Bulletin of the Chemical Society of Japan
Online ISSN : 1348-0634
Print ISSN : 0009-2673
ISSN-L : 0009-2673
Volume 44 , Issue 1
Showing 1-50 articles out of 84 articles from the selected issue
  • Seiki Sakanoue, Noritake Yasuoka, Nobutami Kasai, Masao Kakudo
    1971 Volume 44 Issue 1 Pages 1-8
    Published: 1971
    Released: March 27, 2006
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    [2(C9NH8)+·(C10N6)2−] crystallizes in the form of the space group of Pbcn, with four formula units in the unit cell, and the following unit-cell dimensions: a=13.18, b=15.40, and c=11.56 Å. The structure was determined by obtaining phases directly from the structure-factor magnitudes by means of the symbolic addition procedure. For 1580 non-zero reflections, the final R is 0.147. The crystal structure shows that the packing unit is an “ion-pair” consisting of one di-valent anion and two mono-valent cations. The anion is sandwiched by two cations with weak charge-transfer interaction between them; the closest atomic contact is 2.99 Å. These units stack infinitely, forming a column, along the a axis. Between these stacking columns, there exists a hydrogen bond (N–H···N, 2.84 Å) along the b axis. The (C10N6)2− anion has a C2-2 symmetry; cyano-substituents are tilted out of the plane formed by four central carbon atoms, and the anion takes a propeller shape. The one arm is rotated 13° from the completely planar conformation, while the other two are rotated 24°. On the other hand, the (C9NH8)+ cation seems not to be planar.
  • Shoji Hiroma, Haruo Kuroda, Hideo Akamatu
    1971 Volume 44 Issue 1 Pages 9-15
    Published: 1971
    Released: March 27, 2006
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    Polarized absorption spectra in the 10–40 kK region were observed on single crystals of the ion radical salts of tetracyano-p-quinodimethane (TCNQ), potassium·(TCNQ) and cesium2·(TCNQ)3. The crystal spectra are shown to be markedly different from the solution spectra of the monomer and dimer of TCNQ ion. It is shown that the 7.8 kK band of K(TCNQ) and the 11.1 kK band of Cs2(TCNQ)3 are charge-transfer bands associated with the transfer of an electron from a TCNQ ion to the neighboring TCNQ ion. The first-order and second-order effects were calculated on the local-excitation bands in order to explain the general feature of the observed spectra.
  • Otohiko Nomoto, Harumi Endo
    1971 Volume 44 Issue 1 Pages 16-19
    Published: 1971
    Released: March 27, 2006
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    The sound velocity in aqueous solutions of NH4I and Pb(NO3)2 is investigated in relation to the temperature and the concentration. In both solutions the V(T) curves show maxima Vp at the peak temperature Tp the Tp shifting to a lower temperature with an increase in the concentration. While the shift of Tp is sensibly linear with the concentration for Pb(NO3)2, the curve for NH4I is almost constant up to 25 wt%, though it decreases linearly above this concentration. This corresponds to the rather abrupt change in the degree of dissociation obtained from the conductivity data. The constancy of Tp below 25wt% is tentatively explained on the basis of Danford and Levy’s X-ray diffraction study which concluded that NH3 is included in cavities of the water framework and that the framework molecules are partially replaced by NH3.
  • Hideo Akutsu, Masamichi Tsuboi
    1971 Volume 44 Issue 1 Pages 20-22
    Published: 1971
    Released: March 27, 2006
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    Three copolymers of riboinosinic acid and ribouridylic acid (poly I,U) with uridylic acid contents, 20, 32, and 44% were prepared. The ultraviolet absorption measurements were carried out with aqueous solutions of mixtures of poly I,U and polytribocytidylic acid (poly C) of various mole ratios. It has been shown that a double-helical structure is formed with an I···C type inter-base binding and with the U residue looping out of the helix. The structure was found to break on heating the solution. The process of break down was followed by means of ultraviolet absorption measurements.
  • Hiroko Yamabe, Hiroshi Kato, Teijiro Yonezawa
    1971 Volume 44 Issue 1 Pages 22-27
    Published: 1971
    Released: March 27, 2006
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    The electronic structure, the electronic transition, and the interaction of lone pairs of H2S2, H2O2, and N2H4 for several dihedral angles are studied by the semi-empirical ASMO SCF method, and their dependencies on the dihedral angle is discussed. Also, the interaction of the lone pairs of diimides, N2H2, N2F2, and (CH3)2N2, the relative stability of the cis forms and of their trans form, and the electronic transition energies of these molecules are calculated. The stable forms of N2H2 and (CH3)2N2 are calculated to be of the trans form, but that of N2H2 is the cis form. An energy component analysis of these compounds has been made. The main factor in the lack of stability of the cis form of N2H2 is shown to be the core-core repulsion term, Vnn. On the other hand, in H2S2 and N2H4 not only the Vnn term but also the electrostatic interaction term, \oversetocc\underseti,jΣ(2JijKji), contributes to their instability.
  • Hiroto Fujimaki, Isao Oonishi, Fumio Muto, Akitsugu Nakahara, Yoshimic ...
