Bulletin of the Chemical Society of Japan
Online ISSN : 1348-0634
Print ISSN : 0009-2673
ISSN-L : 0009-2673
Volume 48 , Issue 7
Showing 1-50 articles out of 67 articles from the selected issue
  • Norio Kaneko, Hiroaki Takahashi, Keniti Higasi
    1975 Volume 48 Issue 7 Pages 1961-1964
    Published: 1975
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    Infrared spectra from 4000 to 30 cm−1 of L- and DL-α-alanine and their N-deuterated analogues were measured at temperatures ranging from 295 to 100 K. Highly temperature-dependent bands were observed at 972 cm−1 (at 100 K) for L-α-alanine and 975 cm−1 for DL-α-alanine. The temperature dependence of the half-widths of these bands indicates that above 200 K the vibrational modes are considerably modulated by some motions, possibly arising from breaking of hydrogen bonds. These bands are thus assigned to the first overtone of the NH3+ torsional mode.
  • Michio Matsumura, Hiromichi Uohashi, Masaki Furusawa, Naoto Yamamoto, ...
    1975 Volume 48 Issue 7 Pages 1965-1969
    Published: 1975
    Released: March 27, 2006
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    The photovoltaic effect in gold–naphthacene thin layers has been studied. By excitation in the region of the visible absorption band of naphthacene (2.4–3.0 eV), it was found that the photovoltage consists of two components; one with a short response time, caused by the electron transfer across the boundary between gold and naphthacene, and the other with a long response time, attributable to a diffusion process in the naphthacene film. The lifetime of carriers produced by the former process was estimated to be 0.08 s at least, decaying by the recombination of trapped holes in naphthacene with electrons in gold. Photovoltage was also observed in a region of wavelengths greater than the visible absorption band of naphthacene.
  • Hideaki Fujiwara, Nobuyuki Yoshida, Tsuneo Ikenoue
    1975 Volume 48 Issue 7 Pages 1970-1973
    Published: 1975
    Released: March 27, 2006
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    The NMR dilution shifts of OH proton in several carboxylic acids have been studied for mixtures with N,N-dimethylacetamide (DMA) or pyrazine. The acids treated were acetic, propionic isobutyric, and trifluoroacetic acids. The dilution shifts curve of OH proton in each acid–DMA system showed a characteristic ν-type curve with the minimum value at 0.65–0.75 mol fraction of the acid. The curve for the isobutyric acid-pyrazine system was linear below 0.45 mol fraction of the acid, taking the minimum at 0.75 mol fraction. These curves were explained by assuming the formation of both 1: 1 and 2 (acids): 1(base) complexes in the chemical equilibrium. The formation constants of the complexes and the shifts of OH proton in the 2: 1 complex were estimated for each system. Liability of the complex formation and the structure possible for the 2: 1 complex were discussed.
  • Kazuhiko Shibuya, Kin-ichi Obi, Ikuzo Tanaka
    1975 Volume 48 Issue 7 Pages 1974-1979
    Published: 1975
    Released: March 27, 2006
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    The vacuum-ultraviolet photolysis of cyclopropane in the gas phase has been investigated at room temperature at excitation wavelengths 1470 and 1634 Å. Primary processes are discussed in terms of variations of product yield as a function of conversion and in the presence of additives such as NO, C2D4, and H2. The relative yields of decomposition are determined at both wavelengths. The main primary process is cyclo-C3H6+hv→C2H4+CH2, the yield being 67% at 1470 Å (69% at 1634 Å). The observed product yield responsible for methylene is much less than that for ethylene. However, the yields become equal in the photolysis of cyclopropane with excess hydrogen. The other primary processes are as follows in order of decreasing importance; cyclo-C3H6+hv→C2H3+CH3, 19% (18%), cyclo-C3H6+hv→C3H4+2H, 9% (7%), cyclo-C3H6+hv→C2H2+CH3+H, 3% (4%), cyclo-C3H6+hv→C2H2+CH4, 1% (1%).
  • Keiichi Fukuyama, Tomitake Tsukihara, Yukiteru Katsube, Nobuo Tanaka, ...
    1975 Volume 48 Issue 7 Pages 1980-1983
    Published: 1975
    Released: March 27, 2006
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    The crystals of the p-bromobenzoate of sterigmatocystin, C25H15O7Br, are monoclinic, with the space group of P21 and with two molecules per unit cell with the dimensions of a=13.062(7), b=9.029(4), c=8.942(4) Å, and β=102.25(5)°. The structure was refined by a least-squares method to R=0.055 for 1292 non-zero reflections. The absolute configuration of the molecule was determined by using the anomalous dispersion effect of the bromine atom. The absolute configuration of the bisdihydrofuran ring agrees with that in aflatoxin B1.
  • Hironobu Kakubari, Takao Iijima, Masao Kimura
    1975 Volume 48 Issue 7 Pages 1984-1986
    Published: 1975
    Released: March 27, 2006
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    The skeletal parameters, C–C, C–F, and C···F distances, of 2-fluoropropane have been determined by means of gas electron diffraction. The rg-values obtained are: C–C 1.514±0.004 Å, C–F 1.405±0.005 Å and C···F 2.366±0.006 Å. By a joint analysis of the diffraction data and the spectroscopic moments of inertia, determination of the remaining structural parameters has also been attempted, and the φz value of the CCC angle being found to be 114.6±1.5°.
  • Isao Ando, Atsuo Nishioka, Masahiro Kondo
    1975 Volume 48 Issue 7 Pages 1987-1992
    Published: 1975
    Released: March 27, 2006
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    The principal axes and values for the 13C chemical shielding tensors of carbonyl compounds (formaldehyde, acetaldehyde, acetone, and formic acid), methanol, and n-paraffins (propane and n-butane) have been determined theoretically by the LCGI–MO theory using the MINDO/2 method. Further, their anisotropies have been estimated. These results have then been discussed by comparing them with the observation of Pines et al. and in part compared with the anisotropies in the literature calculated by using other theoretical methods.
