Bulletin of the Chemical Society of Japan
Online ISSN : 1348-0634
Print ISSN : 0009-2673
ISSN-L : 0009-2673
Volume 58 , Issue 1
Showing 1-50 articles out of 83 articles from the selected issue
  • Mutsuyoshi Matsumoto, Minoru Suzuki, Hiroshi Takahashi, Yasukazu Saito
    1985 Volume 58 Issue 1 Pages 1-4
    Published: 1985
    Released: June 27, 2006
    JOURNALS FREE ACCESS
    From analyses of Langmuir-type isotherms and αs-plots for nitrogen adsorption, both the micropore volume and the external surface area have been determined for pillar interlayered montmorillonite (abbreviated as PILM) prepared by intercalating the polynuclear Al cation into the montmorillonite interlayer. The applicability of the Gurvitsch rule to microporous PILM samples was confirmed for adsorption of heptane, whereas the adsorbed amounts of polar adsorbates were dependent on dehydrated states of the alumina pillar. High density of benzene in the micropore independent of calcination temperature suggests some peculiar orientation of benzene in the adsorbed state due to its molecular shape. The interaction of a water molecule with the adsorption site is weak and dependent on the calcination temperature of PILM samples. On this basis, the inhibition of rehydration of the alumina pillar has been discussed.
  • Nobuhito Imanaka, Yasuo Yamaguchi, Gin-ya Adachi, Jiro Shiokawa
    1985 Volume 58 Issue 1 Pages 5-8
    Published: 1985
    Released: June 27, 2006
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    Sodium sulfate mixed with rare earth sulfates(Ln=Y and Gd) and silicon dioxide exhibits a Na2SO4-I-like phase as well as a small amount of silicon dioxide phase. The former phase is excellent in Na+ ion conduction. The electrical conductivity of the Na2SO4–Ln2(SO4)3–SiO2(Ln=Y and Gd) systems is considerably higher than that of pure sodium sulfate. When the Na2SO4–Ln2(SO4)3–SiO2(Ln=Y and Gd) sample is applied as a solid electrolyte for a SO2 gas concentration cell, the measured EMF is in good agreement with the calculated EMF for a SO2 gas concentration range from 0.1% (1000 ppm) to 23%, and 0.32% (3200 ppm) to 10%, respectively.
  • Masaharu Ohba, Kiyoshi Arakawa
    1985 Volume 58 Issue 1 Pages 9-15
    Published: 1985
    Released: June 27, 2006
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    The reference hypernetted chain like integral equation of the interaction site model is solved numerically for a solution of ions in a polar solvent. In our model, the ions and the solvent molecules are taken to be charged hard spheres and polar hard dumb-bells, respectively. Calculated pair correlation functions contain a great deal of interesting information on the short range structure of the ionic solutions: a solvated structure around ions and an effect of ionic charges upon the structure of the solvent. It is found that various types of associated structures of constituent species, such as simple ion pairs, ion triplets, and ion pairs separated by one solvent molecule exist in ionic solutions.
  • Taisei Nakayama, Hiroyoshi Kanai
    1985 Volume 58 Issue 1 Pages 16-22
    Published: 1985
    Released: June 27, 2006
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    Thiocyanatotris(triphenylphosphine)cobalt(I) prepared in situ from bis(thiocyanato)bis(triphenylphosphine)cobalt(II), triphenylphosphine, zinc bromide, selectively hydrogenated conjugated dienes to the corresponding cis-monomenes. The C2-or/and C3-methyl substituted 1,3-butadienes enhance the reactivity by a factor of 2.3 per one methyl group, while C1- or/and C4-methyl substituted 1,3-butadienes lower the reactivity by a factor of 1/23 per one methyl group. In the hydrogenation of cyclic conjugated dienes α-angle (∠C–C=C) is closely related to the hydrogenation rate. The rates of hydrogenation in cyclic ethers are greater than those in acyclic ethers, but the cis-selectivity in acyclic ethers is much higher. Deuterium selectively adds to 1,3-butadiene and 2,5-norbornadiene (bicyclo[2.2.1]hepta-2,5-diene) to give 3,4-dideuterio-1-butene and cis-1,4-dideuterio-2-butene, and endo,endo-5,6-dideuterionorbornene and endo,endo-3,5-dideuterionortricyclene, respectively. A mechanism is proposed which derives from anti-π-allylcobalt hydride or delocalized nortricyclenylcobalt hydride as an intermediate.
  • Takeshi Yamanobe, Isao Ando, Hazime Saito, Ryoko Tabeta, Akira Shoji, ...
    1985 Volume 58 Issue 1 Pages 23-29
    Published: 1985
    Released: June 27, 2006
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    A tight-binding MO-sum-over-state theory has been used to calculate the 13C NMR chemical shift of polyglycine having the forms I and II and that of poly(L-alanine) having the α-helix and β-sheet forms, in order to justify the origin of the conformation-dependent 13C NMR chemical shift previously determined by the cross polarization-magic angle spinning technique. The calculated results on the carbonyl, Cα and Cβ carbons were found to exhibit the conformation-dependent 13C NMR chemical shifts comparable with the experimental data.
  • Tooru Taga, Taneno Kaji, Kenji Osaki
    1985 Volume 58 Issue 1 Pages 30-35
    Published: 1985
    Released: June 27, 2006
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    The crystal structure of the calcium salt of D-glycero-D-gulo-heptonic acid has been determined by the X-ray method. The crystal is monoclinic of space group P21 with unit-cell dimensions of a=10.064(1), b=10.540(2), c=11.340(2) Å, and β=108.92(1)°. The intensity data for 1754 unique reflections were measured with an automatic diffractometer. A trial structure, obtained by the direct method, was refined by the full-matrix least-squares method to R=0.030. The two independent heptonate anions have different conformations, and they chelate a calcium ion in different ways. The calcium ion is surrounded by eight oxygen atoms in a deformed dodecahedral form, the Ca···O distances ranging from 2.40 Å to 2.48 Å. The distortion of the moleular strcuture of the heptonate anions due to the calcium chelation was discussed in relation to the calcium-binding sites on a linear carbohydrate chain.