    1971 Volume 44 Issue 1 Pages 28-33
    Published: 1971
    Released: March 27, 2006
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    The crystal structure of N-salicylidene-α-aminoisobutyratoaquocopper(II), [Cu{OOCC(CH3)2N=CHC6H4O}(H2O)], has been determined from the three-dimensional X-ray diffraction data. The crystals are monoclinic. The cell dimensions are: a=12.30, b=8.45, c=23.84 Å, and β=91.0°. The space group is P21/c, with eight formula units in a unit cell. The structure has been refined by the least-squares method, with anisotropic temperature factors, to an R-value of 0.10. The molecular structures of the complex are essentially the same as those of N-salicyl ideneglycinatoaquocopper(II) hemihydrate and tetrahydrate. The environments of the copper(II) ions are square pyramidal, with one long and four short coordination bonds. The average distances of the two copper environments are: Cu–O, 1.912 and 1.945; Cu–N, 1.961; Cu–O(H2O), 1.989, and Cu–O′ (the bond to the carboxyl oxygen of the adjacent molecule), 2.344 Å. The average bond distances of N=C in the salicylaldimine residue and of N–C in the α-aminoisobutyrate group are 1.271 and 1.504 Å respectively. Neighboring molecules related by a center of symmetry are linked together alternately by hydrogen bonds and coordination bonds (Cu–O′), an infinite chain being formed along the b-axis. However, there are no interactions other than van der Waals forces along the a- and c-axes.
  • Masao Hino, Toshio Sato
    1971 Volume 44 Issue 1 Pages 33-37
    Published: 1971
    Released: March 27, 2006
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    Infrared absorption spectra of the systems of silica gel - H216O,D216O,H218O, and some organic vapors were measured in order to assign the bands senstive to adsorption at 870 and around 950 cm−1. Deuteration of silica gel caused the absorption decrease at 870 cm−1 and the appearance of a band at 620 cm−1. The band around 950 cm−1 appearing by adsorption not only of water but also of organic vapors showed no shift on deuteration, but shifted toward low frequency side by 25 cm−1 on the substitution of 16O of surface silanol groups with 18O. From these facts the bands at 870, 620 and 950 cm−1 were assgned to Si–OH bending, Si–OD bending and Si–O stretching vibrations of surface silanol groups, respectively. The oxygen atom of silanol groups of silca gel was found to exchange with that of adsorbed water molecules even at room temperature for a sample treated at temperature below 300°C. On the other hand, higher reaction temperature of ca. 200°C was necessary for a sample calcined at 800°C. mechanism of the oxygen atom exchange recation was discussed.
  • Hiroshi Masuhara, Michio Okuda, Masao Koizumi
    1971 Volume 44 Issue 1 Pages 38-43
    Published: 1971
    Released: March 27, 2006
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    The electronic structures of semiquinones of anthracene and its related heterocycles were calculated, using the open shell SCF procedure combined with configuration interaction calculations. A general classification and some peculiarities of the observed absorption spectra of these semiquinones can be readily explained by the present theoretical results. The effects of resonance integral and configuration interactions were examined in detail. The results obtained by considering the effect of hyperconjugation were added.
  • Kizashi Yamaguchi, Takayuki Fueno
    1971 Volume 44 Issue 1 Pages 43-48
    Published: 1971
    Released: March 27, 2006
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    The semi-empirical valence-shell SCF MO theory (the INDO method) by Pople et al. has been modified for the purpose of calculating the electronic excitation energies of organic compounds. All the necessary one-center parameters have been evaluated from the valence-state ionization data of Hinze and Jaffé, combined with the Slater-Condon atomic parameters. The INDO method thus modified has been applied to carbonyl compounds and conjugated dienes. The calculated excitation energies have been found to be satisfactory in many respects.
  • Hisanobu Ogoshi, Naruhito Masai, Zen-ichi Yoshida, James Takemoto, Kaz ...
    1971 Volume 44 Issue 1 Pages 49-51
    Published: 1971
    Released: March 27, 2006
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    The infrared spectra of the Mg(II), Co(II), Cu(II), Zn(II), Pd(II), Ni(II), and Ge(IV)Cl2 complexes of octaethylporphyrins have been studied over the range 4000–100 cm−1. Metal sensitive bands have been observed at about 980, 920, 340, 230, and 130 cm−1.
  • Kazuo Sato, Atsuo Nishioka
    1971 Volume 44 Issue 1 Pages 52-55
    Published: 1971
    Released: March 27, 2006
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    The spin-lattice relaxation time T1 and chemical shift of N-methylacetamide (NMA) and N,N-dimethylacetamide (DMA) were measured in D2O and CCl4 solutions. In D2O solution, it has been found that the weak interamide hydrogen bonding of NMA does not affect the spin-lattice relaxation entirely, and the molecular motion of NMA and DMA is almost identical. However, quite different results were obtained for CCl4 solution. The molecular association of NMA in CCl4 solution is strong enough to exhibit appreciable effects on spin-lattice relaxation. The life time of the associated molecules has been estimated to be longer than 10−10–10−11 sec. The association of DMA at high concentration region in CCl4 could be verified from the concentration dependence of the spin-lattice relaxation rate as well as chemical shift.
  • Yoshio Suzuki, Y\={o}ichi Iitaka
    1971 Volume 44 Issue 1 Pages 56-63
    Published: 1971
    Released: March 27, 2006
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    In order to determine the structure of the 3 : 2 adduct (acetylene : isonitrile) obtained by cycloaddition reaction of dimethyl acetylenedicarboxylate with 2,6-dimethylphenylisonitrile and to elucidate the route of the reaction, a heavy atom derivative of this adduct was prepared and subjected to X-ray diffraction analysis. The crystal grown from acetone solution has the composition C36H34N2O12Br2·CH3COCH3 and belongs to monoclinic system with the lattice constants: a=34.13±0.04, b=14.66±0.02, c=8.10±0.01 Å, β=90.5±0.2°. The space group is P21n containing four formula units in the cell. The structure was solved by the heavy atom method and refined by the block-matrix least-squares method for 1482 observed reflections allowing the anisotropic thermal motions for each atom. It has been shown that the chemical structure of the adduct is 1-(4-bromo-2,6-dimethylphenyl)-2-(4-bromo-2,6-dimethylphenyl)imino-1,2-dihydro-3,4,5,5,6,7-hexacarbomethoxy-5H-1-pyrindine.
