Bulletin of the Chemical Society of Japan
Online ISSN : 1348-0634
Print ISSN : 0009-2673
ISSN-L : 0009-2673
Volume 47 , Issue 4
Showing 1-50 articles out of 63 articles from the selected issue
  • Michiko Yonemura, Yoshihide Kotera
    1974 Volume 47 Issue 4 Pages 789-792
    Published: 1974
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    The role of alkali germanates as catalysts in the polymorphic transformation of germanium dioxide was investigated by high-temperature X-ray diffraction method. Lithium germanate and sodium germanate catalyze the transformation in a solid state, the activation energies being larger than 80 kcal/mol. Potassium germanate catalyst plays its role in a liquid state, the activation energy being smaller than that of other catalysts.
  • Michiko Yonemura, Yoshihide Kotera
    1974 Volume 47 Issue 4 Pages 793-796
    Published: 1974
    Released: March 27, 2006
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    The effect of surrounding atmosphere on the phase transformation of germanium dioxide with alkali germanate catalysts was investigated by high temperature X-ray diffraction method. The catalysts were Li2O·7GeO2, 3K2O·11GeO2, K2O·7GeO2 and 2Na2O·9GeO2. The ambient atmospheres were dry or wet nitrogen and oxygen. The effect of atmosphere was found to be not so large as that of the catalyst. Water vapor has prominent effects upon the transformation as in other solid state reactions.
  • Zen-ichi Yoshida, Yoshiyuki Tawara, Shizue Hirota, Hisanobu Ogoshi
    1974 Volume 47 Issue 4 Pages 797-800
    Published: 1974
    Released: March 27, 2006
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    Infrared spectrum in the region 4000–100 cm−1 and Raman spectrum of trisdimethylaminocyclopropenium perchlorate (1) have been measured. Band assignments have been made on the basis of normal coordinate analysis and deuteration of the methyl groups. Remarkable stabilization of cyclopropenium ion due to the peripheral amino groups is attributed to a marked delocalization of the positive charge of the ring on the amino groups through conjugation. Peculiar electronic structure of trisaminocyclopropenium ion is explained in terms of its vibrational spectrum.
  • Kazuo Tsutsumi, Hisao Kajiwara, Hiroshi Takahashi
    1974 Volume 47 Issue 4 Pages 801-805
    Published: 1974
    Released: March 27, 2006
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    Aluminium ion was extracted stoichiometrically from the framework of the faujasite-type zeolite by EDTA treatment. Dealuminated zeolites with various silica/alumina ratios (from 4.80 to 10.29) were obtained. A dealuminated zeolite does not necessarily show the molecular-sieve-type adsorption isotherm of nitrogen. The lattice constant of zeolite decreases with the silica/alumina ratio. The zeolite with an increased silica/alumina ratio has a higher catalytic activity for a cumene-cracking reaction than the parent H-Y4.80 zeolite. It is suggested, on the basis of infrared spectroscopic and calorimetric measurements, that the total number of acid sites decreases with dealumination, while the number of strong acid sites increases. These strong aicd sites seem to contribute to the catalytic activity of dealuminated zeolite.
  • Niro Matsuura, Kisaburo Umemoto, Masako Waki, Zen’ichi Takeughi, ...
    1974 Volume 47 Issue 4 Pages 806-812
    Published: 1974
    Released: March 27, 2006
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    The polarographic behavior of alkali metal ions were studied in propylene carbonate (PC), ethylene carbonate (EC), water, N,N′-dimethylformamide(DMF), and dimethyl sulfoxide(DMSO). The polarographic half-wave potentials measured in these solvents against an aqueous saturated calomel electrode(SCE) were normalized to the potential of SCE in aqueous system by making corrections of potential required for transfer of rubidium ion from water to these solvents. The free energies of transfer of rubidium ion from water to other solvents were calculated by the application of the modified Born equation. The potential series on the normalized potential scale were given in the order DMSO<DMF<water<PC<EC, indicating that the metal ion-solvent interaction increases with increasing the electron donor property of the solvent. The solvent shifts in potential calculated by the application of the modified Born equation disagreed with the experimental results. In order to fit well the calculated solvent shifts in potential with the experimental results, following values of liquid junction potential must be assumed for these solvents; +0.090 V for DMSO, +0.085 V for DMF, +0.004 V for PC, and −0.064 V for EC against the aqueous phase.
  • Niro Matsuura, Kisaburo Umemoto, Zen’ichi Takeuchi
    1974 Volume 47 Issue 4 Pages 813-817
    Published: 1974
    Released: March 27, 2006
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    The relative standard potentials of alkali metals, silver, and thallium metal/ion couples in N,N′-dimethylforrnamide(DMF), dimethyl sulfoxide(DMSO), and propylene carbonate (PC) were measured against an aqueous saturated calomel electrode(SGE). These standard potentials of lithium, sodium, potassium, rubidium, caesium, thallium, and silver are −3.237, −2.898, −3.116, −3.079, −3.079, −0.643, and +0.372 V vs. SGE respectively in DMSO, and −3.163, −2.830, −3.067, −3.040, −3.048, −0.559, and +0.538 V vs. SGE respectively in DMF, and −2.9064, −2.691, −3.002, −2.980, −2.986, −0.402, and +0.813 V vs. SGE respectively in PC. The thallium electrode was found to be stable enough to be used as a reference electrode in these solvents. For the purpose of examining the Debye-Hückel equation for estimating the activity coefficient, the formal potentials of the thallium electrode were measured at various ionic strengths. The Debye-Hückel equation was confirmed to be applicable in these solvents, provided a proper value was chosen for the ionic radius parameter, a, for each solvent–3.6 for DMSO, 5.0 for DMF and 0.0 for PC.
