Bulletin of the Chemical Society of Japan
Online ISSN : 1348-0634
Print ISSN : 0009-2673
ISSN-L : 0009-2673
Volume 48 , Issue 1
Showing 1-50 articles out of 92 articles from the selected issue
  • Shinichi Yamabe, Shigeki Kato, Hiroshi Fujimoto, Kenichi Fukui
    1975 Volume 48 Issue 1 Pages 1-5
    Published: 1975
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    An LCAO MO SCF calculation has been carried out on H2O–HF system with a minimal STO-3G basis set, with respect to three assumed models, i.e. SIGMA, PI, and BIFURCATED models. A configuration analysis of the wave function has shown that charge-transferred electron configurations weakly mix into the original electron configuration in the SIGMA and PI models, while the contribution of charge-transferred configurations is negligibly small in the BIFURCATED model. The SIGMA model has been found to be most stable mainly due to the Coulombic attraction energy between the two species. The intermolecular electron density between the two interacting systems has been investigated by means of a concept of orbital interaction, leading to a conclusion that the mixing-in of the occupied MO’s of H2O with the unoccupied MO’s of HF contributes slightly to the hydrogen bond in the SIGMA and PI models.
  • Gernot Frenking, Hiroshi Kato, Kenichi Fukui
    1975 Volume 48 Issue 1 Pages 6-12
    Published: 1975
    Released: March 27, 2006
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    The stereochemical course of the acid-catalyzed ring-opening polymerisation of ethylene oxide (e.o.) has been investigated on the basis of the CNDO/2 method. By the calculation of the total energy of the interacting system of e.o. and protonated e.o. the most favored reaction path is indicated. The activation energy is found to consist only of the desolvation process. The effect of the deformation of the molecular geometry upon the net charge, the total energy, and the shape of particular MO’s is discussed. It is concluded that the ring strain does not influence the rate. By means of configuration analysis, the dominance of the HOMO–LUMO interaction in the later stage of the reaction has been established. The initiation and propagation reactions follow the same reaction mechanism.
  • Hiroshi Tomiyasu, Hiroshi Fukutomi
    1975 Volume 48 Issue 1 Pages 13-17
    Published: 1975
    Released: March 27, 2006
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    The catalytic action of ferric ions in the U(IV)–U(VI) electron exchange reaction has been studied in the presence of a high concentration of hydrochloric acid. The exchange rate is found to be accelerated by the addition of ferric ions; the observed rate law is given by:
    R=k_0[U(IV)][U(VI)]+k_c[Fe(III)]_0\sqrt[U(IV)][U(VI)]
    An activation energy of 19.7 kcal/mol was calculated for the iron-catalyzed reaction in the U(IV)–U(VI) electron exchange reaction. This value is much smaller than that of 32.2 kcal/mol, which was found in the non-catalytic reaction. The kinetics and equilibrium of the reaction between Fe(III) and U(IV) have also been studied in order to investigate in detail the mechanism of the catalytic reaction. A one-electron-transfer mechanism producing U(V) as an intermediate is estimated from the rate law and supported by the kinetics and equilibrium studies of the Fe(III)–U(IV) reaction.
  • Norio Shimamoto, Keiichiro Hatano, Takashi Katsu, Yuzaburo Fujita
    1975 Volume 48 Issue 1 Pages 18-21
    Published: 1975
    Released: March 27, 2006
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    The results of ESR studies of the amino radicals produced by the photolysis of ammonia adsorbed on the surface of porous Vycor glass at 77 K are described. The observed ESR signal patterns of the amino radicals were remarkably affected by the amount of ammonia on the surface. The isotropic and anisotropic spectra were analyzed by the use of isotopically-substituted amino radicals.
  • Yoshiro Yonezawa, Takayuki Fueno
    1975 Volume 48 Issue 1 Pages 22-25
    Published: 1975
    Released: March 27, 2006
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    The electronic structures of several aliphatic carbonyls, X2CO, CH3COX, and (XCO)2 (X=H, F, CN, CH3), have been investigated by the INDO method. Variations in the calculated electron density, the nπ*-excitation energy, the electron affinity, and the ionization potential with α-X substitution are explained qualitatively in terms of the σ-attracting and π-donating character of F, the π-attracting nature of CN and XCO, and the σ,π-donating property of CH3. The lowest 3* excitation energies and ionization potentials calculated by the UHF method are in reasonable agreement with the experimental values in most cases. The partitioning of the total energy suggests that the C–O bonds of X2CO compounds in the lowest 3* state and the radical anions derived from them are somewhat longer than those of the parent molecules, primarily because of the decrease in the electron-core attraction. The C–C bonds in some (XCO)2 compounds appear to be cloven as easily as the C–X one on thermal activation and electron impact.
  • Kiyoshi Arakawa, Kazumitsu Kojima
    1975 Volume 48 Issue 1 Pages 26-28
    Published: 1975
    Released: March 27, 2006
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    An investigation of the validity of the free volume theory of liquid has been undertaken on the basis of the theory of correlation functions. A formula for free volume without use of a geometrical model has been proposed and discussed. The magnitude of equivalent free volumes obtained from the formula has been found to be nearly equal to that calculated from the entropy of vaporization by means of the free volume theory. The results give support to the physical reality of the concept of free volumes. The communal entropy deduced agrees with that obtained by an expansion formula to the first order of density. A formula for compressibility has also been derived, which gives satisfactory results in comparison with observed data.
