Bulletin of the Chemical Society of Japan
Online ISSN : 1348-0634
Print ISSN : 0009-2673
ISSN-L : 0009-2673
Volume 48 , Issue 4
Showing 1-50 articles out of 58 articles from the selected issue
  • Kazushi Arata, Susumu Akutagawa, Kozo Tanabe
    1975 Volume 48 Issue 4 Pages 1097-1101
    Published: 1975
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    The reaction of 1-methylcyclohexene oxide over solid acids and bases at 108 °C was found to give five main products, 2-methylcyclohexanone (III), 1-methylcyclohexanol (IV), 2-methyl-2-cyclohexene-1-one (V), 2-methyl-enecyclohexanol (VIa), and 2-methyl-2-cyclohexene-1-ol (VIb), with a small amount of 1-methylcyclohexene (I) and unidentified compound (II). The ketone (III) was formed predominantly over zeolite, SiO2–Al2O3, H2SO4/SiO2, AlCl3, and BBr3, while the allyl alcohol (VI) was given by Al2O3 and TiO2. HCl/SiO2 and solid H3PO4 calcined at 400–900°C gave both products, III and VI, in the same amounts, though the latter calcined at 200–300°C formed almost 100% ketone. Solid lithium perchlorate was surprisingly active for the formation of ketone, but other metal per chlorates and lithium salts were quite inactive. Alkaline earth metal oxides and NaOH/SiO2 were almost inactive. The catalytic activity and selectivity as well as the reaction path and mechanism are briefly discussed mainly in connection with acid-base property of solid catalysts.
  • Akio Yamamoto, Yuji Shiro, Hiromu Murata
    1975 Volume 48 Issue 4 Pages 1102-1106
    Published: 1975
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    A rigid-ion model analysis was made for the optically-active crystal vibrations of calcite (CaCO3) and magnesite (MgCO3) with reference to the previous vibrational treatments. The effects of the effective charge distribution on the TO–LO splittings of the lattice modes were examined on the proposed distribution model, and the effective charges have been found: Zca=1.21, Zc=0.20, and Zo=−0.47 in calcite, and ZMg=1.28, Zc=0.21, and Zo=−0.50 in magnesite, all in electron units. The force fields and effective charges determined in the present study reproduce satisfactorily the observed transverse and longitudinal frequencies of the optically-active lattice vibrations.
  • Koichi Oka, Hideo Yamazaki, Yoshihiko Hatano
    1975 Volume 48 Issue 4 Pages 1107-1113
    Published: 1975
    Released: March 27, 2006
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    The effect of addition of sulfur hexafluoride as an electron scavenger on quantum efficiency was investigated for the decay of trapped electrons in 3-methylhexane matrices at 77 K during photobleaching in the wavelength range 700–1900 nm. Since the quantum efficiency for the decay of trapped electrons in pure matrices is independent of the initial concentration, almost all the recombination of liberated electrons with the cations is geminate. The increase in quantum efficiency for the decay of trapped electrons by the addition of the electron scavenger SF6 was analyzed quantitatively. The quantum efficiency for the photoliberation of trapped electrons from the trapping sites may be about unity. The liberated electrons in the absence of the electron scavenger are retrapped or neutralized. The ratio of the former process to the latter at a wavelength greater than 1500 nm is much larger than that at a shorter wavelength. The wavelength dependence of the ratios of the electron scavenging process to these processes has also been discussed.
  • Katsutoshi Ohkubo, Kohji Tsughihashi, Hiromichi Ikebe, Hiroyuki Sakamo ...
    1975 Volume 48 Issue 4 Pages 1114-1117
    Published: 1975
    Released: March 27, 2006
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    The reaction mechanism and kinetic-rate constants of the pentacyanocobaltate(II)-catalyzed hydrogenation of olefins were investigated. The present study with an iterative simulation technique supported the Co(CN)53−+H2→Co(CN)5H3−+H· and Co(CN)53−+H·→Co(CN)5H3− reactions for the uptake of H2 by the cobaltate(II) during the initial stage of the reaction. An examination was also made of the stationary-state approximation used for the kinetic analysis of the reaction.
  • Hiroyuki Yamaguchi, Teruki Ikeda, Hiroaki Mametsuka
    1975 Volume 48 Issue 4 Pages 1118-1122
    Published: 1975
    Released: March 27, 2006
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    Measurements of the dipole moments and acidity constants in the lowest excited singlet states for benzo[c]quinoline, benzo[f]quinoline, and benzo[h]quinoline have been carried out by spectrophotometry. The electronic structures of excited states have been calculated by using the semi-empirical SCF–π–MO CI method, which allows for a bond order-bond length relationship at each iteration. The experimentally-determined dipole moments and acidity constants can not be correlated to the calculated electronic structures of the Franck-Condon states, but they can be correlated to the calculated structures of the equilibrium states for the lowest excited singlet states of three isomeric benzoquinolines.
  • Hiromitu Naono, Toshie Kadota, Tetsuo Morimoto
    1975 Volume 48 Issue 4 Pages 1123-1126
    Published: 1975
    Released: March 27, 2006
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    Two essentially different methods for determining surface water content, i.e., a successive-ignition-loss method and chemical reaction of active hydrogen with methylmagnesium iodide, were applied to the measurement of samples containing pores: silica, alumina, and silica-alumina. It was found that the rate of reaction of methylmagnesium iodide with active hydrogen largely depends upon the pore size distribution. It took 20 min for completion of the reaction on the Aerosil sample having no pores, ca. 1 hr for alumina and silica-alumina which have peaks in the pore size distribution curve at radii 53 and 37 Å, respectively, and 17 hr for porous silica glass and silica gel which have peaks at radii 22 and 19 Å, respectively. The results obtained by the two methods were in good agreement with each other irrespective of the existence of pores in the transitional range. It was confirmed that the nature of the sample is decisive for the population of water content on metal oxides.