  • Katsuko Takaizumi, Toshiki Wakabayashi
    1985 Volume 58 Issue 1 Pages 36-40
    Published: 1985
    Released: June 27, 2006
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    Volume changes upon mixing aqueous solutions of potassium chloride and the quaternary phosphonium chloride, n·Bu4−nPhnPCl, (n=0–4), have been measured at various constant total ionic strengths (I=0.25, 0.5, 1.0) at 25 °C. Based on Friedman’s theory for a mixed electrolyte solution, volume-interaction parameters, υo, were determined at each ionic strength. The dependence of υo on I shows that contributions to the excess volume due to structural effects of a pairwise interaction between the cations and triplet interactions including a single anion are most significant for the Bu4P+ ion and decrease with increasing n. A comparison of the υo’s with the excess-volume properties of the salts in each pure solution shows that the interaction between the phosphonium cations and the potassium ion results in negative contributions to the excess volume of mixing, which also decreases as n increases.
  • Shoji Taen, Yasuhiko Gondo
    1985 Volume 58 Issue 1 Pages 41-46
    Published: 1985
    Released: June 27, 2006
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    The decay of the temperature-independent delayed fluorescence observed in the mixed crystals of phenanthrene in the biphenyl host has been studied at 77 K. That triplet molecules are involved in the mechanism for the emission of temperature-independent delayed fluorescence has been shown by observing the intensities at the instances of the short-pulse excitations effected with different dark periods after the steady-state excitation. It has been found that both the excitation duration and the excitation light intensity affect the decay behavior of the temperature-independent delayed fluorescence. The decay after short-pulse excitation has been observed to be more rapid than the decay after prolonged excitation with the same intensity. When the excitation light intensity is increased with a fixed duration, the delayed fluorescence is observed to decay more rapidly. It is concluded that the decay behavior of the temperature-independent delayed fluorescence can be accounted for in terms of the direct-resonance-interaction mechanism.
  • Takayuki Ohmae
    1985 Volume 58 Issue 1 Pages 47-51
    Published: 1985
    Released: June 27, 2006
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    The propagator method is applied to the study of solvent effects on chemical reactivities of conjugated molecules. It is shoen that the number of π-electrons of a solute molecule (a conjugated molecule) controls the solvent effects on chemical reactivities. The obtained theory is applied to the study of solvent effects on selectivities of pericyclic reactions.
  • Shigenobu Hayashi, Kunio Suzuki, Shigemitsu Shin, Kikuko Hayamizu, Osa ...
    1985 Volume 58 Issue 1 Pages 52-57
    Published: 1985
    Released: June 27, 2006
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    High resolution 29Si nuclear magnetic resonance spectra have been measured using magic angle sample spinning technique for several gallosilicates and aluminosilicates with zeolitic structures. The number of gallium atoms coordinating to the SiO4 tetrahedron was determined by the technique in the same manner as established for aluminium in aluminosilicates. The resonance lines were observed to shift to lower field by the substitution of silicon atoms with gallium as well as aluminium. The magnitudes of lower-field shifts were larger for the substitution by gallium than aluminium. The chemical shift ranges of 29Si nuclei are discussed for gallosilicates with the values for aluminosilicates compared.
  • Hirofumi Kawazumi, Tsuneaki Uchida, Teiichiro Ogawa
    1985 Volume 58 Issue 1 Pages 58-61
    Published: 1985
    Released: June 27, 2006
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    Emission spectra of cyclohexane, methylcyclohexane, trans-decalin and tetramethylethylene were measured under the controlled electron-impact (5–100 eV) excitation. A broad band was observed in the ultraviolet region in addition to lines and bands from such fragments as H, CH, and C2. This broad band was assigned to the fluorescence emission from the excited parent molecule, since its peak and lineshape resemble the fluorescence measured for liquid and since the threshold energy agrees with the absorption onset. The emission cross sections for these emissions were determined at an electron energy of 50 eV.
  • Osamu Ohno, Youkoh Kaizu, Hiroshi Kobayashi
    1985 Volume 58 Issue 1 Pages 62-64
    Published: 1985
    Released: June 27, 2006
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    The delayed fluorescence was observed at room temperature with tetrakis(4-sulfophenyl)porphinatozinc (ZnTPPS4) dyed on poly(vinyl alcohol) (PVA) film. In the film, the T-T annihilation is prohibited since any two molecules in the excited triplet can not encounter during their lifetime. Three types of luminescence emission were observed; fluorescence (S1→S0), phosphorescence (T1→S0) and delayed fluorescence (T1\ ightsquigarrowS1→S0). The delayed fluorescence can be detected only at elevated temperatures where thermal activation from the lowest excited triplet can repopulate the lowest excited singlet.
  • Shigeo Kondo, Yoshinori Koga, Taisuke Nakanaga
    1985 Volume 58 Issue 1 Pages 65-72
    Published: 1985
    Released: June 27, 2006
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    A recently obtained anharmonic ab initio force field of methyl chloride has been improved by the method of “predicate observations” using the observed values of the spectroscopic constants. The newly obtained force field was used to make re-analysis of the absorption intensities of the binary overtone and combination bands for CH3Cl and CD3Cl. Contribution from the electrical anharmonicity to the band intensities was estimated and compared with the ab initio result.
