Bulletin of the Chemical Society of Japan
Online ISSN : 1348-0634
Print ISSN : 0009-2673
ISSN-L : 0009-2673
Volume 51 , Issue 4
Showing 1-50 articles out of 79 articles from the selected issue
  • Seiichiro Koda, Kazumoto Nakamura, Takashi Hoshino, Tsutomu Hikita
    1978 Volume 51 Issue 4 Pages 957-962
    Published: 1978
    Released: April 19, 2006
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    The reaction of hydrogen atoms with acrylaldehyde was investigated in a fast flow reactor equipped with a time-of-flight type mass spectrometer under reduced pressure. Main reaction products were carbon monoxide, ethylene, ethane, methane, and propanal. Consideration of the distributions of the reaction products under various reaction conditions showed that hydrogen atoms attacked the C=C double bond, especially its inner carbon side under reduced pressure. Resulting hot radicals caused subsequent reactions. The relative value of the apparent bimolecular rate constant of the reaction against that of trans-2-butene with hydrogen atoms was 1.6±0.2, which supported the above-mentioned initial reaction.
  • Yoshikazu Ioki, Hiroko Kawana, Kichisuke Nishimoto
    1978 Volume 51 Issue 4 Pages 963-966
    Published: 1978
    Released: April 19, 2006
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    In order to clarify the nature of the intramolecular hydrogen bond between the hydroxyl group and the π-electron system in 2-hydroxybiphenyl, MO calculation based on the CNDO/2 MO method has been carried out. The total electronic energy of the molecule has been divided into one- and two-atomic terms. It was found that the resonance term mainly contributes to the intramolecular hydrogen bond formation. Contribution of other terms is discussed.
  • Aritada Hatta, Hideaki Nohara, Wataru Suëtaka
    1978 Volume 51 Issue 4 Pages 967-973
    Published: 1978
    Released: April 19, 2006
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    A polarized infrared ATR technique was used to demonstrate the orientation of a nematic liquid crystal, N-(p-methoxybenzylidene)-p-butylaniline (MBBA), due to the walls of the electrode and an externally applied DC electric field. Polarized ATR spectra were obtained as a function of the field strength on liquid films 15 (μm thick between a silicon ATR prism and a brass plate serving as electrodes. The observed infrared dichroism revealed the average orientation of molecules in boundary layers about 1 μm thick on the Si electrode surface. The ordering or packing of molecules before application of the field affects the response of molecules to the electric field in a striking manner. Molecular orientations on the Si electrode are discussed in some detail.
  • Takeshi Asai, Hiroshi Saheki, Kayako Hori, Ryôiti Kiriyama
    1978 Volume 51 Issue 4 Pages 974-977
    Published: 1978
    Released: April 19, 2006
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    The magnetic susceptibilities, χ, of α- and β-Cu(NH3)2X2(X=Cl, Br) were measured from 4.2 to 360 K. Those of β-Cu(NH3)2X2 obeyed the Curie-Weiss law above 50 K. The Weiss constants and effective Bohr magneton numbers are −3.5(±1) K and 1.75(±0.01) for X=Cl, and −9.7 K and 1.82 for X=Br. α-Cu(NH3)2Cl2 showed a rounded maximum for χ at 30 K. A linear Heisenberg model with the parameters, J=−23.5(±1) K and g=2.03(±0.03), gave good agreement with observations. α-Cu(NH3)2Br2 had a peak for χ at 47(±2) K. This temperature is probably a Neèl temperature. The strong magnetic interaction of the α-form compounds is related to the compressed coordination octahedron of [Cu(NH3)2X4]2−. All samples used were solid solutions of Cu(NH3)2X2 and NH4X. An analysis of χ suggests that the Cu2+ cations in α-Cu(NH3)2Cl2 are distributed inhomogeneously over a short range. A similar inhomogeneity was also found for the β-Cu(NH3)2X2 samples. In this sense, the β-form may be better described as a solid solution of α-Cu(NH3)2X2 and NH4X rather than as a dimorph.
  • Takuya Maruizumi, Yukio Hiyama, Noriyuki Watanabe, Eiji Niki
    1978 Volume 51 Issue 4 Pages 978-980
    Published: 1978
    Released: April 19, 2006
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    Using proton-nitrogen double resonance in the laboratory frame, the 14N nuclear quadrupole resonances (NQR) of 2,4(1H,3H)-pyrimidmedione[uracil], 2,3-dihydro-2-thioxo-4(1H)-pyrimidinone[2-thiouracil], 2,4(1H,3H)-pyrimidinedithione[2,4-dithiouracil], and 1,3-dihydro-2H-benzimidazole-2-thione[2-mercaptobenzimidazole] have been measured at room temperature. The NQR parameters of uracil and its sulfur-substituted compounds are interpreted by using the Townes and Dailey theory.