  • Yoshie Inomata, Tadaaki Inomata, Takao Moriwaki
    1974 Volume 47 Issue 4 Pages 818-824
    Published: 1974
    Released: March 27, 2006
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    The infrared absorption spectra of DL-tyrosine and six metal DL-tyrosine chelates have been investigated from 4000 to 300 cm−1. A detailed normal coordinate analysis was performed for the metal chelates as a 39-body problem and an approximate description of the vibrational modes has been assigned to the observed frequencies. DL-Tyrosine chelates are found to be coordinated with the metal through nitrogen and oxygen and to have a trans configuration; the same is true for other aliphatic amino acid chelates. The bond-stretching force constants for the metal-nitrogen bonds have been found to decrease in the order Pd(II)>Cu(II)>Zn(II)>Cd(II)>Ni(II)>Co(II). The calculated frequencies, which were obtained using the same force constants as in other aliphatic amino acid chelates, were in good agreement with the observed frequencies.
  • Yoshihiro Masuda, Yoichi Iitaka, Hiroaki Hamano
    1974 Volume 47 Issue 4 Pages 825-828
    Published: 1974
    Released: March 27, 2006
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    In order to determine the stereospecificity and absolute configuration of 1′-(2,5-dimethoxyphenyl)-3′-diethylamino-n-butanol, X-ray structure analysis of its acetate hydrobromide has been carried out. The crystal of the derivative belongs to the monoclinic space group C2, with lattice constants a=14.218, b=8.290, c=18.187Å, β=108.1°, containing four formula units of C18H29O4N·HBr in a unit cell. The structure was solved by the heavy atom method and refined by the block-matrix least squares method to an R value of 0.06. The absolute configuration was determined by the use of the anomalous dispersion method, the configuration at the two asymmetric carbon atoms being found to be S.
  • Hiroshi Kawazura, Yoshiro Yamamoto, Toshio Ohmori, Kentaro Murano, Hir ...
    1974 Volume 47 Issue 4 Pages 829-831
    Published: 1974
    Released: March 27, 2006
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    Novel polymeric radical salts prepared by inserting alkali-metals into semi-conductive polymers derived from poly(tetrahalophenylene sulfides) were found to be effective hydrogenation catalyst for α-olefins; their activity trends as to the sort of alkali-metal and halogen of the matrix polymer were Cs>K>Na and F>Cl>Br respectively. The catalyst also showed an activity for the cis-trans isomerization of hex-2-ene which was proportional to that for the hydrogenation. The activities of the catalyst were discussed in terms of its steric confinement.
  • Toshiaki Tamamura, Takashi Yamane, Noritake Yasuoka, Nobutami Kasai
    1974 Volume 47 Issue 4 Pages 832-837
    Published: 1974
    Released: March 27, 2006
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    The crystal structure of an organic charge transfer salt 2,4,6-triphenylpyrylium-1,1,3,3-tetracyanopropenide has been determined by means of X-ray diffraction. The crystals are monoclinic in the space group P21/a. The unit cell dimensions are: a=13.024, b=21.357, c=8.324Å, β=94.56°. The cation and the anion are nearly planar and form an “ion-pair.” The crystal is built up from infinite columns stacked by these ion-pairs along the c axis. Between two adjacent anions in the neighboring columns, a weak hydrogen bond (C–H···N 3.265 (5), H···N 2.185(4) Å) is present. The charge transfer interaction between the anion and the cation seems to have less influence on the crystal structure than the electrostatic force or the hydrogen bonding.
  • Toshio Ikeda, Yasuki Yamamoto
    1974 Volume 47 Issue 4 Pages 838-840
    Published: 1974
    Released: March 27, 2006
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    The relative values of the Soret coefficients of 0.01 M aqueous solutions of symmetric tetraalkylammonium chlorides (R4NCl, R=Me, Et, n-Pr, n-Bu, and n-Am) were determined by measuring the initial thermoelectric power of “combined thermocells” made up of AgCl electrode systems, taking LiCl as a reference. The results obtained were found to be rather high, higher by about 20% than those previously found on the combined thermocells made up of calomel-electrode systems.
  • Akira Ohyoshi, Shunichi Hiraki, Hideo Kawasaki
    1974 Volume 47 Issue 4 Pages 841-846
    Published: 1974
    Released: March 27, 2006
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    The thermal decomposition of halogenopentaammine- and cis-dmalogenotetraammineruthenium(III) complexes was studied by the techniques of thermogravimetry(TG), differential thermal analysis(DTA), and evolved gas analysis (EGA). The stoichiometry of the decomposition reaction was determined by the analysis of the reaction intermediates and products. The order of decreasing thermal stability, as well as order of temperature of massloss initiation, seems to be: [RuCl(NH3)5]Cl2>[RuBr(NH3)5]Br2>[RuI(NH3)5]I2 for monohalogeno complexes, and cis-[RuCl2(NH3)4]Cl>cis-[RuBr2(NH3)4]Br>cis-[RuI2(NH3)4]I for dihalogeno complexes. Trihalogenotriammine complexes were observed as intermediates for the cases of dichloro and bromo complexes, a simple decomposition reaction was found for the iodo complexes, and then the activation energy for the following reaction was determined: [RuI(NH3)5]I2→RuI3+5NH3, Ea=41.9 kcal/mol and cis-[RuI2(NH3)4]I→RuI3+4NH3, Ea=27.8 kcal/mol. The reaction mechanisms may be summarized as follows: (a) an electron-transfer mechanism, in which the ruthenium(III) was reduced by the ammonia molecule or the halide ion, (b) the thermal splitting of the ruthenium-ammine bond, and (c) the bond formation between the ruthenium(III) and the halide ion after the ion migration from the outersphere to the innersphere of the complex. The predominant factors which control these mechanisms may be the coordinate bond strength of the ruthenium(III) and various ligand species, the relative potential of electron transfer from the ligand to the ruthenium(III), and the ease of halide-ion migration from the outersphere to the innersphere of the complex.
