Bulletin of the Chemical Society of Japan
Online ISSN : 1348-0634
Print ISSN : 0009-2673
ISSN-L : 0009-2673
Volume 39 , Issue 2
Showing 1-50 articles out of 54 articles from the selected issue
  • Thomas Wolfram, C. D. Bass, Roger E. DeWames, L. Lynds
    1966 Volume 39 Issue 2 Pages 201-207
    Published: 1966
    Released: March 27, 2006
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    Using the Green’s function formulae for isotopic frequencies of the XY3 molecule together with the spectral theorem, explicit formulae for the molecular force constants directly in terms of the vibrational frequencies have been obtained. The relationship between the Wilson force constants and the cartesian force constants is discussed and leads to the above formulae. The procedure is applied to the BCl3 and BBr3 molecules and force constants are obtained. A simple procedure for calculating the variations in the force constants with variations in vibrational frequencies is suggested.
  • Thomas Wolfram, Roger E. DeWames
    1966 Volume 39 Issue 2 Pages 207-214
    Published: 1966
    Released: March 27, 2006
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    The Green’s function formalism for the analysis of molecular vibrations has been formulated for the internal or valence coordinate system. A general procedure for calculating isotopic frequencies and changes in force constants associated with the characterization of a perturbed molecule in terms of the unperturbed molecule is developed. It is shown that the internal molecular Green’s function can be constructed from the vibrational frequencies of the unperturbed molecule. Application is made to the XY2Z planar molecule. Exact formulae for the XY2Y(i) molecule are obtained. The shifts in the frequencies of an XY2Z planar molecule due to mass and bond length changes are obtained. It is shown that the A1 modes are unaffected by a change in the X–Z bond length while the B1 modes move to higher frequencies as the bond distance decreases. An explicit expression for the change in the valence bond bending force constant, fα, is obtained as an example of how force constant changes can be studied by means of the Green’s function procedure. Qualitative results for HBCl2 and HBBr2 are obtained which indicate that fα decreases in going from BCl3→ HBCl2.
  • Oyo Mitsunobu, Takashi Ohashi, Motokazu Kikuchi, Teruaki Mukaiyama
    1966 Volume 39 Issue 2 Pages 214-219
    Published: 1966
    Released: March 27, 2006
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    Various symmetrical and unsymmetrical triesters of phosphorous acid have been obtained by the reactions of phosphazo compounds with alcohols or phenols. When a phosphazo compound, amido phosphites or amino phosphine is treated with 2 mol. of N-substituted ethanolamine, the corresponding bis(β-aminoethyl) phosphites or phosphonite is obtained. On the other hand, when the same reaction is carried out with 1 mol. of the ethanolamine, cyclic phosphorous compounds are obtained in fairly good yields. Further, it has been found that the treatment of bis(β-anilinoethyl)phenyl phosphonite with phenyl isocyanate gives 2-phenylimino-3-phenyl-1, 3-oxazolidine.
  • Shunji Nagase, Kiyoshi Tanaka, Hajime Baba, Takashi Abe
    1966 Volume 39 Issue 2 Pages 219-222
    Published: 1966
    Released: March 27, 2006
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    Ethylene and ethane were electrochemically fluorinated in an electrolytic fluorination cell equipped with a bubbler. Several fluorinated ethanes were obtained from these samples in reasonable total-yields with reasonable current efficiencies. The influence of operating conditions on the reaction was investigated. A probable mechanism was described for the formation of the characteristic procucts obtained in the fluorination reaction.
  • Kin’ya Ogawa, Nobuko Tobe
    1966 Volume 39 Issue 2 Pages 223-227
    Published: 1966
    Released: March 27, 2006
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    A spectrophotometric study of the complex formation between iron(III) and sulfosalicylic acid was carried out over the pH range up to 8; further, an attempt was made to test the applicability of sulfosalicylic acid as a reagent for the spectrophotometric determination of iron(III) in the presence of iron(II). The absorption maxima are found at 510 mμ independently of the pH between 1 to 2.5, while they shift in the direction of shorter wavelength as the pH rises. It was concluded that three complex species, Fe(Su), Fe(Su)23−, and Fe(Su)36−, are formed successively in acid solutions; their stability constants were determined to be:
    (Remark: Graphics omitted.)
    where Su3− denotes the sulfosalicylate anion, C6H3(O)(COO)(SO3). If the pH of the solution is adjusted from 3 to 4.5 and if the absorbancy measurements are made at 480 to 490 mμ, sulfosalicylic acid can be used as a reagent for determining iron(III) in the presence of iron(II). The optimum concentration of iron(III) is 2 to 10 p. p. m.; iron(II) does not interfere, even at a concentration of 100 p. p. m.