  • Susumu Tsuchiya, Masami Nakamura, Norihiko Yoshioka
    1978 Volume 51 Issue 4 Pages 981-984
    Published: 1978
    Released: April 19, 2006
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    The temperature-programmed desorption (TPD) chromatograms of propylene from platinum black comprised four peaks: A, B, C, and D, with peak maxima at about 260, 380, 570, and higher than 720 K respectively. Peaks A and B were identified as the mixtures of propylene and propane. Peaks C and D were methane formed from chemisorbed propylene by decomposition as the temperature was raised during the subsequent TPD. The reactivities of various types of chemisorbed hydrogen previously detected by TPD were also investigated with regard to the hydrogenation of propylene. Two types of chemisorbed hydrogen, presumed to be present on the surface in the form of hydrogen atoms chemisorbed on top of platinum atoms and in the bridge form of molecular hydrogen, were found to react with propylene.
  • Harumichi Tsukada, Hirotaka Shimanouchi, Yoshio Sasada
    1978 Volume 51 Issue 4 Pages 985-990
    Published: 1978
    Released: April 19, 2006
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    As the first step in the investigation of the reaction mechanism of a benzocyclobutene derivatives, the title compound has been determined by the X-ray diffraction method. The crystals are monoclinic; space group P21/n; a=28.117(3), b=11.148(1), c=13.167(1) Å, and β=97.26(1)°. The asymmetric unit contains one molecule of the title compound and acetonitrile. The structure was solved by the direct method and refined by the block-diagonal least-squares method to a final R factor of 0.088 for 5456 observed reflections. The molecular framework consists of a planar ten-membered ring from benzodicyclobutene and a slightly folded four-membered ring formed by the addition of tetracyanoethylene (TCNE). Calculation has been undertaken for the non-bonded interaction energy of possible modes of approach between benzodicyclobutene and TCNE. The results are in qualitative agreement with the folding of the four-membered ring.
  • Natsuko Kanzaki, Iwao Yasumori
    1978 Volume 51 Issue 4 Pages 991-995
    Published: 1978
    Released: April 19, 2006
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    The states of O2 and SO2 adsorbed on NaX zeolite were investigated by means of ESR. No oxygen anion radicals were formed thermally on NaX up to 773 K. The adsorption of O2 on γ-irradiated NaX in a vacuum, however, resulted in an ESR spectrum due to O2. Several kinds of O2 species and O3 were found to be formed on NaX by γ-irradiation in the presence of O2. These oxygen anion radicals showed different reactivities with N2O, ethylene and propylene, and transferred electrons to SO2 to form SO2. The SO2 radical was also produced on NaX by raising the temperature from 298 to 573 K after the introduction of SO2. This reacted with O2 to form a radical, like SO4, but upon evacuating the O2, the reaction was reversed to give the original SO2. When the temperature of NaX was further raised to 773 K in the presence of SO2, a spectrum assigned to a polyatomic sulfur radical appeared indicating that SO2 decomposition occurred at high temperature. This polymer radical was stable in an O2 atmosphere at room temperature.
  • Tetsutaro Yoshinaga, Hiroshi Hiratsuka, Yoshie Tanizaki
    1978 Volume 51 Issue 4 Pages 996-1000
    Published: 1978
    Released: April 19, 2006
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    The divided electronic spectra polarized parallel to the long and short axes of molecules of biphenyl, THP (4,5,9,10-tetrahydropyrene), fluorene, and DHPH (9,10-dihydrophenanthrene) were determined by dichroism analysis using the stretched PVA film method. The experimental results are in good agreement with the ones calculated by the LCAO MO SCF CI method. Every compound has a very weak absorption (f≈10−4) as the first band in the region of 32000–35000 cm−1, which is electronically allowed and polarized parallel to the short axis. The intense band (34000–44000 cm−1) of biphenyl consists of a relatively strong (39100 cm−1) band and a weak (40500 cm−1) band: the former is polarized parallel to the long axis and the latter to the short. Both fluorene and DHPH show five well corresponding electronic bands in the region below 45000 cm−1.
  • Masashi Tanaka
    1978 Volume 51 Issue 4 Pages 1001-1008
    Published: 1978
    Released: April 19, 2006
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    The polarized reflection spectra were measured on the crystals of TCNQ complexes with phenothiazine, anthracene, pyrene, acenaphthene, carbazole, hexamethylbenzene, and 1,10-phenanthroline. The crystalline absorption spectra were obtained by the K-K transformation of the reflection spectra. The charge-transfer degree and the stabilization energy in the ground state were estimated for each complex by analysing the charge-transfer bands in the solid state. The charge-transfer degree of the TCNQ–phenothiazine complex is 19.6%, while those of the TCNQ–carbazole, anthracene, and hexamethylbenzene complexes are 12.0, 10.5, and 8.0% respectively. Furthermore, those values for TCNQ–1,10-phenanthroline, acenaphthene, and pyrene are about 5%. The relationship between the charge-transfer excitation energy and the ionization potential of a series of the donor molecules is also discussed.