  • Akira Kuboyama, Sanae Y. Matsuzaki
    1985 Volume 58 Issue 1 Pages 73-77
    Published: 1985
    Released: June 27, 2006
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    The nπ* phosphorescence spectra, and their excitation spectra and lifetimes of 9,10-anthraquinone-2-sulfonate, and -2,6- and -2,7-disulfonates in water–ethylene glycol 1:1 mixture at 77 K have been obtained. These phosphorescence spectra shift to the red with increases in the concentration of the solutions, and show an excitation-wavelength dependence. From the results obtained it is concluded that in the glassy solutions at 77 K an association of these quinones occurs, and that the phosphorescence state of the associates corresponds to the nπ* triplet excimer state, similar to that of the p-quinone aggregates in polycrystalline solutions at 77 K, previously studied.
  • Hideo Matsumura, Hiroyuki Kakoki, Kunio Furusawa
    1985 Volume 58 Issue 1 Pages 78-81
    Published: 1985
    Released: June 27, 2006
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    Hydrophobic adsorption of tetraphenylborate ions (TPB) onto lipid membranes were studied at different pH’s of aqueous phase by using lipid vesicles and monolayers. The amount of adsorbed TPB is much higher at pH 2 than at pH 7.4. This result indicates that the adsorption of hydrophobic ions is affected by the ionization state of surface polar groups of lipids, i.e., that the membrane surface potential plays a role in the adsorption of hydrophobic ions.
  • Shinji Tokitaka, Hayao Imamura, Susumu Tsuchiya
    1985 Volume 58 Issue 1 Pages 82-87
    Published: 1985
    Released: June 27, 2006
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    The temperature-programmed desorption (TPD) chromatograms of cis- and trans-2-butene from platinum black comprised three peaks (A, B, and C) with peak maxima at about 253, 373, and 573 K, respectively. Peak A was identified to be cis- or trans-2-butene and butane. Peaks B and C were from mixtures of cis- or trans-2-butene and butane with a trace amount of propylene. The propylene may have been formed from chemisorbed cis- or trans-2-butene by decomposition as the temperature was raised during the subsequent TPD. The reactivities of various types of chemisorbed hydrogen previously detected by TPD were also investigated with regard to the hydrogenation of 2-butenes. Two types of chemisorbed hydrogen, presumed to be present on the surface in the form of hydrogen atoms, chemisorbed on top of platinum atoms and in the bridge form of molecular hydrogen, were found to react with 2-butenes.
  • Akira Fujimoto, Junko Nakamura, Iwao Yamazaki, Toshiro Murao, Kozo Inu ...
    1985 Volume 58 Issue 1 Pages 88-91
    Published: 1985
    Released: June 27, 2006
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    The fluorescence rise and decay times and UV absorption spectra of 1-methyl-4-amino-5H-[1]benzopyrano-[3,4-c]pyridin-5-one (1-MBPP), 2-methyl-4-amino-5H-[1]benzopyrano[3,4-c]pyridin-5-one (2-MBPP), and the 1-MBPP/acetic acid and 2-MBPP/acetic acid systems have been measured in hydrocarbon and hydroxylic solvents at room temperature and 77 K. From these data, a rapid formation of proton-transferred species (tautomers) was found to occur in an excited state for 1-MBPP (or 2-MBPP) hydrogen-bonded dimers in hydrocarbon at 77 K, and for 1-MBPP (or 2-MBPP) hydrogen-bonded complexes with acetic acid in hydrocarbon at room temperature and 77 K. The rise times of the tautomer fluorescence for the dimers and complexes were less than 65 ps. The observed fluorescence lifetimes of the 1-MBPP and 2-MBPP monomers agreed well with the lifetimes calculated using the integrated absorption intensity and fluorescence quantum yield.
  • Kan Kanamori, Yoko Nunomura, Masumi Takashima, Kiyonori Nagata, Kiyoya ...
    1985 Volume 58 Issue 1 Pages 92-96
    Published: 1985
    Released: June 27, 2006
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    All-trans- and trans(CN),cis(N)-[Co(CN)2(L-ala)2] and trans(CN)-[Co(CN)2(tmdda)] were newly prepared; here, tmdda denotes trimethylenediamine-N,N′-diacetate. These complexes were characterized from their electronic absorption, NMR, and Raman spectra. The CD spectra of two trans(CN) isomers of the bis(L-alaninato) complex are also presented.
  • Masamichi Tsuji, Mitsuo Abe, Minoru Orimo
    1985 Volume 58 Issue 1 Pages 97-102
    Published: 1985
    Released: June 27, 2006
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    Ion-exchange behavior of alkali hydroxide and alkylamines having different sizes and forms on hydrous titanium dioxide ion exchanger (HTDO) were studied. The uptakes of all the cations by HTDO indicated the ion-exchange stoichiometry at a pH range studied. The pH titration curves vary, depending on the cation species and the strength of the bases used: amorphous HTDO(Am-HTDO) behaves as a bifunctional acid towards strong bases and as a monofunctional acid towards weak bases. Am-HTDO shows an affinity series in the increasing order: large ions((C2H5)3NH+, (CH3)4N+, and (n-C4H9)4N+)<ions in medium size (CH3NH+, n-C3H7NH3+, n-C4H9NH3+ etc.)<small ions(Na+, K+, and NH4+). The large ions suffer from a strong steric effect, because of the limited space of the ion-exchange site available. The results correlate with the pore size distribution: the pore radius ranged from 4 to 7 Å in Am-HTDO degassed at 40 °C by a rotary pump. The maximum volume occupied by the alkylammonium ions exchanged (0.2–0.3 cm3/g), calculated by assuming cations to be unhydrated, is in good agreement with the value determined by N2 gas adsorption (0.16 cm3/g). An anatase-type HTDO showed a larger steric effect for uptake of the alkylammonium ions than that by the Am-HTDO, due to a decrease in the ion-exchange cavity.