  • Noboru Yamazaki, Yorikatsu Hohokabe
    1971 Volume 44 Issue 1 Pages 63-69
    Published: 1971
    Released: March 27, 2006
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    Cobaloximes with the general formula: [CoX(DH)2B] or [RCo(DH)2B] (X: Cl, CN. R: Alkyl groups such as methyl, ethyl, n-propyl, i-propyl, n-butyl, benzyl, or hydroxypropyl. DH: Dimethylglyoximato monoanion. B: Bases such as water, nicotinamide, p-toluidine, pyridine, γ-picoline, imidazole, or 4-vinylpyridine), and polymeric cobaloximes with the general formula: [Co(OH)(DH)2(Copoly–AM-VPy)] (Copoly–AM-VPy: a low molecular weight copolymer of acrylamide and 4-vinylpyridine), were synthesized and their infrared and far-infrared spectra were examined. The frequency shifts by changing the axial ligands were discussed.
  • Shigeo Hasegawa, Setsuo Kashino, Yoshinobu Mukahi
    1971 Volume 44 Issue 1 Pages 69-71
    Published: 1971
    Released: March 27, 2006
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    The rate constants of the reaction of benzoyl peroxide with some typical secondary amines, namely, diphenylamine, N-methylaniline, and piperidine, were measured in benzene-nitrobenzene binary mixed solvents. The reaction rates of diphenylamine and N-methylaniline are little influenced by the compositions of the solvents, while the reaction of piperidine proceeds more rapidly in nitrobenzene than in benzene. The isokinetic relationship holds for the reaction of piperidine in the binary mixed solvents. The isokinetic temperature is calculated to be 265°K. The analysis of the behavior of these reactions in the mixed solvents leads to the conclusion that, in the cases of diphenylamine and N-methylaniline, there are no specific interactions between the activated complexes and solvent molecules, whereas in the case of piperidine the activated complex is weakly solvated with the polar nitrobenzene. The reaction of benzoyl peroxide with N-methylaniline and N-n-butylaniline was also studied in benzene. These amines have a higher reactivity than would be expected from their basicity. This higher reactivity is probably due to the resonance stabilization of the activated complex besides the formation of a lessionic activated complex.
  • Akimichi Yokozeki, Kozo Kuchitsu
    1971 Volume 44 Issue 1 Pages 72-77
    Published: 1971
    Released: March 27, 2006
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    The structure and intramolecular motions in triethylenediamine have been investigated by gas electron diffraction with a parallel study of bicyclo[2.2.2]octane in our previous paper. The structural parameters determined by a least-squares analysis on molecular intensities, with estimated limits of error, are as follows: rg(C–N)=1.472±0.007 Å, rg(C–C)=1.562±0.009 Å, ∠C–C–N=110.2±0.4°, ∠C–N–C=108.7±0.4°, rg(C–H)=1.110±0.012 Å and ∠H–C–H=111.5±5.6°. The gas-phase structure is in good correspondence with that in the crystal phase determined by Weiss et al. by X-ray diffraction. The potential function with regard to the twisting motion around the C3 symmetry axis is shown to have a broad minimum around the D3h conformation, being quite analogous to that for bicyclo[2.2.2]octane; in terms of the torsional angle φ about the C–C axis, it probably has a small hump of the order of 100 cal/mol at φ=0° and a double minimum around φ=10°. The above study was made with a new nozzle assembly, by which the sample can be heated to about 200°C. The detail of the design and operation is described.
  • Keiichiro Adachi, Hiroshi Suga, Syûzô Seki
    1971 Volume 44 Issue 1 Pages 78-89
    Published: 1971
    Released: March 27, 2006
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    2,3-Dimethylbutane has two crystalline phases, high temperature form (crystal-I) and low temperature form (crystal-II). On account of the supercooling effect of crystal-I, its glassy crystalline state (non-equilibrium frozen-in state) is established below Tg (76 K) by rapid cooling. The heat capacities for various phases were determined from 13 to 300 K from principal interest in the thermodynamic properties of the glassy crystal. The transition temperature from crystal-II to crystal-I and melting point were determined to be 136.02 K and 145.05 K, respectively. The heats of transition and of fusion were determined to be 6427 J mol−1 and 788 J mol−1, respectively. From these data, the residual entropy and T2 temperature were determined to be 7.4 JK−1 mol−1 and 65 K, respectively. We also calculated the ratio of Tg to T2 for several glassy crystals known hitherto, which amounts to 1.15–1.20. The stabilization effect was studied by the measurement of the change of the configurational enthalpy in the glassy crystalline state. Also, we discovered a new meta-stable intermediate phase (crystal-III) in the course of irreversible transition from the supercooled crystal-I to crystal-II. The thermal properties of this phase were also studied and its residual entropy was determined to be 2.7 JK−1 mol−1.
  • Tsunetake Fujiyama
    1971 Volume 44 Issue 1 Pages 89-93
    Published: 1971
    Released: March 27, 2006
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    Force constants of the Urey-Bradley type are calculated for a series of alkanonitriles. The calculation covers the mononitriles: CH3CN, CH3CH2CN, (CH3)2CHCN, (CH3)3CCN, and the dinitriles: NCCH2CN, NCCHDCN, NCCD2CN, trans-NCCH2CH2CN, gauche-NCCH2CH2CN. The results show that the force constants can be transferred from molecule to molecule as a group. It is also shown that a group of force constants is characteristic of a corresponding chemical structure or a substituent.
  • Kuan Pan, Chin Chan Lai, Teh-Shoon Huang
    1971 Volume 44 Issue 1 Pages 93-96
    Published: 1971
    Released: March 27, 2006
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    The dissociation constant of Ti(C2O4)2 ions in hydrochloric acid media was evaluated from the data obtained by spectrophotometric measurements at 25°C. The average value of pK for the reaction, Ti(C2O4)2=Ti(III)+2C2O42−, at an infinite dilution was estimated as 9.0, while that for the Ti(C2O4)2=Ti3++2C2O42− reaction was evaluated as 8.74.