  • Shigeyoshi Katagiri, Susumu Kohda-Sudoh
    1978 Volume 51 Issue 4 Pages 1009-1011
    Published: 1978
    Released: April 19, 2006
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    The vertical singlet-transition energies of CH4 were calculated using the BO method. Two types of basis sets, minimal and extended, were employed. The vertical transition energy of the lowest singlet state of CH4 was found to be 9.1 eV using the extended-basis set. This transition is assigned to a Rydberg-type transition in agreement with experiments. The other lower excited-states of CH4 may also be assigned to Rydberg transitions. The main features of the present BO calculations do not differ greatly from those of other extended-basis MO calculations. The total energy of the ground state is discussed briefly.
  • Ha Chung Lee, Yutaka Miyahara
    1978 Volume 51 Issue 4 Pages 1012-1015
    Published: 1978
    Released: April 19, 2006
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    Vapor pressure depressions at 40.3 °C and electric conductivities at 25 and 40.3 °C have been measured for Bu4NCl, Bu4NBr, Bu4NI, and Pr4NI in acetone. Experiments were carried out with the greatest care to minimize the contact of salts and their solutions with air. A new representation of activity coefficients has been proposed for the undissociated species. Analysis by means of the representation gives better agreement between the dissociation constants and those obtained from electric conductivities. The very small dissociation constant of Bu4NCl found previously has been corrected.
  • Yasumasa Ikezoe, Shoichi Sato
    1978 Volume 51 Issue 4 Pages 1016-1019
    Published: 1978
    Released: April 19, 2006
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    The G value of water and 2-propanol as well as that of carbon monoxide decreased with decrease in propane concentration below 0.5%, the value of acetone remaining constant. Considering the effects of dose rate and irradiation temperature on the product yields, the results indicate that the formation of water and 2-propanol competes with the back reaction, or the reoxidation of carbon monoxide. A clustered negative ion, O(CO2)n seems to be the oxidizing species responsible both for the back reaction and the formation of water and 2-propanol. The G value of O(CO2)n was estimated to be 1.3. The formation of acetone is independent of the back reaction.
  • Masanao Kato, Nobuo Suzuki
    1978 Volume 51 Issue 4 Pages 1020-1023
    Published: 1978
    Released: April 19, 2006
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    A new expression for excess volumes of binary mixtures is derived. This equation contains four adjustable but physically-meaningful parameters: two non-randomness factors and two partial molar volumes at infinite dilution. The applicability of this equation is tested against data in the literature for several non-ideal mixtures, and it is found that this equation successfully expresses the experimental curves of excess volume, VE, over the entire concentration range. Furthermore, it is demonstrated that the non-randomness factors used in the excess volume expression can be used to estimate the excess Gibbs energy, GE, of binary mixtures based on the Wilson equation.
  • Noriyuki Kinjo, Tsurutaro Nakagawa
    1978 Volume 51 Issue 4 Pages 1024-1026
    Published: 1978
    Released: April 19, 2006
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    The viscoelastic behavior of a homologous series of di-n-alkyl phthalates varying in alkyl chain length from methyl- to nonyl- was studied by means of torsional braid analysis (TBA). The glass transition temperatures, Tg were determined as the temperature at loss maximum. The Tg decreases with increasing alkyl chain length in the di-n-alkyl phthalates, up to dibutyl. Thereafter, the Tg increases gradually with further increase in the alkyl chain length. This behavior can be explained by taking into account two factors which determine the Tg, the molecular weight and the intermolecular interaction. The increase in the number of methylene groups in the phthalates brings about two effects: first, the Tg is increased with increasing molecular weight and, second, the Tg is decreased owing to shielding of the interaction between polar carbonyl groups due to the presence of non-polar methylene groups. When the number of methylene groups is four, the two effects counterbalance each other and the Tg of dibutyl phthalate is the lowest of the di-n-alkyl phthalate series.
  • Jun Sasaki, Junichiro Mizusaki, Kazuo Fueki
    1978 Volume 51 Issue 4 Pages 1027-1031
    Published: 1978
    Released: April 19, 2006
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    The reaction rate, v, at the Ag2S/S(1) interface was determined as a function of the silver activity aAg in Ag2S utilizing a solid-state electrochemical cell, Ag/AgI/Ag2S/Pt. The rate equation was found to be expressed by v=k(aAg)2k′ On the basis of the theory by Kobayashi and Wagner, the rate-controlling step of the Ag2S/S(1) interface reaction is concluded to be S(ad)+e→S2−(ad). The overall reaction rate of silver sulfidization by liquid sulfur can be well explained by the mixed control of a three-step reaction; the Ag2S/S(l) interface reaction, the diffusion of silver ions in Ag2S, and the Ag/Ag2S interface reaction.
  • Junji Hinatu, Hiroshi Masuhara, Noboru Mataga, Yoshiteru Sakata, Soich ...