  • Satoshi Hirayama
    1975 Volume 48 Issue 4 Pages 1127-1132
    Published: 1975
    Released: March 27, 2006
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    The fluorescence and absorption spectra of 2-methyl-1-aceanthrenone (I) and its cation were investigated. The spectra showed well-defined vibrational structures in a wide variety of solvents, but not in ethyl alcohol and acetic acid. The existence of the 1Lb absorption band on the shorter-wavelength side of the 1La band was strongly supported by the different solvent effects of these bands. In non-polar solvents, (I) formed a strongly fluorescent, 1:1, hydrogen-bonded complex with a trichloroacetic acid molecule. The formation constant in n-hexane was determined spectrophotometrically as 3.1×10−2 M−1 at 20 °C. In acidic solutions, pKa and pKa*, were determined as −5.1 and 1.3 for the ground and first excited singlet states respectively. These values are the same as the corresponding values of 9-anthracenecarboxaldehyde (9-CHO-A), reflecting a marked resemblance in the electronic nature of the carbonyl groups of the two compounds. The broad absorption spectra of 9-CHO-A, in contrast to the highly structured spectra of (I), are due to a feasible torsional motion of the carbonyl group of the former compound.
  • Shojun Hino, Tomohiko Hirooka, Hiroo Inokuchi
    1975 Volume 48 Issue 4 Pages 1133-1137
    Published: 1975
    Released: March 27, 2006
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    Photoemissions from pyrene and its derivatives, 1,3,6,8-tetrachloropyrene(TClP), 1,3,6,8-tetrabromopyrene(TBrP), 1,6-dicyanopyrene(CDNP), 1,3,6,8-tetracyanopyrene(TCNP), and 1,3,6,8-tetranitropyrene (TNO2P), were measured. Their photoelectron energy distribution curves(EDCs) were thus obtained; the peaks or shoulder appearing on the EDCs correspond to the ionization potentials of the pyrene molecule. Further, the spectral dependences of their quantum yields(SDQYs) were measured. The ionization potentials obtained from their threshold values were 5.8 eV(pyrene), 6.3 eV(TClP), 6.0 eV (TBrP), 6.3 eV(DCNP), 6.2 eV(TCNP), and 6.6 eV(TNO2P).
  • Tomoo Miyazaki, Masaru Ikeda, Masayuki Shibata
    1975 Volume 48 Issue 4 Pages 1138-1145
    Published: 1975
    Released: March 27, 2006
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    The approximate self-consistent molecular orbital method has been applied to the analysis of the vibrational spectrum of HCN. The frequencies of the fundamental, overtone, and combination bands in the region from about 700 to 12000 cm−1 have been calculated, and their absolute infrared absorption intensities have been estimated, the variational method being used in this calculation. Also, the frequencies and absorption intensities of hot bands, referring to the bending vibration, have been calculated. In comparison with the experimental results, the calculated frequencies were not always appropriate. However, it was found that these results are effective in the analysis of the molecular vibration if the calculated frequencies are discussed along with their infrared absorption intensities.
  • Hisashi Ueda, Naoyuki Todo
    1975 Volume 48 Issue 4 Pages 1146-1151
    Published: 1975
    Released: March 27, 2006
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    The ESR spectra from the catalyst/perylene/purified-benzene system were studied. The surface equilibria, Co3++P\ ightleftharpoonsCo2++P+, Ni3++P\ ightleftharpoonsNi2++P+, and Mo6++P\ ightleftharpoonsMo5++P+, have been established, with the equilibrium constants at 20°C, 3.3×1015, 3.0×1014, and 6.8×109 respectively. In Al2O3–MoO3–CoO, Mo6++Co2+\ ightleftharpoonsMo5++Co3+, is attained; the equilibrium constant obtained was 2.0×10−6, and the corresponding value for Mo6++Ni2+\ ightleftharpoonsMo5++Ni3+ was 2.3×10−5. These results indicate that the roles of NiO and CoO in these catalysts are essentially the same. It has been found that the supporting order was important when CoO and MoO3were supported together, but unimportant when NiO and MoO3 were supported together. Considering the known fact that CoO is a more efficient Co-catalyst of MoO3 than NiO at lower supported concentrations (less than 2%), it has been concluded that CoO is incorporated in the alumina-carrier surface less stereospecifically, but more effectively, than NiO.
  • Azumao Toyota
    1975 Volume 48 Issue 4 Pages 1152-1156
    Published: 1975
    Released: March 27, 2006
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    The energetically most favorable molecular-symmetry groups and geometrical structures of CmHm−4 catacondensed nonalternant hydrocarbons were examined systematically on the basis of the symmetry rule and the semiempirical SCF MO method. The first excitation energies in the fully-symmetrical nuclear arrangements were found to decrease with increasing the number of carbon atoms, showing a tendency to converge to a certain limiting value, ca. 0.8 eV. Molecules larger than a certain critical size (m∼10) were predicted to suffer the second-order Jahn-Teller distortion, exhibiting a double-bond fixation in the peripheral carbon skeleton. Using the most stable geometrical structures obtained, the electronic spectra of these molecules were calculated. Furthermore, the predictions of the stable molecular-shapes in the lowest excited singlet states were briefly mentioned.
  • Ken Hirotsu, Taiichi Higuchi, Akira Shimada, Yuji Hayashi, Takeo Sakan
    1975 Volume 48 Issue 4 Pages 1157-1162
    Published: 1975
    Released: March 27, 2006
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    The title compound crystallizes in the orthorhombic space group P212121, with cell dimensions of a=10.43, b=15.45, c=13.65 Å, and Z=4. The structure was determined by direct methods from photographic data, and was refined by the least-squares method to a final R of 0.098 for 2581 reflections. Rings A and B are subject to steric strains resulting from the formation of a lactone ring. This is reflected in the abnormal values for some bond lengths, angles, and dihedral angles.