  • Kozo Kuchitsu
    1971 Volume 44 Issue 1 Pages 96-99
    Published: 1971
    Released: March 27, 2006
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    A number of definitions with clear physical significance regarding the “average bond angles” (nonlinear case) are presented. Simple expressions of the average angles in terms of the linear and quadratic mean values of the displacements in the internuclear distances are given. The differences in the various average angles for H2O, D2O, CH4, CD4 and SO2 are estimated by means of a normal-coordinate analysis. The differences are shown to be small fractions of one degree. The root-mean-square angles for linear molecules (HCN, DCN, CO2 and CS2) are also calculated.
  • Ariyuki Aihara, Chikazu Kitazawa
    1971 Volume 44 Issue 1 Pages 99-103
    Published: 1971
    Released: March 27, 2006
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    A critical remark on the interpretation of the polarity of cyclohexane-1,4-dione molecule has been made taking into consideration a possible contribution of atomic polarization estimated from the electric permittivity of the compound in the solid state. The value 9.6 cc has been assigned as the minimum for atomic polarization which gives dipole moments, 1.16D (28.6°C), 1.20D (42.9°C), and 1.22D (60.8°C) obtained in benzene solutions. A theoretical calculation of the dipole moment has been made also with an assumed potential barrier of the form, V(θ)=V0. [(π–θ)−2β]⁄2α, in relation to a flexing intramolecular movement of the molecule, where θ is the angle between two carbonyl groups substituted at the opposite sites of the molecule, V0 is the potential for a boat form A (with two carbonyl groups at the bow and the stern), and α, β are constants to be determined by applying boundary conditions: V(θ)=0 for θ=180°–137°, and V(91°)=V0. By taking 2.46D as the bond moment of carbonyl group, the best fit has been realized between the theoretical and experimental dipole moments when V0 is assumed to be close to 6000 cal/mol, i. e., twice as large as the hindering potential for the internal rotation of ethane molecule. Mention has also been made of the mechanism of dielectric absorption by this molecule in benzene solution with particular reference to the flexing motion suggested above.
  • Shuichi Hamada
    1971 Volume 44 Issue 1 Pages 104-107
    Published: 1971
    Released: March 27, 2006
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    The Radical growth rates of the selenium spherulites were measured by the microscopic method at temperatures ranging form 128.4°C to 192.3°C. The radial growth rate increased with an increase in the crystallization temperature up to about 180°C, reached a maximum value of 87.0 μ/min, and then decreased abruptly, judging form the observation of organic polymers at crystallization temperatures near their melting points. The process of the spherulite growth of selnium near the melting point could not be interpreted by only two elementary processes, that of the segmental jump and that of the formation of a two-dimensional nucleus of a critical size. The variation in the radial growth rate of selenium with the temperature was explained by considering the bond-breaking process as an elementary process. The estimated surface free energy at the liquid-crystal interface was 25.1 erg/cm2; this value was a reasonable one.
  • Hisae Enokido, Takako Shinoda, Yo-ichiro Mashiko
    1971 Volume 44 Issue 1 Pages 108-111
    Published: 1971
    Released: March 27, 2006
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    A simplified apparatus has been constructed for determining the purity of organic compounds by time-temperature freezing or melting curves. The sample cell is small and the amount of the sample needed in only 0.2 ml or 2 ml. The thermometers used are a Shimadzu platinum resistance thermometer calibrated by the measurement of fixed points and a chromel p-constantan thermocouple calibrated against a standard platinum thermometer with a precision better than ±0.03°. Purities of several hydrocarbons were determined by measuring their freezing and melting curves.
  • Toshio Tanaka, Koji Tanaka, Tokio Yoshimitsu
    1971 Volume 44 Issue 1 Pages 112-117
    Published: 1971
    Released: March 27, 2006
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    Dimethyltin-bis(N,N-dimethyldithiocarbamate), (CH3)2Sn[S2CN(CH3)2]2, reacts with dihalogenoalkanes to give 1,3-dithiacycloalkyl-2-dimethylimminium dimethyltin halides, (Remark: Graphics omitted.) (n=1 or 2; m=2, 3, or 4; X=Cl, Br, or I). On the other hand, the reactions between dimethyltin bis(N-methyl-N-phenyldithiocarbamate), (CH3)2Sn[S2CN(CH3)(C6H5)]2, and dihalogenoalkanes yield preferentially alkylene bis(N-methyl-N-phenyldithiocarbamate). The difference in reactivity between the two types of complexes is discussed. The infrared and NMR spectra indicate that the positive charge on the dithiacycloalkylimminium ions is more delocalized in the higher homologues. The configurations of dimethyltin trihalide and tetrahalide anions in the solid state and in solution are also presented on the basis of the infrared spectra; the results suggest that, in solution, dimethyltin trihalide anions are more likely to be formed than are dimethyltin tetrahalides.
  • Hideo Akaiwa, Hiroshi Kawamoto, Masanobu Abe
    1971 Volume 44 Issue 1 Pages 117-120
    Published: 1971
    Released: March 27, 2006
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    A highly sensitive method for the spectrophotometric determination of copper(II) with 2-thenoyltrifluoroacetone (TTA) is described. Copper(II) is extracted with TTA in cyclohexane at pH 5.5 and the residual TTA in the organic phase is removed by washing with sodium hydroxide solution containing pyridine. Pyridine is added to the washing solution so that it forms an adduct and prevents the copper-TTA chelate from decomposing during the alkali treatment process. The absorbance of the organic phase is measured at 340 mμ. Beer’s law is followed over the concentration range of 0.1 to 1.0 μg of Cu per ml, the sensitivity being 0.0023 μg Cu/cm2 at 340 mμ. The present method was applied to the analysis of natural water.
