation has been derived for the relation between the dielectric constant e of the dispersion and the volume fraction φ of the disperse phase. (Remark: Graphics omitted.) Where c=1−4π/9√3

Journal ArticleDOI
TL;DR: In this article, the relation between the kind of ligands and extinction coefficients of the first absorption bands of cobaltic complexes has been discussed, and the order of the ligands as to the magnitude of the effect which they exert on extinction coefficients has been determined empirically.
Abstract: The relation between the kind of ligands and extinction coefficients of the first absorption bands of cobaltic complexes has been discussed. The order of ligands as to the magnitude of the effect which they exert on extinction coefficients of the first bands has been determined empirically, thus NCS^-CrO_4^=SO_3^=NO_2^-CO_3^=C_2O_4^=en OH^-NO_3^-SO_4^=Br^-NH_3Cl^-H_2O. For pentammine cobaltic complexes with the sixth ligands, each of which is coordinated with an oxygen atom, a linear relation has been found to hold between νmax’s and emax’s of the first bands. For complexes of the type [CoA4X2], the trans-isomer has larger emax if X has more hyperchromic and trans-pairing effects than A. This investigation was supported by a grant from the Ministry of Education.





Journal ArticleDOI
TL;DR: It was found that the purity of ultracentrifugally isolated TMV was very high in a chemical sense and although the homogeneity withrespect to the length of particles was not always so good, one preparation, TMV-9, was found to have a high degree of homogeneity by the sedimentation and electrophoresis patterns.
Abstract: Tobacco mosaic virus (TMV) was purified by differential centrifugation in a vacuum-type, airdriven ultracentrifuge, first constructed in Japan. The yield of purified TMV was high and about 2 mg. per cc. of the original plant juice. Chemical analyses and physico-chemical examinations (including electrophoresis, sedimentation, diffusion, viscosity and electron microscope measurements) were carried out on the purified preparations to test their purities and homogeneities. It was found that the purity of ultracentrifugally isolated TMV was very high in a chemical sense. Although the homogeneity withrespect to the length of particles was not always so good, one preparation, TMV-9, was found to have a high degree of homogeneity by the sedimentation and electrophoresis patterns. The size and shape of TMV particles were determined on this preparation by several methods.