  • Tetsuya Ohsaka, Yasuo Iida, Tadashi Yoshida
    1975 Volume 48 Issue 7 Pages 1993-2000
    Published: 1975
    Released: March 27, 2006
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    The present work was conducted to investigate the electroreduction of anions (typically S2O82− and BrO3) under the influence of the adsorption of polymers (polyethyleneglycol, alkylphenoxy polyethoxy ethanols and polyvinylpyrrolidone) on the electrode surface. The limiting current of S2O82− reduction was depressed by the polymers in the region from nearly the zero-charge potential to the more negative potential. The half-wave potential of BrO3 reduction shifted towards more negative potential by adding the polymers. In the potential range where the cathodic current was mainly controlled by mass transfer of the anions, the time (tm) needed to complete the formation of a monolayer was obtainable conveniently from the instantaneous current vs. time (It) curve as reported previously for the inhibited reduction of Cd2+ or Cu2+. In the potential range where the current was mainly controlled by charge transfer, an exact determination of tm, by which the maximum surface concentration of polymer was given, was possible only when the instantaneous current density (i) was plotted against t1⁄2. In such a potential range, i was expressed as follows.
    2& i=i_0-(i_0-i_1)(t/t_m)^1/2 & & for tt_m
    or & i=i_1 & & for t>t_m
    Moreover,
    2& \barI_ads/\barI_0=1-\frac1013\fraci_0-i_1i_0(t_d/t_m)^1/2 & & for t_dt_m
    & \barI_ads/\barI_0=1-\frac1013\fraci_0-i_1i_0-\frac313\fraci_0-i_1i_0{1-(t_d/t_m)^-5/3} & & for t_d>t_m
    where i0 and i1 are the instantaneous current densities at θ=0 and 1, \barIads and \barI0 the polarographic currents with and without polymers, td the drop time, tm the time required to attain the saturated adsorption. The relationship between the shift of half-wave potential and (tdtm)1⁄2 (for td≤tm) or (tdtm)−5⁄3 (for td>tm), was introduced and the results were verified for the inhibition effects of polymer on the electroreduction of BrO3 as well as for that on VO2+ reduction.
  • Manabu Sen\={o}, Shinji Tsuchiya, Hideo Kise, Teruzo Asahara
    1975 Volume 48 Issue 7 Pages 2001-2005
    Published: 1975
    Released: March 27, 2006
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    In order to clarify the electron structure of carbonyl-stabilized phosphorus ylides, measurements of X-ray photoelectron spectroscopy (XPS) and combustion heat were performed. NMR and IR spectra were also measured as complementary methods. The results suggest that carbomethoxymethylenetriphenylphosphorane has a major contribution of polar bond (\overset+P—\overset−C) structure, whereas benzoylmethylenetriphenylphosphoranes have a larger contribution of covalent bond (P=C). A dπ–pπ interaction in the P–C bond was interpreted for XPS and NMR. The data for heat of combustion suggest that a large contribution of the polar bond structure brings about stabilization of the ylide molecule. These results show that XPS and combustion heat measurements are useful means for the analysis of ylide bonding.
  • Hatsuho Uedaira
    1975 Volume 48 Issue 7 Pages 2006-2008
    Published: 1975
    Released: March 27, 2006
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    A new method of calculating the free energy of transfer of a solute from a binary to a ternary solution on the mole fraction scale from isopiestic measurements is reported. It was proved that only the new method is consistent.
  • Yoshiyuki Kawashima, Masao Suzuki, Kunio Kozima
    1975 Volume 48 Issue 7 Pages 2009-2013
    Published: 1975
    Released: March 27, 2006
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    The microwave spectrum of 2-pyridinecarbaldehyde has been observed in the region 8–22 GHz. The rotational constants of the ground state are A=5362.52±2.19 MHz, B=1620.07±0.03 MHz, and C=1244.42±0.03 MHz and the inertia defect is −0.075 amu·Å2. This value demonstrates that the molecule is planar in its equilibrium position. The total dipole moment is 3.56±0.07 D, the components of which are μa=3.48±0.05 D and μb=0.76±0.08 D. From these facts it is concluded that the conformation of the molecule is of the O–N s-trans form. The rotational constants of the five vibrationally-excited states have also been determined.
  • Takeshi Ohno, Shunji Kato
    1975 Volume 48 Issue 7 Pages 2014-2016
    Published: 1975
    Released: March 27, 2006
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    UV spectra of [Ni(2,2′-bipyridyl)3]Cl2 and [Ni(2,2′-bipyridyl)(H2O)4]Cl2 in the mixed solvent of methanol and water (4:1) were measured at 4.2 K. No difference between the spectra indicates a small splitting (<90 cm−1) between the exciton states extending through the three 2,2′-bipyridyls. Since the UV spectrum of [Ni(1,10-phenanthroline)3]Cl2 has a band with the progression as that of [Ni(1,10-phenanthroline)(H2O)4]SO4, a molecular exciton interaction between the three 1,10-phenanthrolines is not strong.
  • Toshiaki Ohta, Takashi Fujikawa, Haruo Kuroda
    1975 Volume 48 Issue 7 Pages 2017-2024
    Published: 1975
    Released: March 27, 2006
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    The gas-phase X-ray photoelectron spectra were observed on benzene and its eight mono-substituted derivatives; C6H5X, X=H, CH3, NH2, OH, F, Cl, Br, NO2 and CN. Binding energies of core levels were determined from the observed spectra by using the spectrum simulation technique, and they were compared with the chemical shift predicted from the CNDO/2 charge densities on the basis of the electrostatic potential model. It is shown that the Cls binding energies of benzene derivatives can be generally correlated with atomic charges, qj, by the following equation;
    E_i(Cls)=290.2+22.67q_i+\undersetj\ eweqi∑(q_j/R_ij) eV.
