Bulletin of the Chemical Society of Japan
Online ISSN : 1348-0634
Print ISSN : 0009-2673
ISSN-L : 0009-2673
Volume 49 , Issue 3
Showing 1-50 articles out of 65 articles from the selected issue
  • Kohji Tadasa, Naomi Imai, Tetsuo Inaba
    1976 Volume 49 Issue 3 Pages 579-582
    Published: 1976
    Released: April 19, 2006
    JOURNALS FREE ACCESS
    The Hg-photosensitized reaction of a mixture of H2 and NO has been studied mainly at room temperature. The quantum yield of the H2O formation is nearly unity, independent of the pressures of both H2 and NO. The quantum yield of the N2 formation is proportional to the NO pressure, while that of N2O decreases with the NO pressure; both of them are independent of the H2 pressure. In order to interpret the results concerning the H2O formation, the following process is proposed:
    (i) NO3+NO→2NO2
    NO2+HNO→OH+2NO
    OH+HNO→H2O+NO
    in addition to the well-established H2O-forming process:
    (ii) 2HNO→H2O+N2O
    NO2, one of the reactants in Process (i), is formed by the chain process proposed by Arden and Phillips:
    (iii) H+NO+M→HNO+M
    HNO+2NO→N2+H+NO3
    The (ii) and (iii) processes also coincide with the results of the N2O and N2 formations respectively.
  • Osamu Takizawa
    1976 Volume 49 Issue 3 Pages 583-588
    Published: 1976
    Released: April 19, 2006
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    An organic free radical crystal, the di-p-anisyl nitric oxide (DANO) crystal, was found to exhibit the characteristics of the two-dimensional Heisenberg spin system in its magnetic susceptibility at low temperatures and in its angular dependence of the ESR line width at room temperature. A distinct minimum of magnetic susceptibility due to a phase transition to antiferromagnetic spin ordering was observed at 1.67 K; this is consistent with the results of the NMR measurements, while another unexplainable anomaly was found near 2.7 K. The magnetic anisotropy field, HA, along the a-axis, perpendicular to the magnetic easy-plane, was determined to be (3±1)×102 Oe at 0 K from the analysis of the antiferromagnetic resonance; it was attributed to the magnetic field originating from the spin magnetic dipoles distributed over the radical molecules. The ratio of the anisotropy field to the exchange field within the magnetic two-dimensional plane, HAHE, and that of the Néel temperature to the Weiss temperature, TN⁄θ, were found to be 5×10−3 and 0.34 respectively. The ratio of the inter-plane exchange interaction to the intra-plane one, J′⁄J, was estimated therefrom to be of the order of 10−3.
  • Takakazu Yamamoto, Toshio Saruyama, Yoshiyuki Nakamura, Akio Yamamoto
    1976 Volume 49 Issue 3 Pages 589-594
    Published: 1976
    Released: April 19, 2006
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    Dynamic behavior of acetylacetonato (acac), triphenylphosphine (PPh3) and ethyl (in the case of 1) ligands of NiR(acac)(PPh3)n (R=C2H5, n=1 (1); R=CH3, n=2 (2)) in solution has been studied. PPh3 ligand(s) in 1 and 2 exchange rapidly on NMR time scale with free PPh3 in solution. Addition of excess PPh3 makes the exchange rate much faster and an SN2 mechanism is proposed to explain the acceleration effect. 31P-NMR spectrum of 1 in pyridine shows that the PPh3 ligand is replaced by the solvent molecule. Acac ligands in 1 and 2 also undergo rapid interchange on NMR time scale. The activation energy for the acac interchange is about 10 kcal/ mol. On standing a specifically deuterated ethylnickel complex, Ni(CH2CD3)(acac)(PPh3) 1-d3 in solution, the hydrogens and deuteriums in the ethyl group were scrambled. Appearance of the methyl proton signals in the 1H-NMR spectrum of the deuterated ethylnickel complex after the treatment in solution demonstrates the occurrence of the H–D scrambling in solution. Both 1 and 2 undergo disproportionation reactions in pyridine. The rate of the disproportionation is second-order with respect to the concentration of 2.
  • Yoshifumi Nakacho, Takeshi Misawa, Takaji Fujiwara, Akio Wakahara, Ken ...
    1976 Volume 49 Issue 3 Pages 595-599
    Published: 1976
    Released: April 19, 2006
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    C21H12O6Cl3Zn2OH·2H2O crystallizes in the monoclinic space group P21/c: a=12.779, b=23.732, c=14.749 Å, β=147.98°, and Z=4. The structure was determined by the usual heavy atom method and refined to R=0.039. The complex forms polymeric complex chains in the crystalline state. The ligands around two independent zinc atoms form an unusual trigonal bipyramid and an octahedron, respectively; the coordination geometry apparently differs from that found in the crystal structure of bis(2-chlorobenzoato) zinc(II). The correlation between coordination geometry and catalytic action of zinc atom is also discussed.
  • Nobutake Suzuki, Takeshi Nagai, Hiroshi Hotta, Masamitsu Washino
    1976 Volume 49 Issue 3 Pages 600-605
    Published: 1976
    Released: April 19, 2006
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    The decoloration yields of an Acid Blue 40 neutral aqueous solution, G(-Dye), obtained from the optical density at 610 nm for the nitrogen-, oxygen-, and N2O-saturated solutions, equaled 0.18, 0.29, and 0.51 in the respective early stages. In view of the effects of NCS and NO3 on the G(-Dye), the decoloration is attributable to the attacks of the OH radicals and hydrated electrons on the dye. The rate constants for the reactions of the OH radical and the hydrated electron with Acid Blue 40, obtained from competition reactions with various additives, were (6.6±1.2)×109 M−1s−1 and 1.5×1010 M−1s−1 respectively. In the nitrogen-saturated solutions, the G(-Dye) increased markedly upon the addition of alcohols–for example, up to 1.25 upon the addition of 2 mM butyl alcohol. In this case, at the same time, a new absorption band which is attributable to the formation of the reduction products by the attacks of the hydrated electrons and alcohol radicals on the dye appeared at 460–490 nm. This new absorption band disappeared slowly in the presence of oxygen; the rate of this disappearance was 2.8×10−5s−1. On the other hand, in the oxygen-saturated solutions, the G(-Dye) decreased markeld upon the addition of even a small amount of alcohol.