  • Kin’ya Ogawa, Nobuko Tobe
    1966 Volume 39 Issue 2 Pages 227-232
    Published: 1966
    Released: March 27, 2006
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    A spectrophotometric study of the complex formation between iron(III) and salicylic acid was carried out over the pH range up to 6; further, an attempt was made to test the applicability of salicylic acid as a reagent for the spectrophotometric determination of iron (III) in the presence of iron(II). The absorption maxima of the mixture of iron(III) and salicylic acid are found at 530 mμ independently of the pH between 0.7 to 2.5, while they shift to shorter wavelength when the pH rises above 3. The isosbestic point occurs at 550 mμ between pH values from 3 to 6. It was concluded that three complex species, Fe(Sa)+, Fe(Sa)2, and Fe(Sa)3−3, are formed successively in acid solutions; their stability constants were determined to be:
    (Remark: Graphics omitted.)
    where Sa2− denotes the salicylate anion, C6H4(O)(COO). If the pH of the solution is adjusted from 2 to 3 and if absorbancy measurements are made at 515 to 500 mμ, salicylic acid can be used as a reagent for determining iron(III) in the presence of iron(II). The optimum concentration of iron(III) is 2 to 12 p. p. m.; iron(II) does not interfere, even at a concentration of 100 p. p. m.
  • Takeshi Ohno, Shunji Kato, Masao Koizumi
    1966 Volume 39 Issue 2 Pages 232-239
    Published: 1966
    Released: March 27, 2006
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    Besides the triplet state, semi-reduced eosine (Rd) and semi-oxidized eosine (Ox) were observed as transient intermediates in an aqueous solution; the former has a peak at 408 mμ, and the latter, one at 456 mμ. These two species are produced by the reaction DT+D→Rd+Ox or DT+DT→Rd+Ox. The sum of the rate constants for the reactions DT+D→Ox-+Rd and DT+D→2D is about 8.0×108 M−1 sec−1, approximately equal to the sum of the rate constants for DT+DT→2D and DT+DT→Ox+Rd. Triplet eosine, by reacting with ATU or EDTA, produces two kinds of half-reduced eosine, Rd′ and Rd″, which have absorption spectra similar to those of Rd but with different life-times. These are perhaps loose compounds of half-reduced dye and a half-oxidized reductant. The rate constants for DT+ATU→Rd′ and DT+EDTA→Rd″ are 3.4×105 M−1 sec−1 and 5×105 M−1 sec−1 respectively. Rd disappears bimolecularly by means of the Rd+Ox→2D reaction with the rate constant of 8.8×107 M−1 sec−1. Ox, by reacting with EDTA or ATU, regenerates the original dye with the rate constants of 1×106 and 8×105 M−1 sec−1 respectively. The results enable us to conclude that the D–D mechanism occurs under suitable conditions.
  • Tatsuya Sekine, Yuko Hasegawa
    1966 Volume 39 Issue 2 Pages 240-243
    Published: 1966
    Released: March 27, 2006
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    The complex formation of scandium(III) with chloride and nitrate ions has been investigated at 25°C. Scandium-46 was employed in conjunction with a cation-exchange resin (Dowex 50W X-12, 100–200 mesh) in the H+-form and the ionic strength was maintained at 4.0 M with perchloric acid. The stability constants have been obtained graphically by a curve-fitting method and the following results were obtained.
    (Remark: Graphics omitted.)
  • Tatsuya Sekine, Takeshi Hamada, Mitsuo Sakairi
    1966 Volume 39 Issue 2 Pages 244-246
    Published: 1966
    Released: March 27, 2006
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    The distribution of scandium(III) between organic tributyl phosphate solutions and aqueous perchlorate, nitrate, chloride solutions or mixed solutions of perchlorate-nitrate, perchlorate-chloride has been determined.
    The distribution of scandium between 50% tributyl phosphate - chloroform and 4 M H(Cl, ClO4) or 4 M H(NO3, ClO4) in some chloride or nitrate concentration region was higher than any of that distribution between the organic phase and 4 M perchloric acid, 4 M hydrochloric acid or 4 M nitric acid. It seems that the enhancement of the distribution ratios can be attributed to the extraction of mixed ligand complexes, but no simple relationship has been established between the distribution ratios and the proportion of the complex species in the aqueous phase as calculated from the previous data.
  • Masaru Mitsuishi, Gensaku Aida
    1966 Volume 39 Issue 2 Pages 246-249
    Published: 1966
    Released: March 27, 2006
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    In order to explore the behavior of Alizarine Saphirol SE in water-ethanol mixtures, the absorption spectrum and the conductance of the dye solution were obtained. A characteristic spectrum of the dye aggregate in water is found to change gradually into a monomer spectrum with an increase in the proportion of an added ethanol. Moreover, the dye is found to show marked McBain effect in water, while showing a conductance curve typical of a weak electrolyte in 58.7% (v/v) ethanol.