  • Youkoh Kaizu, Naoaki Misu, Katsuhisa Tsuji, Yoshiaki Kaneko, Hiroshi K ...
    1985 Volume 58 Issue 1 Pages 103-108
    Published: 1985
    Released: June 27, 2006
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    Absorption, magnetic circular dichroism (MCD) and emission spectra as well as preparations of the aluminum(III) complexes of 5,10,15,20-tetraphenylporphin (TPP) and 2,3,7,8,12,13,17,18-octaethylporphin (OEP) are presented. On the basis of the spectral observations, the molecular parameters to describe the lowest (π,π*) excited states of a typical metal porphyrin with only minor perturbation by the incorporated tervalent metal ion were determined. The orbital angular momenta in the excited states were evaluated from the MCD spectra as follows: TPPAlCl, Λz=3.0 h in Q00 band, Λz=±0.61 h Ti in B band and OEPAlCl, Λz=±0.61 h Ti in Q00 band, Λz=0.557 h in band. A Davydov splitting of the Soret band observed for the μ-oxo dimer was interpreted in terms of the exciton coupling between two parallel porphyrin chromophores.
  • Tadashi Hara, Motohiro Toriyama, Takashi Ebuchi
    1985 Volume 58 Issue 1 Pages 109-114
    Published: 1985
    Released: June 27, 2006
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    A highly sensitive detector for the HPLC of protein has been manufactured by making use of the phenomenon that the catalytic activity of copper(II) against the chemiluminescence between luminol and hydrogen peroxide is lowered in the presence of protein. According to the present detector, 2×10−4–1×10−1 g/dm3 protein could be determined, with the detection limit of 10 ng. By combining the present detector with a TSK-GEL G3000SW column, 2×10−3–1×10−1 g/dm3 ovalbumin could be determined, with the detection limit of 50 ng. The ovalbumin in 2×10−2 g/dm3 could be determined by the internal-standard method with a coefficient of variation of 8.65% (n=5). Care had to be taken in the detection of the protein acting as a chemiluminescent catalyst.
  • Fukiko Yamada, Tomihiro Nishiyama, Yasuki Suzuura, Tatsuo Yamamura
    1985 Volume 58 Issue 1 Pages 115-119
    Published: 1985
    Released: June 27, 2006
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    A series of 4-benzylphenols, 2-methyl-4-benzylphenols, 4-methyl-2-benzylphenols and 4-methoxy-2-benzylphenols have been prepared and evaluated as antioxidants for tetralin at 60 °C by means of an oxygen-absorption method. Very good activities have been observed with a series of 4-methoxy-2-benzylphenols. The electrochemical oxidation potentials of these compounds were determined using linear-sweep voltammetry. The antioxidative activities were found to correlate with both the 13C NMR chemical shifts (δ) of the ipso-carbon of the OH substituent and their peak potentials (Ep).
  • Shinkiti Koto, Naohiko Morishima, Hiroko Sato, Yuko Sato, Shonosuke Ze ...
    1985 Volume 58 Issue 1 Pages 120-122
    Published: 1985
    Released: June 27, 2006
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    A step-by-step synthesis of O-β-D-glucopyranosyl-(1→2)-O-β-D-glucopyranosyl-(1→6)-D-glucopyranose through the dehydrative β-D-glucosylation using 2-O-acetyl-3,4,6-tri-O-benzyl-D-glucopyranose and the ternary system of p-nitrobenzenesulfonyl chloride, silver trifluoromethanesulfonate, and triethylamine is described.
  • Hiroshi Akimoto, Akiyoshi Kawai, Hiroaki Nomura
    1985 Volume 58 Issue 1 Pages 123-130
    Published: 1985
    Released: June 27, 2006
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    The carcinogenic γ-carbolines 3-amino-1,4-dimethyl-5H-pyrido[4,3-b]indole (1) and 3-amino-1-methyl-5H-pyrido[4,3-b]indole (2) were synthesized efficiently by the following procedures. The key method involved the acid-catalyzed cyclization of 2-acetamido-3-(2-indolyl)alkanoic acids to 1,2-dihydro-γ-carbolines. This was followed by dehydrogenation to the γ-carbolinecarboxylates and conversion of the ester group to the carboxyl and finally to the amino one by Curtius rearrangement. Alternative methods involved the thermolysis of 4-(1-benzotriazolyl)-3,6-dimethyl-2-pyridinamine to synthesize 1 and the condensation of 3-acetylindole-2- acetonitrile with ammonia to synthesize 2. The structures of γ-carbolines 1 and 2 were unambiguously established by comparing samples of each synthesized by the two different routes. A selective and one-step synthesis of ethyl 2-acetamido-3-(2-indolyl)alkanoates was newly exploited starting from diethyl acetamidomalonate and quaternary ammonium salts of 2-[1-(dimethylamino)alkyl]indoles.
  • Osamu Kikuchi, Hideki Yoshida
    1985 Volume 58 Issue 1 Pages 131-135
    Published: 1985
    Released: June 27, 2006
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    A model in which two zwitteriorts play a significant role was employed to account for solvent and substituent effects on photochemical reactions of β-t-butylstyrene. These zwitterions are formed by 90° rotation about the external C=C double bond. Semi-empirical MINDO/3 calculations showed that these zwitterions can be two channels which give the observed reacation products. The model also elucidated satisfactorily the photochemical reactions of para substituted β-t-butylstyrenes.
  • Masao Tsukayama, Kunihiro Fujimoto, Tokunaru Horie, Mitsuo Masumura, M ...