  • Tsunetake Fujiyama, Masao Kakimoto, Tetsuo Suzuki
    1976 Volume 49 Issue 3 Pages 606-610
    Published: 1976
    Released: April 19, 2006
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    The band widths of the infrared absorption spectra were observed for binary solutions of methyl iodide, methyl cyanide, chloroform, and carbon disulfide. The observed bands are: the v1 fundamental of chloroform in carbon disulfide and in carbon tetrachloride; the v2 fundamental of methyl iodide in methyl cyanide, nitromethane, benzene, carbon disulfide, and carbon tetrachloride; the 2v2 band of methyl iodide in methyl cyanide, and the v8 and 2v8 bands of methyl cyanide in methyl iodide. The concentration dependence of a band width was explained in terms of the concentration fluctuation. The theory was compared with the observed band widths, together with the light-scattering data. A fluctuation volume was related with the intermolecular interactions in these binary solutions.
  • Fuyuhiko Inagaki, Seizo Takahashi, Mitsuo Tasumi, Tatsuo Miyazawa
    1976 Volume 49 Issue 3 Pages 611-616
    Published: 1976
    Released: April 19, 2006
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    The Pr(III)- and Eu(III)-induced shifts of 1H nuclear magnetic resonances of thymidine 3′,5′-cyclic phosphate were observed in D2O solution. The results indicated that the induced shifts were primarily of dipolar origin and that the magnetic susceptibility tensor had effective axial symmetry. The ratios of shifts intrinsic to the lanthanide-substrate 1 : 1 complex were determined after correcting for the contributions of the complex formation shifts (diamagnetic terms). The Gd(III)-induced perturbations of the spin-lattice relaxation times were also observed, and the ratios of relaxation rates were obtained. A computer search was then performed to find out the molecular conformation of this cyclic nucleotide which best fitted the shift and relaxation ratios. As a result the phosphate-ring part was found to have a typical chair conformation. The effective symmetry axis of the magnetic susceptibility tensor coincided with the bisector of the OPO angle almost completely. It was rather difficult, however, to establish the conformation of the deoxyribose ring from the shift and relaxation ratios alone. The use of the additional information from the vicinal 1H–1H coupling constants (J1′2′ and J1′2″) was necessary for obtaining a reasonable conformation of the entire molecule. The compatibility of the information from the lanthanide-ion probe and the spin coupling constants (3JHH other than J1′2′ and J1′2″ and 3JHP) is discussed along with the limitations of both methods.
  • Ichiro Hanazaki
    1976 Volume 49 Issue 3 Pages 617-622
    Published: 1976
    Released: April 19, 2006
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    The optical rotatory power for the lower electronic transitions of several o,o′-dinitrobiphenyl derivatives is examined on the basis of a theoretical method previously developed and applied to metal chelate compounds and binaphthyl derivatives. The theoretical energy, absorption intensity, and rotational strength are shown to be in reasonable agreement with the observed absorption and circular dichroism spectra, confirming the applicability of the theory to the optical activity of this simple type of dissymmetric molecules. In addition, the origin of the rotational strength for the n-π* transition is examined in detail. The results indicate that the n-π* transition gains its intensity and rotatory power through the interaction of the nonbonding electrons in a nitro group with the π electron system in the other nitrobenzene ring.
  • Katsumi Hirose, Motoharu Tanaka
    1976 Volume 49 Issue 3 Pages 623-626
    Published: 1976
    Released: April 19, 2006
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    Hydration of pyridine bases in benzene has been studied by partition at 25 °C, the total concentration of pyridine bases being less than 1.0 M in benzene. The studied pyridine bases include pyridine, 2-methylpyridine, 4-methylpyridine, 2,6-dimethylpyridine, 3,5-dimethylpyridine, 2,4,6-trimethylpyridine, 2-chloropyridine, 2-bromopyridine, 3-bromopyridine and 2,6-dibromopyridine. Hydrated species with different composition are formed: the composition of the hydrated species (base to water ratio) is as follows: (1 : 2) for 2,6-dibromopyridine, (1 : 1) and (1 : 2) for 2-chloro- and 2-bromopyridine, (1 : 1) and (2 : 1) for 3-bromopyridine, (1 : 1), (1 : 2) and (2 : 1) for 4-methylpyridine and pyridine itself, and (1 : 1), (1 : 2), (2 : 1) and (2 : 2) or (2 : 3) for the other methyl derivatives. A linear free energy relationship has been observed between the hydration in benzene for the monomer monohydrate and the protonation in water of the corresponding base.
  • Makoto Misono, Yukio Aoki, Yukio Yoneda
    1976 Volume 49 Issue 3 Pages 627-633
    Published: 1976
    Released: April 19, 2006
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    The stereochemistry (anti or syn mode) of elimination reactions of 2-bromobutane and 2,3-dibromobutane over alkali-ion exchanged silica gels (Li, Na, K, and Cs) was determined at 100–300 °C from the products of the diastereomeric isomers of each alkyl bromide. They were erythro- and thero-2-bromobutanes-3-d1 and meso- and dl-2,3-dibromobutanes. The steric course of dehydrobromination of 2-bromobutane changed nearly reversibly between syn and anti mode by the partial exchange of a surface proton with K+ or Cs+ ion, although the surface structure seemed to remain unchanged by the exchange procedure. On the other hand, the exchange with Na+ or Li+ ion did not change the steric course. Dehydrobromination of 2,3-dibromobutane proceeded by anti mode over Na-, K-, and Cs–SiO2, while SiO2 and Li–SiO2 were not active. The poisoning effect of acidic and basic reagents as well as the indicator test revealed that basic sites played important roles over K- and Cs–SiO2 where anti elimination prevailed, and that weakly acidic sites were responsible for syn elimination.