  • Tasuku Murakami, Kazuko Ogino, Hiromi Kobayashi, Hiroshi Yamazaki, Kaz ...
    1971 Volume 44 Issue 1 Pages 120-124
    Published: 1971
    Released: March 27, 2006
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    Kinetics of aquation has been studied with pentamminecobalt(III) complexes containing aliphatic amino acids (γ-aminobutyric acid, ε-aminocaproic acid, α-amino-isobutyric acid, ornithine, and proline), aromatic acids (benzoate, anthranilic, and p-aminobenzoic acid), and α-substituted acetates (monochloroacetate and glycolate). Anation rate constants were obtained for glycine, β-alanine, and ε-aminocaproic acid, and equilibrium constants between [CoH2O(NH3)5]3+ and [Co(NH3)5amH]3+ (amH=amino acid), Keq were calculated. The free energy plot logkaq vs. logKeq gave a straight line with a gradient 0.6. This value has been discussed in terms of two possible mechanisms. The dependence of acid catalysed aquation rate constant, kH+ on pKa of carboxylate group of the amino acid is written as logkH+=0.5 pKa+ const., while that for α-substituted acetates log kH+=pKa+ const. Such a difference in the slope is interpreted as due to the electrostatic influence of–NH3+ group of coordinated amino acid.
  • Masao Okubo, Kazuhiro Maruyama, Jir\={o} Osugi
    1971 Volume 44 Issue 1 Pages 125-129
    Published: 1971
    Released: March 27, 2006
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    Benzoyl peroxide was found to react with Grignard reagents (RMgBr) in tetrahydrofuran at 0°C to form PhCOOR and PhCOOMgBr. The latter which was isolated as a complex containing two molecules of the solvent, can be coordinated by benzoyl peroxide to form an orange-colored complex. Similar complexes were found to be formed in the cases of some substituted benzoyl peroxides. The initial stage of the reaction was studied with the technique of competitive reaction. The results can be explained by assuming the coordination of the carbonyl oxygen atom of benzoyl peroxide to the Grignard magnesium atom. The effect of the substituent of the peroxide on the reaction was discussed.
  • Juntaro Tanaka, Takao Katagiri, Kiyomi Ozawa
    1971 Volume 44 Issue 1 Pages 130-132
    Published: 1971
    Released: March 27, 2006
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    The stereochemistry of the reduced products of the iridenes was studied, and the main product produced by the thermal isomerization from pinane was confirmed to be 1-trans-2-dimethyl-trans-3-isopropenylcyclopentane, unlike as in the literatures. Moreover, the ozonolyses of the iridenes were reexamined in detail, and the following results were obtained: 1) When the ozonides were decomposed with Na2CO3-H2O2, the substituent on C-3 was epimerized. 2) On the other hand, when the ozonides were treated with Zn-CH3COOH, no such epimerization occurred. Consequently, it was found that the former method when used for the confirmation of iridenes, did not give good results for assignments of these compounds.
  • Kiyomi Nakamura
    1971 Volume 44 Issue 1 Pages 133-138
    Published: 1971
    Released: March 27, 2006
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    The reaction of polyalkylated aromatic compounds with fuming nitric acid has been investigated with respect to the effects of substituents and added electrolytes on the ease and extent of the concurrent side-chain nitrooxylation and nuclear nitration. Relative reactivity of substituted pentamethylbenzenes C6(CH3)5X for side-chain substitution decreases from 1 to 2×10−2 to 4×10−4 to 3×10−6 with the change of substituent groups from methyl to hydrogen to bromine to nitro in accordance with the ionic character of the reaction. Added electrolytes have profound influence on the reaction rates, but the ratio of products from side chain nitrooxylation and nuclear nitration remains almost unchanged, indicating that both processes share a common intermediate. The relative amount of side-chain substitution depends closely on the positional relationship of alkyl groups in the nucleus, and preferential formation of p-alkylbenzyl nitrates is always observed. It is concluded from the results, that the side-chain nitrooxylation products are formed by way of the polar intermediate common with the ring nitration products. Some plausible reaction sequences are briefly discussed.
  • Masao Kitajima, Wataru Sekiguchi, Asaji Kondo
    1971 Volume 44 Issue 1 Pages 139-143
    Published: 1971
    Released: March 27, 2006
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    Modified red cells that have a reinforced membrane and hemoglobin which is difficult to denature are prepared by treating red cells with some isocyanates. These modified cells have the same shape as normal red cells, but they are not lysed by osmotic pressure or by the actions of any reagents except for some ionic surface-active agents. No agglutination was observed when they were mixed with the blood of foreign animals or with blood of different blood groups. The hemoglobin within the cell gave a reversible oxygenation curve and had a high oxygen affinity. Toluene-2,4-diisocyanate was found to be the most suitable reagent among the many isocyanates examined. A suspension reaction method which consists of the addition of an isocyanate emulsion to a red-cell suspension at 5°C is developed for the modification process.
  • Satoru Makisumi, Michinori Waki, Nobuo Izumiya
    1971 Volume 44 Issue 1 Pages 143-148
    Published: 1971
    Released: March 27, 2006
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    Six linear decapeptides having the same sequence of amino acids of gramicidin S, wherein the N-terminal amino acid is acylated with formyl or acetyl group, the C-terminal amino acid is in a form of its amide or ethanolamide and the N,C-terminal ones are free, were synthesized to obtain a more reliable picture of the cyclic structure to the antibacterial activity of gramicidin S. All these linear decapeptide analogs were found to be active to some extent against several microorganisms.