  • Seiichi Kondo
    1966 Volume 39 Issue 2 Pages 249-253
    Published: 1966
    Released: March 27, 2006
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    The temperature broadening of the chlorine quadrupole resonance line-width was studied in three ethane derivatives (1, 1, 1-trichloroethane, hexachloroethane and 1, 1, 1, 2-tetrachloro-2, 2-dimethylethane) below the plastic crystalline phases. Most of the resonance frequencies observed at the temperature of liquid nitrogen were equal to those reported in the literature. The energies of activation (2.2, 2.6 and 4 kcal./mol. respectively for the three compounds mentioned above) were obtained from the line-width versus temperature curves in the low temperature phases. It was suggested, considering the smallness of the energies of activation, that the vibrational rotation of the molecule as a whole rather than the internal axial rotation may exist in those phases.
  • Shô Itô, Kahei Takase, Norio Kawabe, Hiroshi Sugiyama
    1966 Volume 39 Issue 2 Pages 253-256
    Published: 1966
    Released: March 27, 2006
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    Two new methods have been developed to synthesize pyrazolotropone derivatives. 2-Methoxy-3, 5, 7-tribromotropone reacts with diazomethane to yield 4, 6-dibromo-7-methoxy-1-methyl-8(1H)-cyclohepta[c]pyrazolone, whereas the alkaline treatment of 4-acetyltropolone tosylhydrazone provides 3′-methylpyrazolo[3, 4-c]tropolone and 3′-methylpyrazolo[4, 3-d]tropolone. The structure of these products has been elucidated.
  • Isao Kamiya, Ryojirô Iwaki
    1966 Volume 39 Issue 2 Pages 257-263
    Published: 1966
    Released: March 27, 2006
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    A kinetic study of the chemiluminescence in alkaline solutions of several xanthene dyes with hydrogen peroxide was carried out in the hope of gaining some insight into the mechanism of the luminescent reaction. When the concentrations of sodium hydroxide and hydrogen peroxide were kept constant, the decay curve of the luminescence was represented by It=Aexp(−at), where It is the light intensity at time t ; a is equal to the rate constant of the decomposition of the dye (first order with respect to the dye concentration) and A is a parameter proportional to the initial dye concentration. The lifetime of the luminescent reaction was prolonged by the addition of such organic solvents as alcohol and dioxane; the a value decreased, while the A value remained unchanged. Both the a value and the A value increased with the elevation of the reaction temperature.
  • Isao Kamiya, Ryojirô Iwaki
    1966 Volume 39 Issue 2 Pages 264-269
    Published: 1966
    Released: March 27, 2006
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    The emission spectra of uranine and esoine chemiluminescence with hydrogen peroxide were measured photoelectrically and were compared with the fluorescence spectra of the dyes. The apparent spectra did not give the true energy distribution of the emitted light, because self-absorption took place. When the dyes were oxidized with ozonized air, the apparent emission spectra were very similar to those obtained when the dyes were oxidized with hydrogen peroxide. This would indicate that the emitting species are the same in the two reaction systems. The emission from the dye-ozone reaction was intense, and the spectrum could be compared with the fluorescence spectrum by employing a system with a low dye concentration. The coincidence of the two spectra was clearly demonstrated. The chemiluminescence spectrum of uranine at a high dye concentration in the presence of hydrogen peroxide was compared to the “chemi-fluorescence” spectrum of the luminol-dye system. The two systems gave almost the same spectrum. It may be concluded that the emissions from uranine and eosine chemiluminescence are the fluorescence emissions of the dyes and that the emitting species are the excited singlet states of uranine and eosine.
  • Isao Kamiya, Ryojirô Iwaki
    1966 Volume 39 Issue 2 Pages 269-276
    Published: 1966
    Released: March 27, 2006
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    The intensity of uranine chemiluminescence decreased when trypaflavine was added to the system. The enfeebling action seemed to be due to external quenching. On the contrary, the intensity of eosine chemiluminescence was enhanced by the presense of uranine. The values of Δ and σ are defined by the following equations:
    (Remark: Graphics omitted.)
    where IUE, IU and IE are the intensities measured in uranine-eosine, uranine and eosine systems respectively, and where T is the duration of eosine chemiluminescence. Δ increased with the increase in either the concentration of uranine or that of eosine, while σ increased only when the ratio of the uranine concentration to the eosine concentration increased. Δ increased with the increase in the temperature, while σ was little affected by the temperature. Δ increased upon the addition of organic solvents, while σ was little affected by the addition of the organic solvents. The enhancing action is due neither to the production of a stable compound which emits strongly nor to the increase in the rate of the decomposition of the dye. One possible mechanism of the enhancing action is that energy is transferred from an energy-rich intermediate produced by the reaction to an unoxidized uranine or eosine.
  • Isao Kamiya, Ryojirô Iwaki
    1966 Volume 39 Issue 2 Pages 277-281
    Published: 1966
    Released: March 27, 2006
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    On the basis of the results shown in the previous papers, the following reaction scheme was proposed for the chemiluminescent reaction. Hydrogen peroxide decomposes spontaneously to the radical (R·). A portion of the radical then reacts with the dye molecule (E) to produce an energy-rich intermediate (ME*): E+R·→ME* The energy-transfer takes place from ME* to an unoxidized dye, so the dye is excited electronically: ME*+E→E*+··· However, most of the ME* is decomposed by non-radiative processes. E* is deactivated by fluorescence emission processes (E*→E+hν) or quenching processes (E*+E→E+E). According to this reaction scheme, most of the experimental results can be explained reasonably. It is expected that further experimental evidence, such as the detection of an intermediate, will verify the theory.