  • Koji Tanaka, Toshio Tanaka
    1974 Volume 47 Issue 4 Pages 847-850
    Published: 1974
    Released: March 27, 2006
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    Ten N,N-dialkylselenocarbamate complexes of palladium(II) and platinum(II), [(C6H5)3P]2Pd[SeC(O)NR2]2(1), [(C6H5)3P]2Pt[SeC(O)NR2]2 (2) (R=CH3, C2H5, n-C3H7, and n-C4H9), [CH3(C6H5)2P]2Pd[SeC(O)N-(CH3)2]2 (3), and [CH3(C6H5)2P]2Pt[SeC(O)N(CH3)2]2 (4), have been prepared. The infrared spectra and molecular-weight determinations indicate that the selenocarbamate ligand is bonded to the palladium(II) or platinum(II) through the selenium atom, with a free carbonyl group in the solid state, while in 1 and 2 two and one triphenylphosphine dissociate in a dilute solution to exist as compounds with bidentate selenocarbamate, Pd[SeC(O)NR2]2 and [(C6H5)3P]Pt[SeC(O)NR2]2, respectively. The 1H- and 31P-NMR spectra of 3 and 4 reveal that they have a trans-configuration. The same configuration is suggested for the N,N-dibutyl derivative of 2 on the basis of the spin-spin coupling constant between the 31P and 195Pt nuclei.
  • Goro Wada, Yoshiko Sahira, Kyoko Ohsaki, Fusako Shinoda
    1974 Volume 47 Issue 4 Pages 851-854
    Published: 1974
    Released: March 27, 2006
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    The electron transfer reaction between Fe(II) and Fe(III) in N,N-dimethylformamide (DMF) was found to be influenced by the presence of perchloric acid, chloride ion, and water in the reaction system. This suggests that the reaction involves chemical species such as partially hydrated iron, its deprotonated iron, and FeCl2+ and FeCl2+. The individual rate constants in DMF, containing a small amount of water, are k0=33.6 M−1s−1 for Fe2+–Fe3+, k1=1.2×102 M−1s-−1 for Fe2+–FeCl2+, and k2=∼103 M−1s−1 for Fe2+–FeCl2+ at μ=0.20 M and 25°C. The formation constant for FeCl2+ was determined to be K1=(2.0±0.3)×104 M−1 at μ=0.20 M and 25°C. In the mixed solvents of DMF and water, the apparent rate constant exhibited a minimum at a certain water concentration. The activation parameters for the reactions Fe2+–Fe3+ and Fe2+–FeCl2+ are ΔH0\ eweq=8.3 kcal/mol, ΔS0\ eweq=−24 cal/deg·mol, ΔH1\ eweq=4.5 kcal/mol, and ΔS1\ eweq=−34 cal/deg·mol, respectively. The results are compared with those in H2O, D2O, and DMSO.
  • Kazuko Ogino, Tokue Kumagai
    1974 Volume 47 Issue 4 Pages 855-859
    Published: 1974
    Released: March 27, 2006
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    Pfeiffer effect was studied in aqueous solutions containing tris(phenanthroline)metal(II) (metal=zinc or nickel) complexes and various alkaloids. The results were interpreted quantitatively from the viewpoint of stereoselective association and the resulting equilibrium shift. The contribution of π-π interaction between the complex and the alkaloid conjugate systems to the stereoselective association is suggested. NMR data were found to be consistent with the π-π interaction. Relation between the sign of the Pfeiffer rotation and the absolute configuration of the complex is presumed.
  • Masao Okubo, Hisahiro Kusakabe, Tsunenori Hiwatashi, Kazuo Kishida
    1974 Volume 47 Issue 4 Pages 860-863
    Published: 1974
    Released: March 27, 2006
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    When MgBr2 prepared in anhydrous tetrahydrofuran was added to a mixture of olefin and benzoyl peroxide, the peroxide decomposed at a moderate rate at room temperature. Olefin dibromide and magnesium benzoate were obtained in nearly quantitative yields. The effects of p- and m-substituents of peroxide and of the structure of olefin were studied. A complex consisting of MgBr2 and peroxide was formed. Abstraction of brominium cation from the complex by the olefinic double bond was proposed.
  • Michihiko Asai, Hiroshi Matsui, Shigeo Tazuke
    1974 Volume 47 Issue 4 Pages 864-870
    Published: 1974
    Released: March 27, 2006
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    Photocyclodimerization of N-vinylcarbazole(VCZ) catalyzed by Cu(ClO4)2·6H2O(Cu(II)) in tetrahydrofuran was investigated under irradiation at 365 nm. At [Cu(II)]0=10−2 M in air, when [VCZ]0 was less than 0.4 M, only 1,2-trans-dicarbazylcyclobutane(D) was formed, but when [VCZ]0 was higher than 0.5 M, rapid cationic polymerization commenced after about 0.3 M of VCZ had been converted to D. Any consumption of Cu(II) could not be detected in the course of reaction. The change of reaction course from dimerization into polymerization in the midway of reaction was presumably brought about by the consumption of oxygen. Kinetic expression for dimerization rate(Rd) was obtained as follows:
    R_d∞I_0^I.0[VCZ]_0^I.0[Cu(II)]_0^0
    The quantum yield for D production was much larger than 1, indicating production of D via chain mechanism.