    1978 Volume 51 Issue 4 Pages 1032-1036
    Published: 1978
    Released: April 19, 2006
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    Absorption spectra of inter- and intramolecular exciplex systems of pyrene and N,N-dimethylaniline in alcoholic solution were obtained by means of ns laser photolysis. The spectra of intermolecular systems can be reproduced by the superposition of bands of the pyrene anion and the N,N-dimethylaniline cation. Similar results were obtained with intramolecular systems of P1 and P2, where Pn is (1-pyrenyl)-(CH2)n-(p-dimethylaminophenyl). The absorption band of P3 exciplex is structureless and very broad, the position of the maximum remaining unchanged. From the relation between absorption spectra and conformation of intramolecular systems, it is concluded that the broad band is due to the sandwich type of structure of the donor cation and the acceptor anion. Anomalous behavior of intermolecular exciplexes in alcoholic solutions is discussed on the basis of their absorption spectra.
  • Kazuo Nomura, Akira Matsubara, Hideo Kimizuka
    1978 Volume 51 Issue 4 Pages 1037-1040
    Published: 1978
    Released: April 19, 2006
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    Utilizing a liquid membrane-aqueous inorganic electrolyte system, the membrane permeability to ion α estimated from the conductance and potential data, Pα, and that at zero electric current estimated from the salt flow and potential data, Pα0, were determined. A solution of calcium hexadecyl sulfate dissolved in 1-octanol and calcium chloride were used as the liquid membrane and the inorganic electrolyte, respectively. The results showed that Pca0Pcl0PcaPcl≈10 and Pcl0Ps0, where subscript s refers to the salt. The latter result indicates that the diffusion of a salt through the membrane is governed by the co-ion permeation. It was shown that Pα0 is smaller than Pα and that Pα decreases with increase in the concentration of external calcium chloride solution while Pα0 is nearly independent of the concentration. The difference between Pα and Pα0 can be explained in terms of the elements of permeability and conductance matrices estimated from the electrical and salt flow data.
  • Tadashi Sugano, Kyuya Yakushi, Haruo Kuroda
    1978 Volume 51 Issue 4 Pages 1041-1046
    Published: 1978
    Released: April 19, 2006
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    The polarized absorption spectra over the range, 5000–37000 cm−1, were observed on the single crystals of the highly-conductive, mixed-valence tetrathiafulvalenium salts, (TTF)Br0.71, (TTF)I0.71, and (TTF)(SCN)0.57, by using a microspectrophotometer. The spectra of these crystals were very similar to each other. The observed spectra were successfully interpreted in terms of the localized model, considering the charge transfer transitions between TTF species and the local excitations associated with the intramolecular transitions of the molecule and ion of TTF. The spectrum of the (TTF) (ClO4) crystal were also studied to aid the interpretations of the spectra of the mixed-valence TTF salts.
  • K. V. Uma, S. M. Mayanna
    1978 Volume 51 Issue 4 Pages 1047-1050
    Published: 1978
    Released: April 19, 2006
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    The kinetics of oxidation of 4-hydroxy-4-methyl-2-pentanone (diacetone alcohol) by sodium N-chloro-p-toluenesulfonamide (Chloramine-T, RNClNa) in presence of hydrochloric acid (0.05–0.6 M) has been studied at 30 °C. The reaction follows first order kinetics with respect to chloramine-T. The reaction rate depends on the square of the [H+] and independent of the alcohol concentration. The energy and entropy of activation have been found to be 65.56 kJ mol−1 and −73.81 JK−1 respectively. The rate of reaction has been affected by the addition of potassium chloride and dioxane to the reaction mixture. A mechanism has been proposed involving diacetone alcohol and H2OCl+ formed by the hydrolysis of chloramine-T. Applying steady state condition to RNHCl, a rate expression has been given to account for the observed results. Kinetic data have been used in the analytical estimation of diacetone alcohol in acidic medium.
  • Wolfgang Pies, Alarich Weiss
    1978 Volume 51 Issue 4 Pages 1051-1061
    Published: 1978
    Released: April 19, 2006
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    The 79Br-NQR spectra of anilinium bromide, C6H5NH3Br\ominus, of anilinium-d3 bromide, C6H5ND3Br\ominus, and of aniliniunw-d5 bromide, C6D5NH3Br\ominus, have been investigated in the temperature range 77≤T⁄K≤350. The three compounds show an order-disorder phase transition near room temperature. The respective transition temperatures have been determined as 296.9 K (C6H5NH3Br\ominus), 291.5 K (C6H5ND3Br\ominus), and 297.6 K (C6D5-NH3Br\ominus). The large value of the 79Br-NQR frequency (v=17.780 MHz at 77 K for C6H5NH3Br\ominus) and the large 1H–2D isotopic shift of this frequency (≈400 kHz at 77 K by deuteration of the NH3-group) have been interpreted in terms of hydrogen bonding N-H…Br\ominus. The state of order in the high temperature modification is discussed in the light of the 79Br-NQR spectrum. The 79Br-NQR frequency of the Br\ominus ion in the low temperature modification is related to the change in the monoclinic angle β and to the temperature dependence of the order parameter s∝{(TcT)⁄Tc}1⁄3.