    By using this relation and the observed Cls binding energies, the atomic charge analysis is carried out. Satellite bands were observed in the Cls spectra as well as in some other core-electron spectra of benzene derivatives. Theoretical calculations are carried out on the energies and probabilities of shake-up transitions. It is concluded that the observed satellites are mainly due to the shake-up processes associated with the excitations of π electrons.
  • Takashi Okada, Takayuki Fueno
    1975 Volume 48 Issue 7 Pages 2025-2032
    Published: 1975
    Released: March 27, 2006
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    The density functions representing electron pairs are extracted from two-electron density matrices by operating irreducible tensor operators in a two-electron spin space. Properties of these functions are examined, and the generalized Penney-Dirac bond orders are defined between atomic orbitals. Significance of the bond orders in chemical valence problems is discussed.
  • Yoshihiro Kojima
    1975 Volume 48 Issue 7 Pages 2033-2038
    Published: 1975
    Released: March 27, 2006
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    The bis(L-hydrogenaspartato)trimethylenediaminecobalt(III) complex has been prepared by the reaction of the trans-[CoCl2(tn)2]+ complex with L-aspartic acid, and its eight stereoisomers have been separated by an ion-exchange chromatographic method. The six isomers are trans(O)-Λ and -Δ, cis(O)cis(N)-Λ and -Δ and trans(N)-Λ and -Δ isomers, in which either aspartate ion forms the five-membered chelate ring through an N atom of the amino group and an O atom of the α-carboxylate group. The remaining isomers are Λ- and Δ-trans(O) ones containing a five-membered chelate ring and a six-membered ring of L-aspartate ions. On the other hand, stereoselective formations have been found in the Λ,Δ, and Λ isomers for the trans(O), cis(O)cis(N), and trans(N) isomers respectively. It has become apparent that these stereoselectivities agree with those found for the corresponding l-pn and en complexes, while the orders of the formation amounts for the three geometrical isomers disagree.
  • Hajime Kanatomi, Yoichi Demura, Ichiro Murase
    1975 Volume 48 Issue 7 Pages 2039-2043
    Published: 1975
    Released: March 27, 2006
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    Copper(II), Ni(II), Co(II), Zn(II), and Be(II) chelates of N,N′-bis(salicylidene)-2-aminobenzylamine and its methyl and dimethyl salicylidene derivatives have been prepared and characterized. According to the molecular models, the ligands are favorable to tetrahedral arrangement on complex formation. The spectral and magnetic properties revealed that all the Co(II) and some of the Cu(II) chelates were pseudo-tetrahedral, while the Ni(II) and other Cu(II) chelates were square-planar, with a considerable angle strain. This ligand property is somewhat inconsistent with the conclusion derived from N,N′-bis (salicylidene) polymethylenediamine chelates, in which the trimethylene analogue could not take a pseudotetrahedral arrangement around a metal ion. The difference in stereochemistry between the two ligands with the same number of bridging carbon atoms will be discussed on the basis of the flexibility and the steric requirement of the central chelate ring.
  • Mitsuyo Fukui, Kenji Itoh, Yoshio Ishii
    1975 Volume 48 Issue 7 Pages 2044-2046
    Published: 1975
    Released: March 27, 2006
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    Iminophosphorane complexes of palladium [(C6H5)3P=N–C6H4–X-p]PdCl2(CH3CN) (X=NO2, 1A; COO-C2H5, 2A; Cl, 3A; H, 4A; CH3, 5A) have been prepared by ligand-substitution reaction between (C6H5CN)2PdCl2 and the parent iminophosphoranes, followed by recrystallization from acetonitrile-ethyl acetate. Other iminophosphoranes (X=OCH3, and (C6H5)2(CH3)P=N–Si(CH3)3), however, gave only dimeric complexes with the [(Iminophosphorane)PdCl2]2 composition. Complexes 1A5A and {[(C6H5)3P=N–C6H4–X-p]PdCl2}2 (X=NO2, 1B; COOC2H5, 2B; Cl, 3B; H, 4B; CH3, 5B) are also discussed. The ligand-exchange reaction of 2B and 5B with α,α′-bipyridine, (C6H5)3P, and (CH3O)3P took place, liberating the parent iminophosphorane.
  • Kazuo Narita, Nobuyuki Tsuda
    1975 Volume 48 Issue 7 Pages 2047-2051
    Published: 1975
    Released: March 27, 2006
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    Color center formation and brightness depreciation by 185 nm radiation were studied in calcium halophosphates containing various additives. Partial bleaching experiments show that the depreciation of plaque brightness is due to the absorption of 254 nm radiation by color centers, the reabsorption of luminescence by color centers being unimportant. In unactivated Ca halophosphates, the stronger the 185 nm absorption of additives, the weaker the color center formation. In Sb- and Mn-activated Ca halophosphates, however, no clear relation is found between the 185 nm absorption of additives and the brightness depreciation. The effect of cesium on improving lamp performance is described.
  • Makoto Chikira, Taro Isobe
    1975 Volume 48 Issue 7 Pages 2052-2056
    Published: 1975
    Released: March 27, 2006
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    The computer simulations of the ESR spectra for the triplet-state dimers of the title complexes in frozen solutions revealed that the dimeric structures change markedly upon nitro-substitutions at the positions of 3 or 5 in the phenyl-rings of the Schiff bases. It was also found that some of these nitro-substituted copper(II) complexes form 1: 1 molecular complexes with bis(N-salicylideneisopropylaminato)copper(II) in toluene. The dependence of the ESR spectral intensities for the ΔM=2 transitions upon the temperature in the range of 1.57–4.2 K indicated that the intra-dimer spin-exchange interactions are weakly anti-ferromagnetic (0.7–2.2 cm−1).