  • Osami Nakasugi, Michihiro Ishimori, Teiji Tsuruta
    1974 Volume 47 Issue 4 Pages 871-875
    Published: 1974
    Released: March 27, 2006
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    The infrared spectra of diethylcadmium(CdEt2) in a variety of different solvents were measured. The affinity of CdEt2 toward oxygen and sulfur bases was studied by infrared frequency shifts of CdEt2. Linear relationships were observed for the plots of the two frequency shifts Δνa(C–Cd–C) of CdEt2 vs. Δνa(C–Zn–C) of ZnEt2 and Δνa(C–Cd–C) vs. Δν(O–D) of CH3OD. The deviation of the plots for the systems of CdEt2 with cyclic sulfides from the linear behavior was interpreted in terms of dative back-bonding from CdEt2 to sulfides. The enhanced reactivity of the Cd–S compound toward propylene oxide compared to that of the Cd–O compound was considered to result from a harder acid character of the Cd atom in the Cd–S compound caused by its back-bonding nature.
  • Hitomi Suzuki, Shigeru Maruyama, Terukiyo Hanafusa
    1974 Volume 47 Issue 4 Pages 876-880
    Published: 1974
    Released: March 27, 2006
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    The reaction of trichlorotrimethylbenzenes with fuming nitric acid has been investigated. Trichloropseudocumene underwent both side-chain nitrooxylation and nuclear oxidation to give 2,5,6-trichloro-3,4-dimethylbenzyl nitrate, 3,5,6-trichloro-2,4-dimethylbenzyl nitrate, and 3,6-dichloro-4-nitro-2,4,5-trimethylcyclohexa-2,5-dienone. Trichloromesitylene yielded a mixture of several carbonyl compounds, from which 3,5-dichloro-4-hydroxy-2,4,6-trimethylcyclohexa-2,5-dienone and two nitro-ketones, tentatively formulated as 2,4,6-trichloro-5-hydroxy-6-nitro-2,3,5-trimethylcyclohex-3-enone and 3,5-dichloro-2-hydroxy-6,6-dinitro-2,4,5-trimethylcyclohex-3-enone, were obtained as crystalline products by chromatography and fractional extraction. Trichlorohemimellitene behaved similarly towards the nitrating agent to give 2,6-dichloro-4-hydroxy-3,4,5-trimethylcyclohexa-2,5-dienone as the major product. The competitive modes of side-chain nitrooxylation and formation of cyclic ketones have been described.
  • Chisako Yamagami, Akira Sera, Kazuhiro Maruyama
    1974 Volume 47 Issue 4 Pages 881-884
    Published: 1974
    Released: March 27, 2006
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    The effect of pressure on the solvolysis rates of representative primary, secondary, and tertiary tosylates was investigated in three representative solvents—formic acid, aqueous acetone, and methanol. The calculated activation volumes for these reactions were found to depend on the substrate structure and on the nature of solvent in a systematic manner. The activation volumes for kc-like reactions were less negative than those for ks-like reactions. In the case of the nearly ks-like reactions, the activation volume was found to be governed by the partial molal volume of the initial state.
  • Kiyoshi Kikuchi, Masaru Yamaguchi
    1974 Volume 47 Issue 4 Pages 885-887
    Published: 1974
    Released: March 27, 2006
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    A new carotenoid, ternstroemiaxanthin, was isolated as a main constituent from the red seeds of “Ternstroemia japonica,” and the structure of the pigment was determined to be 3-hydroxy-β,ψ-caroten-18′-al (I) by spectral and chemical methods.
  • Michio Kobayashi, Ritsuko Nishi, Hiroshi Minato
    1974 Volume 47 Issue 4 Pages 888-890
    Published: 1974
    Released: March 27, 2006
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    The rates of hydrolysis of ethyl p-substituted benzenesulfinates were determined in acidic and alkaline media; the rates were greater in the former with the sulfinates containing electron-releasing substituents, ρ=−0.54 (20°C); and in the latter with the sulfinates containing electron-withdrawing substituents, ρ=1.60. The mechanisms of the hydrolysis are discussed.
  • Michio Kobayashi, Akira Mori, Hiroshi Minato
    1974 Volume 47 Issue 4 Pages 891-893
    Published: 1974
    Released: March 27, 2006
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    Alkyl phenyl sulfilimines, benzyl phenyl sulfilimine and the corresponding sulfoximines were found to exchange their α-hydrogens with deuteriums in heavy water when the medium was alkaline. No exchange was observed when the medium was acidic or neutral. The rates of exchange in a sulfilimine were greater than those of the corresponding sulfoximine. The kinetics of these H-D exchange reactions were investigated by use of pyridine as a catalyst, and the reaction mechanism was discussed.