  • S. Noor Mohammad
    1978 Volume 51 Issue 4 Pages 1062-1067
    Published: 1978
    Released: April 19, 2006
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    Semi-empirical potential energy surfaces for some alkali-trimer complexes have been calculated using the simplest form of London equation. In the calculations use has been made of two new exponential potentials for the singlet and triplet states of diatomic molecules. The calculated potential surfaces at small internuclear distances show shallow well extending into the entrance and exit valleys without an energy barrier. The complexes are seen to be stable over all configurations; they are most stable however in the linear symmetric configuration. The force constants corresponding to bending and stretching deformations have been calculated for homonuclear trimers only. It has been observed that unlike stretching, the bending deformations do not sensitively affect the energy variation of the ground state.
  • Hideyuki Nishimoto, Tadatsugu Yoshikuni, Akira Uehara, Eishin Kyuno, R ...
    1978 Volume 51 Issue 4 Pages 1068-1071
    Published: 1978
    Released: April 19, 2006
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    The following nickel(II) complexes with meso- or dl-2,3-butanediamine (abbreviated to meso-bn and dl-hn, respectively) were prepared: [Ni(meso-bn)3]X2·2H2O, [Ni(meso-bn)2]X2 and [Ni(H2O)2(dl-bn)2]X2 (X=Cl, Br). It was found from the changes in the absorption spectra and magnetic susceptibilities that [Ni(meso-bn)3]X2·2H2O complexes, when heated to 188 (X=Cl) and to 233 °C (X=Br), respectively, undergo transformations from octahedral to square planar structures with the loss of two moles of lattice water and one mole of coordinated meso-bn. [Ni(H2O)2(dl-bn)2]X2 complexes were similarly found to transform from octahedral to square planar structures at 120 (X=Cl) and at 110 °C (X=Br), respectively with the evolution of two moles of coordinated water. After this transformation, the resulting complexes underwent the inverse transformation from square planar to octahedral structure at 170 °C, without any weight change. The effect of the configurational difference between meso- and dl-hn on the formation of tris and bis(2,3-butanediamine) complexes is also discussed.
  • Tetsuo Katsuyama, Toshihiko Kumai
    1978 Volume 51 Issue 4 Pages 1072-1077
    Published: 1978
    Released: April 19, 2006
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    The kinetics and mechanism of the ligand-substitution reactions of triethylenetetraminecadmium(II) ion (Cd(II)-trien) and tetraethylenepentaminecadmium(II) ion (Cd(II)-tetren) with ethylenediaminetetraacetatocuprate(II) ion (Cu(II)-edta) were studied spectrophotometrically at I=0.2 M (1 M=1 mol dm−3) and at 25.0 °C. The ligand-substitution reactions were catalyzed by traces of either edta or the polyamine (triethylenetetramine and tetraethylenepentamine). The substitution reactions were shown to proceed by means of a chain reaction mechanism where the chain-propagating steps are the reactions of the metal complexes with the free ligands. Each chain-propagating step was investigated. The ligand-substitution reactions of Cd(II)-trien and Cd(II)-tetren with edta were studied by the use of the chain reactions in the pH range of 8.8–10.2. The rate law is expressed as: −d[CdR2+]/dt=kL[CdR2+][edta4−]+kHL[CdR2+][Hedta3−], where R refers to trien or tetren. The rate constants, kL and kHL, were determined at 25.0 °C and I=0.2 M as: kL=(1.3±0.2)×106 M−1 s−1 and kHL=(6.5±1.5)×104 M−1 s−1 for Cd(II)-trien, and kL=(3.6±0.4)×105 M−1 s−1 and kHL=(1.0±0.2)×104 M−1 s−1 for Cd(II)-tetren.
  • Keiichiro Fuwa, Kenji Notsu, Kin-ichi Tsunoda, Hideaki Kato, Yuko Yama ...
    1978 Volume 51 Issue 4 Pages 1078-1082
    Published: 1978
    Released: April 19, 2006
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    Japanese Tea Leaves, prepared by pulverizing with an agate ball mill and sieving with a Saran fiber sieve (50 mesh) were assessed as a possible biological standard reference material for elemental analysis. The metal content of the tea leaves was determined independently at two laboratories using atomic absorption and flame emission spectrometry. Neutron activation analysis was also performed to determine the content (21 elements) of Tea Leaves. For some elements the result from the various methods were compared. The characteristics of Tea Leaves are discussed and the elemental composition is compared to that of Orchard Leaves (NBS SRM, 1571). The most significant characteristic of Tea Leaves was the high manganese content.