  • Shuichi Seto, Hiroko Sasaki, Kyozo Ogura
    1966 Volume 39 Issue 2 Pages 281-285
    Published: 1966
    Released: March 27, 2006
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    The reaction of 5-aminotropolone with diketene gave a minor product and 5-aceto acetamidotropolone, which had previously been described (K. Ogura et al., This Bulletin, 38, 306 (1965)). This unknown compound was obtained as a main product when 5-acetoacetamidotropolone was treated with diketene in the presence of triethylamine. From its oxidative degradation and its NMR spectrum, this compound was proved to be 3-acetyl-4-hydroxy-6-methyl-1-(tropolon-5′-yl)pyridone-2. Furthermore, for the sake of the structural determination, 3-acetyl-4-hydroxy-6-methylpyridone-2 and its deacetylated product were prepared.
  • Mihir K. Saha
    1966 Volume 39 Issue 2 Pages 285-287
    Published: 1966
    Released: March 27, 2006
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    A few mineral acids, namely hydrochloric, hydrobromic and sulfuric acid, have been used as photoinitiators for the polymerization of methyl methacrylate in aqueous media in the presence of ultraviolet light. The endgroups incorporated in the resulting polymers have been determined by the application of the sensitive “Dye Techniques” lately developed in our laboratory. On the basis of the endgroup results, attempts have then been made to explain the mechanism of such polymerization, and also the nature of the initiating species involved.
  • Goro Yamaguchi, Yasushi Kubo, Hiroshi Ogawa
    1966 Volume 39 Issue 2 Pages 287-295
    Published: 1966
    Released: March 27, 2006
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    The fracture properties of corundum crystals have been examined on various artificial corundums, such as electrically-fused corundum, Verneuil-flame-fused corundum and hydro-thermally-synthetised corundum. The specimens were ground to a tihckness of less than 5/100 mm. The microscope generated in the grinding process were observed by means of a polarizing microscope. The orientation of the c-axis (C) and the crack normal to the section normal (T) was measured using a universal stage. The direction of the crack has a close relation to the crystal orientation of the thin section. Frequent irregular cracks intercrossing one another occur in crystals ground with T∧G angles from 0° to 50°. Cleavage cracks along the {10\={1}1} plane take place prominently in the range of T∧C angles from 50°to 80°. Rare irregular cracks streaming in one direction take place in the range of T∧C angles from 80° to 90°. The heat treatment in air of titania-containing corundum decreases the number of cracks in the crystal. The results have been interpreted on the basis of the cohesion strength theory of M. D. Shappel (Am. Mineralogist, 21, 75 (1936)). In order to explain the limited range of the ocurrence of cleavage cracks, a model has been proposed in which the shearing along the cleavage plane takes place prior to the crack nucleation in the corundum crystal.
  • Goro Yamaguchi, Yasushi Kubo, Hiroshi Ogawa
    1966 Volume 39 Issue 2 Pages 295-299
    Published: 1966
    Released: March 27, 2006
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    In an investigation into the fracture properties of thin-sectioned corundum crystals, it was noticed that microcracks in electrically-fused corundum obey a hexagonal symmetry in spite of the rhombohedral symmetry of the corundum structure. This fact suggests that the corundum crystals consist of several twins, which have the same optical direction and which cannot be distinguished microscopically. The X-ray Laue back-reflection and etching techniques were applied to commercial 16-mesh grains of electric furnace-fused alumina abrasives. Corundum crystals grown over the crystal size of hundreds of μ to 1 mm. in electric-furnace fusions were found to be generally composed of several penetration twins with a twinning plane (0001). The twins are considered to be growth twins arising in the cooling process. The impurity composition and heat treatment have no marked effect on twinning. The twin junction is highly stable both mechanically and chemically. Cleavage cracks generated in individual crystals are stopped at the twin boundary.
  • Kunio Okamoto, Hiroto Yamada, Issei Nitta, Haruo Shingu
    1966 Volume 39 Issue 2 Pages 299-306
    Published: 1966
    Released: March 27, 2006
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    The SN1 phenolyses of optically active α-phenylethyl chloride in binary mixtures of organic solvents and certain substituted phenols (i. e., phenol, p-cresol, p-chloro- and p-nitro-phenol) proceed in the presence of aniline and of triethylamine to give the corresponding α-phenylethyl substituted-phenyl ethers with a predominantly-retained configuration. In binary mixtures of benzene and various phenols, the extents of retention for the ethers are slightly reduced at the higher base concentrations. However, in binary solvents of acetonitrile and certain phenols, the optical purities of the ethers with retained configurations decrease continuously with the base concentrations, while at the higher concentrations (∼0.4 M) the steric courses change to the inverted course. The C-alkylated (α-phenylethylated) derivatives of these phenols, isolated along with the phenyl ethers, have inverted configurations, irrespective of the configurations of the corresponding phenyl ethers. These results are all consistent with a mechanism in which a molecule of the phenol reacts with the SN1 ion-pair intermediate of the phenolysis to give a phenyl ether with a retained configuration, probably by SNi-like four-center substitution, whereas the reaction of a phenoxide anion with the SN1 intermediate proceeds predominantly by the Walden inversion mechanism yielding a phenyl ether and α-phenylethylated phenols with inverted configurations.