    1985 Volume 58 Issue 1 Pages 136-141
    Published: 1985
    Released: June 27, 2006
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    2′,4′,5,7-Tetrahydroxyisoflavone was partially benzoylated with benzoyl chloride to give 7-benzoyloxy-2′, 4′,5-trihydroxyisoflavone. The condensation of the 7-(benzoyloxy)isoflavone with 2-methyl-3-buten-2-ol, followed by the hydrolysis of the resultant 3′-(3-methyl-2-butenyl)isoflavone gave licoisoflavone A. Its 5′-(3-methyl-2-butenyl) isomer was also synthesized from 5-benzoyloxy-2′,4′,7-trihydroxyisoflavone in a similar manner.
  • Takehiko Tsuruta, Tetsuya Harada, Hiroshi Nishino, Kazu Kurosawa
    1985 Volume 58 Issue 1 Pages 142-145
    Published: 1985
    Released: June 27, 2006
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    The reaction of 2-(4-methoxyphenyl)-4-chromanone with Mn(OAc)3 in the presence of LiCl gave 3,3-dichloro-2-(4-methoxyphenyl)-4-chromanone. The reactions of 2-phenyl-4-chromanone, 1-phenyl-1-propanone, 1,2-diphenylethanone, and 1-tetralone similarly yielded α,α-dichloro derivatives in good yields. 2,2,2-Trichloroacetophenones were obtained from 2,2-dichloroacetophenones, but in the absence of LiCl, 2,2-dichloroacetophenones gave 2,2,3,3-tetrachloro-1,4-butanediones. KCl, NaCl, NH4Cl, AlCl3, and CaCl2 were also employed as the Cl ion source. Synthetic applicability and the reaction mechanisms are discussed briefly.
  • Chiaki Kuroda, Takayoshi Nakamura, Hiroshi Hirota, Katsumi Enomoto, Ta ...
    1985 Volume 58 Issue 1 Pages 146-151
    Published: 1985
    Released: June 27, 2006
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    (3R,6S,7S,1(10)E,4Z)- and (3R,6S,7S,1(10)E,4Z)-3-Methoxymethoxy-13-nor-1(10),4-germacradieno-12,6-lactones were synthesized from (−)-carvone, utilizing anionic oxy-Cope rearrangement to construct a ten-membered ring compound.
  • Tomoshige Kobayashi, Makoto Nitta
    1985 Volume 58 Issue 1 Pages 152-157
    Published: 1985
    Released: June 27, 2006
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    In the presence of hexacarbonylmolybdenum, substituted isoxazoles undergo a cycloaddition reaction with dimethyl acetylenedicarboxylate across the C-4–C-5 bond to give 3,4-bis(methoxycarbonyl)pyridine derivatives. In a similar cycloadition of isoxazoles with methyl propiolate, 4-(methoxycarbonyl)pyridine derivatives were also obtained. The β-carbon atom of methyl propiolate could intervene in the bonding with the C-5 position of the isoxazoles regioselectively. A mechanism involving a complexed 2-oxa-3-azabicyclo[3.2.0]hepta-3,6-diene derivative and the subsequent N–O and C-1–C-5 bond cleavage leading to a complexed (β-keto vinyl)nitrene intermediate is proposed for the formation of pyridine derivatives. In order to clarify the mechanistic aspect, the reaction of 4-phenyl-2-oxa-3-azabicyclo[3.2.0]hepta-3,6-diene and its related compounds were also studied to give pyridine derivatives.
  • Naoki Inamoto, Shozo Masuda, Jun Niwa
    1985 Volume 58 Issue 1 Pages 158-164
    Published: 1985
    Released: June 27, 2006
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    The electronic substituent effect in the aliphatic systems was investigated using ab initio calculation at STO-3G and 4-31G levels. The relative energy changes, δΔE, in isodesmic reaction of the 4-substituted bicyclo[2.2.2]octane-1-carboxylic acids were compared with those for 1-substituted bicyclo[2.2.2]octanes(XC8H13), CH3X, and H–X molecules perturbed with isolated pure point charges. The interaction energies between isolated dipole and point charge system, F–H···(±), were proportional to the reciprocal square of the distance between the center of dipole and the charge. Isodesmic reaction energies for the present systems at the distance longer than 5 Å can be practically explained by charge-dipole interaction. From the comparison of δΔE in XCH3···(±), XC8H13···(±), and XC6H5···(±) systems with those for X–H···(±), it was concluded that the pure field parameters for various substituents should be determined on the basis of the isodesmic reaction energy for X–H···(±) system. Correlations between δΔE in X–H···(±) system and the field parameters recently proposed, σF and σI(gas), were generally better in the cases calculated at 4-31G level than those at STO-3G level.
  • Kimio Shindo, Sumio Ishikawa, Tetsuo Nozoe
    1985 Volume 58 Issue 1 Pages 165-171
    Published: 1985
    Released: June 27, 2006
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    2-Chlorotropone reacted with o-aminobenzenethiol to give 2-(o-aminophenylthio)tropone, which readily cyclized in dilute methanolic HCl to afford the title benzothiazine (9). Although 9 was stable under basic conditions, its N-methyl cation reversibly afforded the ring-opened 2-[o-(methylamino)phenylthio]tropone in alkali. Oxidation of 9 with hydrogen peroxide in methanol underwent a rearrangement reaction to afford (exclusively) phenothiazine and its 1-formyl derivative. A similar H2O2 oxidation of 10-methoxycyclohepta[b][1,4]benzothiazine gave mainly methyl phenothiazine-1-carboxylate and 3-formyl-1-methoxy phenothiazine. Further oxidation of these products with hydrogen peroxide yielded thier S-oxides and S,S-dioxides. The reactivities of these cycloheptabenzothiazines are discussed in connection with those of the O- and N-analogues.
  • Yukito Murakami, Akio Nakano, Hidetsugu Ikeda, Toru Imori, Kazunari Ak ...