  • Nobumasa Kamigata, Hiroshi Minato, Michio Kobayashi
    1974 Volume 47 Issue 4 Pages 894-897
    Published: 1974
    Released: March 27, 2006
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    Benzoyl peroxide (BPO) was decomposed in benzene in the presence of trifluoroacetic acid. The thermal reaction is first order in BPO, and the activation energy and activation entropy are 18.7 kcal/mol and −26.3 e. u., respectively. The isomer distributions in the phenylation and benzoyloxylation of substituted benzenes determined indicate that the phenylation and benzoyloxylation are electrophilic substitution reactions. The reaction mechanisms are discussed.
  • Yoshihisa Suzuki
    1974 Volume 47 Issue 4 Pages 898-903
    Published: 1974
    Released: March 27, 2006
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    On treating inosine with aqueous dilute alkali hydroxide (pH 10) over 100°C, three types of reactions have been found to occur in competition with one another: (1) the hydrolysis of the glycosidic bond to give hypoxanthine and D-ribose, (2) the opening of the pyrimidine ring at C-2 to give 5-amino-1-β-D-ribofuranosyl-4-imidazolecarboxamide, and (3) the isomerization of the ribose moiety to give mainly 9-β-D-ribopyranosyl hypoxanthine. The last two are newly-found reactions, and the products were isolated through column chromatography using Dowex 50W. The products are obtainable in yields of 30 and 10% respectively under optimum conditions. Hypoxanthine was cleaved in an alkaline solution to give 5-amino-4-imidazolecarboxamide, and 5′-inosinic acid was supposed to give 5-amino-1-β-D-ribofuranosyl-4-imidazolecarboxamide-5′-monophosphate. The ring-opening reaction at C-2 was not observed for adenosine or guanosine.
  • Kazuhisa Hiratani, Takeshi Nakai, Makoto Okawara
    1974 Volume 47 Issue 4 Pages 904-908
    Published: 1974
    Released: March 27, 2006
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    The reactions of 2-cyano-2-dimethylamino-1,3-dithiolane (2) with electrophiles (organic halides and perchloric acid) and nucleophiles were investigated. It was found that 2 dissociated partially to 2-dimethylamino-1,3-dithiolan-2-ylium (1) and cyanide ions in polar solvents. In the reactions of 2 with electrophiles, nitriles were obtained along with the formation of salts of 1. The reactions of 2 with nucleophiles were studied since 2 was expected to be a precursor of the cation 1. In some cases, its reactivity differs from that of perchlorate of 1. A mechanism was discussed in which the cyanide ion might behave as a base to abstract a proton from the nucleophiles.
  • Katsuaki Hagio, Naoto Yoneda, Hisashi Takei
    1974 Volume 47 Issue 4 Pages 909-916
    Published: 1974
    Released: March 27, 2006
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    The cyclic sulfonium ylides, 4-dimethylsulfuranylidene-2,3-dioxotetrahydrofuran derivatives (8), were synthesized in good yields by reactions of methyl and ethyl dimethylsulfuranylidenepyruvates (3 and 4) with carbonyl compounds. The reactions of 8 with p-toluenesulfonyl chloride and benzoyl chloride gave 4-methylthio-3-(p-toluenesulfonyloxy)- and 4-methylthio-3-benzoyloxy-2-oxo-2,5-dihydrofuran derivatives respectively in high yields. The ylides (8) reacted with mercaptans to afford 4-substituted products (1416), whereas, on the reactions with thiourea, the demethylation of the dimethylsulfonium group proceeded exclusively.
  • Shunzo Fukatsu, Aiko Sawa, Sumio Umezawa
    1974 Volume 47 Issue 4 Pages 917-919
    Published: 1974
    Released: March 27, 2006
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    6-(β-Glycosylamino)purines have been synthesized in good yields by condensation of 4-amino-5-nitro-6-chloropyrimidine with masked glycosylamines followed by hydrogenation of nitro group, cyclization with triethyl orthoformate and removal of protecting groups.
  • Sakae Uemura, Kazuo Zushi, Akira Tabata, Akio Toshimitsu, Masaya Okano
    1974 Volume 47 Issue 4 Pages 920-927
    Published: 1974
    Released: March 27, 2006
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    Some new alkoxythallium(III) compounds of olefins, C6H5C(R1)(OR3)CH2Tl(OCOR2)2 [I], are prepared from styrene and α-methylstyrene with thallium(III) acetate and isobutyrate in various alcohols. I(R1=H) reacts with copper(I) iodide, bromide, chloride, cyanide and thiocyanate to afford the corresponding alkyl halides and pseudohalides, C6H5CH(OR3)CH2X [II], in various organic solvents, acetonitrile being the solvent of choice for the purpose of preparing II. The addition of potassium salt has a remarkable effect in improving the yield of II. The halo- and pseudohalodethallation occur at the position where thallium is attached previously to alkyl carbon. An ionic concerted intermolecular scheme is proposed as a reaction mechanism for the preparation of II. The data of NMR and IR spectra of I are briefly discussed.
  • Tetsuji Ohata, Akira Matsumoto, Masayoshi Oiwa
    1974 Volume 47 Issue 4 Pages 928-931
    Published: 1974
    Released: March 27, 2006
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    Triallyl citrate (TAC) was copolymerized with allyl benzoate (ABz), vinyl acetate (VAc), vinyl chloride (VC), acrylonitrile (AN), and styrene (St) at 60°C with benzoyl peroxide or 2,2′,-azobisisobutyronitrile as the initiator; it was considered kinetically in terms of cyclocopolymerization. The following monomer reactivity ratios were obtained: VAc: r1=1.29, r2=0.76, rc=0.61; ABz: r1=1.63, r2=1.10, rc=0.47; VC: r1=0.40; r2=1.90, rc=0.31; AN: r1=0.01, r2=8.7; St: r1=0.03, r2=53.0, where r1, rc and r2 denote the monomer reactivity ratio of the uncyclized, cyclized, and monovinyl radicals respectively. In the copolymerization of TAC with AN, the penultimate effect was also observed: r1=r1′=0.01, r2=k122k121=11, r2′=k222k221=5.