  • Nobuaki Tsuchihashi, Hiroyuki Nomori, Masahiro Hatano, Shigeo Mori
    1975 Volume 48 Issue 1 Pages 29-32
    Published: 1975
    Released: March 27, 2006
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    A poly-γ-ethyl-L-glutamate solution with a cholesteric color exhibits a circular dichroism due to the selective reflection of circularly polarized light of one sense by the cholesteric helical structure existing in the solution. On the other hand, an induced circular dichroism is observed in the wavelength region corresponding to the absorption bands of an achiral dye molecule when the molecule is dissolved in the poly-γ-benzyl-D-glutamate liquid crystalline phase. The two modes of circular dichroism are correlated to the structure and the chirality of the cholesteric phase of concentrated polyglutamate solutions.
  • Hideki Sakai, Tokio Yamabe, Hiroshi Kato, Shinichi Nagata, Kenichi Fuk ...
    1975 Volume 48 Issue 1 Pages 33-36
    Published: 1975
    Released: March 27, 2006
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    The singlet transition energies and oscillator strengths of several divalent sulfur compounds are calculated by the semi-empirical ASMO–SCF method. It is shown that the UV absorption bands with transition energies of 5–6 eV observed in these sulfur compounds can be assigned to n-σ1*, n-σ2*, or σ-σ1*, implying that the 3d orbitals of the sulfur atom do not play an important role in these electronic transitions or may contribute absorption bands with higher transition energies.
  • Yoshio Matsunaga, Eiji Osawa, Ryuzo Osawa
    1975 Volume 48 Issue 1 Pages 37-40
    Published: 1975
    Released: March 27, 2006
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    The isomerization from true phenolates to charge-transfer complexes by phase transitions in Hertel’s five amine-picric acid complexes was confirmed by spectroscopic examinations. The amines and the estimated heats of transition were as follows: o-bromoaniline, 6.7; o-iodoaniline, 6.2; 1-chloro-2-naphthylamine, 8.0; 1-bromo-2-naphthylamine, 8.2; 1,6-dibromo-2-naphthylamine, 3.3 kcal/mol. The transition temperatures and/or the heats in the naphthylamine complexes were shown to be markedly reduced by crushing the crystals. The chargetransfer complexes have electrical resistivities lower by a factor of many decades than the isomeric phenolates. Phase transitions without isomerization were found in the metastable 1-halo-2-naphthylamine complexes of the charge-transfer type.
  • Yoshifumi Tanimoto, Noboru Hirota, Saburo Nagakura
    1975 Volume 48 Issue 1 Pages 41-45
    Published: 1975
    Released: March 27, 2006
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    Absorption and phosphorescence spectra were studied for p-methylacetophenone in 3-methylpentane—isopentane mixed solvent at low temperature. From the concentration and temperature dependencies of the absorption spectrum, it is concluded that the monomer-dimer equilibrium exists in the solution of the p-methylacetophenone at low temperature. The phosphorescence of p-methylacetophenone in the mixed solvent at low temperature was found to be composed of two components, with lifetimes of 23 and 42 ms at 77 K. They are ascribed to the π,π* triplet states of the monomer and dimer, respectively.
  • Kiyokazu Fuke, Saburo Nagakura
    1975 Volume 48 Issue 1 Pages 46-49
    Published: 1975
    Released: March 27, 2006
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    The reflection spectra of a [2.2]-paracyclophane crystal were measured in the 17000–62000 cm−1 region with incident light polarized parallel and perpendicular to the a-axis. From analysis of the reflection spectra by the Kramers-Kronig method, the a-axis and c-axis polarized absorption spectra in the 38000–60000 cm−1region were obtained. The c-axis polarized spectrum was obtained for the first time. The 43000 cm−1 band in the c-axis spectrum was assigned to the transitions to the 1B1u(p) and 1B1u (CT) states. The band around 48000 cm−1 was assigned to the transition to the 1B3u-state, corresponding to the transition to the 1E2g -state in benzene.
  • Akio Urushiyama, Masayoshi Nakahara, Yukio Kondo
    1975 Volume 48 Issue 1 Pages 50-54
    Published: 1975
    Released: March 27, 2006
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    The absorption spectra of the single-crystals of several hexachloroiridate(IV) salts and the doped crystals of the hexachlorostannate(IV) salts and the hexachloroplatinate(IV) salt with the IrCl62− anion were measured. Distinct dichroisms appeared in the polarized absorption spectra of all the anisotropic crystals studied. The splittings of the bands and the dichroisms of the spectra were interpreted in terms of the lowering of the symmetry of the IrCl62− anions in the crystal. The absorption bands at 19760 and 20000 cm−1 in the spectra of (CH3NH3)2-Sn(Ir)Cl6 could be assigned to the E′g→E″u and E′g→E′u transitions respectively from their polarizations in the double group, D3d*. Similarly, the bands at 23100, 23500, and 24500 cm−1 were assigned to the E′g→E′u, E′g→E″u, and E′g→E′u transitions respectively. The polarized absorption spectra of Na2IrCl6·6H2O and Na2Pt-(Ir)Cl6·6H2O were also interpreted, assuming that the IrCl62 anions in these crystals were of the D4d symmetry.
  • Masayuki Otake, Tadaaki Otaki
    1975 Volume 48 Issue 1 Pages 55-59
    Published: 1975
    Released: March 27, 2006
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    ESR spectra of the chemically reduced molybdovanadophosphoric heteropoly acids (H3+xMo12−xVxPO40·nH2O, where x=1 and 2) were observed in the solution and glassy state in various organic solvents. On addition of equimolar amounts of reductants such as SnCl2·2H2O, HSCH2CH2SH, and CH3SCH3, a transient ESR signal(B) appeared with eight hfs lines referred to as V(IV), I=7⁄2, and with <g>=1.96 and <T>=−0.83×10−2cm−1. However, it disappeared within ca. 5 hr at 20°C and another signal(C) with <g>=1.962 and <T>=−1.00×10−2 cm−1 gradually increased in intensity. The hyperfine coupling constant of the transient species was thus unusually small as compared with that of the ordinary V(IV) species and the C species. The mechanistic pathways of the reduction were discussed. The splitting observed in the low-field parallel components of the B signal was satisfactorily explained by a “geometrical charge isomerism” characteristic of the structure of the heteropoly anion. The origin of the unusually small hfs constant was discussed in the light of its molecular structure.