  • Kunio Okamoto, Nobuko Uchida, Seiki Saitô, Haruo Shingu
    1966 Volume 39 Issue 2 Pages 307-311
    Published: 1966
    Released: March 27, 2006
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    Competitive solvolysis has been conducted in binary solvents of water and ethanol on optically active α-phenylethyl chloride at 40.0°C. The extents of inversion (α%) for solvolysis products, i. e., α-phenylethyl alcohol and α-phenylethyl ethyl ether, have been calculated from the optical rotations of these products isolated after ten half-lives, and the values of α% have been plotted VS. the volume percentage of water. In the region of 90% aqueous ethanol, the two α% lines for the alcohol and the ether intersect with each other. This intersection of the two lines conflicts with any single mechanism for the borderline SN reactions, whereas the dual mechanism can explain this phenomenon without any difficulty. In the region of a 100% water-solvent (a typical medium for the SN1 solvolysis), the two lines do not converge to the same α% value. On the basis of these findings, a general mechanism of racemization for the SN1 solvolysis has also been discussed.
  • Naoko Tsubaki, Kiichi Nishimura, Yoshio Hirose
    1966 Volume 39 Issue 2 Pages 312-315
    Published: 1966
    Released: March 27, 2006
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    Full analyses of the essential oils obtained from Yomena (Aster indicus L.), Yomogi (Artemisia princepts Pamp.) and Hog weed (Ambrosia elatior L.) were carried out. Each essential oil was separated by fractional distillation under reduced pressure, and the fractions thus obtained were identified.
  • Masaji Ohno, Masaru Okamoto, Seiichi Torimitsu
    1966 Volume 39 Issue 2 Pages 316-320
    Published: 1966
    Released: March 27, 2006
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    The addition reactions of cis, trans, trans-1, 5, 9-cyclododecatriene with cis-addition reagents, such as osmium tetroxide, potassium permanganate, diimide, and nitrosyl chloride, have been investigated. It has been shown that the first attack of each reagent preferentially takes place at one of the trans double bonds. The reactions with osmium tetroxide and potassium permanganate at room temperature afforded cis-5, trans-9-cyclododecadiene-trans-1, 2-diol in 89 and 59% yields respectively. The glycol was then further oxidized with osmium tetroxide into cis-y-9-cyclo-dodecene-1, 2, 5, 6-tetrol in a 60% yield. The reduction of the cyclotriene with diimide, generated in situ by the oxidation of hydrazine, afforded cis-cyclododecene in 60—82% yields. The addition of nitrosyl chloride in the presence of hydrochloric acid afforded 2-chlorocyclodode-cadienone oxime in a quantitative yield; this was then reduced into cyclododecanone oxime, obtained in a quantitative yield, by catalytic reduction with palladium-charcoal.
  • Muneo Handa
    1966 Volume 39 Issue 2 Pages 321-326
    Published: 1966
    Released: March 27, 2006
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    Uranium tetraiodide is oxidized to triuranium octoxide through three intermediates, which are deposited on silica powder heated to temperatures of about 400, 300 and 200°C respectively. The intermediates are produced by the action of oxygen contained in small amounts in a helium stream (1/100–1/10000 atm.) on uranium tetraiodide. The intermediates are considered to be compounds consisting of uranium, iodine and oxygen. Chemical analysis, the measurement of the melting point and X-ray analysis show that the compound deposited at the temperature of 400°C is uranium triiodide, while the compounds deposited at 300 and 200°C are both uranium tetraiodides. Three hypotheses have been formulated to interpret the above phenomenon, in which the reaction of uranium iodides with iodine has been studied.
  • Takayuki Suga, Tamon Matsuura
    1966 Volume 39 Issue 2 Pages 326-329
    Published: 1966
    Released: March 27, 2006
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    The results obtained in the preceding papers (Parts I–III) of this series showed that, on oxidation with t-butyl chromate, the primary alcohol without a π-electron system on the carbon α to the hydroxymethyl group yields the corresponding ester in a comparable yield, together with the aldehyde and the acid, and also that the cyclic α-glycol with two secondary hydroxyl groups affords the corresponding cyclic ester, along with the glycol fission product. Chemical examination and infrared spectroscopic study have now proved that the course of the formation of these esters does not follow the direct esterification of the alcohol with the acid formed from it by oxidation, but rather involves the formation of a hemiacetal intermediate between the original alcohol and the aldehyde produced from the alcohol, and the subsequent oxidation of the hemiacetal. The oxidation of alcohols with t-butyl chromate has also been discussed generally on the basis of the results of our previous papers and of the present work.