  • Masao Okubo
    1975 Volume 48 Issue 7 Pages 2057-2061
    Published: 1975
    Released: March 27, 2006
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    In the reaction of benzophenone with phenylmagnesium bromide, the concentration and life-time of the ketyl radical were influenced greatly by the substitution of ortho-hydrogen atoms of both the two reactants by methyl group. From the results of visible absorption and ESR measurements and also of product-analysis, the ketyl radical was considered to be a common intermediate towards normal and abnormal reaction products. The existence of an equilibrium between monomeric and dimeric states of the ketyl radical was also proposed.
  • Koichi Honda, Akira Yabe, Hideaki Tanaka
    1975 Volume 48 Issue 7 Pages 2062-2067
    Published: 1975
    Released: March 27, 2006
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    The photochemical reactions of dimethyl 1,8-naphthalene diacrylate (I) in solution are found to be cis,trans isomerization and concomitant intramolecular cycloaddition through a triplet state (ET is ca. 40 kcal/mol). Cyclization reaction gives naphtho[1′,8′]bicyclo[3.1.1]hept-2-ene-6-exo,7-endo-dimethyl dicarboxylate (VI), its 6-endo, 7-endo substituted isomer (VII) and cis-anti-naphtho[1′,8′]bicyclo[3.2.0]hept-2-ene-6,7-dimethyl carboxylate (II) in a ratio of ca. 85: 10: 5. Predominant formation of crossed adducts is discussed, taking into consideration the ground-state conformations of (I). Biradical mechanism is proposed for the cyclization to explain the stereochemistry of the crossed products.
  • Shuichiro Asao, Naoki Toshima, Hidefumi Hirai
    1975 Volume 48 Issue 7 Pages 2068-2074
    Published: 1975
    Released: March 27, 2006
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    Irradiation of N-acetyldiphenylmethyleneamine (II) in toluene solution gave N-(1,1,2-triphenylethyl)acetamide and N-(1,1-diphenylmethyl)acetamide in 11% and 4.4% yields, respectively. The former is an addition product of toluene to the C=N bond of imine II, and the latter a hydrogenation product of II. The same kind of addition and hydrogenation products as those in toluene were obtained on irradiation of imine II in ethylbenzene, cumene, o-, m-, and p-xylene, mesitylene, p-methoxytoluene, and p-cyanotoluene, respectively. Two kinds of competitive reaction processes are proposed from the results of the substituent effects for the phenyl ring of toluene, the effect of the additives such as sensitizers and quenchers, and the dependence of the photoreaction yields on the concentration of the additive. The photoreaction proceeds not only by the “chemical sensitization” mechanism derived from the ketyl radical of benzophenone, a hydrolyzed product of II, but also by the mechanism through the excited state of II itself.
  • Masanobu Hidai, Tomoji Hikita, Yoshimasa Wada, Yuzo Fujikura, Yasuzo U ...
    1975 Volume 48 Issue 7 Pages 2075-2077
    Published: 1975
    Released: March 27, 2006
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    Palladium complexes, Pd(CO)(PPh3)3, Pd3(CO)3(PPh3)4, Pd3(CO)3(PPh3)3, and PdCl2(PPh3)2 were found to be excellent catalysts for the carboxymethylation of various organic halides under very mild conditions. The carboxymethylation reaction is considered to proceed via acyl complexes as the intermediates.
  • Kazuo Yoshihara, Yoshio Hirose
    1975 Volume 48 Issue 7 Pages 2078-2080
    Published: 1975
    Released: March 27, 2006
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    The sesquiterpenes of ginseng have been studied. From the volatile oil, fifteen compounds were characterized. Three of those compounds, α-panasinsene,β-panasinsene and β-neoclovene, were new compounds and were characterized in this paper. Panasinsenes are considered as intermedial compounds in isomerization of caryophyllene to neoclovene.
  • Mitsuhiro Kinoshita, Satoshi Mariyama
    1975 Volume 48 Issue 7 Pages 2081-2083
    Published: 1975
    Released: March 27, 2006
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    Natural (2R,3S,4S)-4-arnino-3-hydroxy-2-methyl-5-(3-pyridyl)pentanoic acid (1) present in antibiotic pyridomycin was synthesized. The 5,6-anhydro-1,2-O-isopropylidene-3-C-methyl-α-D-allofuranose (4) was prepared from (the known) 3-deoxy-1,2;5,6-di-O-isopropylidene-3-C-methyl-α-D-allofuranose (2). Regiospecific introduction of 3-pyridyl group to the C–6 of 4 was effected by 3-pyridyllithium. The product (5) was converted to the 5-azido derivative (7) by the SN2 substitution reaction of the 5-mesylate (6) of 5. Hydrolysis of 7 followed by two-stage oxidation with periodate-bromine in aqueous acetic acid afforded (2R,3S,4S)-4-azido-3-formyloxy-2-methyl-5-(3-pyridyl) pentanoic acid (9), which was transformed to the dihydrochloride of 1.