  • Akira Sadakane, Tadashi Iwachido, Kyoji Tôei
    1975 Volume 48 Issue 1 Pages 60-63
    Published: 1975
    Released: March 27, 2006
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    The distribution of alkali metal picrate complexes of macrocyclic polyether (dibenzo-18-crown-6) between water and benzene was investigated. The polyether-cation complexes were found to be of a 1:1 stoichiometry. The formation of 2:1 complexes was recognized for Rb and Cs in a large excess of the poiyether. The extractability of complex cation-picrate ion-pairs decreases in this sequence: K>Rb>Cs>Na>Li. The values of the extraction constants (logKex) were determined to be 4.65, 3.75, and 3.07 for K, Rb, and Cs compounds respectively. The thermodynamic quantities for the extraction process were calculated from the change in the extraction constants with the temperature. The extraction reactions are all exothermic, accompanied by an entropy decrease.
  • Noriaki Manada, Hisashi Okawa, Sigeo Kida
    1975 Volume 48 Issue 1 Pages 64-66
    Published: 1975
    Released: March 27, 2006
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    New binuclear complexes Cu2X2dar(en-R)2 and [Cu2dar(dien)2](ClO4)2·H2O were synthesized, H2dar(A)2being a Schiff base prepared from 4,6-diacetylresorcinol and an amine A;A stands for N,N-dialkylethylenediamine-(=en-R, R=C2H5 or iso-C3H7) or diethylenetriamine(=dien). Mononuclear complexes CuXHdar(en-R) were also prepared for comparison. Two copper(II) ions of the binuclear complexes are separated from each other by the benzene ring. Magnetic susceptibilities of the compounds were measured in the temperature range 77.4∼300 K. It was found by means of the plots of χA−1 versus T that all the compounds obey the Curie-Weiss law. The Weiss constants for the binuclear complexes (−10∼−34 K) indicate the presence of antiferromagnetic interactions between copper(II) ions through the conjugated π-system of 4,6-diacetylresorcinol moiety, whereas those of the mononuclear complexes are practically zero, showing that the intermolecular interaction is negligibly small.
  • Kunio Ohzeki, Mayumi Ikeuchi, Tomihito Kambara
    1975 Volume 48 Issue 1 Pages 67-68
    Published: 1975
    Released: March 27, 2006
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    It was found that ferric ions are removed from resin by acetylacetone(Hacac) to form trisacetylacetonatoiron-(III), Fe(acac)3. By the addition of a small amount of pyridine-water mixture to the iron(III)-form resin in acetylacetone milieu, the ferric ions are quantitatively removed from the resin, and in their place the pyridinium ions are adsorbed onto it. The reaction was successfully applied to the synthesis of Fe(acac)3 in over 95% yield.
  • T. Tomoyoshi Takahashi, J. Yasuo Satoh
    1975 Volume 48 Issue 1 Pages 69-72
    Published: 1975
    Released: March 27, 2006
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    A new type of SN2′ reaction in which the nucleophile enters to the leaving group occurs in the acylolysis of 4β-bromo-3-keto-5β-steroids (1) to give 2α-acyloxy-3-keto-5β-steroids (2) as a product. This reaction pathway was observed by NMR and by tlc.
  • Isao Shibuya, Masahiro Kurabayashi
    1975 Volume 48 Issue 1 Pages 73-76
    Published: 1975
    Released: March 27, 2006
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    2,4,6-Triphenyl-1,3-oxazinium perchlorate reacts with active methylene compounds to give several butadiene derivatives and various pyridine derivatives. The reactions seem to proceed as follows: The carbanion from an active methylene compound attacks the 6-position of the oxazinium ring, and opens the ring to form a butadiene as an intermediate, which is then recyclized to a pyridine derivative according to a characteristic mode. The mode of recyclization differs with the constituent of each active methylene. There are five modes characteristic of cyano-, ester-, amido- and benzoyl constituents and nitromethane. A compound containing two different constituents usually follows either of the two possible modes.
  • Fumio Yamamoto, Shigeru Oae
    1975 Volume 48 Issue 1 Pages 77-79
    Published: 1975
    Released: March 27, 2006
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    Kinetic investigation carried out on the reaction between O-2,4-dinitrophenylhydroxylamine and neutral nucleophiles revealed that the reaction is a typical SN2 reaction on the trivalent nitrogen atom. Moreover, the order of reactivities of common nucleophiles was found to be somewhat similar to that of the nucleophilicities toward sp3 carbon atom. However, unlike the SN2 reaction on sp3 carbon atom, the SN2 reaction on the trivalent nitrogen atom found to be not very sensitive to the steric effect of substituted pyridine.
  • Masao Tsukayama
    1975 Volume 48 Issue 1 Pages 80-81
    Published: 1975
    Released: March 27, 2006
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    7,8-Dimethoxy-2,2-dimethylchroman was obtained from pyrogallol trimethyl ether and β,β-dimethylacrylyl chloride via the corresponding chroman-4-one. The Friedel-Crafts reaction of the chroman with acetyl chloride yielded 6-acetyl-7-hydroxy-8-methoxy-2,2-dimethylchroman. The dehydrogenation of the acetylchroman with DDQ in anhydrous benzene afforded ripariochromene A. Ripariochromene A was converted into methylripariochromene A
  • Takashi Toda, Shoji Ryu, Yohichi Hagiwara, Tetsuo Nozoe
    1975 Volume 48 Issue 1 Pages 82-84
    Published: 1975
    Released: March 27, 2006
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    Chemical properties of l-azaazulan-2-one (I) and its 3-substituted derivatives such as 3-acetyl, 3-cycloheptatrienyl and 3-ethoxycarbonyl were investigated. It was shown that the electrophilic substitution reactions take place at the 3-position, replacement of the substituents occuring in some cases by the reactions with cationoid reagents. The Beckmann rearrangement, Curtius rearrangement, Hofmann degradation reaction, Stevens-McFadyen reaction, etc. of these compounds are described.