  • Ren Nakao, Tsugio Fukumoto, Jitsuo Tsurugi
    1974 Volume 47 Issue 4 Pages 932-934
    Published: 1974
    Released: March 27, 2006
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    The reduction of methyl acetate with chlorinated hydrosilanes, HSiCl3−nRn(R=CH3 or OCH3, n=0–2), and triethylsilane under γ irradiation has been studied. The hydrosilanes other than triethylsilane reduce the ester to ethyl methyl ether. The reaction rate is proportional to the hydrosilane concentration and is independent of the methyl acetate concentration. The results indicate that the rate-determining step in the reduction reaction is the hydrogen abstraction from the hydrosilanes. The reactivities of the chlorinated hydrosilanes in the reaction increase with the progressive chlorine substitution on the silicon atom and may be due to the susceptibility of each H–Si bond toward free radicals, (Remark: Graphics omitted.).
  • Kin-ya Akiba, Satoru Matsunami, Chikahiko Eguchi, Naoki Inamoto
    1974 Volume 47 Issue 4 Pages 935-937
    Published: 1974
    Released: March 27, 2006
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    1,1,3,3-Tetrasubstituted 2-nitrosoguanidines, the attempted syntheses and UV spectra of which are reported, are unstable, and decomposed into the corresponding ureas and nitrogen, only 2-nitroso-1,1,3,3-tetraphenylguanidine (1f) being obtained as a pure compound. The reaction of 1f with phenyl isocyanate gave pentaphenylguanidine, probably through 1,4-cycloaddition.
  • Akikazu Kakehi, Suketaka Ito
    1974 Volume 47 Issue 4 Pages 938-941
    Published: 1974
    Released: March 27, 2006
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    Pyridinium methoxycarbonylmethylides(58), readily obtainable from their corresponding salts(14), reacted with various acrylates to afford dimethyl 2,3-trans-dihydroindolizine-1,3-dicarboxylate derivatives(920) in moderate yields. These dihydroindolizines were very stable and were not aromatized by heating. However, treatment with lead tetraacetate gave the corresponding indolizine derivatives(2132) in good yields. The configuration at C-2 and C-3 positions in these dihydroindolizines was assigned to trans from their NMR and by comparison with an authentic specimen(12).
  • Norisuke Hata, Tsugio Saito
    1974 Volume 47 Issue 4 Pages 942-945
    Published: 1974
    Released: March 27, 2006
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    In order to elucidate the mechanism of the photoinduced substitution reaction of 2-quinolinecarbonitrile in alcohols or ethers, measurements of the absorption and fluorescence spectra and the photochemical reactions were carried out in ethanol, t-butyl alcohol, or diethyl ether; consequently, an interesting relationship has been found to exist between the fluorescence intensity and the photoreactivity. The photosubstitution reaction can reasonably be assumed to be initiated by a hydrogen-atom abstraction from an alcohol or ether by the nitrogen atom of the quinoline nucleus. The experimental results indicated that such a hydrogen-atom abstraction was markedly facilitated by a hydrogen-bond formation of the nitrogen lone pair of the quinoline nucleus with ethanol or water: further, the reactive excited singlet state (S1) was presumed to be of a π,π* nature.
  • Akira Matsumoto, Joung Hee Lee, Masayuki Yoshida, Osamu Simamura
    1974 Volume 47 Issue 4 Pages 946-949
    Published: 1974
    Released: March 27, 2006
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    2,3,5,6-Tetra-aryl-1,2,4,5-tetra-azapentalenes (II) have been prepared by the dimerization of arylazoethynylarenes (I). The properties of the new ring system are discussed on the basis of their reactivities.
  • Takeshi Kotanigawa
    1974 Volume 47 Issue 4 Pages 950-953
    Published: 1974
    Released: March 27, 2006
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    It was confirmed from the infrared spectra of phenol chemisorbed on ZnO–Fe2O3 that the surface species were characterized by a loss of O–H stretching (3250 cm−1) and by in-plane bending vibration (1370 cm−1) as well as by a phenol ring vibration (1472 cm−1) and a shift of the C–O stretching mode from 1230 cm−1 to 1248 cm−1. From these data, phenoxide surface species were proposed. Furthermore, the dissociative adsorption of phenol was discussed by taking account of the acidity and basicity of the catalyst. That is, in the case of the adsorption, phenol was thought to sit on the acid and the base site. Based on the above discussion, a mechanism for the selective methylation at the ortho position of phenol was proposed. On the other hand, it was found from the infrared spectrum that a surface species similar to zinc formate appears on the chemisorption of methanol. Therefore, it may be possible to consider that methanol adsorbed on the base site decomposes via formate-like surface species to form carbon dioxide, carbon monoxide, and hydrogen.