  • Yasuaki Okamoto, Hajime Nakano, Toshinobu Imanaka, Shiichiro Teranishi
    1975 Volume 48 Issue 4 Pages 1163-1168
    Published: 1975
    Released: March 27, 2006
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    XPS techniques were used to clarify the state of supported cobalt catalysts. In order to characterize Co2+ and Co3+, the spin-orbit splitting of the 2p level, which is considered to be affected by the exchange interaction between the unpaired 3d electrons and 2p electrons, was found to be very useful. The interaction between catalyst and support was investigated. The state of supported cobalt was determined: Co2O3 on SiO2, Co2O3+ CoAl2O4 on γ-Al2O3, and LaCoO3 on La2O3. The order of the strength of the chemical interaction between cobalt and support is as follows:
    La_2O_3>γ-Al_2O_3>SiO_2.
    This fact was also confirmed by reduction experiments.
  • Shigemi Matsumoto, Masahiro Nitta, Kiyoshi Ogawa, Kazuo Aomura
    1975 Volume 48 Issue 4 Pages 1169-1171
    Published: 1975
    Released: March 27, 2006
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    The effects of the degree of exchange and the dehydration upon the structural stability of silver-exchanged forms of the synthetic zeolite Linde 4A have been investigated by means of DTA, X-ray diffraction, and adsorption studies. The relative intensity of the X-ray powder diffraction decreased with an increase in the extent of Ag+-exchange, though it indicated no accurate information on the crystallinity. An exotherm on the DTA curves which shifted to a lower temperature with the degree of exchange became an indication of the collapse of the structure; this was in good agreement with the specific surface area of the sample heated at a higher temperature. From these results, the silver-exchanged zeolite A was concluded to be thermally unstable and to lose its crystal structure at a lower temperature than the original sodium form. It is also proposed that the comparison of the X-ray powder diffraction intensity is not suitable as a method for judging the crystallinity of zeolites A.
  • Shunzo Yamamoto, Shigeru Tsunashima, Shin Sato
    1975 Volume 48 Issue 4 Pages 1172-1175
    Published: 1975
    Released: March 27, 2006
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    The pressure dependences of the emission intensities at 326.1 and 432 nm in the cadmium-photosensitized reaction of ammonia have been measured. In order to interpret the nonlinear Stern-Volmer plots for the quenching of the 326.1 nm resonance line, the following reactions have to be taken into account in the reaction scheme: Cd*+NH3\ ightleftharpoonsCdNH3*V, CdNH3*V+M→CdNH3*+M. The pressure dependence of the emission from the CdNH3* complex (at 432 nm) was also well explained in terms of a reaction scheme involving the above reactions.
  • Akira Kotera, Takahide Saito, Naomichi Iso, Haruo Mizuno, Nobuo Taki
    1975 Volume 48 Issue 4 Pages 1176-1179
    Published: 1975
    Released: March 27, 2006
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    The number-average molecular weight and intrinsic viscosity of phycocyanin, isolated from Porphyra tenera, have been determined by osmotic pressure and viscosity measurements at various values of pH and ionic strength. The molecular shape and size for phycocyanin aggregates were also discussed by comparing the experimental values of sedimentation coefficient and intrinsic viscosity with the calculated results obtained by using the shell model theory. It is shown that the aggregate of phycocyanin at pH 5.4 is a hexamer of molecular weight 256000 and the structure consists of six juxtaposed monomers. The monomer is a prolate ellipsoid of 35 Å in diameter and 105 Å length. This structure for the hexamer is consistent with the model proposed by Jennings. At pH 6.8, it is shown that the number-average molecular weight of phycocyanin depends on the ionic strength in solution.
  • Koichi Kobayashi
    1975 Volume 48 Issue 4 Pages 1180-1185
    Published: 1975
    Released: March 27, 2006
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    The effects of several anionic surfactants—sodium α-sulfolaurate, sodium laurate, sodium dodecylsulfate, and cationic surfactants, dodecylpyridinium chloride, and dodecyltrimethylammonium chloride—on the bubble flotation of Cu2+ ions were studied. Sodium α-sulfolaurate was found to be most effective for the flotation of Cu2+ ions. The flotation rate (percent removed) increased sharply from zero at about pH 6, and a rate larger than 95% was attained in the pH region of about 7 to 11. Cationic surfactants alone could float Cu2+ ions only slightly. They floated most of the Cu2+ ions upon the addition of bentonite, however. A flotation rate of about 90% was attained in the pH region larger than about 6. This was explained by the Cu2+ ions being removed as polynuclear species, which combined directly with an anionic surfactant or a cationic surfactant with the aid of bentonite.
  • Yuichi Fujimura, Takeshi Nakajima
    1975 Volume 48 Issue 4 Pages 1186-1190
    Published: 1975
    Released: March 27, 2006
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    A rate expression for the intramolecular nonradiative transition where a promoting mode acts also as an accepting mode at the same time has been derived within the statistical limit. The dependence of the nonradiative transition rate on the shift of the equilibrium point of the promoting mode in the relevant electronic states, Δp, has been examined for two cases, i) excited \ ightsquigarrow ground states and ii) excited \ ightsquigarrow excited states, in aromatic hydrocarbons which satisfy the above condition.
  • Michio Kitamura, Hiroaki Baba
    1975 Volume 48 Issue 4 Pages 1191-1195
    Published: 1975
    Released: March 27, 2006
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    Absorption and fluorescence spectra, fluorescence and phosphorescence quantum yields and lifetimes of 1-and 2-naphthaldehyde and their derivatives have been measured in rigid glass solution at 77 K. Naphthaldehydes and acetonaphthones are non-fluorescent, whereas naphthoyl chlorides and methyl naphthoates are fluorescent. Upon formation of a hydrogen bond with ethyl alcohol, 2-naphthaldehyde and 2-acetonaphthone become fluorescent, and 1-naphthoyl chloride increases in fluorescence quantum yield by a factor of about 65. The rate constants for intersystem crossing in these three molecules decrease by about two orders of magnitudes as a result of hydrogen bonding. The decrease of the rate constants is attributed to elevation of the (n, π*) level and the resulting change in its position relative to the (n, π*) level. The experimental results are discussed in relation to the current theories of radiationless transition, and are found to conform to the theory in which both spin-orbit coupling and nuclear kinetic-energy operators are treated as the perturbation causing intersystem crossing.