  • Takao Hara, Yasukazu Ohkatsu, Tetsuo Osa
    1975 Volume 48 Issue 1 Pages 85-89
    Published: 1975
    Released: March 27, 2006
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    The oxidation of cumene and acrolein was carried out using metal polyphthalocyanines as a catalyst. The catalyst activated an oxygen molecule to form a phthalocyanine–O2 complex, which then abstracted the hydrogen atom of a reactant to initiate the oxidation. The catalyst had no effects on the decomposition of cumene hydroperoxide, formed selectively in the oxidation of cumene. The addition of a small amount of pyridine induced a drastic shortening of the induction period as well as a considerable increase in the oxidation rate. The initiation mechanism assumed on the basis of findings on the desorption of oxygen from the catalyst and on the effect of pyridine was confirmed by a kinetic study of the homogeneous liquid-phase oxidation of acrolein.
  • Sh\={o}ichi Kikkawa, Takatoshi Hayashi, Masakatsu Nomura, Noboru Otsu
    1975 Volume 48 Issue 1 Pages 90-95
    Published: 1975
    Released: March 27, 2006
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    The chlorination of methylcyclohexane in several molten metal chloride mixtures (ZnCl2/KCl/NaCl, CuCl/ KCl/NaCl, AlCl3/KCl/NaCl, and CuCl2/KCl/NaCl) has been carried out, using nitrogen gas as a diluent, at three levels of temperature (250, 350, and 450°C. The reactions in both ZnCl2 and CuCl melts were studied extensively, the former representing the molecular-type melt and the latter standing for the partially-ionic-type one. These reactions gave 1-, 2-, 3-, and 4-chloro-methylcyclohexanes and 1-, 3-, and 4-methylcyclohexenes as primary products, along with smaller amounts of toluene and methylcyclohexadiene. The formation of these olefins were interpreted by the subsequent elimination (by a carbonium-ion mechanism) of HCl catalytically enhanced by these melts from the methyl-chlorocyclohexane derivatives. The difference observed in the product distributions between ZnCl2 and CuCl melts was also explained by the studies of the effect of hydrogen chloride produced in these reactions over molten salts.
  • Takenori Kusumi, Nobuo Ohno, Hiroshi Kakisawa
    1975 Volume 48 Issue 1 Pages 96-100
    Published: 1975
    Released: March 27, 2006
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    The cyclization of 2,3-dimethyl-2-phenethyl-3-cyclohexen-1-one 6a with aluminum chloride gave 4a,cis-10a-dimethyl-3,4,4a,9,10,10a-hexahydro-1 (2H)-phenanthrone 8a. The stereochemistry of the latter was established by synthesizing 4a,cis-10a-dimethyl-1,2,3,4,4a,9,10,10a-octahydrophenanthrene 10 through Diels-Alder reaction of 3-formyl-4a,cis-8a-dimethyl-4a,5,6,7,8,8a-hexahydro-2(1H)-naphthalenone 20 with butadiene.
  • Sanshiro Komiya, Akio Yamamoto, Sakuji Ikeda
    1975 Volume 48 Issue 1 Pages 101-107
    Published: 1975
    Released: March 27, 2006
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    Dihydridotetrakis(triphenyIphosphine)ruthenium(II) 1 initiates the polymerization of α-substituted olefins of high e-values such as acrylonitrile and forms unstable complexes with olefins of low e-values. Molecular weight of the polymer obtained by the polymerization of acrylonitrile with 1 was independent of polymerization time and increased linearly with the monomer concentration. The rate of polymerization was measured by a dilatometry and compared with the rate of decomposition of 1 in the presence of acrylonitrile followed by a spectroscopic method. The rate of decomposition of 1 was found to be equivalent to the rate of initiation of polymerization and can be expressed by the following equations:
    -\fracddt[Ru]=k[Ru], \frac1k=A+{B+C[PPh_3]}/[monomer]
    On the basis of the kinetic results and the independence of molecular weight of the polymer on time, a mechanism involving a slow initiation step followed by rapid propagation and termination steps is proposed.
  • Kiyoshi Kondo, Noboru Sonoda, Hiroshi Sakurai
    1975 Volume 48 Issue 1 Pages 108-111
    Published: 1975
    Released: March 27, 2006
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    A novel selenium catalyzed synthetic reaction of carbonates was investigated. The reaction of alkoxides with carbon monoxide in the presence of stoichiometric amount of selenium gave carbonates in high yields under atmospheric pressure at 20°C in THF. When the resultant reaction solution was made to react continuously with the mixture gas of carbon monoxide and oxygen, catalytic formation of carbonates was achieved. Isolation of Se-alkyl monoselenocarbonate from the reaction mixture by addition of alkyl halide indicated that carboalkoxy sodium selenide might be formed as an intermediate in the course of present reaction. In connection with these reactions, the reaction of carbonyl selenide with sodium alkoxide in alcohol was also studied.
  • Toshichika Sato, Yoshihiko Moriyama, Hajime Nagano, Yoshiaki Tanahashi ...