  • Koichi Mizuno, Jun-ichiro Take, Yukio Yoneda
    1976 Volume 49 Issue 3 Pages 634-637
    Published: 1976
    Released: April 19, 2006
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    Chemisorbed p-nitroaniline (PNA) gives two bands at 245 and 445 nm on silica-alumina and one band at 450 nm on alumina. The present paper deals with the nature of these chemisobed species and of the chemisorption sites. Kinetic studies of PNA chemisorption onto silica-alumina from cyclohexane solution revealed that the chemisorbed species responsible for the 245 nm band was formed with an activation energy by 0.9 kcal/mol smaller than that responsible for the 445 nm band. The two bands on silica-alumina are due conclusively to two different chemisorbed species. Comparison among UV absorption spectra of PNA in various solutions and on various solid surfaces led to the conclusion that the 245 nm band is ascribable to PNA chemisorbed on Bronsted acid sites and the 445 and 450 nm bands to PNA chemisorbed on Lewis acid sites (i.e. surface Al3+ ions).
  • Tsutomu Fukuyama, Kazuko Oyanagi, Kozo Kuchitsu
    1976 Volume 49 Issue 3 Pages 638-643
    Published: 1976
    Released: April 19, 2006
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    Molecular structures of 5-thiabicyclo[2.1.1]hexane and 7-thianorbornane (7-thiabicyclo[2.2.1]heptane) were studied by gas electron diffraction. For 7-thianorbornane the rotational constants obtained by Hirota et al. by microwave spectroscopy were also taken into account. Least-squares analyses gave the following rg bond distances and valence angles (rα for 5-thiabicyclo[2.1.1]hexane and rav for 7-thianorbornane): for 5-thiabicyclo[2.1.1]hexane, (C1–C2, C2–C3)av=1.539±0.016 Å, C1–C6=1.564±0.024 Å, C–S=1.865±0.004 Å, (C–H)av=1.110±0.008 Å, ∠C–S–C=69.5±0.6 ° and the dihedral angles (C1SC4)-(C1C2C3C4)=115.2±1.7° and (C1C6C4)-(C1C2C3C4)=116.1±2.4°; for 7-thianorbornane, C1–C2=1.538±0.006 Å, C2–C3=1.561±0.015 Å, C–S=1.837±0.004 Å, (C–H)av=1.115±0.008 Å, ∠C–S–C=80.2±0.8 °, the dihedral angle (C1C2C3C4)-(C4C5C6C1)=115.0±1.2° and ∠C1H–C–H=106±5°. The uncertainties represent the estimated limits of experimental error. The C–S bond length in 5-thiabicyclo[2.1.1]hexane is longer than that in dimethyl sulfide by 0.06 Å and that in 7-thianorbornane by 0.03 Å. The C–S–C angle in 5-thiabicyclo[2.1.1]hexane is smaller than that in dimethyl sulfide by about 30° and that in 7-thianorbornane by about 11°. The C1–C6 bond in 5-thiabicyclo[2.1.1]hexane is longer than the weighted average of the C1–C2 and C2–C3 bond lengths. The C1–C2 bond in 7-thianorbornane is longer than the C2–C3 bond.
  • Shigeki Onuma, Hironao Inoue, Shuzo Shibata
    1976 Volume 49 Issue 3 Pages 644-647
    Published: 1976
    Released: April 19, 2006
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    The crystal and molecular structure of tris-(2,2,6,6-tetramethylheptane-3,5-dionato)lutetium(III) has been determined by X-ray diffraction method. The space group is Pmn21, and the unit cell is orthorhombic with a=17.713(4), b=10.638(2), c=9.973(3) Å, and Z=2. The structure is isomorphous with the erbium analogue. The atomic parameters of the molecule (except for hydrogen atoms) were refined by the block-diagonal least-squares method to an R of 0.053. Three chelate rings are planar. One of them lies in the crystallographic mirror plane, and the other two rings are symmetrically related to each other with respect to this mirror plane. Six oxygen atoms of the three β-diketones form a distorted trigonal prism around the central lutetium ion, the average Lu–O distance being 2.19 Å.
  • Tsunetake Fujiyama, Jun Nakagawa, Isao Suzuki, Ichiro Nakagawa, Takehi ...
    1976 Volume 49 Issue 3 Pages 648-658
    Published: 1976
    Released: April 19, 2006
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    A high-resolution vacuum spectrometer for the near and medium infrared has been designed and built with capability of resolving 0.03 cm−1. The spectrometer consists of the fore-optics with a built-in White cell, a 2.5 m Littrow-McCubbin type monochromator which utilizes a 31.6 lines/mm echelle grating with the ruled area of 102 mm×206 mm, and an order-sorter which is essentially a prism spectrometer of Wadsworth mount. Details of the design, construction, and performance of the instrument are described.
  • Inam Jawed
    1976 Volume 49 Issue 3 Pages 659-662
    Published: 1976
    Released: April 19, 2006
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    The effect of temperature on the infrared spectroscopic parameters of hydrogen bonds between a number of phenol-nitrile systems has been studied. The. infrared frequency shift always decreases with increase in temperature. The variation of half width of the hydrogen bonded band, however, is not regular and is within the error of measurement. The intensity of the bonded band shows a general decrease with rise in temperature. All these variations are interpreted as being indicative of the weakening of the hydrogen bond with increase in temperature.
  • Subir K. Roy, Kamalendu Sengupta, S. B. Roy
    1976 Volume 49 Issue 3 Pages 663-665
    Published: 1976
    Released: April 19, 2006
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    The dielectric absorption in 4-methylthiophenol and 4-chlorothiophenol in the liquid state has been studied in 0.8, 1.25, 1.62 and 3.49 cm microwave regions. Molecular and intramolecular relaxation times, their relative weight factors and the heats of activation have been determined. The results have been discussed and compared with other related molecules.