  • Zenzo Morita, T. M. Abul Hossain, Toshiro Iijima
    1975 Volume 48 Issue 4 Pages 1196-1199
    Published: 1975
    Released: March 27, 2006
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    A model cationic dye, m-nitrobenzylamine (NBA), was synthesized, and the diffusion and adsorption behavior in polyacrylonitrile was investigated by the cylindrical film roll method. pKa of NBA was determined spectroscopically to be 9.2 at 25 °C. The diffusion was concentration dependent and was described by the chemical potential gradient model. The temperature dependence of the diffusion coefficients above Tg, which was found to be 65 °C from the inflection point of Arrhenius plot, could be described by WLF equation, where C1g and C2g are 1.64 and 17.09 (deg.) at pH 4.2, and 2.41 and 33.11 (deg.) at pH 6.8, respectively. Adsorption isotherm of NBA was obtained at 95 °C and pH 1.5, 4.2 and 6.8. The adsorption of NBA, bis(m-nitrobenzyl)amine and Malachite Green at pH 4.2 and those of NBA and bis(m-nitrobenzyl)amine at pH 6.8 were more or less the same. It is concluded that the adsorption of cationic compounds on polyacrylonitrile is virtually dependent upon the ion exchange mechanism. But the presence of sodium chloride in the dye bath did not change the adsorption of NBA at pH 4.2 and 95 °C. The surface concentration of NBA was gradually increased with rise of temperature at pH 1.5, 4.2 and 6.8.
  • Hayami Yoneda, Ushio Sakaguchi, Yoshiaki Nakashima
    1975 Volume 48 Issue 4 Pages 1200-1204
    Published: 1975
    Released: March 27, 2006
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    An argon ion laser has been used to partially photoresolve the following tris(β-diketonato)chromium(III) complexes; Cr(acac)3, Cr(3-X-acac)3 (X=Cl, Br, I, and NO2), Cr(tfac)3, and Cr(bzac)3, where the abbreviations are acac=acetylacetonate ion, 3-X-acac=γ-substituted acetylacetonate ion, tfac=trifluoroacetylacetonate ion, and bzac=benzoylacetonate ion. From the wavelength dependence of the steady state resolution yield, the method of photoresolution has been confirmed to allow the determination of the ORD and CD spectra of optically pure enantiomers. The ORD and CD spectra of the above-mentioned compounds are given.
  • Fujio Mizukami
    1975 Volume 48 Issue 4 Pages 1205-1212
    Published: 1975
    Released: March 27, 2006
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    The tetramine ligands, 4,6-dimethyl-3,7-diaza-1,9-nonanediamine (2,3″, 2-tet), 6,8-dimethyl-2,5,9,12-tetraazatridecane (N,N′-Me2-2,3″, 2-tet), and 4,9-dimethyl-5,8-diaza-2,11-dodecanediamine (3″,2,3″-tet), were prepared by using RR- and RS-2,4-pentanediamine as the starting material. Six kinds of trans-dichloro cobalt(III) complexes with these ligands were prepared and characterized. Among these complexes, three kinds of optically active complexes were obtained. The RR-2,4-pentanediamine and RS-2,4-pentanediamine parts in these complexes were considered to take a λ-skew-boat and a chair conformation respectively on the basis of molecular models, PMR, and the absorption and CD spectra.
  • Shiro Gohda
    1975 Volume 48 Issue 4 Pages 1213-1216
    Published: 1975
    Released: March 27, 2006
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    A simple and convenient chemical procedure for the determination of As(III), As(V), Sb(III) and Sb(V) by thermal neutron activation analysis is proposed and applied to the study of the valence state of As and Sb in sea water. Immediately after sampling, As(III) and Sb(III) were separated from As(V) and Sb(V) by extracting their diethyldithiocarbamates with chloroform, and then back-extracted into diluted nitric acid. As(V) and Sb(V) in the aqueous phase were collected by thionalide cocrystallization. They were then irradiated for 30 min at a neutron flux of 2×1013 n/(cm2·s), and treated in the same manner as described in the previous report. The As and Sb were determined by gamma-ray spectrometry. Sea water has been found to contain 1.56–2.45 μg As/l and 0.37–0.60 μg Sb/l. 80–97% of arsenic and 70–94% of antimony existed as the pentavelent species, only 5–20% as the trivalent species, and the remainder was probably included in suspended matter.
  • Masaaki Iwatsuki, Norio Tsukada, Tsutomu Fukasawa
    1975 Volume 48 Issue 4 Pages 1217-1221
    Published: 1975
    Released: March 27, 2006
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    An X-ray diffraction method has been developed for the determination of the composition of a magnesium-containing β-eucryptite solid solution which consists of a pseudo-ternary system, SiO2–Mg1⁄2AlO2–LiAlO2. Standard samples of the solid solution within the range of 60–75 mol% SiO2 and 0–15 mol% Mg1⁄2AlO2 were prepared from high-purity materials by the “glass-crystallization” technique. The diffraction angles of the (206) and (212) planes were measured from the center of gravity of the profile recorded on a chart by a counter diffractometer. After having been corrected for various systematic errors, both angles were used for the calculation of the lattice constants. It was found that Mg1⁄2AlO2 and LiAlO2 contributed similarly to a0, but in a different way to c0. The composition of the solid solution in a commercial glass-ceramic could be determined from the correlation between the composition and the lattice constants. The standard deviation of the determination from one measurement was about 0.2–0.4 mol%, and the time required for analysis was about 30 min.