  • Tsuneo Sowa, Shunji Ouchi
    1975 Volume 48 Issue 7 Pages 2084-2090
    Published: 1975
    Released: March 27, 2006
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    5′-Nucleotides were directly prepared by selective phosphorylation with phosphoryl chloride in the presence of water and pyridine in acetonitrile. The rate of phosphorylation with phosphoryl chloride was markedly improved by the addition of suitable amounts of water and pyridine; the maximal formation of 5′-nucleotides was obtained by mixing these three reactants phosphoryl chloride, water, and pyridine in a molar ratio of 2 : 1 : 2 at a low temperature, followed by adding nucleosides corresponding to a one-fourth or one-fifth of the phosphoryl chloride. By mixing phosphoryl chloride, water, and pyridine in acetonitrile under controlled conditions, a hygroscopic complex (Complex 1), an active phosphorylating agent in the present phosphorylation of nucleosides, was isolated. It was identified as an adduct composed of tetrachloropyrophosphate and pyridinium chloride by means of its infrared spectra and by its chromatographic behavior. One of the proposed structures of the adduct is trichloropyrophosphopyridinium chloride. Both the selectivity in the 5′-hydroxyl group of the nucleosides and the yield of 5′-nucleotides increase upon the addition of pyridinium chloride in the phosphorylation of the unprotected nucleosides with tetrachloropyrophosphate. In the phosphorylation with tetrachloropyrophosphate, the H+ derived from pyridinium chloride in acetonitrile is considered to increase the selectivity for the 5′-hydroxyl group by decreasing the reactivity of the hydroxyl groups in the ribose moiety of the nucleosides with the adduct. Similar results were obtained in the phosphorylation with phosphoryl chloride in the presence of pyridinium chloride in acetonitrile. Thus, several procedures for the selective phosphorylation of unprotected nucleosides to 5′-nucleotides are available.
  • Takeshi Ito, Kunio Mori, Tsutomu Mizoroki, Atsumu Ozaki
    1975 Volume 48 Issue 7 Pages 2091-2094
    Published: 1975
    Released: March 27, 2006
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    It was found that palladium-black is a highly active catalyst for the carbonylation of iodobenzene with carbon monoxide and methanol in the presence of potassium acetate, triethylamine, or tributylamine to give methyl benzoate. The kinetic study of the carbonylation showed that the oxidative addition of iodobenzene to a palladium(0) complex is rate-determining, and that the bases affect considerably the rate-determining step.
  • Akio Horinaka, Ruka Nakashima, Masaharu Yoshikawa, Teruo Matsuura
    1975 Volume 48 Issue 7 Pages 2095-2098
    Published: 1975
    Released: March 27, 2006
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    The present investigation was undertaken in order to see whether singlet oxygen-oxidation of unconjugated cyclic dienes having spatially close double bonds causes a particular transannular reaction as previously observed with 1,5-cyclooctadiene which gave 4-hydroxy-5-cyclooctenone. Most cyclic dienes tested underwent normal “ene” reaction to give allylic hydroperoxides. Thus, on dye-sensitized photooxygenation followed by reduction with sulfite, dicyclopentadiene, cis,trans-1,5-cyclodecadiene, trans,trans,trans1,5,9-cyclooctadiene, 1,4-cyclooctadiene, 1,3-cyclooctadiene and germacrone yielded a stereoisomeric mixture of tricyclo[5.2.1.02,6]decan-4,8-diene-3-ols, cis,cis-2,7-cyclodecadienol, a stereoisomeric mixture of two 2,5,9-cyclododecatrienols, 2,4-cyclooctadienol, endo-3,8-peroxide of cyclooctene, and germacra-3,7(11),10(14)-trien-9-ol-6-one(E), respectively. Under similar conditions, norbornadiene, and cis,cis-1,6-cyclodecadiene remained virtually unchanged.
  • Yoshihiro Shigemasa, Masayuki Shimao, Chikahiro Sakazawa, Teruo Matsuu ...
    1975 Volume 48 Issue 7 Pages 2099-2102
    Published: 1975
    Released: March 27, 2006
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    The formose reaction, the calcium hydroxide-catalyzed condensation of formaldehyde to monosaccharides, was potentiometrically analyzed. The oxidation-reduction potential varied in a characteristic way and gave information of considerable importance. Some appreciable transition points in the oxidation-reduction potential curve showed satisfactorily the occurrence of a phase change such as an induction period and saccharide-forming and saccharide-decomposing stages. With regard to the fundamental operating conditions, vigorous stirring and an increase in the dissolved oxygen elongated the induction period. Furthermore, the latter diminished the yield of saccharide under the lower limit of the critical range of the calcium hydroxide concentration.
  • Masahiro Fukuda, Kazuhito Kan, Yoshiki Okamoto, Hiroshi Sakurai
    1975 Volume 48 Issue 7 Pages 2103-2105
    Published: 1975
    Released: March 27, 2006
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    1-Dimethylamino-1-methoxy-1-alkenes (ketene O,N-acetals), 1-dimethylamino-1-ethylthio-1-alkenes (ketene S,N-acetals) and 1,1-bis(dimethylamino)ethylene (ketene N,N-acetal) reacted with diethyl phosphite to give the corresponding (E)-diethyl 1-dimethylamino-1-alkenylphosphonates. Although ketene diethylacetal (ketene O,O-acetal) reacted with diethyl phosphite to give diethyl 1,1-diethoxy-1-ethylphosphonate, 1,1-bis(ethylthio)-1-alkenes (ketene S,S-acetals) did not react with diethyl phosphite.
  • Mikio Nakamura, Michinori Oki
    1975 Volume 48 Issue 7 Pages 2106-2111
    Published: 1975
    Released: March 27, 2006
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    A series of 9-aryltriptycene derivatives have been prepared and their internal rotation about the CAr–C9 bond has been examined by DNMR technique. The PMR behavior of these compounds is best interpreted by assuming a back and forth rotation rather than a full rotation. The barriers to rotation of compounds with one substituted benzo group have been found to be in the range 13–15 kcal/mol, whereas those with two substituted benzo bridges are lower than 9 kcal/mol. The low barrier of these compounds relative to 9-alkyltriptycenes is attributed to the rise in energy of the ground state. The stable conformation of the 9-aryltriptycenes is also discussed.