    1985 Volume 58 Issue 1 Pages 172-180
    Published: 1985
    Released: June 27, 2006
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    Four amphiphiles having dipeptide segments, which consist of one histidyl residue and another amino acid residue, and the dihexadecyl moiety for the double-chain segment (N+C5AlaHis2C16, N+C5LeuHis2C16, N+C5PheHis2C16, and N+C5HisAla2C16) were synthesized, and the aggregate morphology of them was characterized by electron microscopy and differential scanning calorimetry. The amphiphiles, which have the histidyl residue bound to the dihexadecylamine component (N+C5AlaHis2C16, N+C5LeuHis2C16, N+C5PheHis2C16) formed both multi- and single-walled aggregates in the aqueous dispersion state, while their sonicated solutions involved only single-walled vesicles. On the other hand, the amphiphile, which has the alanyl residue bound to the dihexadecylamine component (N+C5HisAla2C16) afforded tubular aggregates in the aqueous dispersion. The hydrolysis of enantiomeric esters of various hydrophobic nature, which was carried out in the single-walled vesicles, showed relatively small enantioselectivity. The reasons for such catalytic performance of the vesicles were discussed from the kinetic and mechanistic viewpoints; the kinetic analysis being carried out on the basis of the organic pseudo-phase concept.
  • Kimiaki Imafuku, Toshio Kobayashi, Hisashi Matsumura
    1985 Volume 58 Issue 1 Pages 181-184
    Published: 1985
    Released: June 27, 2006
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    The methylation of 4-styryltropolones with diazomethane afforded 2-methoxy-4-styryltropones (2a–g) and 2-methoxy-6-styryltropones. The reactions of 2a–g with hydrazine gave 2-hydrazino derivatives, which were converted to 2-chloro derivatives 5a–g. Ammonolysis of 5a–g afforded 2-amino-5-styryltropones (7a–g) by ciné substitution reaction. The compounds 7a–g were hydrolyzed to give the corresponding 5-styryltro-polones. Some interesting by-products were also found in these synthetic processes.
  • Masaki Takai, Motoo Tori, Takahiko Tsuyuki, Takeyoshi Takahashi, Akiko ...
    1985 Volume 58 Issue 1 Pages 185-193
    Published: 1985
    Released: June 27, 2006
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    Epoxidation of alnus-5(10)-en-3β-yl acetate with m-chloroperbenzoic acid gave a 5α,10α-epoxide, treatment of which with boron trifluoride etherate afforded multiflora-5,8-dien-3β-yl acetate. On hydrogenation and hydrolysis, the diene gave isomultiflorenol.
  • Takahiro Hosokawa, Toshiyuki Ohta, Yoshihiro Okamoto, Shun-Ichi Muraha ...
    1985 Volume 58 Issue 1 Pages 194-200
    Published: 1985
    Released: June 27, 2006
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    Ketoximes, when treated with KO2 (1 equiv) in the presence of di-μ-chlorobis(2-methylallyl)dipalladium(II) (0.1 equiv per Pd) in dichloromethane, give methylene dioximes in moderate yields. This alkylation of ketoximes with CH2Cl2 is also promoted by the use of potassium carbonate in the presence of phase-transfer catalysts such as 18-crown-6. Study on the reactivity of a series of ketoximes in these reactions shows that proton abstraction by base is a crucial step in the latter reaction. By contrast, in the former system the reactivity is supposed to be controlled by nucleophilicity of the oximate anion coordinated to palladium(II). Application of the present reaction to (E,E)-1,2-diketone dioxime such as dimethylglyoxime leads to the formation of novel 21-membered ring heteromacrocyclic compounds in which oxime units are sequentially linked by methylene bridge.
  • Akiko Yoshiyama, Tsutomu Nonaka, Manuel M. Baizer, Tse-Chuan Chou
    1985 Volume 58 Issue 1 Pages 201-206
    Published: 1985
    Released: June 27, 2006
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    As electrochemical method was developed for converting 2,3-butanediol in dilute aqueous solutions to acetaldehyde by “in-cell” indirect anodic oxidation using a periodate/iodate redox mediatory system. Under optimum conditions, current efficiency for the desired acetaldehyde was close to 80% and the formation of by-products such as acetic acid, acetoin, and biacetyl was minimized or suppressed.
  • Seiji Hidaka, Eizo Matsumoto, Fujio Toda
    1985 Volume 58 Issue 1 Pages 207-210
    Published: 1985
    Released: June 27, 2006
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    Photoindeced electron transport across bilayer lipid membrane was studied, using chlorophyllin (Chln), a water-soluble derivative of chlorophyll. Photoreduction of methylviologen (MV2+) by ascorbate was observed only in the liposome system containing ascorbate in the internal aqueous phase and MV2+ in the external aqueous phase. This suggests asymmetry of bilayer lipid membrane. This reaction rate was not affected by the addition of carbonyl cyanide m-chlorophenylhydrazone in the system buffered by tris(hydroxymethyl)aminomethane (Tris), but strongly affected by N-2-hydroxyethylpiperazine-N′-2-ethanesulfonic acid. In the system buffered by Tris, a proton carrier is not Chin having carboxyl groups but Tris possessing primary amine group. Replacement of the central Mg of Chin with Zn gives a higher rate of MV2+ photoreduction, but when Cu was used in place of Zn, photoreduction was not observed. The central metal may affect the redox potential and the life time of excited Chln.