  • Yoshiaki Ito, Shinichi Kawaguchi
    1978 Volume 51 Issue 4 Pages 1083-1089
    Published: 1978
    Released: April 19, 2006
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    Hydrolysis of Co(NO2)4(AA) (AA=en or tn) was studied in acidic and basic aqueous solutions by the spectrophotometric method. In faintly acidic solution (6>pH>4) the aquation proceeds reversibly to attain an equilibrium with Co(NO2)3(H2O) (AA), Keq being (1.71±0.03)×10−2 and (3.55±0.06)×10−2 mol·1−1 for AA=en and tn, respectively, at 25.0 °C and μ=0.1. With increasing concentration of hydrogen ion the acid-catalyzed pathway becomes increasingly important. In basic solution (12.2>pH>9.5) Co(NO2)3(OH)(AA) was formed irreversibly as the first product. Kinetic data of these hydrolysis reactions are interpreted in terms of the dissociative mechanism involving a five-coordinate intermediate Co(NO2)3(AA). The rates of nitrite release from Co(NO2)4(tn) ((9.27±0.03)×10−4s−1) and deaquation from Co(NO2)3(H2O)(tn) ((3.95±0.12)×10−4 s−1) are several times greater than those for the corresponding ethylenediamine complexes ((2.08±0.01)×10−4 and (5.46±0.10)×10−5 s−1, respectively.
  • Masutaro Abe, Kunio Ohzeki, Tomihito Kambara
    1978 Volume 51 Issue 4 Pages 1090-1093
    Published: 1978
    Released: April 19, 2006
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    Mutual coagulation takes place, when a suspension of finely divided cation exchanger is added to that of anion exchanger. The resulting mixed resin is bulky and easily separated from the solution by filtration. A rapid and selective collection of a trace amount of copper(II) ion was carried out by the combined use of mixed resin and 8-quinolinol-5-sulfonic acid (H2qs). The copper(II) collected on the mixed resin in the form of [Cu(qs)2]2− was brought into solution from the resin with ethylenediaminetetraacetate, converted into copper(II)–diethyldithiocarbamate, extracted into methyl isobutyl ketone, and determined by atomic absorption spectrometry. The method was satisfactorily applied to the determination of a trace amount of copper(II) in well water.
  • Toshishige M. Suzuki, Shin-ichi Kamiyama, Tetsuo Kimura
    1978 Volume 51 Issue 4 Pages 1094-1097
    Published: 1978
    Released: April 19, 2006
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    Copper (II) complexes of a series of quadridentate ligands, N,N′-di-8-quinolylethylenediamine (dqen), (R)-N,N′-quinolylpropylenediamine {(R)-dqpn}, and (R,R)-N,N′-di-8-quinolyl-1,2-cyclohexanediamine -{(R,R)-dqchxn}, have been prepared. Their d-d absorption spectra, magnetic moments, and molar conductivities indicate that the complexes have a five-coordinated structure, in which one of the quinoline groups of the ligands occupies an apical position. The circular dichroism (CD) spectra of the optically active ligands and their complexes exhibit exiton couplets in the ligand’s π*←π transition region. From the signs of the couplets, the preferable configurations of the (R)-dqpn and (R,R)-dqchxn complexes are assigned to Δ.
  • Akimasa Yajima, Ryoko Matsuzaki, Yuzo Saeki
    1978 Volume 51 Issue 4 Pages 1098-1100
    Published: 1978
    Released: April 19, 2006
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    The details of the reaction between vanadium trichloride oxide and hydrogen sulfide were examined at 20 and 60 °C. The main products by the reaction were vanadium dichloride oxide, sulfur, and hydrogen chloride. In addition to these products, small amounts of vanadium trichloride, vanadium tetrachloride, disulfur dichloride, and sulfur dioxide were formed. The formations of the above-mentioned reaction products can be explained as follows: The first stage is the reaction between vanadium trichloride oxide and hydrogen sulfide, 2VOCl3(1)+H2S(g)→2VOCl2(s)+S(s)+2HCl(g). Then the resulting sulfur reacts with the unreacted vanadium trichloride oxide, 2VOCl3(1)+2S(s)→2VOCl2(s)+S2Cl2(1). The resulting disulfur dichloride subsequently reacts with the unreacted vanadium trichloride oxide, 2VOCl3(1)+S2Cl2(1)→2VCl4(1)+S(s)+SO2(g). The resulting vanadium tetrachloride reacts with the sulfur formed during the reaction, 2VCl4(1)+2S(s)→2VCl3(s)+S2Cl2(1), and also reacts with hydrogen sulfide, 2VCl4(1)+H2S(g)→2VCl3(s)+S(s)+2HCl(g).
  • Hiro Kuma, Kyoji Motobe, Shoichiro Yamada
    1978 Volume 51 Issue 4 Pages 1101-1103
    Published: 1978
    Released: April 19, 2006
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    Cobalt(II), nickel(II), copper(II), zinc(II), and manganese(II) complexes with 2-thiophenealdehyde oxime have been prepared and characterized mainly on the basis of electronic spectra and magnetic data. The cobalt(II) and nickel(II) complexes isolated are of the general formulae: (A) MX2(oxime)4 (X=Cl, Br); (B) M(NCS)2(oxime)2. These compounds and ZnCl2 (oxime)4 are all six-coordinated, and the complexes (B) are probably multinuclear. Copper(II) and manganese(II) form complexes of the formula MX2 (oxime)2 (X=Cl, Br). Possible structures for these complexes are also discussed. 2-Thiophenealdehyde oxime is unidentate in all these complexes, being coordinated through the nitrogen atom.