  • Hitomi Suzuki, Katsuro Ishizaki, Shigeru Maruyama, Terukiyo Hanafusa
    1975 Volume 48 Issue 7 Pages 2112-2115
    Published: 1975
    Released: March 27, 2006
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    Direct action of fuming nitric acid upon tetrachloro-o- and -m-xylenes at room temperatur led to the formation of 3,5,6-trichloro-1,2-dimethyl-4-oxocyclohexa-2,5-dienyl nitrate and 2,5,6-trichloro-1,3-dimethyl-4-oxocyclohexa-2,5-dienyl nitrate, respectively, as the major products. In contrast, tetrachloro-p-xylene was simply converted into 2,3,5,6-tetrachloro-4-methylbenzyl nitrate. Plausible reaction sequences as well as criteria as a basis for predicting the propensity of polysubstituted alkylaromatics towards unusual nitration have been discussed.
  • Hitomi Suzuki, Hajime Yoneda, Terukiyo Hanafusa
    1975 Volume 48 Issue 7 Pages 2116-2119
    Published: 1975
    Released: March 27, 2006
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    9,10-Dimethylphenanthrene and 9-methyl-10-ethylphenanthrene gave 9-methyl-10-nitromethylphenanthrene and 9-ethyl-10-nitromethylphenanthrene, respectively, as major product, when treated with fuming nitric acid in dichloromethane at low temperatures. In contrast, 9,10-diethylphenanthrene yielded a comparable mixture of products arising from side-chain nitration and side-chain nitrooxylation, which on chromatography over deactivated alumina gave 9-ethyl-10-(α-nitroethyl)phenanthrene and 9-ethyl-10-(α-hydroxyethyl)phenanthrene as main isolable products. 9-Methylphenanthrene and 9-ethylphenanthrene were both simply nitrated at the ring position to give the corresponding 9-alkyl-10-nitrophenanthrenes in good yields. No side-chain attack was observed. Factors responsible for determining which one of the competitive pathways will be followed have been discussed.
  • Shosuke Yamamura, Hajime Irikawa, Yasuaki Okumura, Yoshimasa Hirata
    1975 Volume 48 Issue 7 Pages 2120-2123
    Published: 1975
    Released: March 27, 2006
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    The structure of yuzurimine-C, one of the yuzurimine-type alkaloids, was unambiguously determined on the basis of chemical evidences coupled with its spectral data. Particularly, application of the 13C NMR spectra plays an important role in the structural elucidation.
  • Isamu Watanabe, Tsutomu Tsuchiya, Sumio Umezawa, Hamao Umezawa
    1975 Volume 48 Issue 7 Pages 2124-2126
    Published: 1975
    Released: March 27, 2006
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    The title compound (7), which is active against resistant bacteria producing phosphotransferase I, was synthesized from lividomycin A through a cyclic carbamate derivative (3). Selective hydrolysis of the carbamate ring followed by acylation of the free C-1-amino group with (S)-2-hydroxy-4-aminobutyric acid by the active ester method led to 7.
  • Mizue Fujio, Masaaki Mishima, Yuho Tsuno, Yasuhide Yukawa, Yoshio Taka ...
    1975 Volume 48 Issue 7 Pages 2127-2133
    Published: 1975
    Released: March 27, 2006
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    The chemical shifts of the hydrogen bonded OH proton of m- and p-substituted phenols, and 4-substituted 2-cresols, 3-cresols, and 2,6-xylenols were determined in DMSO. The effects of substituents on the hydroxyl chemical shift of these series were correlated linearly with each other (correlation coefficient>0.999), except for the bulky planar substituents in the 3-cresol series which may be subject to the steric loss of their coplanarity with the benzene ring. The substituent effects were treated successfully with the equation, Δδ=ρ(σ0+rΔ\barσR). The phenol series gave r=0.673 and ρ=1.530. The same r value appeared to be applicable to all the other series with negligible changes in the ρ value. Deviations from the correlation of particular substituents, in particular those having acidic hydrogen, were attributed to the modification of the electronic nature of substituents arising from the strong substituent-DMSO interaction.
  • Shigeru Ikuta, Kenji Yoshihara, Takanobu Shiokawa
    1975 Volume 48 Issue 7 Pages 2134-2138
    Published: 1975
    Released: March 27, 2006
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    We have proposed a new fragmentation mechanism and successfully applied it to various monosubstituted alkanes RX. The fragmentation mechanism can be described as follows: (1) The bond scission first occurs where the electrons exist densely in the particular occupied molecular orbital correlated to the particular ionization. (2) Process (1) competes with the electron redistribution. (3) In the higher-energy region, secondary scission also occurs. The breakdown curves of the CH3NH2+, CH3SH+, and CH3Br+ produced by charge-exchange reactions have been obtained by the use of a perpendicular double-mass spectrometer. The experimental results can be satisfactorily explained by the proposed mechanism on the basis of the calculated eigenvectors of the various molecular orbitals.
  • Fumio Hirata, Kiyoshi Arakawa
    1975 Volume 48 Issue 7 Pages 2139-2144
    Published: 1975
    Released: March 27, 2006
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    A useful method to investigate the thermodynamic properties of aqueous electrolyte solutions was presented on the basis of the perturbation theory of fluids, where a primitive model was used as a reference system. A perturbation potential of a square type was applied. An analytical solution of the mean spherical model (MSM) equation obtained by Waisman and Lebowitz was used as the thermodynamic functions of the reference system, and an ionic distribution function in electrolyte solutions was derived. The values of the energy parameters which represent the depth of the well were determined by a comparison of the observed values of the thermodynamic quantities with the calculated ones.
  • Akira Kuboyama, Fumio Kobayashi, Satomi Morokuma
    1975 Volume 48 Issue 7 Pages 2145-2148
    Published: 1975
    Released: March 27, 2006
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    The π→π* S–S absorption spectra of 9,10-phenanthrenequinone and 3-bromophenanthrenequinone in solutions up to the vacuum. UV region were obtained. On the other hand, MO calculations of the π-electronic systems of these quinones were carried out by means of the P–P–P method. The π→π* absorption bands of these quinones were assigned on the basis of the calculated results. The blue-shift of the longest-wavelength π→π* band of phenanthrenequinone due to the bromine-atom substitution at its 3-position was observed. Similar facts are found in aromatic carbonyl compounds, fluorenone and acetophenone.