    1975 Volume 48 Issue 1 Pages 112-114
    Published: 1975
    Released: March 27, 2006
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    Two new furanosesquiterpenes, isolated from Ligularia Fischeri Turcz. (collected at Shiramine), were shown to be 1β,10β-epoxyfuranoeremophilan-6β-ol (1) and 1β,10β-epoxyfuranoeremophilan-6β-yl 2-hydroxymethylprop 2-enoate (2).
  • Yoshihiko Ito, Toshiro Konoike, Syotaro Fujii, Junichiro, Setsune, Tak ...
    1975 Volume 48 Issue 1 Pages 115-117
    Published: 1975
    Released: March 27, 2006
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    A reaction of 2-halo-1-olefin-1-carboxylic acids with isonitrile and Cu2O is described. o-Chlorobenzoic acid is treated with ter-butyl isocyanide and Cu2O at 80°C to produce benzoic acid (1a), phthalic anhydride (2a), N-tert-butylphthalisoimide (3a) and N-tert-butylphthalimide (4a) in 5, 14, 18, and 32% yields, respectively. With 2-chloro-1-cyclohexene-1-carboxylic acid, a similar result is observed. However, the reaction of acyclic 2-chloro-1-olefin-1-carboxylic acid such as β-chlorocrotonic acid with isonitrile and Cu2O does not give any products corresponding to 1—4. These reactions are interestingly compared with the reaction of o-iodobenzoic acid and copper-(I) acetylide producing 3-alkylidenephthalide. A reaction mechanism involving a transient intermediate of α,β-unsaturated β-lctone (11) is proposed for the present reaction.
  • Jun Niwa
    1975 Volume 48 Issue 1 Pages 118-124
    Published: 1975
    Released: March 27, 2006
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    The diamagnetic contribution of the hydrogen atom, in the C–H bond and that from its bonded carbon have been semi-empirically expressed. By considering the “ring-current” effect in addition to such contributions, a semi-empirical expression has been obtained for 1H chemical shifts relative to the unsubstituted compound in substituted aromatic side-chains. The applicability of the expression has been examined for m- and p-substituted phenylacetylenes, styrenes, toluenes, and benzaldehydes.
  • Yukito Murakami, Hiroki Kondo
    1975 Volume 48 Issue 1 Pages 125-129
    Published: 1975
    Released: March 27, 2006
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    The pyridoxal-catalyzed α,β-elimination of S-(p-substituted phenyl)cysteines was studied at 50°C and μ=0.10 (KNO3) in 79% (v/v) aqueous acetonitrile in the presence of organic bases of different strength. The rate increased with an increase in basicity. The kinetic solvent isotope effect (kH2OkD2O) of 1.15 is consistent with the reaction mechanism in which the α-proton abstraction occurs by the direct attack of a base on the proton. The elimination rate was insensitive to a change in the electronic nature of a leaving thiophenol, indicating that the α-proton abstraction can be referred to the rate-determining step. The rate showed a considerable dependence on the water content, as reflected on the activation parameters for reactions in 79% (v/v) aqueous acetonitrile as well as in water. The larger destabilization due to water-solvation at the transition state in the aqueous reaction system seems to cause a lower reactivity relative to the organic solvent system. The catalysis of benzene analogs demonstrated that the hydroxyl group adjacent to the aldehyde in pyridoxal plays a major role in the nonenzymatic α,β-elimination reactions.
  • Shunzo Yamamoto, Motoaki Takaoka, Shigeru Tsunashima, Shin Sato
    1975 Volume 48 Issue 1 Pages 130-135
    Published: 1975
    Released: March 27, 2006
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    The emission of the resonance line at 326.1 nm (5 3P1→5 1S0) and the absorptions of Cd(3P0) at 340.4 nm (5 3D1←5 3P0) and of Cd(3P1) at 346.6 nm (5 3D2←5 3P1) have been measured as functions of the pressure of foreign gases at 250°C. At the pressures higher than 1 Torr of any rare gas, an equilibrium was established between 5 3P1 and 5 3P0 states. The efficiency of nitrogen in producing the 5 3P0 state from the 5 3P1 state was found to be more than 103 times those of rare gases. The quenching efficiencies of nitrogen, carbon monoxide, and carbon dioxide for the resonance radiation at 326.1 nm were also measured by using argon as the diluent gas. The halfquenching pressures obtained were 73±3, 0.47±0.01, and 0.096±0.003 Torr for nitrogen, carbon monoxide, and carbon dioxide respectively.
  • Yoshifumi Tanimoto, Tohru Azumi, Saburo Nagakura
    1975 Volume 48 Issue 1 Pages 136-139
    Published: 1975
    Released: March 27, 2006
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    The polarization and Zeeman splitting of the T←S0 absorption were measured with the acetophenone single crystal at 4.2 K. From the analyses of the polarization behavior and the Zeeman splitting pattern, it is concluded that the 26110 cm−1 band is in-plane polarized and has the character of the n,π* type transition.
  • Yusaku Ikegami, Shuichi Seto
    1975 Volume 48 Issue 1 Pages 140-143
    Published: 1975
    Released: March 27, 2006
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    The anion radicals of 5-nitro-, 3-nitro-, and 3,5-dinitro-tropolonates and of 2-methoxy-5-nitrotropone were generated electrolytically in N,N-dimethylformamide. Hyperfine structures of these ESR spectra were reasonably interpreted with the spin density calculations. The results for the 3-nitro- and 3,5-dinitro-tropolonates suggested that the 3-nitro groups were twisted about 40 and 55°, respectively, from the ring plane.