  • Shigeo Nishimura, Tetsuo Shu, Tomoyoshi Hara, Yuzuru Takagi
    1966 Volume 39 Issue 2 Pages 329-333
    Published: 1966
    Released: March 27, 2006
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    The hydrogenation of aniline with the hydroxide-black catalysts of ruthenium and rhodium was investigated, using various alcohols as solvents. The formation of dicyclohexylamine increased in the following order with respect to the solvents: t-butyl alcohol≅isopropyl alcohol << ethyl alcohol < methyl alcohol. It was shown that the addition of a small amount of alkali greatly hinders the formation of dicyclohexylamine. The effects of added ammonia and dicyclohexylamine were also investigated. The addition of ammonia retarded the rhodium-catalyzed hydrogenation much more seriously than the hydrogenation with ruthenium, but it was found that in the presence of alkali the hydrogenation with rhodium was not inhibited by the addition of ammonia.
  • Takeo Yamamoto, Shizuo Fujiwara
    1966 Volume 39 Issue 2 Pages 333-343
    Published: 1966
    Released: March 27, 2006
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    In an attempt to examine various existing methods for the analysis of high-resolution NMR spectra, the statistical theory has been applied to the least-squares iteration method presented by Arata, Shimizu and Fujiwara. The standard errors of chemical shifts and spin-spin coupling constants, and the singularity in the normal equation, have been discussed. Two sets of parameters which are placed close together have a possibility of producing a singularity in the normal equation. A way of eliminating the singularity has been presented. The method thus presented has then been applied to an analysis of the vinyl proton spectra of acrylic acid in carbon tetrachloride and in aqueous solutions of various pH values. It has been found that the spin-spin coupling constants do not change beyond the range of experimental errors under the conditions of the present study. The change in chemical shifts has been discussed in terms of the possible conformations of the molecules.
  • Masaji Miura, Hiromitu Naono, Mitunori Hara
    1966 Volume 39 Issue 2 Pages 344-347
    Published: 1966
    Released: March 27, 2006
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    The crystallization of strontium sulfate has been conductometrically investigated in the presence of triphosphate under various pH values of the solution. The amount of triphosphate adsorbed on the crystal surface of strontium sulfate has been estimated as a function of the pH of the solution. The action of triphosphate in stabilizing the supersaturated solution of strontium sulfate and the amount of triphosphate adsorbed on the crystal surface depend remarkably on the pH of the solution; further, the two are closely correlated with each other. It has been concluded from these facts that the adsorption of triphosphate plays an important role in the stabilization of the supersaturated solution of strontium sulfate.
  • Kimiko Matsuo, Masamichi Tsuboi
    1966 Volume 39 Issue 2 Pages 347-352
    Published: 1966
    Released: March 27, 2006
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    The thermal transition profile (melting profile) of the double-helical complex of polyriboinosinic acid plus polyribocytidylic acid, poly(I+C), into random coils in solution has been examined by the observation of the ultraviolet absorbance at 248 mμ of the solution. The effects of Na+, Mg2+, NH4+, CH3NH3+(CH2)nNH3+ (where n=2, 3, 4, 5, 6, and 8), spermidine, spermine, actinomycin D, and poly-L-lysine upon the melting profile have been observed. Among the diamines examined, that with n=3 has been found to have the maximum effect. Poly-L-lysine has been found to form a complex with poly(I+C) in the solution with a stoichiometric mole ratio of NH2 : P=0.5 : 1.
  • Tomozo Koh, Iwaji Iwasaki
    1966 Volume 39 Issue 2 Pages 352-356
    Published: 1966
    Released: March 27, 2006
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    A photometric method capable of determining tetrathionate by exactly the same procedure as that used for pentathionate and hexathionate has been established. The optimum pH ranges for the reactions of tetrathionate, pentathionate and hexathionate with cyanide are 8.3–12.1, 8.0–8.8, and 7.8–8.9 respectively for the recommended procedure. From a consideration of the above experimental facts, it has been concluded that tetrathionate can be determined accurately by exactly the same procedure as that used for pentathionate and hexathionate when the pH value is within the range from 8.3 to 8.8. To the standard tetrathionate solution first the buffer solution and then a solution of sodium cyanide are added in order that the pH value of the mixture solution after the addition of the cyanide solution may be within the 8.3–8.8 range. The mixed solution is kept in the thermostat at 40°C for 30 min.; the tetrathionate is thereby converted into thiocyanate quantitatively. After the addition of a ferric nitrate - perchloric acid solution, the absorbancy of the solution of ferric-thiocyanate complex formed is measured at the wavelength of 460 mμ.