  • Takeshi Kotanigawa, Mitsuyoshi Yamamoto
    1974 Volume 47 Issue 4 Pages 954-957
    Published: 1974
    Released: March 27, 2006
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    With regard to the ZnO–Fe2O3 catalyst used for the selective methylation at the ortho position of phenol, the pore structures of the catalysts prepared by five processes were studied. The pore structures of these catalysts were determined by converting the detailed nitrogen desorption isotherm data to the pore-volume distribution. These catalysts had two types of pores, a micropore at about 20 Å and a macropore at 80 Å or more. These pores were sensitive to the sintering conditions. The micropore sizes were independent of the calcination temperature, but the macropore sizes were made proportionally larger with a rise in the calcination temperature. The macropore sizes were related to the particle sizes of the zinc ferrite formed by the solid reaction of ZnO with Fe2O3.
  • Hitoshi Ogata, Jun Kitayama, Masanori Koto, Shinji Kojima, Yoshimasa N ...
    1974 Volume 47 Issue 4 Pages 958-961
    Published: 1974
    Released: March 27, 2006
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    The vacuum ultraviolet absorption spectra down to 65000 cm−1 and Hel photoelectron spectra were measured for CH3CHO and RCOCH3 (R=CH3 to t-C4H9). Assignments of the absorption bands are proposed with the aid of photoelectron spectra and CNDO/2 type molecular orbital calculations. Special notice has been paid to the similarity of the vibrational structure between the lowest ionization potential bands of photoelectron spectra and the second bands of vacuum ultraviolet absorption spectra.
  • Makoto Tsunashima, Hiroshi Takahashi
    1974 Volume 47 Issue 4 Pages 962-964
    Published: 1974
    Released: March 27, 2006
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    The effects of the S/Cd mol ratios of cadmium sulfide precipitates on the particle size, the hexagonality, and the brightness of cadmium pigments were studied. The precipitates were prepared by mixing an aqueous solution of cadmium nitrate with either sodium sulfide or hydrogen sulfide. Then, cadmium pigments were made of these precipitates by heat-treatment under an atmosphere of oxygen or nitrogen. The characteristics of the pigments were affected by the following three factors; particle size, hexagonality, and brightness. These factors were closely related to the S/Cd mol ratio of the precipitates of the cadmium pigments. We found the minimum points on the curves of the particle size, the hexagonality, and the brightness in relation to the S/Cd mol ratio. From these results, it was concluded that the optimum range of the S/Cd mol ratios of the precipitates for the characteristics of the cadmium pigments was 0.98±0.01.
  • Masaru Ohsaku
    1974 Volume 47 Issue 4 Pages 965-975
    Published: 1974
    Released: March 27, 2006
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    Infrared spectra of polythiomethylene (PTM) and polythiomethylene-d2 (PTM-D2) observed by a Nujol mull method are reported, and their spectra are assigned. Normal coordinates of bis (methylthio)methane, CH3SCH2SCH3, bis(methylthiomethyl) sulfide, CH3SCH2SCH2SCH3, bis[methylthio(methylthio)]methane, CH3SCH2SCH2SCH2SCH3, PTM, and PTM-D2 have been treated. The force field used in the computation is a modified Urey-Bradley type. The skeletal conformation of these model compounds in the solid state is confirmed to be the [G] form. The relations between the degree of n and their CH2 deformation fundamentals are explained by the concept of the frequency-phase difference. The calculated frequencies are compared with those of experiment. A comparison of the force fields of PTM and polyoxyme hylene (POM) is also briefly made.
  • Chiaki Hirose
    1974 Volume 47 Issue 4 Pages 976-979
    Published: 1974
    Released: March 27, 2006
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    The use of a nondiagonal weight matrix in a least-squares analysis of the quantities which themselves are derived from another least-squares analysis is discussed in relation to the analysis of rotational constants in determining molecular geometry. The method is applied to the calculation of the rs structure of ethylene oxide, and the result is compared with those obtained by Kraitchman’s formula and by a least-squares fit by the use of a diagonal weight matrix.
  • Teiki Iwaoka, Michio Kondo
    1974 Volume 47 Issue 4 Pages 980-986
    Published: 1974
    Released: March 27, 2006
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    It has been established that chlorpromazine undergoes photooxidation via its cation radical, yielding chlorpromazine 5-sulfoxide as an ultimate photoproduct. Molecular oxygen has been found indispensable not only for the formation of chlorpromazine cation radical but also for the formation of the sulfoxide from the radical. Oxygen atom in the sulfoxide originates from the atmospheric oxygen and not from water, which was ascertained by both tracer experiment and kinetic analysis. It was concluded that phenazathionium ion is not involved in the reaction. The possibility of singlet oxygen participation in the photooxidation was also ruled out. An intermediate, which is formed from the cation radical, was found as a precursor of the sulfoxide and was tentatively assigned as a peroxyl type radical.
  • Kenji Sorimachi, Toshifumi Morita, Haruo Shizuka
    1974 Volume 47 Issue 4 Pages 987-990
    Published: 1974
    Released: March 27, 2006
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    The photochemical reaction of [2.2]metacyclophane at 2537 Å has been studied spectrophotometrically. Photocyclization took place to give 4,5,9,10-tetrahydropyrene not only in aerated but also in degassed solutions. The quantum yields for the reaction were independent of the irradiation time, concentration of starting material, light intensity, and addition of piperylene. However, the reaction quantum yields increased with temperature rise. The quantum yields in the aerated system were somewhat larger than those in the degassed system. Radiationless deactivation in S1(ππ*) was very efficient, whose quantum yield was assumed to be ∼0.99, judging from the small reaction quantum yield (less than 0.01) and the lack of fluorescence and phosphorescence. It is proposed that the photocyclization of the molecule originates from S1(ππ*) to give intermediate M which is subsequently convreted into the product or the starting material. Activation energies in these processes were estimated.