  • Kazuo Doi, Tomoaki Sasaki, Kenzo Hijikata
    1975 Volume 48 Issue 1 Pages 144-146
    Published: 1975
    Released: March 27, 2006
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    The electrical conductivity a of polycrystalline tellurium dioxide (paratellurite; purity: 6-nine) was measured as a function of the oxygen partial pressure (1–760 mmHg) at temperatures between 475 and 550°C. The relations between the experimental values of logσ and 1⁄T were well represented by straight lines, giving the apparent activation energy of about 1.36 eV. The oxygen-pressure dependence of the isothermal conductivity was well expressed by the σ∝Po21⁄6 relation; this may be interpreted by assuming that electron holes with fullyionized oxygen interstitials predominantly act as charge carriers. The p-type behavior in the conduction process was also confirmed by thermal emf measurements.
  • Toshiyuki Hirohashi, Shigeho Inaba, Hisao Yamamoto
    1975 Volume 48 Issue 1 Pages 147-156
    Published: 1975
    Released: March 27, 2006
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    Various thiophene derivatives such as 4-phenyIthienopyrimidines (1), 2-acetylamino-3-benzoylthiophenes (2), 5-phenyl-1,4-thienodiazepines (3) and 5-phenyl-1,4-thienodiazepine-4-oxides (4) have been prepared. Their proton magnetic resonance spectra show that Hα and Hβ of the thiophene ring become more shielded with an increase in bulk of ortho substituent of the benzene ring. This is attributed to the shielding effect of the benzene ring; a steric repulsion between ortho substituent of the benzene ring and some atoms on another moiety of each molecule. Such a repulsion should bring the benzene ring out of the plane of the thiophene ring. The degree of shielding on Hβ by the benzene ring is found to increase in the order 1<2<3<4. This can be taken to indicate that the amount of steric repulsion depends not only on the bulk of ortho substituent of the benzene ring but also on the geometry of each ring system of 14.
  • Mutsuaki Murakami, Susumu Yoshimura
    1975 Volume 48 Issue 1 Pages 157-162
    Published: 1975
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    We studied the crystallization processes of the complex ion-radical salt of 7,7,8,8-tetracyanoquinodimethan (TCNQJ and the N-methylquinolinium cation. A variety of solvents, rates of crystallization, and concentrations of the solution gave three groups of crystals. The crystals in the first group, which were crystallized as black rods, occluded the solvent molecules in the crystals, and their resistivities were in the range of 2.8–26 Ωcm. Those in the second group were crystallized into the form of fine needles or fine powders. Although the TCNQ-to-cation ratios in the salts varied from 1.6 to 2.2, their electrical resistivities were almost all the same (about 1.00 Ωcm), and these crystals were thought to have a metastable crystal structure. The crystals in the third group were crystallized in the form of triclinic prisms, which belonged to a stable crystal of a high resistivity (1100 Ωcm). The appearance of multiple forms is interpreted on the basis of Ostwald’s “Law of Stages” of crystallization and also on the basis of information on the structures of the one-dimensional TCNQ, columns of the other complex ion-radical salts of TCNQ.
  • Hiroshi Kawabe
    1975 Volume 48 Issue 1 Pages 163-166
    Published: 1975
    Released: March 27, 2006
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    All the aminations of chloromethylated polystyrene (CMPS) and benzyl chloride with i- and s-butylamine in N,N-dimethylformamide (DMF), in dioxane, and in DMF-dioxane mixtures conformed to the ordinary second-order kinetics. The activation parameters in the pure solvents revealed that the much higher amination rate in DMF than in dioxane was due to both the lower value of ΔH\ eweq and the higher value of ΔS\ eweq in DMF. The rate of amination in DMF–dioxane was investigated as a function of the composition of the mixed solvent. The observed rate constants in DMF–dioxane mixtures fell substantially on the curves calculated on the basis of Kondo and Tokura’s theory concerning reaction rates in binary mixed solvents. It is suggested in this paper that the higher rate of amination in DMF is due to the strong solvation of the activation complex in DMF to form an addition product, and that it is also due to the relative increase in the configurational entropy of the reaction system at the transition state from dioxane to DMF.
  • Ichimin Shirotani, Akifumi Onodera, Nobuko Sakai
    1975 Volume 48 Issue 1 Pages 167-170
    Published: 1975
    Released: March 27, 2006
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    The electrical resistance of alkali metal cation–TCNQ anion radical simple salts was measured over the wide pressure range from 0 to 500 kbar at room temperature. The least resistivities for Group A (Li–, Na–, K–, and Rb(I)–TCNQ) are about 0.2–3 Ωcm, while those for Group B (Rb(II)– and Cs–TCNQ) are about 0.06–0.1 Ωcm. The possibility of insulator-metal transition at high pressures is discussed. Above 140–175 kbar the electrical resistance of simple TCNQ salts increases with an increase in the pressure and drifts upward with the time. The solid-phase reaction is observed under very high pressures.
  • Yoshinobu Shiokawa, Shin Suzuki
    1975 Volume 48 Issue 1 Pages 171-174
    Published: 1975
    Released: March 27, 2006
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    The isotropic Rayleigh ratios in two-component systems are discussed in terms of the fluctuation of the thermodynamic quantities. It is found that the isotropic Rayleigh ratio, Ris, is the sum of the concentration scattering, Rc, due to fluctuation of the concentration and the so-called density scattering, Rd:
    R_is=R_c+R_d
    Thus, the cross-term of the concentration scattering and the density scattering, suggested by Bullough, is not included in the above expression. Our conclusion is confirmed by the determination of the molecular weight of sucrose.