  • Ko Wakabayashi, Masaru Tsunoda, Yasushi Suzuki
    1971 Volume 44 Issue 1 Pages 148-152
    Published: 1971
    Released: March 27, 2006
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    During the liquid-phase chlorination of CH3CN, a trimerization reaction occurred to yield four s-triazine derivatives, 2-methyl-4,6-bis(trichloromethyl)-s-triazine (I), 2-chloromethyl-4,6-bis(trichloromethyl)-s-triazine (II), 2-dichloromethyl-4,6-bis(trichloromethyl)-s-triazine (III), and 2,4,6-tris(trichloromethyl)-s-triazine (IV). The structure of each s-triazine derivative has been assigned on the basis of the results of elemental analysis and the spectral (particularly Mass and NMR) data after each derivative had been separated in a pure form using the gas-liquid chromatographic (GLC) method. The product composition was seen to depend upon the rate of the chrorination of CH3CN and the presence of a catalyst. The s-triazine I was shown to be the precursor of the s-triazines II and III; the pathways for the formation of the s-triazine IV were also investigated. Then, the selective cotrimerization of CH3CN with its chlorinated compounds was investigated; this yielded the s-triazine I, a useful intermediate of pesticides and resines. The reaction was found to provide a new method of preparing s-triazine I.
  • Hiroshi Yamamoto, Masaru Nakata, Shiro Morosawa, Akira Yokoo
    1971 Volume 44 Issue 1 Pages 153-158
    Published: 1971
    Released: March 27, 2006
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    5,6,8,9-Tetrahydro-7H-pyrimido[4,5-d]azepine and some of its derivatives were synthesized. 6-Acetyl-3-hydroxy-4,5,7,8-tetrahydro-6H-pyrazolo[3,4-d]azepine was also synthesized.
  • Sannamu Lee, Reiko Ohkawa, Nobuo Izumiya
    1971 Volume 44 Issue 1 Pages 158-161
    Published: 1971
    Released: March 27, 2006
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    In order to investigate the contribution to antibacterial activity of the D-phenylalanine residues at 4- and 4′-position in gramicidin S, 4,4′-D-alanine-gramicidin S (XX) and 4-D-alanine-semigramicidin S (XXI) were prepared and tested for antibacterial properties. XX exhibited recognizable activity though weaker than that of gramicidin S, whereas XXI showed no activity on any of the microorganisms tested.
  • Teruaki Mukaiyama, Katsuaki Hagio, Hisashi Takei, Kazuhiko Saigo
    1971 Volume 44 Issue 1 Pages 161-166
    Published: 1971
    Released: March 27, 2006
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    It was found that various kinds of α-substituted carbonyl-stabilized sulfonium ylides were conveniently prepared from the corresponding sulfonium salts by treating with 50% aqueous sodium hydroxide. The reactions of sulfonium ylides with succinic anhydride afforded furofuran derivative by one step procedure in yields ranging these from 5 to 14%. The structures of furofuran derivatives were confirmed by IR spectrum, NMR sepctrum, degradation, and its behavior toward alkali and acid.
  • Shigeo Nishimura, Mamoru Katagiri, Tetsuo Watanabe, Masayoshi Uramoto
    1971 Volume 44 Issue 1 Pages 166-172
    Published: 1971
    Released: March 27, 2006
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    The hydrogenation and hydrogenolysis of ethyl 4-methyl-1-cyclohexenyl ether (I) have been investigated with six unsupported platinum metals as catalysts at 25°C under atmospheric pressure of hydrogen. The hydrogenation of I in ethanol was accompanied by the formation of 4-methylcyclohexanone diethyl acetal (II), the extent of which depended on the nature of the catalyst metals. The ratio of the acetal formation to hydrogenation increased with respect to the catalyst metals in the sequence Os<Ru<Ir<<Rh<Pd<Pt. The amount of the hydrogenolysis to give methylcyclohexane increased in the order Pd≅Ru<<Os<Rh<Ir<<Pt at an initial stage of the hydrogenation in ethanol. This order in hydrogenolysis was explained in terms of the action of the ionized hydrogen on the catalyst surface and the olefin isomerization activity of the catalyst metals. The stereochemistry of the hydrogenation of I was also studied and the results were interpreted on the basis of the proposed mechanism. I was also hydro-genated in t-butyl alcohol and isopropyl ether as solvents and, except in a few cases, the proportion of hydrogenolysis decreased with solvent in the order ethanol>t-butyl alcohol>isopropyl ether. The stereoselectivity in ether formation did not differ much among the solvents except over palladium.
  • Takashi Ando, Masazumi Nakagawa
    1971 Volume 44 Issue 1 Pages 172-177
    Published: 1971
    Released: March 27, 2006
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    In order to ascertain the effect of ring strain on the electronic spectra of cyclic acetylenes, a series of p,p′-bridged cyclic tolans (Vn, n=11, 12, 13, 14, and 18) has been synthesized. It was found that the increasing ring strain exerted an appreciable hypochromic effect and also caused a slight bathochromic shift of the absorption band. The bathochromic shift observed in the p,p′-bridged cyclic tolans (Vn) forms a contrast with the hypsochromic shift observed in the strained o,o′-bridged cyclic diphenyldiacetylene (VI, n=3).
  • Mutsuo Kataoka, Takashi Ando, Masazumi Nakagawa
    1971 Volume 44 Issue 1 Pages 177-184
    Published: 1971
    Released: March 27, 2006
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    The polymethylene ether derivatives of o,p′-dihydroxydiphenvlacetylene (VIIn, n=7,8,9,10,11 and 12) have been synthesized by the Fritsch-Buttenberg-Wiechell rearrangement. The electronic, infrared, and NMR spectra of VIIn were examined. It was observed that the increasing ring strain had a hypochromic effect, with a hypso-chromic shift of the long-wavelength band in the electronic spectra of VIn making a contrast with the bathochromic shift in the strained p,p′-bridged cyclic tolans.