  • Hiromichi Okamura, Eiichi Miki, Kunihiko Mizumachi, Tatsujiro Ishimori
    1976 Volume 49 Issue 3 Pages 666-670
    Published: 1976
    Released: April 19, 2006
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    K6[Co2(CN)10(N2O2)]·2H2O (orange salt) was prepared by reaction of [Co(NO)(NH3)5]Cl2 with an aqueous solution of potassium cyanide. K6[Co2(CN)10(N2O2)]·4H2O (yellow salt) was obtained by adding an aqueous solution of the orange salt to methanol. On the basis of IR and Raman spectra for their 14NO- and 15NO-salts, and of IR spectra for their gaseous decomposition products, the orange salt is considered to be a linkage isomer of the yellow salt with respect to the trans-hyponitrito bridge. It is presumed that the orange salt is potassium μ-(trans-hyponitrito-N,N′-bis{pentacyanocobaltate(III)}, the yellow salt being potassium μ-(trans-hyponitrito-O,O′)-bis{pentacyanocobaltate(III)}.
  • Yasuyoshi Torii, Hideo Matsumoto
    1976 Volume 49 Issue 3 Pages 671-674
    Published: 1976
    Released: April 19, 2006
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    It was found that oxygen deficient pyrochlore solid solutions Pb2Ta2−2xM2xO7−x with M=Ti, Sn, and Zr exist over wide ranges. The formation of oxygen deficient pyrochlore structure results from the occupancy of Pb2+ ions in the A position, which have a high polarizability. Their reflectance and infrared absorption spectra, and dielectric constants were measured. With the increase of M4+ ions, the color turned lemon yellow to reddish yellow, and the dielectric constants increased. The infrared absorption spectra in their pyrochlore solid solutions were similar to those in PbTiO3 and PbZrO3. The infrared properties of two strong absorption bands observed were discussed in comparison with those in the perovskites.
  • Hitoshi Masuda, Chiyoshi Kamizawa, Masazi Matsuda, Takashi Nakane, Tsu ...
    1976 Volume 49 Issue 3 Pages 675-678
    Published: 1976
    Released: April 19, 2006
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    Fundamental research into the treatment of the chromic plating rinse by reverse osmosis were carried out with Loeb-type skinned membranes. The effect of the pH on the transport of chromic acid was quantitatively investigated. With the increase in pH, chromic acid dissociates to form a divalent ion, CrO42−, and the rejection by the membrane increases. For example, the rejection of 0.01 M chromic acid at pH 3 was 83%, while it was 96% at pH 7.25, both at 40 atm. The permeation behavior of additives such as sodium hexafluorosilicate and chromium (III) sulfate was also examined, mainly in connection with their dissociation in the solution. In the case of the concentration of chromic acid, the rejection remained constant up to about 15000 ppm, while the flux decreased considerably with an increase in the concentration.
  • Katsuhiko Miyoshi, Yasushige Kuroda, Yuji Isoe, Hayami Yoneda
    1976 Volume 49 Issue 3 Pages 679-682
    Published: 1976
    Released: April 19, 2006
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    Influence of lower alcohols (methanol to butanol) was examined on the Pfeiffer effect of the [Zn(phen)3]2+-l-malic acid and -d-tartaric acid systems in water at 25 °C (phen=1,10-phenanthroline). It was found that the Pfeiffer rotation αp decreases linearly with molar concentration CA of added alcohols for both systems, and that the logarithm of the rate of the decrease in αp with CA is a linear function of the number of methylene groups in added alcohol molecules. This is well interpreted on the assumption that added alcohol molecules adhere to [Zn(phen)3]2+ ion, thereby preventing the complex and chiral acid from coming into contact with each other. The enthalpy change per methylene group on passing from the alcohol environment to the complex environment was estimated to be ca. 0.7 RT.
  • Yukito Murakami, Yasuhiro Aoyama
    1976 Volume 49 Issue 3 Pages 683-688
    Published: 1976
    Released: April 19, 2006
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    The interaction of various bases with the cobalt(II) complexes of 1,19-disubstituted tetradehydrocorrins (Co(II)–TDHC) was investigated. The parent cobalt(II) complexes were shown to undergo ready reduction at the nuclear cobalt(II) with the unsolvated hydroxide ion as well as with bulky triethylamine. A relatively large positive reduction potential of Co(II)–TDHC is responsible for these novel electron transfer reactions. Less hindered amines (B), on the other hand, failed to show such electron transfer reactions with the cobalt(II) complexes and Co(II)–TDHC became the pentacoordinated complex by taking up an amine base in the axial position: Co(II)–TDHC+B\ ightleftharpoonsB–Co(II)–TDHC. For the interaction of 4-substituted pyridines with the cobalt(II) complex, the general behavior of the equilibrium constants was interpreted in terms of the amine basicity and the Hammett equation by referring to the corresponding behavior of the porphyrin complexes. The weaker coordination tendency of some aliphatic amines and hindered pyridines toward Co(II)–TDHC was attributed to their electronic and steric effects in the coordination process. The intrinsic correlation between electronic and stereochemical characteristics pertaining to the tetradehydrocorrin skeleton and the nature of nuclear cobalt(II) was discussed on the basis of these observations.
  • Kazuo Imaeda, Takeo Kuriki, Keiko Ohsawa
    1976 Volume 49 Issue 3 Pages 689-692
    Published: 1976
    Released: April 19, 2006
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    Oxygen in zinc compounds was determined by a modification of the method of Schütze. Oxygen in some zinc compounds such as zinc oxide, zinc acetate and zinc oxalate could not be determined by the usual method. The carrier gas method of adding carbon was employed for the determination of total oxygen. Total oxygen could be determined by the addition of 5 mg of carbon to a sample boat and heating at 1000 °C. The determination was also carried out by the carrier gas method by addition of 2 mg naphthalene. As a result, total oxygen could be determined by the addition of 2 mg of naphthalene.