  • Takeo Saito, Akira Iwama
    1975 Volume 48 Issue 1 Pages 175-183
    Published: 1975
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    Two kinds of polymer spheres polyurethane (PU) and carboxyl-terminated poly butadiene (CTPB), ca. 3 and 5 mm, respectively, in diameter and used currently as fuel and/or binder constituents in solid and hybrid rocket propellants, were ignited electrically with a nichrome fiber in several oxidizing gases over the range 5–30 kg/cm2. Their combustion phenomena were studied photographically with a 16 mm movie camera. The combustion flame was observed by means of direct photographs, both the variation of diameter with time and the location of contact surface being measured with shadow photographs. It was shown that PU spheres are entirely liquefied, involving slight swelling just after ignition, and then burn in a similar manner to that of distilled hydrocarbon droplets. CTPB spheres were found to expand remarkably after ignition. At the first stage the surrounding product gases formed a diffusion flame, their apparent diameters remaining nearly constant for a short time. At the second stage the remainder of the carbonaceous substance continued to burn, turning to surface combustion. It can be predicted that in an actual rocket combustion chamber the surface of the fuel-binder for PU propellants is wet and that of GTPB propellants is covered with carbonaceous layer during the course of steady state burning. The overall mass burning rate is proportional to a half and 0.3 power of total pressure for PU and CTPB, respectively, depending slightly on the kind of inert gas for dilution of the oxidizing atmosphere in both cases. A combustion model for CTPB is presented and Compared with experimental results.
  • Noritetsu Yoshida, Kozo Hirota
    1975 Volume 48 Issue 1 Pages 184-190
    Published: 1975
    Released: March 27, 2006
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    The reaction of methylacetylene with hydrogen and deuterium was studied over five Group VIII metals (Pd, Pt, Rh, Ir, and Ru) at 25°C. Among these metals, palladium was the most selective for the propylene formation; the selectivity varied from metal to metal (Pd>Pt>Rh>(Ni)>Ru>Ir). A new result was obtained over ruthenium; the isomerization of methylacetylene to allene occurred simultaneously with the hydrogenation over only this metal. In the reaction with deuterium, the stereoselectivity of the metals was investigated on the products by analyzing them by the microwave spectroscopic and mass spectrometric methods. Only three hydrogen atoms were deuterated in the propylene produced over Ni, Pd, and Pt; in conformity with the above, the deuterated positions of propylene-d1 and -d2 were limited to three in the methylene and methylidyne groups. No such tendency was observed for Ir, Rh, and Ru, where the methyl hydrogens were also deuterated. The relative yield of the cis-1,2-d2 species, always the most abundant product, decreased in this order: Pd>Pt>Ir>Ru>(Ni)>Rh at 70% conversion. A reaction mechanism which explains the relative yields of isotopic isomers of deuteropropylenes except for the methyl-deuterated species was proposed, assuming an adsorbed radical as an intermediate. The calculated isomer distributions based on the scheme coincided well with those observed in the cases of Pd, Pt, and Ni, but not in those of Ir, Rh, and Ru.
  • Masataka Okuyama, Tadayoshi Yoshida, Tadaaki Tanii, Masahito Kunugi, I ...
    1975 Volume 48 Issue 1 Pages 191-194
    Published: 1975
    Released: March 27, 2006
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    Stable bimolecular films (bilayers) were found to be formed in aqueous solutions from myristyl alcohol or from mixtures of myristyl alcohol and myristic acid. The electric capacitance and resistance of these bilayers were measured in solutions of pH 3–8. The capacitance of mixed bilayers was larger than that of myristyl alcohol bilayers (0.58 μF/cm2). When the bilayers were formed from sample solutions having mole ratios 1/1 and 2.3/1 (myristic acid to myristyl alcohol), the capacitance had minima at ca. pH 7. The resistance of mixed bilayers at ca. pH 5 was smaller than one tenth of that of the myristyl alcohol bilayer (ca. 7×108 Ω·cm2). The results are explained in terms of (i) van der Waals attraction between hydrocarbon chains, (ii) the tendency for myristic acid to form expanded layers, (iii) the head group attraction between the myristic acid ion and myristyl alcohol, and (iv) the tendency for myristic acid ions to dissolve in the aqueous phase.
  • Shigeyoshi Sakaki, Hiroshi Kato, Takashi Kawamura
    1975 Volume 48 Issue 1 Pages 195-200
    Published: 1975
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    A parametrization in a CNDO-type MO method is presented for Pt compounds. By the use of this parametrization, the electronic spectra of PtCl42− are calculated; they agree well with the experimental spectra in transition energies and assignments. MO calculations with this parametrization are carried out on Pt(II)–ethylene, Pt(II)–acetylene, Pt(0)–ethylene, and Pt(0)–acetylene complexes. The calculated transition energies of Zeise’s salt also agree well with the experimental values. In Pt(II) complexes, electrons are donated from ethylene and acetylene to the Pt atom, while they are little donated in Pt(0) complexes. The TT-bonds of ethylene and acetylene are weaker in Pt(0) complexes than those in Pt(II) complexes. These results are the consequence of the stronger π-acceptor coordination bond in Pt(0) complexes than in Pt(II) complexes. Acetylene coordinates to the Pt atom more strongly than does ethylene. The coordination bonds of ethylene and acetylene are stronger in Pt(0) complexes than in Pt(II) complexes.
  • Yasuo Miki
    1975 Volume 48 Issue 1 Pages 201-208
    Published: 1975
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    The equilibria for the hydrogenation of n-propylbenzene, isopropylbenzene, 1-methyl-2-ethylbenzene, 1-methyl-3-ethylbenzene, and 1-methyl-4-ethylbenzene were determined experimentally over the temperature range of 250 to 450°C and under hydrogen pressures ranging from 5 to 50 atm. The data were then used to calculate the values of the free energy and the equilibrium constant of the above reactions and the values of standard free energy of formation from the elements for n-propylcyclohexane, isopropylcyclohexane, 1-methyl-cis-2-ethyl-cyclohexane, 1-methyl-trans-2-ethylcyclohexane, 1-methyl-cis-3-ethylcyclohexane, 1-methyl-trans-3-ethylcyclohexane, 1-methyl-cis-4-ethylcyclohexane, and 1-methyWrawj-trans-ethylcyclohexane.