  • Hiroshi Kobayashi, Mitaka Kobayashi, Youkoh Kaizu
    1975 Volume 48 Issue 4 Pages 1222-1227
    Published: 1975
    Released: March 27, 2006
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    Arenetricarbonylchromium forms a charge-transfer complex with 1,3,5-trinitrobenzene (1,3,5-TNB), while arenetricarbonylmolybdenum and -wolfram do not form a charge-transfer complex with 1,3,5-TNB. On the other hand, arenetricarbonylchromium, -molybdenum and -wolfram form a charge-transfer complex with tetracyanoethylene (TCNE). Since the intramolecular charge transfer from coordinated arene to carbonyls increases in the molybdenum and wolfram derivatives, 1,3,5-trinitrobenzene cannot form a molecular complex accepting an electronic charge of the coordinated arene. In the case of TCNE, however, a molecular complex is formed by an inner-sphere charge-transfer interaction between the acceptor and the central metal atom. Thus the stability of the TCNE molecular complexes is dependent upon the charge density of the central metal atom and also the steric effects due to the functional groups in coordinated arenes. The ionization potentials of the molybdenum and wolfram derivatives observed for their TCNE molecular complexes are almost equal but higher than those of the corresponding chromium derivatives, whereas the highest stability is obtained for the molybdenum derivatives.
  • Tomoaki Inoue, Junnosuke Fujita, Kazuo Saito
    1975 Volume 48 Issue 4 Pages 1228-1232
    Published: 1975
    Released: March 27, 2006
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    Silicon(IV) complexes of 4 kinds of β-diketonate have been resolved and their racemization has been kinetically studied in 1,1,2,2-tetrachloroethane (TCE) and acetonitrile (AN) at 30 to 80 °C. Ultra-violet absorption spectroscopy and isotopic exchange studies with labelled ligands verified intra-molecular mechanism. A similar rate formula to that for the tris(acetylacetonato)silicon(IV) was obtained: k0=k1+k2[acid or base]. Increase in basicity of the ligand decreases the rate. Introduction of methyl group on the central carbon of the six-membered chelate ring markedly enhanced the racemization. It seems as if the intermediate species with a unidentate ligand tends to take trans form around the C=C axis and retards the recombination, giving rise to bigger k values. Mechanism of acid and base catalysis was also discussed.
  • Yoshiro Terai, Hiroaki Kido, Junnosuke Fujita, Kazuo Saito
    1975 Volume 48 Issue 4 Pages 1233-1236
    Published: 1975
    Released: March 27, 2006
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    Replacement of the coordinated trans-2-butene in trans(N,olefin)[PtCl(L-pro)(S,S-trans-2-butene)] (L-pro=L-prolinate anion) by various olefins in acetone has been studied at −20 to +23 °C. The rate is proportional to concentrations of the complex and the olefin nucleophile. No solvent path is observed. The second order rate constant k2 (10−4 to 10−1 M−1 s−1 at 8.0 °C) can be the measure of each substitution. The ΔH\ eweq is around 10 kcal/mol, and ΔS\ eweq ranges from −25 to −46 cal/mol K. Substitution of cis-2-butene for the asymmetrically coordinated trans-2-butene-3H gives equal k2’s on the measurement of CD strength and on that of isotopic exchange. Similar substitution of trans-2-butene gives significantly larger k2 on isotopic exchange than that on CD measurement, indicating sterically selective substitution with retention of configuration. Substitution of ethylene derivatives with various groups on the carbon atoms gives different k2’s depending on the kind of substituents. The steric interaction between the olefin nucleophile and the coordinated ligands seems to be a very important factor in determining the ease of substitution.
  • Kuniaki Seo, Saburo Inokawa
    1975 Volume 48 Issue 4 Pages 1237-1239
    Published: 1975
    Released: March 27, 2006
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    The reactions of diethyl ethylphosphonite with 3-O-acetyl-5-deoxy-5-iodo-1,2-O-isorpopylidine-α-D-xylofuranose (Ia) or 3-O-benzoyl-5-deoxy-5-iodo-1,2-O-isopropylidene-α-D-xylofuranose(Ib) afforded IIa or IIc, respectively. Similarly, using diethyl butylphosphonite in place of diethyl ethylphosphonite, IIb and IId were obtained. Treatment of IIb with methanolic sodium methoxide gave 5-deoxy-1,2-O-isopropylidene-5-(methoxybutylphosphinyl)-α-D-xylofuranose together with a small amount of 5-(3-O-cyclo-butylphosphinate)-5-deoxy-1,2-O-isopropylidene-α-D-xylofuranose(VII). Compound VII was also obtained from the reaction of 5-deoxy-5-iodo-1,2-O-isopropylidene-α-D-xylofuranose(VIII) and diethyl butylphosphonite. The reaction of IIa or IIc with sodium dihydrobis(2-methoxyethoxy)aluminate gave 5-deoxy-5-(ethylphosphinyl)-1,2-O-isopropylidene-α-D-xylofuranose(IIIa). Similarly, 5-(butylphosphinyl)-5-deoxy-1,2-O-isopropylidene-α-D-xylofuranose(IIIb) was obtained from IIb, IId, VI, and VII. Hydrolysis of IIIa and IIIb with sulfuric acid gave 5-deoxy-5-(ethyl-phosphinyl)-(IVa) and 5-(butylphosphinyl)-5-deoxy-D-xylopyranose(IVb), respectively. Acetylation of IVa and IVb with acetic anhydride in pyridine gave the corresponding O-acetates Va and Vb.