  • Yoshihisa Suzuki, Kentaro Hara, Tsuneo Hirahara
    1975 Volume 48 Issue 7 Pages 2149-2152
    Published: 1975
    Released: March 27, 2006
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    Among several basic amino acids, only the L-lysine free base was found to form a crystalline salt with inosine. A specific stereochemical arrangement of these two molecules, inosine and L-lysine, is considered to be involved in such a crystalline salt-formation on the basis of the fact that D-lysine did not form a crystalline salt with inosine. Part of the equilibria were determined at 10 °C for the inosine–L-lysine–water and inosine–L-lysine-60 w/w % aqueous ethanol systems. The salt was unstable against water, while it was stable against aqueous ethanol (containing more than about 40% ethanol). The solubility of the salt in water was summarized as follows: logS (w/w %) =0.0219t+0.624. The X-ray powder diffraction data of the salt are given.
  • Shin-ichi Ohno, Hisashi Nagayama, Kiyoshi Okazaki, Shin Sato
    1975 Volume 48 Issue 7 Pages 2153-2157
    Published: 1975
    Released: March 27, 2006
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    The yields for the ionization and excitation from each molecular orbital of a water molecule irradiated by 10 keV electrons were calculated using the classical binary-encounter approximation. On further assuming fragmentation processes of the excited or ionized states consistent with the photochemical and mass spectrometrical results in the literature, we obtained, as the radiolysis yields of water vapor: G(electron)=2.96; G(OH)=0.04; G(H3O+)=3.00; G(H)=4.83–5.21, including G(‘hot’ H-atoms)≤0.87; G(H2)=0.28–1.15; G(O)=0.83–1.21; G(OH)=6.70–7.08, and G(–H2O)=G(ionized water)+G(excited water)=2.91+4.96=7.87.
  • Nobutake Suzuki, Takeshi Nagai, Hiroshi Hotta, Masamitsu Washino
    1975 Volume 48 Issue 7 Pages 2158-2163
    Published: 1975
    Released: March 27, 2006
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    The decoloration yield of an Acid Red 265 neutral aqueous solution, G(-Dye), equaled 1.00±0.04, regardless of the dose rate and the initial dye concentration in the early stage. The G(-Dye) increased to 1.46 in the presence of nitrous oxide, but was independent of the presence of oxygen and acetone. In nitrogen-saturated solutions, the G(–Dye) increased markedly upon the addition of alcohols—for example, up to 1.83 upon the addition of 2 mM n-butyl alcohol. On the other hand, in oxygen-saturated solutions, the G(-Dye) decreased markedly upon the addition of even a small amount of alcohols. The effects of alcohols, namely, the G(-Dye) in both the solutions were in the order of their reactivity with OH radicals. The decoloration is attributable to the attack of the OH radicals formed by the radiolysis of water to the dye. The increase in the G(-Dye) for the nitrogen-saturated solutions containing alcohols is attributable to the attack of the alcohol radicals (R\dotCHOH) formed by the reactions of alcohols with OH radicals. In the oxygen-saturated solutions, the R\dotCHOH radicals are converted to the peroxides, which do not react with the dye. The rate constant for the reaction of the OH radical with Acid Red 265, obtained by using various additives from the competition reaction method, is 9.3±1.4×109 M−1 s−1. The effects of CNS, glucose, and phenol were also examined.
  • Shigekazu Kumakura
    1975 Volume 48 Issue 7 Pages 2164-2167
    Published: 1975
    Released: March 27, 2006
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    The title compound crystallizes in the space group C2⁄c with a=18.85(2), b=6.15(1), c=27.94(2) Å, β=111.3(1)°, and Z=8. The structure was determined from the photographic X-ray data and was refined by the block-diagonal least-squares method to R=0.10 for 1006 observed reflections. Centrosymmetrically related molecules in the crystal form a dimer by means of weak intermolecular C–H···O hydrogen bonds. The thietane skeleton of the compound is bent with the dihedral angle, CαSCα/CαCβCα, of 148.7°. The average distance of the C–S bonds is 1.87 Å, while that of the C–C’s in the thietane ring is 1.58 Å. The conformation of the C–Cl bonds with respect to the thietane ring is (3a4e). The transannular S···Cl distance is 3.42 Å. The CNDO/2 calculation reveals that the 3d–3p bonding overlap is present between these atoms. The bond angles involving the ring substituents deviate greatly from those observed for cis-2,2-diphenyl-3,4-dichlorothietane. These deformations may be explained in terms of dipole-dipole interactions.
  • Kazuhiko Ishizu, Fujito Nemoto, Koji Yamamoto, Masao Nakazaki
    1975 Volume 48 Issue 7 Pages 2168-2171
    Published: 1975
    Released: March 27, 2006
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    The ENDOR spectra have been observed for the anion radicals of 3,3′- and 3,4′-polymethylenebiphenyl with various chain lengths. The hyperfine coupling constants of the ring protons of the 3,3′-derivatives are comparable with those of the reference derivative, m,m′-bitolyl, and the biphenyl ring is considered to take the planar conformation. When the chain length is shortened and the polymethylene chain increases its probability of being held on the biphenyl aromatic plane, strong through-space interactions are observed between the aromatic π and the polymethylene pseudo-π orbital. In 3,4′-polymethylenebiphenyl with shorter chain lengths, the coplanar phenyl rings are twisted out by the polymethylene span and the magnitudes of the spin densities at the ortho-position are reduced by the resonance inhibition between two phenyls. McLachaln’s MO calculations predict that the twisting angles between the two phenyls are similar to the value reported for 2,2′-bitolyl anion radical. In contrast to the case of the 2,2′-bitolyl anion radical, however, a conformational change in biphenyl resulting from the delocalization of the unpaired electron is suppressed by a tight lock of the rotation of the phenyl groups in the polymethylene derivatives.