  • Tadao Uyehara, Jun-ichi Yamada, Koichi Ogata, Tadahiro Kato
    1985 Volume 58 Issue 1 Pages 211-216
    Published: 1985
    Released: June 27, 2006
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    The 4-alkyl, 4-alkenyl, and 4-aryl derivatives of bicyclo[3.2.2]nona-3,6-dien-2-one (9) were prepared from 9 itself by ultrasound-promoted Barbier reaction followed by PCC oxidation. Photochemical transformation of the 4-(4-methyl-3-pentenyl) derivative of 9, namely 13, in THF–water gave endo-7-[exo-7-(4-methyl-3-pentenyl)bicyclo[4.1.0]hept-2-ene]acetic acid (14). Acid 14 was converted into endo-7-methyl-exo-7-(4-methyl-3-pentenyl)bicylo[4.1.0]heptan-2-one (4), a key intermediate of (±)-sesquicarene and (±)sirenin total syntheses. Furthermore, a highly stereospecific total synthesis of (±)-sesquicarene was acomplished by the photochemical transformation of the 1-methyl derivative of 13 prepared from 2-methyltropone (21).
  • Hiroshi Nishino
    1985 Volume 58 Issue 1 Pages 217-222
    Published: 1985
    Released: June 27, 2006
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    The reaction of olefins with malonamide in the presence of manganese(III) acetate gave 2-buten-4-olides and/or 1H-pyrrol-2(5H)-ones in one-step, short reaction time, and moderate yields. The product distribution can be accounted for in terms of the stabilization of the intermediate carbocation in the oxidation process. The synthetic application and limitation, and the oxidation mechanism for the formations of α,β-unsaturated γ-lactones and γ-lactams are discussed.
  • Takeo Takahashi, Kotaro Yamauchi, Takahiro Masuda
    1985 Volume 58 Issue 1 Pages 223-226
    Published: 1985
    Released: June 27, 2006
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    Rate constants for reactions of dichloride anion radical with nucleosides, nucleotides, and polynucleotides were determined in neutral aqueous solutions of potassium chloride by the conventional flash photolysis. The reactivities of these compounds toward the anion radical are in the order: bases>nucleosides>nucleotides>polynucleotides. This trend is similar to that observed with the corresponding reactions with hydroxyl radical. A comparison of the reactivities of nucleosides, nucleotides, and polynucleotides toward dichloride anion radical with those toward hydroxyl radical has revealed that the reactivities of these compounds are governed mainly by their base moiety. This trend in the reactivities is discussed in terms of steric effect.
  • Osamu Neda, Kotaro Yamauchi, Takahiro Masuda
    1985 Volume 58 Issue 1 Pages 227-229
    Published: 1985
    Released: June 27, 2006
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    Determination of rate constants for reactions of dichloride anion radical was conducted by conventional flash photolysis of aqueous solutions of KCl and K2S2O8, where no participation of HOCL−· is expected in decay kinetics of dichloride anion radical. The optimum conditions found for the determination are 0.1 mol dm−3 KCl and 10−4 mol dm−3 K2S2O8. Under the present experimental conditions, S2O82− serves to convert chloride ion to dichloride anion radical through reaction with hydrated electron produced by photolysis of chloride ion. For glycyltryptophan, the competition method was employed, because its transient absorption overlaps the absorption due to dichloride anion radical. The rate constants determined are almost the same as those obtained in N2O-saturated aqueous solution of KCl (1 mol dm−3). The reactivity of dipeptides toward dichloride anion radical is discussed.
  • Katsuhiko Ueno, Masaru Shiraki, Mitsuhiko Sato, Norio Saito
    1985 Volume 58 Issue 1 Pages 230-235
    Published: 1985
    Released: June 27, 2006
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    The structures of two dihydroxycoumarin glucosides, esculetin 6-glucoside (E6G) and escultin 7-glucoside (E7G) have been determined by the X-ray analysis. The crystal data are: E6G, C15H16O9·1.5H2O, orthorhombic P212121 with a=11.358(2), b=36.850(9), c=7.663(1) Å and Z=8: and E7G, C15H16O9·2H2O, orthorhombic P212121 with a=4.507(1), b=13.077(3), c=27.748(5) Å and Z=4. Both structures were solved by the direct method and refined by the least-squares to the final R values of 0.073 (2036 reflections) for E6G and 0.069 (1037 reflections) for E7G. The geometries of the glucosyl linkages in E6G and E7G are different: the torsion angles around the glucosidic C–O bond are −58.2° and 14.3° for the two crystallographically independent E6G molecules and 9.9° for E7G. The glucosidation at the 6-hydroxyl group causes little effect on the conjugation of the coumarin moiety, whereas the conjugation is greatly decreased in the glucosidation at 7-hydroxyl group. This fact suggests that E6G is energetically more stable than E7G. The enzymatic transglucosidation from 7- to 6-hydroxyl group may proceed utilizing such an energy difference.
  • Hiroshi Miura, Hitoshi Ishiguro, Masashi Osawa, Kazunori Sasagawa, Kaz ...
    1985 Volume 58 Issue 1 Pages 236-241
    Published: 1985
    Released: June 27, 2006
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    The Fischer-Tropsch reaction was examined over reduced molybdenum catalysts using heteropoly compounds as catalyst precursors. Improvement in reducibility was realized by the use of heteropoly compounds. Metallic molybdenum powder with a very large surface area was obtained by the reduction of H3PMo12O40. Its catalytaic activity was one order higher than conventional Mo catalysts. Using different salts of 12-molybdophosphoric acid, various additives were introduced under equivalent conditions and their addition effects were studied.
  • Masao Onda, Takashi Motoda, Ichiro Yamaguchi
    1985 Volume 58 Issue 1 Pages 242-246
    Published: 1985
    Released: June 27, 2006
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    Microwave spectra of 4-chlorophenol were observed in the frequency ranges 8–18 and 26.5–40 GHz. Rotational constants were obtained for the ground vibrational states of three isotopic species, 35ClC6H4OH, 37ClC6H4OH, and 35ClC6H4OD, and for the first excited state of C–Cl out-of-plane bending mode for 35ClC6H4OH. All the b-type Q-branch transition lines of the OH species split into doublets, but those of the OD species do not. The separation of doublets is 158.99±0.16 MHz for the ground state of 35ClC6H4OH. An analysis of the doublets on the basis of the pseudo-symmetric internal rotor model gives the barrier height to the internal rotation of hydroxyl group as V2=13.98±0.37 kJ mol−1 for the 35Cl species. The V2 value obtained is compared with the theoretical V2 value calculated for 4-X-phenols (X=H, F, Cl) by means of ab initio MO with the 4-31G basis set.