  • Takayoshi Iio, Sho Takahashi
    1975 Volume 48 Issue 4 Pages 1240-1244
    Published: 1975
    Released: March 27, 2006
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    With the aid of optical rotatory dispersion, circular dichroism, and infrared spectra, the conformations of the sequential polypeptides of L-leucine and glycine, (Leu3Gly)n, (Leu2Gly)n, (LeuGly)n, and (LeuGly2)n, were studied and compared with the conformation of poly-L-leucine. It was shown that the polymers (Leu)n, (Leu3Gly)n, (Leu2Gly)n, and (LeuGly)n could be α-helical in solution, but (LeuGly2)n was not. The order of the stability of the α-helix of these polymers was found to be: (Leu)n>(Leu3Gly)n∼(Leu2Gly)n>(LeuGly)n>(LeuGly2)n. This was attributed to interactions between side chains of L-leucines which were regularly arranged on the α-helix.
  • Sei-ichiro Imamura, Takafumi Otani, Hiroshi Teranishi
    1975 Volume 48 Issue 4 Pages 1245-1248
    Published: 1975
    Released: March 27, 2006
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    Cyclohexene was oxidized in glacial acetic acid with a Cu(II)–Cl catalyst. In addition to the main oxidation products, 3-cyclohexenyl chloride, 3-cyclohexenyl acetate, 2-chlorocyclohexanol-(1), cyclohexene oxide, and hydrogen chloride were produced. The mechanism of the formation of these compounds was investigated in detail: the deactivation of the catalyst was explained by chloride ion transfer.
  • Takaaki Horaguchi, Takahachi Shimizu, Tsuneo Suzuki
    1975 Volume 48 Issue 4 Pages 1249-1253
    Published: 1975
    Released: March 27, 2006
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    Two kinds of methods of synthesizing naphtho[1,8-bc]furans (Vla–VId) are described. In the first method, naphtho[1,8-bc]furans (Vla–VId) were obtained by the decarboxylation of IIa–IId, which had previously been prepared from Ia-Id and ethyl bromoacetate. The yields of IIa–IId from Ia–Id were 45, 43, 49, and 46% respectively. In the second method, VIa–VId were obtained by heating Va–Vd with acetic anhydride and sodium acetate. The yields of VIa–VId were 34, 46, 46, and 70% respectively.
  • Shinpei Aburaki, Norio Konishi, Mitsuhiro Kinoshita
    1975 Volume 48 Issue 4 Pages 1254-1259
    Published: 1975
    Released: March 27, 2006
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    Natural (+)blastmycinone [(+)1a] and its three (2R)-diastereomers [(+)1b, (−)1c, and (−)1d] were synthesized through stereospecific routes via the corresponding (−)blastmycinolactol [(−)2a] and its diastereomeric hydroxylactones [(+)2b, (−)2c, and (−)2d] from methyl 4,6-O-benzylidene-3-C-butyl-3-deoxy-α-D-altropyranoside (4) prepared by the Grignard reaction of methyl 2,3-anhydro-4,6-O-benzylidene-α-D-mannopyranoside (3) with butylmagnesium chloride. By the synthesis the relative configurations of natural type of racemic blastmycinone and its all diastereomers were completely established.
  • Katsuyuki Aoki
    1975 Volume 48 Issue 4 Pages 1260-1271
    Published: 1975
    Released: March 27, 2006
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    The crystal structures of the 1:1 complexes of inosine 5′-phosphate with cobalt (C10H11O8N4PCo,7H2O) and inosine 5′-phosphate with nickel(C10H11O8N4PNi,7H2O) have been determined from single-crystal X-ray data collected on an automated diffractometer. The both isomorphous crystals belong to orthorhombic system, space group P212121 with four formula units in the unit cell of dimensions a=10.859, b=25.987, c=6.845 Å for the cobalt complex and a=10.812, b=25.898, c=6.845 Å for the nickel complex respectively. The structure of the cobalt complex was determined by three-dimensional Patterson and Fourier methods and that of the nickel complex was elucidated from that of the cobalt complex. Both were refined by the block-diagonal least-squares method including anisotropic temperature factors. The final R values were 0.051 and 0.075 for the cobalt and nickel complexes, respectively. All of the 25 hydrogen atoms in the case of the cobalt complex and 22 hydrogen atoms in the case of the nickel complex were found. The hypoxanthine bases related by the two-fold screw axis parallel to c are extensively overlapped at a distance of 3.42 Å for both complexes. The nucleotides have the preferred anti conformation about the glycoside linkage with the ribose ring showing the C(3′)-endo pucker. The torsion angles around the C(5′)–O(5′) bond are 161.6° (cobalt complex) and 162.0° (nickel complex). In the both complexes, therefore, the phosphate group has the extended conformation. The metals are not directly bonded to the phosphate oxygen atoms but are bonded to the nitrogen atom N(7) of the base and to five water oxygen atoms. There is extensive hydrogen bonding involving the hypoxanthine ring, the phosphate anion, the hydroxyl groups of the furanose ring and seven water molecules in the crystal.
  • Junzo Yamashita, Kiyoshi Sasaki, Takao Kawamura, Koichi Higuchi, Shota ...
    1975 Volume 48 Issue 4 Pages 1272-1275
    Published: 1975
    Released: March 27, 2006
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    The dimerization of propene by potassium catalyst was carried out at 180 °C in n-heptane to give 4-methyl-1-pentene as a major product. The effects of the addition of metal powders, potassium alkoxides and tertiary amines were investigated. The selective production of 4-methyl-1-pentene on adding metal powders increased in the order of Cu, Ag>Mg, Co>Al, Fe, Ni, Zn. When long-chain alkoxides were added to the potassium–copper catalyst system, potassium catalyst was observed to be dispersed, the relative reaction rates increased, and the isomerization of 4-methyl-1-pentene formed was retarded. Thus, the selectivity increased more than 90% after 40% conversion of propene. The potassium–copper–aliphatic tertiary amine-catalyst system caused the yield of 4-methyl-1-pentene to increase in a similar manner to the potassium–copper–alkoxide-catalyst system and inhibited the formation of the carbonaceous substance covering the surface of the catalyst, and the selectivity was not lowered after a higher conversion of propene.