  • Hayami Yoneda, Ushio Sakaguchi, Yoshiaki Nakashima
    1975 Volume 48 Issue 1 Pages 209-213
    Published: 1975
    Released: March 27, 2006
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    A theory is presented which couples the proton chemical shift induced by the paramagnetic anisotropy with the chemical shift of the central cobalt-59 nucleus. The theory has been successfully applied to twenty cobalt-(III) α-aminocarboxylate complexes. It is shown that it can be used not only to assign proton NMR signals but also to determine the structure of the complex and, in certain cases, the conformation of ligand molecules.
  • Akio Nakamura, Kazuo Tajima, Tsunetaka Sasaki
    1975 Volume 48 Issue 1 Pages 214-218
    Published: 1975
    Released: March 27, 2006
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    The effect of the pH on the adsorption of an ampholytic surfactant, N-dodecyl-β-alanine (NDA), at the nitrogen/solution interface was studied by the radiotracer method, using a tritiated compound. The saturated amount of NDA adsorption was found to depend on the pH of the bulk solution; it shows a flat maximum in the isoelectric region from pH 4 to 10, and decreases distinctly on the both acid and alkaline sides. The Gibbs adsorption isotherm for an aqueous solution of the ampholytic surfactant was derived. Using this relation, the amount of adsorption in the pH range from 2 to 6 was calculated from the surface tension vs. concentration and the surface tension vs. pH relations observed for the NDA solution. The calculated values were in good agreement with those obtained by the radiotracer method. The degree of dissociation of the adsorbed monolayer was estimated from the pH dependence of NDA and the chloride ion adsorption.
  • Yoshio Takasu, Shun-ichi Maru, Yoshiharu Matsuda, Hazime Shimizu
    1975 Volume 48 Issue 1 Pages 219-221
    Published: 1975
    Released: March 27, 2006
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    A potentiostatic polarization method, Auger electron spectroscopy (AES), and photoelectron spectroscopy (XPS) were used to examine the composition of the passive films formed on Cu–Ni alloys anodized in an acid. The Flade potential of pure nickel in 0.5 M HClO4 at 25 °C was −0.085 V (vs. SCE), while those of the alloys varied linearly from 0.180 V at 95%Ni to 0.310 V at 47%Ni. Analysis by AES and XPS revealed that (a) the passive region contained nickel and copper in the same ratio as the alloy, and (b) the chemical species of the film were made of NiO and copper oxide (Cu2O and/or CuO). The Flade potential was assumed to be governed by the mixed potential of the formation of such oxides.
  • Renichi Kondo, Salah A. Abo-El-Enein, Masaki Daimon
    1975 Volume 48 Issue 1 Pages 222-226
    Published: 1975
    Released: March 27, 2006
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    Kinetics and mechanisms of hydrothermal reactions of the systems slag-lime-water (I) and slag-quartz-lime-water (II) have been studied. In the initial stage of reaction in system (I), nearly amorphous calcium silicate hydrate with low lime content was formed and continued to grow in strength. Formation of hydrogarnet (3CaO·Al2O3·SiO2·4H2O) accompanied by the crystallization of calcium silicate hydrate caused a reduction in strength. In the reaction in system (II), a product with high lime content was formed which was then changed into a low lime product after complete consumption of free lime. Slag was highly reactive but inhibited reaction of quartz, especially during the initial stage of the hydrothermal solidification process. The rate of hydrothermal reaction as well as the characteristics of the products change considerably with temperature.
  • Emiko Ohyoshi, Junko Oda, Akira Ohyoshi
    1975 Volume 48 Issue 1 Pages 227-229
    Published: 1975
    Released: March 27, 2006
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    A method to facilitate the analysis of the complex formation by a polybasic acid has been applied to the study of uranyl citrate complexes. The amount of the uranyl ion in equilibrium with the complexing agent was determined by the cation-exchange method. In this experiment, the uranyl-ion concentration was kept within a 105–106 M range in order to eliminate polymeric species. By using a series of solutions prepared so as to keep [H3Cit] nearly constant and to vary [H2Cit2−] and [HCit3−] in the 2.2–2.9 pH range, it has been found that three kinds of complexes, UO2H3Cit+, UO2H2Cit, and UO2HCit, were present in the solution. Approximate values of their formation constants were obtained.
  • Akira Ohyoshi, Shunichi Hiraki, Tomio Odate, Susumu Kohata, Junko Oda
    1975 Volume 48 Issue 1 Pages 230-233
    Published: 1975
    Released: March 27, 2006
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    The Kinetics of the thermal substitution reaction of hexaammineruthenium(III) halides and cis-dihalogenotetraammineruthenium(III) halides have been studied in the solid state. The reaction rates and kinetic parameters were determined for these two reactions; [Ru(NH3)6]X3→[RuX(NH3)5]X2+NH3, (X=Br, I) and cis-[RuX2(NH3)4]X→[RuX3(NH3)3]+NH3, (X=Cl, Br). The values of the rate constant, the activation energy, and the activation entropy were 2.10×10−5 s−1 (at 161°C), 23.3 kcal mol−1, and −29.3 e.u. for the hexaammine bromide, and 2.92×10−5s−1 (at 162 °C), 31.3 kcal mol−1, and −10.1 e.u. for the cis-dibromotetraammine bromide. The SN2 mechanism is more probable for the former reaction, while the SN1 mechanism is more probable for the latter reaction.
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