  • Ayako Goto, Masumi Takemoto, Fumio Endo
    1985 Volume 58 Issue 1 Pages 247-251
    Published: 1985
    Released: June 27, 2006
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    Micellization of hexa(oxyethylene) dodecyl ether (C12E6) was studied in water and in ethanol–water mixtures at different temperatures by gel filtration on Sphacryl S-200. Standard enthalpies and entropies of micellization were determined from variation of critical micelle concentration(cmc) with temperature. Compensation plots were obtained, slopes for alcohol–water mixtures being indentical with that for pure water. Therefore, the micelle formation in water and ethanol–water mixtures has been explained in terms of its bulk structure. Gel fitration of C12E6 micelle with addition of a large amount of ethanol has led to a finding that the micelle size gradually becomes small with increasing ethanol content until micelles disappear above 35%v/v.
  • Mikio Yagi, Kazuhiro Makiguchi, Atsushi Ohnuki, Kazuhiro Suzuki, Jiro ...
    1985 Volume 58 Issue 1 Pages 252-257
    Published: 1985
    Released: June 27, 2006
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    Two sets of triplet-state ESR spectra corresponding to the s-cis and s-trans conformers of 2,2′-bipyridine have been observed in mixtures of water with various alcohols at 77K. The intensity ratio of the ESR signal for the s-cis conformer to that for the s-trans conformer depends on the composition of the mixture and on the sample-cooling rate. From the analysis of the phosphorescence spectra, the lowest triplet state of the s-cis conformer is estimated to be close to that of the s-trans conformer. An anomalous ESR signal which cannot be ascribed to either the s-cis conformer or the s-trans conformer has been observed in a 1-propanol-water mixture. The geometries of these conformers are discussed from their observed zero-field splitting parameters, together with their potential energy diagrams, as obtained by an ab initio calculation.
  • Yoshiro Shigetomi, Masaaki Kojima, Junnosuke Fujita
    1985 Volume 58 Issue 1 Pages 258-265
    Published: 1985
    Released: June 27, 2006
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    The chiral bidentate ligands, (2-aminoethyl)methylphenylarsine (mpan) and (2-aminoethyl)butylphenylarsine (bpan) were prepared and resolved by preparing their palladium(II) complexes containing, respectively, (R)-N,N-dimethyl-1-(2-naphthyl)ethylamine and (S)-N,N-dimethyl-α-methylbenzylamine. The optically actaive free arsine ligands can be readily liberated from the palladium(II) complexes, and complexes of the type, [MIIX2L] (MII=Pd, Pt; X=Cl, Br, I; L=R-mpan, S-bpan) were prepared. The absorption and circular dichroism (CD) spectra of these and related complexes were recorded, and the absolute configurations of the arsenic atoms were assigned by comparing the CD spectra with those of analogous phosphine complexes. The optically active arsines in diethyl ether solution racemize by the addition of hydrochloric acid at room temperature, but their palladium(II) complexes in acetonitrile–ethanol solution containing hydrochloric acid are very optically stable and do not racemize by refluxing for a long time.
  • Jun-ichi Aihara
    1985 Volume 58 Issue 1 Pages 266-269
    Published: 1985
    Released: June 27, 2006
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    The conjugated systems of ferrocene and related compounds were constructed using five equivalent 3d orbitals of iron and carbon 2pz orbitals of the cyclopentadienyl or pentadienyl groups. Ferrocene with such a conjugated system was found to have positive resonance energy due to cyclic conjugation, and was characterized as a three-dimensional aromatic species.
  • Yukio Tanaka, Norio Ohtomo, Kiyoshi Arakawa
    1985 Volume 58 Issue 1 Pages 270-276
    Published: 1985
    Released: June 27, 2006
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    A structure analysis of neutron and X-ray diffraction data of liquid methanol was performed by applying a general theoretical procedure for the fluid system composed of molecular clusters. The calculated structure factor curves are found to reproduce the essential features of observed ones. It was concluded that in liquid methanol chain clusters consisting of three or four hydrogen-bonded molecules are dominant on the average.
  • Kazuo Nomura, Akira Matsubara, Hideo Kimizuka
    1985 Volume 58 Issue 1 Pages 277-281
    Published: 1985
    Released: June 27, 2006
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    The biionic membrane potential was measured with the system in which a solution of calcium chloride was separated by a liquid membrane from a solution of another metal chloride. Four kinds of liquid membranes were prepared by dissolving calcium hexadecyl sulfate, stearate, cholate or deoxycholate in aqueous 1-octanol. All of the membranes studied were nearly permselective to cation. The membrane potential was analysed according to the Goldman-type equation based on the irreversible thermodynamics. The slope of a linear portion of the biionic potential vs. logarithmic activity curve showed fairly good agreement with the theoretical slope, i.e., 2.303×2RT⁄(ZCa+ZM)F per a ten-fold increase in activity, where ZCa and ZM were the valencies of calcium ion and another metal ion M existing across a membrane, respectively. The selective permeation coefficients of various metal ions were estimated for each membrane. The surprisingly small differences in the selective permeation coefficient between uni- and bi-valent cations were observed for the liquid membranes with calcium stearate, cholate or deoxycholate, while the about ten-fold increase in the coefficient per valency was observed for the liquid membrane with calcium hexadecyl sulfate. These results were discussed according to the theory previously presented.
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