  • Tadashi Sasaki, Toshiyuki Yoshioka, Yasuyuki Suzuki
    1971 Volume 44 Issue 1 Pages 185-189
    Published: 1971
    Released: March 27, 2006
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    ω-Chloroisonitrosoacetophenone was treated with ethylenic and acetylenic dipolarophiles to afford 3-benzoylisoxazolinines and -isoxazoles, respectively. With m-nitrobenzaldoxime or m-nitrobenzonitrile, it yielded 3-benzoyl-5-(m-nitrophenyl)-1,2,4-oxadiazole. The phenylhydrazones of the 3-benzoylisoxazole and -oxodiazole thus produced were converted to the corresponding 1,2,3-triazoles thermally or by the treatment with a base. The photoinduced rearrangement of 3-benzoyl-5-phenylisoxazole afforded 2-benzoyl-5-phenyloxazole. Treatment of ω-chloroisonitrosoacetophenone with aziridine afforded a new type of aziridine oximes, which was converted to 2-benzoyloxazoline.
  • Teruaki Mukaiyama, Kazuhiko Saigo, Hisashi Takei
    1971 Volume 44 Issue 1 Pages 190-192
    Published: 1971
    Released: March 27, 2006
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    It was found that α-bromo-α-hydroxyimino compounds were obtained in good yields by the reactions of sulfonium bromides, such as dimethylphenacylsulfonium bromide, acetonyldimethylsulfonium bromide and ethoxycarbonylmethyldimethylsulfonium bromide, with isopropyl nitrite. On the other hand, (α-hydroxyiminophenacyl and -acetonyl)pyridinium bromides were obtained in quantitative yields by the reactions of pyridinium bromides, such as phenacylpyridinium bromide and acetonylpyridinium bromide, with isopropyl nitrite. Further, the reactions of α-bromo-α-hydroxyimino compound or (α-hydroxyiminophenacyl)pyridinium bromide, which were obtained by the above mentioned reactions, with several nucleophiles were studied.
  • Toshio Nakagawa, Tetsuyoshi Takamoto
    1971 Volume 44 Issue 1 Pages 192-196
    Published: 1971
    Released: March 27, 2006
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    7-(3′-Deoxy-3′-nitro-β-D-glucopyranosyl)theophylline (1) was treated with acetic anhydride in the presence of boron trifluoride, perchloric or phosphoric acid as a catalyst to afford the corresponding 2′,4′,6′-tri-O-acetate (4) in 87, 60 and 48% yields, respectively. With galacto-isomer (2), tri-O-acetate (6) was obtained in a high yield by the use of phosphoric acid or a large excess of perchloric acid as a catalyst, while 4′,6′-di-O-acetate (5) was selectively prepared in 82% yield when a trace of perchloric acid was used. The similar preparation of 4′,6′-di- and 2′,4′,6′-tri-O-acetates (7 and 8) of manno-isomer (3) was also carried out in the presence of boron trifluoride and phosphoric acid, respectively. The positions of the acetyl groups in the diacetates 5 and 7 were unequivocally deduced from NMR data.
  • Teruaki Mukaiyama, Mitsunori Hashimoto
    1971 Volume 44 Issue 1 Pages 196-199
    Published: 1971
    Released: March 27, 2006
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    Phosphorylation of alcohols and phosphates forming mixed esters of phosphoric acid and pyrophosphate by the oxidation-reduction condensation with triphenylphosphine and 2,2′-dipyridyl disulfide has been investigated. n-Butyl p-nitrophenyl phosphate was obtained in 80% yield when p-nitrophenyl dihydrogen phosphate was treated with one equiv. each of triphenylphosphine and 2,2′-dipyridyl disulfide in the presence of three equiv. of anhydrous n-butyl alcohol at room temperature. It was found that P1,P2-bis(p-nitrophenyl)pyrophosphate was obtained in 91% yield when p-nitrophenyl dihydrogen phosphate was treated with 1.5 equiv. each of triphenylphosphine and 2,2′-dipyridyl disulfide.
  • Toshio Kawato, Takahiko Inazu, Tamotsu Yoshino
    1971 Volume 44 Issue 1 Pages 200-203
    Published: 1971
    Released: March 27, 2006
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    Two new macrocyclic compounds, I and II, which incorporate, respectively, four or eight benzene rings and intervening methylene bridges attached to their para positions, were synthesized. The UV, IR, and NMR spectra of these paracyclophanes were compared with a corresponding open-chain compound, III.
  • Satoru Watanabe, Takayuki Suga, Tsuyoshi Shishibori, Tamon Matsuura
    1971 Volume 44 Issue 1 Pages 204-207
    Published: 1971
    Released: March 27, 2006
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    The intramolecular interaction of oxirane and cyclopropane rings with a hydroxyl group in the alicyclic α,β-epoxy-, β,γ-epoxy-, and cyclopropyl alcohols was investigated by means of the infrared spectroscopy. cis-α,β-Epoxyalcohols (II, IV and V) showed a free hydroxyl band, an interacted hydroxyl band with a C–O bond of the oxirane ring, and/or a band due to a O–H···O hydrogen bond, whereas trans-epoxyalcohols (I and III) showed only a free hydroxyl band. The interaction between the hydroxyl group and a C–C bond of the oxirane ring was likely to be absent. β,γ-Epoxyalcohols revealed a hydroxyl band interacting with lone-pair electrons of the oxirane oxygen, in addition to a free hydroxyl band. The O–H··· cyclopropane interaction was found with 2-(1-methylcyclopropyl)-5-methylcyclohexanols (VII and VIII). The correlation of the infrared spectra with the conformation of the interacting groups is also discussed.