  • Kyoko Nishizawa, J. Yasuo Satoh
    1975 Volume 48 Issue 4 Pages 1276-1279
    Published: 1975
    Released: March 27, 2006
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    The reaction of cyclohexanones with copper(II) chloride gave polychlorinated cyclohexanediones directly in fairly good yields. With methylcyclohexanones, in general the type of product depends on the number of methylene groups between the carbonyl group and the methyl-substituted carbon in the starting material. A possible mechanism for the reaction is discussed.
  • Minoru Imoto, Yoshiaki Nakamura, Tatsuro Ouchi
    1975 Volume 48 Issue 4 Pages 1280-1281
    Published: 1975
    Released: March 27, 2006
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    Dimethylmercury was found to give a methyl radical (·CH3) by the reaction with Cu(II)-ion in the presence of water. Generation of ·CH3 was proved by scavenging with 1,3,5,-triphenylverdazyl. Radical polymerization of methyl methacrylate and acrylonitrile was carried out with the system dimethylmercury/water/Cu(II)or Fe(III)-ion.
  • J. Yasuo Satoh, C. Akira Horiuchi, Akira Hagitani
    1975 Volume 48 Issue 4 Pages 1282-1284
    Published: 1975
    Released: March 27, 2006
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    The polyhalogenation of 5β-cholestan-2-one (I) in acetic acid containing hydrogen halide occurs in this positional order: C1→C3→C3 and finally at C1, which has the largest steric hindrance. The tetrahalogenation of the ketone (I) yields 1,1,3,3-tetrachloro-5β-cholestan-2-one (IXb), but fails to give the tetrabromo derivative; rather, it yields 1β,3,3-tribromo-5β-cholestan-2-one (Va), 1,1,3-tribromo-5β-cholest-3-en-2-one (VIIIa), and 1β,3-dibromo-5β-cholest-3-en-2-one (VIa). The conformations of the dihalo-, the trihalo-, and the tetrachloroketone derivatives are discussed in connection with the ORD, CD, IR, and NMR spectra.
  • Masao Tomoi, Toshio Yoneyama, Hiroshi Kakiuchi
    1975 Volume 48 Issue 4 Pages 1285-1290
    Published: 1975
    Released: March 27, 2006
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    The electronic spectra of 9-(ω-methoxyalkyl) and 9-(ω-dimethylaminoalkyl)fluorenyl salts of alkali cations were measured in ethereal solvents. The relative amounts of the contract ion pairs connected with the 9-substitu-ents (R) decreased in this order: R=(CH3)2N–(CH2)2–>CH3O–(CH2)2–>CH3O–(CH2)3–>(CH3)2N–(CH2)3–>>CH3O–(CH2)4−≈n-C4H9−. This behavior was explained in terms of the formation of an intramolecular association between the hetero atoms in the substituents and the counter ions; such an association favored the formation of the contact ion pair. The interaction of magnesium fluorenide and cyclopentadienide with hexamethylphosphoramide (HMPA) was studied by means of NMR spectroscopy in ether or tetrahydrofuran. The fluorenide changed from a covalent type to a solvent-separated ion pair by the coordination of three HMPA with the magnesium. The cyclopentadienide was proposed to change from a contact ion pair to a solvent-separated ion pair by means of two-step process in which the cyclopentadienyl ions became successively separated from the magnesium ion.
  • Mamoru Omori, Masayasu Kurono, Seishi Yajima
    1975 Volume 48 Issue 4 Pages 1291-1295
    Published: 1975
    Released: March 27, 2006
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    The polycondensation reaction of acetylferrocene and furfural was investigated in the presence of concentrated H2SO4 as a catalyst without solvent. Stoichiometric reaction took place with 2 mol of acetylferrocene and 5 mol of furfural. Polycondensation afforded satisfactory results when 1 mol of acetylferrocene was treated with 2–7 mol of furfural. The structural evidence for these products was derived from chemical and infrared analyses. Density, micro Vickers hardness, magnetic susceptibility, and thermal behavior of these products were measured in comparison with those of other resins.
  • Ryohei Yamagughi, Mituyosi Kawanisi
    1975 Volume 48 Issue 4 Pages 1296-1300
    Published: 1975
    Released: March 27, 2006
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    The photosensitized polar addition of acetic acid to 4-homoadamantene (I) gave 2,4-dehydrohomoadamantene (II), 2-adamantylmethyl acetate (IIIa), and 4-homoadamantyl acetate (IVa). The same treatment of I in pivalic acid gave analogous products, II, 2-adamantylmethyl pivalate (IIIb), and 4-homoadamantyl pivalate (IVb). It was shown that II and III were derived from the 4-homoadamantyl cation (V). On the other hand, the diazotization of 4-homoadamantylamine (XV) in the presence of acetic acid gave I, II, and IVa, whereas it has been reported that a buffered acetolysis of 4-homoadamantyl tosylate (XIV) gave I and IVa, but not II. The formation of II may be explained by assuming a different energy state of V of different origin; it proves a vibrationally excited nature of V generated in the photosensitized polar addition reaction.
  • Masahiro Minabe, Kazuo Suzuki
    1975 Volume 48 Issue 4 Pages 1301-1303
    Published: 1975
    Released: March 27, 2006
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    Rotational isomers of 9,9′: 9′,9″-terfluorenyl were obtained by the addition of 9-lithiofluorene to 9,9′-bifluorenylidene (III). 2,7-Dibromo- (VI) and 2,7,2″,7″-tetrabromo-9′,9″-terfluorenyl (VIII) resulted from similar reactions of the corresponding bromo-derivatives. 9-Lithio-9,9′-bifluorenyl was treated with 9-bromo-9,9′-bifluorenyl to give 9,9′-bis(9,9′-bifluorenyl) (X), 9,9′: 9′,9″-terfluorenyl isomers (mp 293 °C (dec) (I) and mp 257 °C (dec) (II)), 9,9′-bifluorenyl (IX), III, and fluorenone. The isomerization of I by metallic potassium gave the other rotamer II, which decomposed into its components, IX, III, and fluorene (IV).