  • Kenichi Morinaga, Kunio Nakano, Shigeru Saito, Keizo Nakamura
    1966 Volume 39 Issue 2 Pages 357-361
    Published: 1966
    Released: March 27, 2006
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    The oxidation-reduction behavior of tris(1,10-phenanthroline)cobalt complexes at a dropping mercury electrode has been studied by the d. c. and a. c. polarographic methods. The trivalent cobalt-phenanthroline complex ion is reduced in two steps in 1 M sodium sulfate in a quite similar way as the trivalent cobalt-dipyridyl complex ion. Both electrode processes, cobalt(III)→cobalt(II) and cobalt(II)→cobalt(I), are considered to be reversible. The univalent cobalt-phenphenanthroline complex has been obtained as a black powder by the reduction of the divalent cobalt complex with sodium borohydride; the atomic ratio of nitrogen to cobalt has been found to be close to six. The ethanolic solution is brown-black, in remarkable contrast with that of the corresponding dipyridyl complex, deep blue.
  • Yoshiharu Izumi, Susumu Tatsumi, Masami Imaida, Yoshio Fukuda, Shiro A ...
    1966 Volume 39 Issue 2 Pages 361-364
    Published: 1966
    Released: March 27, 2006
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    The asymmetric hydrogenation catalyst has been prepared by the modification of Raney nickel with solutions of (−)-2-methyltartaric acid (A), (+)-2-methyltartaric acid (B) and (+)-2,3-dimethyltartaric acid, and its asymmetric hydrogenation activity has been measured by the hydrogenation of methyl acetoacetate to optically active methyl 3-hydroxybutyrate. The asymmetric activity of the catalyst is much influenced by the pH and the temperature of the modifying solution. Generally, (+)-2-methyltartaric acid (B) and (+)-2,3-dimethyltartaric acid have a high asymmetric activity in reaction to Raney nickel. The highest asymmetric activity has been obtained by modification with (+)-2-methyltartaric acid (B) and with it the specific rotation of the hydrogenation product has been found to be [α]D20 +11.72° (without a solvent) under the optimum conditions. This value means that the product is 78% composed of the dextro- and 22% of the levorotatory form. On the other hand, the asymmetric activity of the catalyst modified with (−)-2-methyltartaric acid (A) is very low and quite different from that of the catalyst modified with (+)-2-methyltartaric acid (B). It has been supposed that this difference depends on the stereoisomerism of the threo-erythro form of the 2-methyltartaric acid molecule.
  • Shigeru Oae, Yutaka Ohnishi, Seizi Kozuka, Waichiro Tagaki
    1966 Volume 39 Issue 2 Pages 364-366
    Published: 1966
    Released: March 27, 2006
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    1, 4-Diazabicyclo(2, 2, 2)octane readily forms an addition complex with two moles of bromine. This complex has been found to be an excellent oxidizing agent for the selective oxidation of various sulfides to the corresponding sulfoxides when the reaction is performed in an aqueous medium. The bromine-addition complexes of pyridine and quinoline have also been found to be useful for the same purpose. The reaction has been shown to be a superb way of incorporating 18O into sulfoxides.
  • Nobuyuki Tanaka, Kazuko Ogino (née Ebata), Gen Sato
    1966 Volume 39 Issue 2 Pages 366-369
    Published: 1966
    Released: March 27, 2006
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    The polarographic diffusion current of some tervalent substitution-inert complex cations decreases by the addition of sulfate. From the change in diffusion current the association constants of substitution-inert complex and sulfate ions are obtained at ionic strength 0.1 (NaClO4) and 25°C. The values are 69±8, 58±8 and 4×10 for [Co(NH3)6]3+–SO42−, [Cr(NH3)6]3+–SO42− and [Cr(H2O)6]3+–SO42 respectively. The formation of [Co(NH3)6]3+–HSO4 is negligibly small compared with that of [Co(NH3)6]3+–SO42−.
  • Michiya Itoh, Saburo Nagakura
    1966 Volume 39 Issue 2 Pages 369-375
    Published: 1966
    Released: March 27, 2006
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    The ESR and electronic absorption spectra have been measured with the 1-methyl-4-carbo-methoxy-, 1-methyl-4-carbamido-, 1-methyl-4-acetyl- and 1-methyl-4-cyanopyridinyl radicals. From the analysis of their ESR spectra by the aid of a spectrum accumulator, we have been able to determine the nitrogen and hydrogen hyperfine splitting constants of these pyridinyl radicals, from which the spin distributions have then been evaluated. These radicals except for the 1-methyl-4-carbamidopyridinyl radical, have been found to show three absorption bands, at 300–350 mμ, at about 400 mμ and at about 600 mμ. From the results of the ESR and electronic absorption spectra, the electronic structures of these pyridinyl radicals have been concluded to be similar to those of the 4-substituted pyridine anion radicals. The preparation of 1,2,6- and 1,3,5-trimethyl-4-substituted pyridinyl radicals has been attempted. The latter radicals, except for the 1,3,5-trimethyl-4-cyanopyridinyl radical, were not detected by the ESR and electronic absorption spectra, because the steric hindrance of the methyl groups at the 3 and 5 positions prevents them from achieving the resonance stabilization due to the 4-substituent.