  • Teruzo Asahara, Manabu Sen\={o}, Keiryo Mitsuhashi, Yohsuke Ichikawa
    1971 Volume 44 Issue 1 Pages 207-210
    Published: 1971
    Released: March 27, 2006
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    The polycondensation reactions of ferrocene with terephthaloyl and adipoyl chloride were investigated in the presence of AlCl3, ZnCl2, or FeCl3 as the catalyst and in dichloromethane, n-hexane, carbon tetrachloride, or dioxane as the solvent. With terephthaloyl chloride, the highest polymer yield was obtained when AlCl3 in n-hexane was used, and the product was mainly of a polyketone structure. The polycondensation with adipoyl chloride afforded the most satisfactory result when ferrocene was treated in liquid adipoyl chloride with neither catalyst nor solvent, and a product with the expected structure was obtained. The average molecular weights of the products are in the range of 3000–7000. Polymers obtained by polycondensation with terephthaloyl and succinyl chloride are paramagnetic and show the temperature dependence characteristic of semi-conductivity.
  • Satoru Makisumi, Shuji Matsuura, Michinori Waki, Nobuo Izumiya
    1971 Volume 44 Issue 1 Pages 210-214
    Published: 1971
    Released: March 27, 2006
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    A linear decapeptide, HCO-D-Phe-Pro-Val-Orn-Leu-D-Phe-Pro-Val-Orn-Leu-NHCH2CH2OH, which has been identified as an immediate precursor of gramicidin S was synthesized in order to define the physical and biological properties of this peptide. The synthetic product possessed practically no antibacterial activity against any of the microorganisms tested, though the optical rotatory dispersion feature of this peptide was quite similar to that of gramicidin S. Stability of the terminal blocking groups of this peptide to the action of hydrogen chloride in methanol was also discussed.
  • Kensuke Shima, Yoshiki Sakai, Hiroshi Sakurai
    1971 Volume 44 Issue 1 Pages 215-218
    Published: 1971
    Released: March 27, 2006
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    The photocycloaddition of acetone to cyclooctene (COE) or 1,3-cyclooctadiene (COD) yields isomeric cis-and trans-oxetanes in good yields. Kinetic studies of these reactions reveal that the photoaddition of acetone to COE proceeds via the attack of the triplet acetone on the ground state COE, while the addition to COD probably occurs by the attack of the excited singlet acetone on the ground state COD.
  • Yoshio Otsuji, Yasuhiro Tsujii, Akihiko Yoshida, Eiji Imoto
    1971 Volume 44 Issue 1 Pages 219-223
    Published: 1971
    Released: March 27, 2006
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    β-Keto sulfoxides were prepared by the reaction of the esters with the methylsulfinyl carbanion. The nitrosation of the β-keto sulfoxides, RCOCH2SOCH3 (R=C6H5, C6H5CH2CH2, n-C3H7), with sodium nitrite and hydrochloric acid gave the corresponding α-chloro-α-isonitroso ketones, RCOC(=NOH)Cl, in high yields. However, the nitrosation of α-substituted β-keto sulfoxide, RCOCH(R′)SOCH3, in a similar manner afforded the α-isonitroso ketones, RCOC(=NOH)R′. The mechanisms of these reactions were studied.
  • Yoshio Otsuji, Yasuhiro Tsujii, Akihiko Yoshida, Eiji Imoto
    1971 Volume 44 Issue 1 Pages 223-226
    Published: 1971
    Released: March 27, 2006
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    The nitrosation of dimethylphenacylsulfonium bromide (I) with sodium nitrite and hydrochloric acid in water gave 3,4-dibenzoyl-1,2,5-oxadiazole 2-oxide (II) in a 76% yield. The nitrosation of I in a similar manner in 1 : 1 dioxane-water afforded ω-chloro-ω-isonitrosoacetophenone (III) in an 80% yield. The treatment of III with triethylamine produced II through benzoylnitrile oxide (IX). 1,3-Dipolar cycloadditions of IX generated from III were conducted, using methyl methacrylate, styrene, acrylonitrile, and ethyl chloroformate as dipolarophiles, to yield the expected cycloadducts. The mechanisms of these reactions are discussed.
  • Hitomi Suzuki, Kiyomi Nakamura
    1971 Volume 44 Issue 1 Pages 227-231
    Published: 1971
    Released: March 27, 2006
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    The nitration of a series of the titled pentamethylbenzene derivatives has been investigated in order to know the orienting effect of substituent groups for the side-chain nitrooxylation. The nitrooxylation was found to occur almost exclusively at the methyl groups adjacent to the electron-withdrawing substituents (NO2, COOH, and COOCH3), while with the compounds containing electron-donating groups (OH and OCH3) the main reaction led to the conversion into cyclohexadienone, with the concomitant formation of small amounts of meta-nitrooxylated product. Pentamethylacetanilide underwent side-chain nitrooxylation along with some deacetylation. The location of the nitrooxymethyl group seems to be most likely ortho and meta, the latter being predominant.
  • Yoshitaka Mushika, Tsujiaki Hata, Teruaki Mukaiyama
    1971 Volume 44 Issue 1 Pages 232-235
    Published: 1971
    Released: March 27, 2006
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    A novel method for the preparation of mixed diesters of phosphoric acid has been investigated. It was found that mixed diesters of phosphoric acid were prepared by the reaction of alkyl 2-chloromethyl-4-nitrophenyl hydrogen phosphates with alcohols in dry pyridine. On the other hand, these diesters were also obtained from dialkyl 2-chloromethyl-4-nitrophenyl phosphates on hydrolysis under mild conditions. By using both of these methods, analytically pure samples of mixed diesters of phosphoric acid could be obtained in high yields.
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