  • Mutsuo Yamada, Masatoshi Fujimoto
    1976 Volume 49 Issue 3 Pages 693-696
    Published: 1976
    Released: April 19, 2006
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    A new procedure is proposed to obtain pure Semi-Xylenol Orange (SXO) and Xylenol Orange (XO) from ca. 100 mg of synthetic mixture using preparative thin-layer chromatography on cellulose layer ca. 2 mm thick. Development with a composite solvent, 55–60 ml of 1-butanol saturated with 25% aqueous acetic acid-0.6–0.8 ml of 28% aqueous ammonia, forms two discrete zones of different pH values on the layer. The zones favor a sharp separation of polybasic Brønsted acids with structures similar to those of SXO and XO. SXO and XO are in the protonated forms corresponding to the pH values of the given zones. XO is located near the starting line in the lower zone of higher pH and SXO migrates through the layer in the upper part of the same zone. Both SXO and XO constitute the compact and concentrated bands. Each run takes only 3 hr. 18 mg of SXO and 36 mg of XO are obtained as sodium salts from 100 mg of the synthetic mixture.
  • Haruo Sato, Takeshi Tominaga
    1976 Volume 49 Issue 3 Pages 697-700
    Published: 1976
    Released: April 19, 2006
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    The thermal decomposition of [Fe(bipy)3]Cl2·5H2O in nitrogen was investigated by means of Mössbauer spectroscopy. Two isomers of Fe(bipy)Cl2 were found to occur in the decomposition sequence; one of them appears to be identical with the rose-red form of Fe(bipy)Cl2 prepared by the wet process. The structures of the two isomers were determined on the basis of the Mössbauer spectra, the infrared and Raman spectra, the powder X-ray patterns, and the magnetic moments of these compounds. It has been concluded that tris(2,2′-bipyridine)iron(II) chloride presumably decomposes in the following sequence:
    [Fe(bipy)3]Cl2·5H2O→Fe(bipy)2Cl2→orangeFe(bipy)Cl2(monomeric, tetrahedral)→rose-redFe(bipy)Cl2(polymeric, octahedral)→FeCl2
  • Hitoshi Ohtaki, Toshio Yamaguchi, Masunobu Maeda
    1976 Volume 49 Issue 3 Pages 701-708
    Published: 1976
    Released: April 19, 2006
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    X-ray scattering measurements have been carried out for concentrated aqueous solutions of divalent transition-metal perchlorates of manganese(II) to zinc(II). The radial distribution curves showed that each central metal ion was octahedrally surrounded by six water molecules at the distances of 2.20 Å for Mn2+–OH2, 2.12 Å for Fe2+–OH2, 2.08 Å for Co2+–OH2, 2.04 Å for Ni2+–OH2, and 2.08 Å for Zn2+–OH2. The results from the radial distribution curves were confirmed by the direct analysis of reduced intensities. Concentrated aqueous solutions of copper(II) and zinc(II) sulfates have also been measured. The bond distances of 1.94 Å for the Cu2+–OH2 (equatorial), 2.38 Å for the Cu2+–OH2 (axial) and 2.08 Å for Zn2+–OH2 were consistent with those obtained for the perchlorate solutions. No evidence for the contact ion pairs of metal and sulfate ions was found by the present X-ray measurements. The bond energies between metal ions including copper ion were discussed by application of the Garrick model with a slight modification.
  • Fujio Izumi, Yoshinori Fujiki
    1976 Volume 49 Issue 3 Pages 709-712
    Published: 1976
    Released: April 19, 2006
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    The hydrothermal growth of anatase has been investigated at 480–650 °C and 500–1000 atm. Only rutile was formed in KF solutions. On the other hand, anatase was found to crystallize in solutions containing 5 wt% KF+0.1–10 wt% K2HPO4 at temperatures up to 600 °C, accompanied by small amounts of K2Ti6O13 on the addition of 5–10 wt% of K2HPO4. The optimum growth conditions were: mineralizer solution, 5 wt% KF+1–2.5 wt% K2HPO4; temperature, 550–600 °C; pressure, 1000 atm. Anatase crystals were found as irregular aggregates of dipyramidal grains, blue and transparent. Individual crystals grown at a low supersaturation were characterized by well-developed {101} and {103} faces. The observed habit agrees with the expectations based on Hartman’s PBC theory. The presence of phosphate ions favored anatase formation in NH4F solutions as well, and the retrograde solubility of TiO2 was observed. The reaction scheme for anatase formation has been proposed. The polymorphic crystallization of TiO2 under hydrothermal conditions has been shown to be greatly affected by the complexing anions, such as fluoride or phosphate, in mineralizer solutions.
  • Masaru Tada, Kyo Miura
    1976 Volume 49 Issue 3 Pages 713-715
    Published: 1976
    Released: April 19, 2006
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    γ-Methyl groups of mesityl oxide (I), dypnone (II), 2-isopropylidenecyclopentanone (III), and pulegone (IV) were deuterated by ultra-violet irradiation in methanol-d. It has been claimed that these ketones are not enolized by photo-excitation, but the formation of enol by irradiation was proved by infrared spectroscopy at a low temperature and was correlated to the photo-deuteration. The photo-enolization was deduced to occur from an n–π* singlet excited state.
  • Fujio Takahashi, M. B. Rahman, Hirotoshi Maeda
    1976 Volume 49 Issue 3 Pages 716-718
    Published: 1976
    Released: April 19, 2006
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    Polarographic studies of the aerobic oxidation of catecholamines under the influence of FMN in various concentrations, and spectrophotometric investigations of the formation of FMN–catecholamine complexes, have been carried out. By following the course of the oxidation reaction polarographically, the rate constants have been found. The oxidation of catecholamines by air was found to be disturbed through complex formation and to be facilitated by light illumination. The equilibrium constants for the formation of some catecholamine complexes with FMN have been calculated.