  • Matsuji Takebayashi, Tadao Shingaki, Takakimi Mihara
    1966 Volume 39 Issue 2 Pages 376-379
    Published: 1966
    Released: March 27, 2006
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    The effect of free radical sources on the reaction of thiols with propylene oxide has been studied. In the presence of free radical sources, such as benzoyl peroxide, tetraphenylhydrazine and tetra-methylthiuram disulfide, the reaction gives a single addition product, 1-aryl(or aralkyl)thio-2-propanol, in the same manner as when alkaline catalysts are employed. When l(+)-propylene oxide is used, an optically-active 1-thio-2-propanol is obtained. However, azobisisobutyronitrile manifests no catalytic influence on the reaction. Mercury-vapor light also has no effect on the interaction of thiols and propylene oxide, while the light leads to the decomposition of thiols. The mechanism of the reaction has been discussed in terms of a thiyl anion intermediate.
  • Hiroyuki Hiraoka, Russell E. Hardwick
    1966 Volume 39 Issue 2 Pages 380-386
    Published: 1966
    Released: March 27, 2006
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    Upon treatment with certain reagents, the photochromes, α- and γ-(2,4-dinitrobenzyl)pyridine and 2, 4, 2′, 4′-tetranitrodiphenylmethane form stable, blue-colored compounds which probably have chromophoric structures similar to those of the photochromic modifications of the original compounds (two examples of the permanently colored compounds are the N-methyl bases and the products from reactions with epoxy compounds). Kinetic and spectrophotometric studies of these colored compounds and of the anions of the original photochromes are reported. These results are compared with data on the photochromic tautomers.
  • Ichimin Shirotani, Hiroo Inokuchi, Shigeru Minomura
    1966 Volume 39 Issue 2 Pages 386-390
    Published: 1966
    Released: March 27, 2006
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    The electrical conductivity and the temperature dependency of the organic semiconductors, five simple polycyclic aromatic compounds, two charge transfer complexes and a free radical, have been observed up to 1.6×105 kg./cm2. The conductivity thus increases to 105–107 times that at atmospheric pressure, while the band gaps decrease to about one fifth of the ordinary values. These abrupt changes may be caused by the overlapping of π-electron clouds of adjacent aromatic molecules.
  • Tadao Hayakawa, Kaoru Harada, Sidney W. Fox
    1966 Volume 39 Issue 2 Pages 391-395
    Published: 1966
    Released: March 27, 2006
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    The sequences, α-aspartyl-L-serylglycine and α-glutamyl-L-serylglycine, appear in the “active site” of many esteratic enzymes. The free tripeptides were synthesized in this study. In order to avoid difficulties encountered in more conventional synthetic routes, N-carbobenzoxy-L-aspartyl (β-benzyl ester)-O-benzyl-L-serylglycine dibenzyl ester and N-carbobenzoxy-L-glutamyl (γ-benzyl ester)-O-benzyl-L-serylglycine dibenzyl ester were synthesized. These protected peptides were converted to the free tripeptides upon hydrogenolysis, which removed all of the four protecting groups simultaneously. Several derivatives of these tripeptides were also synthesized.
  • Yukito Murakami, Katsumi Mera
    1966 Volume 39 Issue 2 Pages 396-397
    Published: 1966
    Released: March 27, 2006
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  • J. S. Chadha, G. K. Sharma
    1966 Volume 39 Issue 2 Pages 398
    Published: 1966
    Released: March 27, 2006
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  • Masumi Koishi, Kenjiro Meguro
    1966 Volume 39 Issue 2 Pages 399
    Published: 1966
    Released: March 27, 2006
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  • Tosio Moriwake
    1966 Volume 39 Issue 2 Pages 401-402
    Published: 1966
    Released: March 27, 2006
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  • Mariko Inarida
    1966 Volume 39 Issue 2 Pages 403
    Published: 1966
    Released: March 27, 2006
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  • Yoshio Tazima, Sadao Yuguchi
    1966 Volume 39 Issue 2 Pages 404
    Published: 1966
    Released: March 27, 2006
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  • Yasuhiko Shirota, Toshikazu Nagai, Niichiro Tokura
    1966 Volume 39 Issue 2 Pages 405
    Published: 1966
    Released: March 27, 2006
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  • Hideo Tsujikawa, Kenji Fueki, Zenichiro Kuri
    1966 Volume 39 Issue 2 Pages 406
    Published: 1966
    Released: March 27, 2006
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  • Takumi Katsumoto, Akiko Honda
    1966 Volume 39 Issue 2 Pages 407
    Published: 1966
    Released: March 27, 2006
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  • Kunio Okamoto, Masayuki Hayashi, Haruo Shingu
    1966 Volume 39 Issue 2 Pages 408
    Published: 1966
    Released: March 27, 2006
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