  • Shunzo Yamamoto, Kazuyuki Tanaka, Shin Sato
    1975 Volume 48 Issue 7 Pages 2172-2175
    Published: 1975
    Released: March 27, 2006
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    A luminescence similar to the photosensitized luminescence of ammonia was observed in the cadmium-photosensitized reaction of water, alcohols, and ethers. The quantum yields of the luminescence with these compounds were much smaller than that with ammonia. The rate constants for the formation of the excited complexes between the excited cadmium atoms and the substrates generally increased with a decrease in the ionization potentials of the substrates. This shows that the complex has the characteristics of a charge-transfer type. On the other hand, the efficiencies of the quenching of the resonance radiation at 326.1 nm by ethers were smaller than those of alcohols. It is concluded that the quenching through the formation of the complex is a minor process in the quenching of the resonance radiation by water, alcohols, and ethers.
  • Tamotsu Wasa, Soichiro Musha
    1975 Volume 48 Issue 7 Pages 2176-2181
    Published: 1975
    Released: March 27, 2006
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    The construction of a microdetector, based on the principle of polarography, for liquid chromatography and its application are described. The characteristics of the flow cells with a horizontal dropping mercury electrode (HDME), a vertical dropping mercury electrode (DME), and a mercury plated platinum electrode (Hg–Pt) are compared with each other. The flow cell has been applied to the analysis of a mixture of nitropyridine derivatives, such as 2-amino-3-nitropyridine (A3N), 2-amino-5-nitropyridine (A5N), 2-hydroxy-3-nitropyridine (O3N), 2-hydroxy-5-nitropyridine (O5N), and 2-nitroaminopyridine (NA), by means of a reversed-phase partition column or an ion-exchange column. In quantitative analysis, a standard deviation of better than 3% can be obtained.
  • Enzo Tachikawa, Yasuyuki Aratono
    1975 Volume 48 Issue 7 Pages 2182-2184
    Published: 1975
    Released: March 27, 2006
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    The HT and DT yields from the nuclear transformation of 6Li(n,α)T in H2O–D2O binary mixtures were studied in the liquid phase. The (HT/H2O)/(DT/D2O) ratio was nearly constant at 1.60±0.08 over the whole range of mol fractions of D2O in the presence of I2 as a scavenger. Using the kinetic model with reasonable assumptions, the relative efficiencies for the kinetic moderation of H2O, HDO, and D2O were determined. The results indicate that the collision of recoil T atoms with HDO, with a large fractional energy loss, must occur as frequently as with H2O.
  • Masatoshi Watabe, Sadao Yoshikawa
    1975 Volume 48 Issue 7 Pages 2185-2186
    Published: 1975
    Released: March 27, 2006
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    Systematic correlations in CD spectra are found when the CD spectra of the isomers of the [Co(L-aspartato)(L-2,4-diaminobutyrato)] complex, the [Co(N)3(O)3] type, are compared with those of the isomers of the [Co(L-2,4-diaminobutyrato)2]+, the [Co(N)4(O)2] type, and those of the isomers of the [Co(L-aspartato)2], the [Co(N)2,(O)4] type.
  • Yoshihisa Matsui, Toyoaki Kurita, Masao Yagi, Tetsuo Okayama, Kazuo Mo ...
    1975 Volume 48 Issue 7 Pages 2187-2191
    Published: 1975
    Released: March 27, 2006
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    Copper(II) forms a 2: 1 complex with cyclodextrin in an alkaline solution. The complexes with α- and β-cyclodextrins were isolated from solutions by the addition of ethanol. They are labile, and, upon heating, the Cu(II) is reduced to Cu(0). The role of the hydroxide ion was examined by means of potentiometrie and conductometric titrations; it was found that the reaction of 1 mol of α-cyclodextrin with 2 mol of Cu(OH)2consumes 2 mol of the hydroxide ion, whereas 3 mol of the hydroxide ion are consumed for the reaction of β-cyclodextrin. Polarimetric measurements showed that the optical rotation of cyclodextrin changes from dextrorotatory to levorotatory upon the formation of the Cu(II)-cyclodextrin complex. It was suggested, with a molecular model, that the two pairs of C2 and C3′ secondary hydroxyl groups of contiguous glucose units are cross-linked by the Cu(OH)2Cu ion bridge in the α-cyclodextrin complex and by Cu(OH)(O2−)Cu ion bridge in the β-cyclodextrin complex. Furthermore, the circular ring of cyclodextrin may be distorted to the ellipsoidal form by the complex formation, causing a pronounced change in the optical rotation.
  • Yoshitane Kojima, Masanori Matsui, Keiji Matsumoto
    1975 Volume 48 Issue 7 Pages 2192-2196
    Published: 1975
    Released: March 27, 2006
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    X-Ray structure analysis has elucidated that the reaction of Nδ-salicylidene-L-ornithine and palladium(II) acetate in DMF results in the amine exchange and racemization of the ligand, yielding (Nα-salicylidene-D-ornithinato)(Nα-salicylidene-L-ornithinato)dipalladiuna(II). The yellow crystals are monoclinic, a=15.15(2), b=9.80(1), c=15.67(2) Å, β=111.3(1)°, space group P21c, and Z=2. The structure was solved by the Patterson and Fourier techniques and was refined by the least-squares method to R=0.105. The complex molecule has a center of symmetry by which D- and L-Schiff-base ligands are interrelated. Each Pd atom has a square-planar coordination by means of two O and Nα atoms of one ligand, and the Nδ atom of the other one, the two N atoms being in the trans position. The H2Nδ–(CH2)3–CH–Nα fragments of the two ligands bridge the two Pd atoms, giving a 14-membered ring.
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