  • Tohru Inoue, Kazuo Nomura, Hideo Kimizuka
    1976 Volume 49 Issue 3 Pages 719-723
    Published: 1976
    Released: April 19, 2006
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    The catalytic effect of the mixed micelles of lauroylamino acids (LauAm) and detergents on the hydrolysis of p-nitrophenyl acetate has been studied. The amino acids used for the synthesis of LauAm were glycine, serine, histidine, tyrosine, lysine, and arginine. Cetyltrimethylammonium bromide (CTAB), polyoxyethylene dodecyl ether (C12E6) and sodium dodecyl sulfate (SDS) were used for the preparation of the mixed micelles with LauAm. Among the detergents used, only CTAB remarkably enhanced the catalytic activity of LauAm. A reaction scheme was proposed, and the rate constant for the catalytic activity of LauAm was estimated from the kinetic data. The effect of pH was also studied. Discussions were given of the mechanism of the catalytic action on the basis of the present study.
  • Yoshiaki Kusuyama, Yoshitsugu Ikeda
    1976 Volume 49 Issue 3 Pages 724-726
    Published: 1976
    Released: April 19, 2006
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    The ionization constants of trans-2-substituted cyclopropanecarboxylic acids were determined in water and 50% aqueous ethanol at 25 °C. The substituent effects thus obtained were interpreted by the use of the four parameter equations presented by Yukawa and Tsuno. The transmitting resonance effect of trans-cyclopropylene is about a quarter that of trans-vinylene and a half that of p-phenylene.
  • Fumio Ando, Kumao Ohashi, Jugo Koketsu
    1976 Volume 49 Issue 3 Pages 727-729
    Published: 1976
    Released: April 19, 2006
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    Tris(diethylamino)bismuthine (I) reacted with the sterically unhindered carbonyl compounds to give the corresponding enamines. The reactivity of the metal amides M(NR2)n (M=As, Sb, Bi, and Ti; R=Me and Et) toward the carbonyl compounds was examined. The order of reactivity: Bi>Sb>Ti>As was observed for the addition reaction that took place as the first step in the reaction. On the other hand, the order of enamine formation was Sb>Ti>As>Bi. The effectiveness of the amination reaction depends both on the reactivity of metal amides to carbonyl groups and also on the affinity for oxygen of metal atoms. Although bismuth amide gives the addition product very rapidly, because of its poor affinity for oxygen, the addition products decompose thermally on prolonged standing or on distillation giving large amounts of starting carbonyl compounds along with small amounts of enamines.
  • Shigeru Oae, Tadamitsu Sakurai
    1976 Volume 49 Issue 3 Pages 730-736
    Published: 1976
    Released: April 19, 2006
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    The reactions of the title compounds with various nucleophiles were found to proceed through either elimination or nucleophilic substitution on the nitrogen atom depending on both the structure of the substrate and the nature of nucleophiles used. The effect of substituent and the primary isotope effect (kHkD of 7.6 and 8.1 with NaN3 and LiCl at 30 °C) on the elimination of O-(p-nitrobenzoyl)-N,N-dibenzylhydroxylamine revealed that the reaction is an E2 process involving the rate-determining proton abstraction by base and proceeds via an ionic transition state of an ideal concerted type. Nucleophilic substitution on the trivalent nitrogen atom has been inferred for the reactions with such nucleophiles as diethyl sulfide, p-toluenethiol and sodium cyanide on the basis of product distribution.
  • Takaaki Horaguchi, Takahachi Shimizu, Teishiro Abe
    1976 Volume 49 Issue 3 Pages 737-740
    Published: 1976
    Released: April 19, 2006
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    A compound, 6-methoxy-2a,3,4,5-tetrahydro-2H-naphtho[1,8-bc]furan-5-one (XX), was prepared in a 72% yield by heating 3-(5-methoxy-2,3-dihydrobenzofuran-3-yl)propionic acid (XIX) with polyphosphoric acid. However, when 3-(5-methoxybenzofuran-3-yl)propionic acid (IX) or 3-(2-benzoyl-5-methoxybenzofuran-3-yl)propionic acid (XIII) were treated with polyphosphoric acid, the product was 7-methoxy-2,3-dihydro-1H-cyclopenta[b]benzofuran-3-one (XI) rather than the corresponding naphtho[1,8-bc]furan derivatives, Also, neither naphtho[1,8-bc]furan nor cyclopenta[b]benzofuran derivatives were obtained from 3-(2-benzyl-5-methoxybenzofuran-3-yl)propionic acid (XIV) or 3-(2-ethyl-5-methoxybenzofuran-3-yl)propionic acid (XVII).
  • Koji Kimura, Masakazu Takamura, Shigeru Koshibe, Masayoshi Juro, Yoshi ...
    1976 Volume 49 Issue 3 Pages 741-745
    Published: 1976
    Released: April 19, 2006
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    The photochemical ring expansion of dispiro substituted cyclobutane-1,3-diones in methanol has been investigated. The formation of ring expansion product was strongly dependent on the spiro ring size of dispiro substituent. The ring expanded acetal was obtained in a low yield when the spiro ring of dispiro substituted cyclobutane-1,3-diones was a five- or seven-membered ring. This is the first example of photochemical ring expansion from cyclobutane-1,3-diones. A mechanism is postulated.
  • Sadatoshi Akabori, Michiko Ohtomi, Katsuhiko Arai
    1976 Volume 49 Issue 3 Pages 746-747
    Published: 1976
    Released: April 19, 2006
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    Aromatic aldehydes were treated with potassium cyanide in the presence of a crown ether in water or in aprotic solvents to give benzoins in high yields, although similar reactions in the absence of the crown ether proceeded sluggishly in general. The catalysis is believed to be due to the ability of the crown ether to bring anions into the organic phase.
  • Akira Haneda, Takeshi Imagawa, Mituyosi Kawanisi
    1976 Volume 49 Issue 3 Pages 748-749
    Published: 1976
    Released: April 19, 2006
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    Thermal reaction of 3-phenylsydnone with isoprene or 2,3-dimethylbutadiene gave 2-methyl- or 2,6-dimethyl-7-phenyl-1,7-diazatricyclo [2.2.1.02,6]heptane, together with 3-isopropenyl-1-phenylpyrazole. The former is the product of the double 1,3-dipolar cycloaddition. A similar reaction with 1,3-butadiene gave only 3-vinyl-1-phenylpyrazole.