  • Yasuhiko Shirota, Isamu Tsushi, Hiroshi Mikawa
    1974 Volume 47 Issue 4 Pages 991-996
    Published: 1974
    Released: March 27, 2006
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    The fluorescence of a series of aromatic hydrocarbons was quenched by the addition of fumaronitrile, which is consistent with the charge-transfer or electron-transfer mechanism. The fluorescence quenching was accompanied by the appearance of a new, broad structureless emission band attributed to the fluorescence from the exciplex in non-polar or slightly polar solvents. In highly polar solvents only quenching of the fluorescence occurred. The energies of the band maxima of the exciplex fluorescences and the magnitude of the ionization potentials of a series of fluorescers showed a good correlation with each other. Solvent and temperature dependence of the exciplex fluorescence was examined and discussed. The present aromatic hydrocarbon-fumaronitrile system also formed a charge-transfer complex in their ground states at relatively high concentrations of each component. The selective excitation of the ground state charge-transfer complex gave rise to the fluorescence emission in a fluid solution at room temperature at the same wavelength region as observed for the exciplex fluorescence. It was susgested that the electronic structure of the fluorescent state of the exciplex and the excited charge-transfer complex is the same.
  • Yasuaki Shimoishi
    1974 Volume 47 Issue 4 Pages 997-1002
    Published: 1974
    Released: March 27, 2006
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    Selenium(IV) reacts with 4-nitro-o-phenylenediamine to form 5-nitropiaselenol, which is detected by means of a gas chromatograph equipped with an electron-capture detector. By this highly sensitive method, the determination of very small amounts of selenium in plant materials has been investigated. Fuming nitric acid digests the plant sample completely, and the selenium is converted to the quadrivalent state. No loss of selenium can be found by this treatment. A method is proposed for the determination of selenium in plant materials at levels as low as 0.005 μg/g in dried material.
  • Hiroji Aiba, Akira Yokoyama, Hisashi Tanaka
    1974 Volume 47 Issue 4 Pages 1003-1007
    Published: 1974
    Released: March 27, 2006
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    The copper(II) complexes of histidine and its related compounds in aqueous solution were investigated by potentiometric, spectrophotometric, and magnetic methods. The presence of a diolated binuclear copper(II) complex was indicated in the 1 : 1 histamine-copper(II) system by quantitative analysis of the titration data and the antiferromagnetic character of the complex. The titration data could not be quantitatively interpreted owing to precipitation, but the formation of a similar diolated copper(II) complex was also shown in the 1 : 1 histidinecopper(II) system by the magnetic properties of the complex. From a comparison of the spectral properties of the pertinent complexes, it was shown for the neutral 2 : 1 histidine-copper(II) complex that histidine binds to copper(II) through the amino and imidazole groups in the chelate plane and through the carboxyl group in the apical position. In the copper(II) complexes of histidine and histamine, it was shown that ionization of the pyrrole nitrogen of the imidazole ring is promoted, causing a spectral blue shift.
  • Kazuo Ando, Takashi Tokoro Yama, Takashi Kubota
    1974 Volume 47 Issue 4 Pages 1008-1013
    Published: 1974
    Released: March 27, 2006
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    The reaction of 1,2-bis(2-cyano-3-methoxyphenyl)propionitrile (1) with diethyl carbonate and sodium ethoxide gave a red pigment 2, C22H19N3O4 in 79% yield. It afforded 5-amino-4,7-dimethoxy-11H-indeno[1,2-c]isoquinolin-11-one (4) on treatment with alkaline hydrogen peroxide. The “red pigment” has been confirmed to have a novel 5H-indeno[1,2-c]isoquinoline structure which transforms into colorless 11H-indeno-[1,2-c]isoquinoline form in an acidic medium. The mechanism of the formation of 2 from 1 imparts an interesting problem as regards carbanion reactivity.
  • Kazuo Ando, Takashi Tokoroyama, Takashi Kubota
    1974 Volume 47 Issue 4 Pages 1014-1017
    Published: 1974
    Released: March 27, 2006
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    The structure of 5-amino-4,7-dimethoxy-11H-indeno-[1,2-c]isoquinolin-11-one (2) derived by the degradation of the “red pigment” has been confirmed by synthesis. 5,6-Dihydro-4,7-dimethoxy-11H-indeno[1,2-c]isoquinoline-5,11-dione (3) obtained from 2 was used as a relay compound. This was first converted into 2 by chlorination with phosphorus oxychloride and treatment with ammonia. Subsequently 3 was synthesized from 2-(2-carboxy-3-methoxyphenyl)-4-methoxyindane-1,3-dione (13) via 4,7-dimethoxy-11H-indeno[1,2-c]isocoumarin-11-one (12).
  • Kazuyuki Maeda, Ichiro Moritani, Akio Sonoda
    1974 Volume 47 Issue 4 Pages 1018-1019
    Published: 1974
    Released: March 27, 2006
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    The photoreaction of 2,2-diphenylvinyl ketones leading to 1,1,4,4-tetraphenylbutadiene, which seems to formally involve α-cleavage of vinyl ketones.
  • Gunzi Saito, Yoshio Matsunaga
    1974 Volume 47 Issue 4 Pages 1020-1021
    Published: 1974
    Released: March 27, 2006
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    The simultaneous operation of charge-transfer and proton-transfer interactions was demonstrated in the orange complex and also in the brown complex of a 3 : 2 composition. The former one quickly becomes the yellow monohydrate of the 1 : 1 salt upon exposure to air.
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