  • Mamoru Omori, Toshio Hirai, Seishi Yajima
    1978 Volume 51 Issue 4 Pages 1104-1109
    Published: 1978
    Released: April 19, 2006
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    Ultra-fine iron particles were dispersed in a glasslike carbon matrix by the heat treatment of acetylferrocenefurfural resins. The dispersed iron particles were investigated by means of X-ray and electron diffraction analyses and by means of electron microscopy. In resins heat-treated at 400 °C, iron particles of varying diameters were observed by means of electron microscopy. The crystal structure of the iron particles was analyzed by means of X-ray and electron diffractions. Finely subdivided iron particles were identified as hexagonal, close-packed (hep) and expanded, body-centered cubic (bec) irons. The hep iron is the high-pressure phase of iron metal. The ultra-fine iron particles were coagulated to larger particles by heat treatment above 400 °C. The size of their unit cell was the same as that of standard bec iron.
  • Tadashi Hara, Kaoru Fujinaga, Katsuya Tsuji
    1978 Volume 51 Issue 4 Pages 1110-1113
    Published: 1978
    Released: April 19, 2006
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    An improvement has been made in the pyrolytic sulfurization gas chromatographic method, by which the atomic ratio between C, H, O, and N in a sample can be simultaneously determined. Analysis was carried out by use of the correction factors instead of calibration curves. Correction factors were obtained by use of five standard compounds, naphthalene, thiourea, cyanoguanidine, sucrose, and amidosulfuric acid. The method is simple, accurate, and applicable to various compounds.
  • Akira Tai, Motomasa Imaida
    1978 Volume 51 Issue 4 Pages 1114-1117
    Published: 1978
    Released: April 19, 2006
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    Four stereoisomers of methyl 3-hydroxy-2-methylbutyrate (I), (+)-threo-I, (−)-threo-I, (+)-erythro-I, and (−)-rythro-I, were prepared, and their absolute configurations were determined. The configurations of (+)-threo-I, [α]D20+36.80° (c 5, methanol) and (+)-erythro-I, [α]D20+14.32° (c, 5, methanol) were assigned to (2S, 3S) and (2S, 3R) respectively.
  • Masatoshi Inoue, Toshimasa Sakaki, Takaji Fujiwara, Ken-ichi Tomita
    1978 Volume 51 Issue 4 Pages 1118-1122
    Published: 1978
    Released: April 19, 2006
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    The title complex crystallizes in the monoclinic space group P21/c. The unit-cell dimensions are a=11.287(5), b=5.110(3), c=26.391(3) Å, and β=107.07(2)°. The crystal structure was solved by a direct method. By block-diagonal least-squares refinements, the R-value dropped to 0.069. All the nitrogen and oxygen atoms in the complex participate in the hydrogen bonding. No prominent overlapping between pyridine and indole rings is observed in the crystal. Both molecules are hydrogen-bonded to form infinite-layered structures perpendicular to the c-axis; those structures are held together by van der Waals contacts.
  • Masatoshi Inoue, Toshimasa Sakaki, Takaji Fujiwara, Ken-ichi Tomita
    1978 Volume 51 Issue 4 Pages 1123-1127
    Published: 1978
    Released: April 19, 2006
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    The title complex crystallizes in the monoclinic space group of P21/c. The unit-cell dimensions are a=6.673(4), b=19.017(8), c=13.394(7) Å, and β=110.54(2)°. The crystal structure was solved by a direct method. By block-diagonal least-squares refinements, the R-value converged to 0.062. In this complex, a salt bridge is found between the anionic carboxyl group of phenylacetic acid (PAA) and the cationic amino group of tryptamine (TPA). All the hydrogen atoms attached to the nitrogen atoms participate in the hydrogen bonding. The two complex molecules are hydrogen-bonded around a center of symmetry to form one unit, which is held together by van der Waals contacts in the b- and c-directions. Each unit is also stabilized by forming a hydrogen bond with the unit of the neighboring cell translated in the a-direction.
  • Shizuko Eguchi
    1978 Volume 51 Issue 4 Pages 1128-1132
    Published: 1978
    Released: April 19, 2006
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    The mass spectrum of phenazine, a nitrogen-containing aromatic compound, was investigated in detail using a combination of ion kinetic energy spectroscopy and defocusing technique. In the fragmentation of the singly charged ions the molecular ion lost H· in the first stage to give an [M−1]+ or [M−2]+ ion, which was degraded via the expulsion of CN· or C2H2 in the next stage and of HCN or C2H3· in a later stage. Doubly charged ions also appeared in considerable intensity, and the fragmentation sequence differed significantly from that of the singly charged ions.