  • Kazuaki Ichikawa, Toru Takagi, Kazuo Fukuzumi
    1976 Volume 49 Issue 3 Pages 750-753
    Published: 1976
    Released: April 19, 2006
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    Cyclopentadienylsodium and phenylethynylsodium are effective cocatalysts with WCl6 in the homogeneous olefin metathesis. The optimum mole ratios of C5H5Na and PhC≡CNa to WCl6 ranged more widely—from 1.5 to 3.0 and from 1.5 to 2.5 respectively—than that of BuLi to WCl6. The formation of the Friedel-Crafts products was extremely small—such as 1—%, if the cocatalyst/WCl6 ratio was about 2. The new catalyst systems were less poisoned by ether than the other catalyst systems and were hardly deactivated in the course of the reaction. The characteristics of these catalyst systems were discussed.
  • Ichiro Shimao, Hirokazu Hashidzume
    1976 Volume 49 Issue 3 Pages 754-757
    Published: 1976
    Released: April 19, 2006
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    Azoxybenzenes (1) were heated at 245–250 °C to give azobenzenes (2), 2-hydroxyazobenzenes (3), 2-hydroxy-azoxybenzenes (4), 4-hydroxyazobenzenes (5), and 4-hydroxyazoxybenzenes (6). Compounds 4 and 6 were mostly composed of α-isomers. In the reaction of azoxytoluenes, their methyl groups were oxidized to formyl groups. It was proposed that 4 and 6 were the intermediates of the thermal rearrangement of 1 to 3 and 5.
  • Kunio Mori, Tsutomu Mizoroki, Atsumu Ozaki
    1976 Volume 49 Issue 3 Pages 758-761
    Published: 1976
    Released: April 19, 2006
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    Rhodium trichloride effectively catalyzes the arylation of ethylene with iodobenzene in the presence of an amine to give styrene, although neither rhodium-powder nor chlorotris(triphenylphosphine)rhodium(I) is effective. The efficacy of the amine in increasing the yield of styrene is remarkable with tertiary and secondary amines but negligible with a primary amine. The difference among these amines in their interaction with rhodium trichloride is explained by their steric hindrance based on the isolation of the Rh(III)–amine complex only with primary amine.
  • Suketaka Ito, Yumo Tanaka, Akikazu Kakehi
    1976 Volume 49 Issue 3 Pages 762-766
    Published: 1976
    Released: April 19, 2006
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    A new synthesis of 2,5-diaryltetrazoles is given by the reaction of N-phenylsulfonylbenzhydrazidoyl chlorides with arylhydrazines and the action of potassium carbonate on the intermediate product formed in the initial reaction. Thirty tetrazoles carrying H, CH3, Cl, Br, or NO2 as the para-substituent of the 2-phenyl group, and H, CH3, Cl, CH3O, CN, or NO2 as that of the 5-phenyl group, were synthesized in 70–16% yields, respectively. The reaction may proceed via the concerted elimination of benzenesulfinate ion from the intermediate 1,3-diaryl-5-phenylsulfonylformazanide anion taking a quasi-aromatic configuration.
  • Hiroshi Fukase, Hidesuke Iwasaki
    1976 Volume 49 Issue 3 Pages 767-770
    Published: 1976
    Released: April 19, 2006
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    The C-3 side chain moiety of C-2801X, a new cephamycin-type antibiotic, was almost quantitatively obtained by Dowex 50-catalyzed hydrolysis, and its structure was established as 3,4-dihydroxy-α-methoxycinnamic acid (I) by spectroscopic analyses and synthesis. The full structure of C-2801X was also assumed to be XIII by NMR analysis.
  • Sigeru Torii, Tsutomu Okamoto
    1976 Volume 49 Issue 3 Pages 771-774
    Published: 1976
    Released: April 19, 2006
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    The synthesis of cubebol and the related compounds from (−)-carvone is described. In the preparation of the key intermediate, 7,10-trans-2,6-epi-2-acetoxy-7-isopropyl-10-methyltricyclo[4.4.0.01,5]decan-4-one (10) the electrochemical acetoxylation reaction could be used as an effective method for introducing the acetoxy group at C-2 carbon atom instead of the carboxy function of 7,10-trans-2,6-epi-4-oxo-7-isopropenyl-10-methyltricyclo-[4.4.0.01,5]decan-2-carboxylic acid (6a). The condensation of (+)-p-menth-8-en-2-one (2a) prepared from (−)-carvone with dimethyl succinate afforded Stobbe half-ester 3, which provided the diazoketone 4 smoothly. Thermal decomposition of 4 in benzene gave intramolecular adducts 5a and 5b (4 : 1). Hydrolysis of 5a afforded 6a in ca. 40% yield. Electrolysis of 6a in AcOH-t-BuOH-Et3N (2 : 1 : 0.1) using platinum electrodes gave 10 in 72% yield. Elimination of acetic acid gave two isomers 11a and 11b (3 : 1) in 87% yield and subsequent methylation of 11a afforded 7-isopropyl-4,10-dimethyltricyclo[4.4.0.01,5]deca-2-en-4-ol (12) in 82% yield, which on hydrogenation gave the desired product 1a (36.5%) along with the epimer 1b (36.5%).
  • Hiraku Shinozaki, Hiroki Ogawa, Masaru Tada
    1976 Volume 49 Issue 3 Pages 775-778
    Published: 1976
    Released: April 19, 2006
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    The bromination and mercuration of cis-2-methoxycyclohexyl(pyridine)cobaloxime (I) gave trans-1-bromo-2-methoxycyclohexane (V) and trans-2-methoxycyclohexylmercury(II) chloride (VII), along with other byproducts derived from the cyclohexene formed by β-elimination. β-Elimination is an exclusive degradation path with trans-2-hydroxycyclohexyl(pyridine)cobaloxime(II). The reaction of cis and trans-4-t-butylcyclohexyl(pyridine)cobaloximes (III and IV) gave trans and cis-1-bromo-4-t-butylcyclohexanes (X and XI), and trans and cis-4-t-butylcyclohexylmercury(II) chloride, with an exculsive or preferential inversion at the reaction center. These results show that the SE2 reaction of alkyl cobaloxime takes a stereochemical course of inversion.