  • Toyoki Kunitake, Seiji Horie
    1975 Volume 48 Issue 4 Pages 1304-1309
    Published: 1975
    Released: March 27, 2006
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    Imidazole-4-carbohydroxamic acids (I) and its N-methylhydroxamic acid derivative (II) were synthesized from imidazolecarboxylic acid and hydroxylamines, and the catalytic hydrolysis of p-nitrophenyl acetate was studied. The reaction was analyzed by the pseudo-first-order kinetics and the burst kinetics. The hydrolysis proceeds via the formation and the subsequent decomposition of the acetyl hydroxamate intermediate. The acylation rate with these catalysts were comparable to those observed with other simple hydroxamic acids. On the other hand, the deacylation of the acetyl intermediate of II was greater than expected and increased with pH. This suggests that the intramolecular imidazole group (neutral and/or anionic species) assists deacylation, thus increasing the overall efficiency of catalysis.
  • Janusz Dabrowski, Michal Tencer
    1975 Volume 48 Issue 4 Pages 1310-1314
    Published: 1975
    Released: March 27, 2006
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    Acylic aliphatic trans β-alkoxy-α,β-unsaturated ketones, R1COCR2=CHOR3, have been shown to exhibit restricted rotation around both the Csp2–Csp2 and Csp2–O single bonds. The conformational equilibria between the EZZ, EEZ, EZE and EEE rotamers, estimated from comparison of the IR band intensities, are dependent on the steric requirements of the alkyl substituents. The sequence of the νC=O and νC=C vibrational frequences is νC=O(s-cis/O-s-trans)>νC=O(s-cis/O-s-cis)>νC=O(s-trans/O-s-trans)>νC=O(s-trans/O-s-cis)>νc=C(s-trans/O-s-trans)>νC=O(s-trans/O-s-cis)>νC=C(s-cis/O-s-trans)>νC=C(s-cis/O-s-cis). The wave number differences ΔνC=CC=O(s-cis/O-s-trans)=75–85 cm−1, ΔνC=CC=O(s-cis/O-s-cis)=80—100 cm−1, ΔνC=CC=O(s-trans/O-s-trans)=20—30 cm−1 and ΔνC=CC=O(s-trans/O-s-cis)=35–50 cm−1.
  • Yoshihisa Suzuki, Kentaro Hara
    1975 Volume 48 Issue 4 Pages 1315-1316
    Published: 1975
    Released: March 27, 2006
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    Inosine was found to form 1 : 1 crystalline complexes with 2,4-, 2,5-, 2,6-, 3,4-, 3,5-dihydroxybenzoic acids, and with 3,4,5-trihydroxybenzoic acid, but was found to give no crystalline complex with benzoic acid, o-, m-, p-hydroxybenzoic acids, 2,3-dihydroxybenzoic acid, or 2,3,4-trihydroxybenzoic acid.
  • Hiroshi Sato, Taro Koshii, Hiroaki Takahashi, Keniti Higasi
    1975 Volume 48 Issue 4 Pages 1317-1318
    Published: 1975
    Released: March 27, 2006
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    The dielectric constants and losses of six isomeric pentyl alcohols have been measured in the frequency range of 1–0.35 GHz at 25 °C. The relaxation times of these alcohols decrease with an increase in the steric hindrance of the hydroxyl group.
  • Takaharu Matsubara, Toshio Tanaka
    1975 Volume 48 Issue 4 Pages 1319-1320
    Published: 1975
    Released: March 27, 2006
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    The melting point of N-methylacetamide–silver nitrate adduct AgNO3·2NMA was found to be 46–47 °C which is in large disagreement with that reported by Paul and Chadha. The discrepancy was interpreted to result from the tendency of the adduct to lose NMA at high temperatures or at low partial pressures of NMA.
  • Chung-gi Shin, Yasuchika Yonezawa, Yasuo Sekine, Juji Yoshimura
    1975 Volume 48 Issue 4 Pages 1321-1322
    Published: 1975
    Released: March 27, 2006
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    The reaction of ethyl α,β-unsaturated α-cyanocarboxylates with triethyl phosphonate gave ethyl α-cyano-β-diethoxyphosphinyl-carboxylates in about 50% yields.
  • Kenryo Namba, Shuichi Suzuki
    1975 Volume 48 Issue 4 Pages 1323-1324
    Published: 1975
    Released: March 27, 2006
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    The photochromism of 1-(β-carboxyethyl)-3,3-dimethyl-6′-nitrospiro[indoline-2,2′-2H-benzopyran] (I) was studied in water-dioxane. It was found that (I) exhibits normal photochromism in dioxane and reverse photochromism on addition of water to the solution.
  • Hiroyuki Yamaguchi, Takeshi Nakajima
    1975 Volume 48 Issue 4 Pages 1325-1326
    Published: 1975
    Released: March 27, 2006
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    The electronic structures and spectra of fundamental quinarene molecules, 19 (Fig. 1) and some of their diphenyl derivatives (Fig. 2) have been studied by using the variable bond-length SCF LCAO-π-MO CI method.
  • Masao Okubo
    1975 Volume 48 Issue 4 Pages 1327-1328
    Published: 1975
    Released: March 27, 2006
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    The reaction of 2,4,6-trimethylbenzophenone with phenyl-MgBr in tetrahydrofuran was examined by ESR technique. A high amount of the ketyl radical was detected. An electron-transfer mechanism was proposed to explain the formation of o-biphenylyl mesityl ketone.
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