  • Koichi Narasaka, Kenso Soai, Yukiko Aikawa, Teruaki Mukaiyama
    1976 Volume 49 Issue 3 Pages 779-783
    Published: 1976
    Released: April 19, 2006
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    Silyl enol ethers react with α,β-unsaturated ketones and esters in the presence of TiCl4 or in the coexistence of TiCl4 and Ti(Oi-Pr)4 to give 1,5-dicarbonyl compounds in good yields. The reactions of acetals derived from α,β-unsaturated ketones with silyl enol ethers in the coexistence of TiCl4 and Ti(Oi-Pr)4, followed by successive addition of 1,2-ethanedithiol, give the Michael products, δ-keto ethylene thioacetal, in good yields. The reaction of silyl enol ethers with acetals derived from α,β-unsaturated aldehydes also gives the Michael products when Ti(OCEt3)4 is employed instead of Ti(Oi-Pr)4 in the above experiment and is successfully applied to the simple synthesis of dihydro rose oxide.
  • Sanshiro Komiya, Akio Yamamoto
    1976 Volume 49 Issue 3 Pages 784-787
    Published: 1976
    Released: April 19, 2006
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    Carbon dioxide reacts with RuH2(PPh3)4 to give its insertion product, hydridoformatotris(triphenylphosphine)ruthenium(II). The reversibility of the CO2 insertion has been demonstrated. Insertion products of carbon disulfide and adducts of sulfur dioxide with ruthenium also have been obtained by the reactions of carbon disulfide and sulfur dioxide with various ruthenium dihydride complexes, RuH2L4 (L=PPh3, PPh2H, PPh2Me, PPhMe2). These compounds were characterized by IR and NMR spectroscopy, elemental analysis and chemical reactions.
  • Masuo Funabashi, Haruo Sato, Juji Yoshimura
    1976 Volume 49 Issue 3 Pages 788-790
    Published: 1976
    Released: April 19, 2006
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    The title compounds were prepared stereoselectively from 1,2: 5,6-di-O-isopropylidene-3-C-methylene-α-D-ribo-hexofuranose (1) and 3-O-benzyl-1,2-O-isopropylidene-5-C-methylene-6-O-trityl-α-D-xylo-hexofuranose (5b) by the successive epoxidation and reduction, and from 3-O-benzyl-1,2-O-isopropylidene-6-O-trityl-α-D-xylo-hexofuranos-5-ulose (5a) by the Grignard reaction, respectively.
  • Kazuhiro Maruyama, Tetsuo Otsuki, Yoshinori Naruta
    1976 Volume 49 Issue 3 Pages 791-795
    Published: 1976
    Released: April 19, 2006
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    Behavior of radicals produced in the photochemical reaction of 9,10-phenanthrenequinone was investigated by use of CIDNP and ESR technique. By comparison of the sign of CIDNP signals in formation of and in decomposition (photochemical or thermal) of adducts, the rearrangement of adducts, e.g., from the 1,2-adduct to 1,4-adduct and vice versa, was proposed. Although the adducts are stable enough to isolate in general, they decomposed photochemically or thermally to give the mixture of 9,10-phenanthrenediol (or its quinhydrone), the dehydrogenated dimer of hydrogen donor, and others as minor product.
  • Hideki Rai, Junkichi Yamada
    1976 Volume 49 Issue 3 Pages 796-806
    Published: 1976
    Released: April 19, 2006
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    In order to find the optimum conditions for the preparation of satisfactory reinforcing filler from Matsune (M) acid clay, two series of fillers of M hard clay (CaO 0–9%: drying 110 °C, 5 hr for M-1 series; calcination 600 °C, 1.5 hr for M-2 series: wet ball-milling 6–24 hr) were investigated with respect to their structure, physicochemical properties and morphology. Treatment with hydrated lime (CaO 3%), followed by calcination (600 °C, 1.5 hr) and mechanical disintegration (wet ball-milling 18 hr) was found to give good results. Calcination after the lime treatment gives rise to adequate dehydroxylation as well as dehydration of the montmorillonite, calcium silicate hydrates (CSH) and excess silica remaining. This process helps to restrain the great surface activity of acid clay and facilitate pulverization of the final products combined with the effect of inhibiting polycondensation of the montmorillonite and α-cristobalite due to an even formation of the CSH distributed on the interlayer surfaces and the interfaces of the minute crystallites.
  • Masao Hashimoto
    1976 Volume 49 Issue 3 Pages 807-808
    Published: 1976
    Released: April 19, 2006
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    Many-body effects in (N2)n systems are discussed on the basis of CNDO/2-Clementi SCF calculations of the deviation from the pairwise additivity. The manybody effects cancel each other out, and this makes the deviation from the pairwise additivity only a small percentage of the pairwise interaction in the rather high n-mers.
  • Akira Fujimoto, Akio Sakurai, Eiichi Iwase
    1976 Volume 49 Issue 3 Pages 809-810
    Published: 1976
    Released: April 19, 2006
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    Luminescence spectra and lifetimes are presented for the rare earth ions sensitized by [1]benzopyrano[3,4-c]pyridine-4,5(3H)-dione derivatives in dilute solutions. It is to be noted that, among the benzopyranopyridine derivatives investigated, 2-phenyl-[1]benzopyrano[3,4-c]pyridine-4,5(3H)-dione brings about the most efficient sensitization for the luminescence of europium and terbium ions. Some discussions are made of the energy-transfer processes from these excited benzopyranopyridine derivatives to terbium ions.
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