  • Teruyuki Hayashi, Hiroshi Nakanishi
    1978 Volume 51 Issue 4 Pages 1133-1136
    Published: 1978
    Released: April 19, 2006
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    The spin-lattice relaxation times (T1) of the 13C nuclei in 5-ethyl-5H-dibenzophosphole (1) were studied. The 13C NMR signals of the quarternary carbons of 1 in the aromatic region, whose assignments are very difficult by other techniques, were successfully assigned by means of the spin-lattice relaxation method. The dipolar relaxation terms and their reciprocal values were calculated by the use of the internuclear-distances between the carbon nuclei and hydrogen or phosphorus ones, and were compared with the observed T1 values. It was found by studying the observed T1’s of the ethyl group in 1 that the rotation around the C–P bond is more strongly restricted than that around the C–C single bond.
  • Chung-gi Shin, Yasuhiro Kosuge, Masanori Yamaura, Juji Yoshimura
    1978 Volume 51 Issue 4 Pages 1137-1141
    Published: 1978
    Released: April 19, 2006
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    The Diels-Alder reactions of cyclopentadiene with ethyl (E)- and (Z)-3-nitrocrotonate were carried out to give only the (2+4)-nitro adduct as a mixture of three diastereomers, while that of the diene with ethyl (Z)-3-nitrocinnamate gave two kinds of cycloaddition products, (2+2)- and (2+4)-nitro adducts. All the nitro adducts were reduced with aluminum-amalgam to give the corresponding mono- and dihydroxyamino compounds, in which vicinal endo-ethoxycarbonyl-endo-hydroxyamino derivatives cyclized readily to give tricyclic compounds containing isoxazolidinone ring. The stereochemistry of all the new compounds were established on the basis of IR and NMR spectroscopic analyses.
  • Hiroshi Fukuda, Yasuo Kikuchi
    1978 Volume 51 Issue 4 Pages 1142-1144
    Published: 1978
    Released: April 19, 2006
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    Mixing of chitosan with sodium carboxymethyldextran having opposite charge gave rise to the formation of novel water-insoluble precipitates. The mole ratios of N/COO in the polyelectrolyte complexes thus prepared were estimated to be 0.248–1.658. It was found that pH, mole ratio of N/Na and the order of mixing play an important role in determining the composition ratio of N/COO in the polyelectrolyte complexes. IR spectroscopic studies, blood clotting test, elementary analyses, the color reaction with Toluidine Blue and studies on solubility of polyelectrolyte complexes revealed that there is no noticeable interactions between –COOH groups and –OH groups. However, the –NH3+ groups in chitosan participate in the binding with carboxymethyldextran, probably through its –COO groups, in the polyelectrolyte complexes. It seems that the number of binding sites between –NH3+and -COO groups in the polyelectrolyte complexes at pH 3.0 is smaller than those prepared at pH 6.5. Both the polyelectrolyte complexes prepared at pH 3.0 and 6.5 suppressed the coagulation of blood. This anti-thrombogenic property should be related to elution of anti-thrombogenic carboxymethyldextran.
  • Takashi Tamaki
    1978 Volume 51 Issue 4 Pages 1145-1152
    Published: 1978
    Released: April 19, 2006
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    The photo-excitation of anthracene (1) in the presence of benzoyl chloride and its p- or m-substituted compounds (2) gave the corresponding 2- and 9-aroylanthracenes. No isomeric 1-aroylanthracenes (3) were detected. The aroyl chlorides (2) were found to quench the fluorescence of 1. The quenching constants obtained increased with increasing electron-withdrawing ability of the substituents and are in agreement with those independently obtained from the quantum yield determinations. The efficiency of the photoaroylation was dependent on the solvent polarity. The results suggest a plausible photochemical mechanism, which involves a CT complex formed from 1 in the excited singlet state and 2 in the ground state. This complex formation is supported by the positional selectivity exhibited in the product distribution.
  • Tsuneo Saito, Etsuo Niki, Takeo Shiono, Yoshio Kamiya
    1978 Volume 51 Issue 4 Pages 1153-1157
    Published: 1978
    Released: April 19, 2006
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    The rates and products of ozonization of atactic polypropylene and polystyrene were studied in carbon tetrachloride at 30 and 70 °C. Atactic polypropylene underwent cleavage statistically by ozone to give oxygenated products. The molecular weight of polypropylene decreased with the progress of ozonization. Most chain ends of ozonized polypropylene were suggested to be carboxylic acids. Ozonization of polystyrene brought about crosslinking as well as chain scission, giving rise to broadening of molecular weight distribution. The major product from polystyrene was carboxylic acid.
  • Susumu Akutagawa, Takanao Taketomi, Hidenori Kumobayashi, Kiyoshi Taka ...
    1978 Volume 51 Issue 4 Pages 1158-1162
    Published: 1978
    Released: April 19, 2006
    JOURNALS FREE ACCESS
    Isoprene oligomerization was effected with a catalyst system Ni(OR)(η3-C3H5)PPh(NEt2)2 (R=n-C11H23, n-C15H31) to give a linear trimer fraction above 70% yield. The major component of the trimer fraction is (E)-7,11-dimethyl-3-methylene-1,6,10-dodecatriene (trans-β-farnesene) (1). The minor constituents of the fraction are (E)-2,6-dimethyl-10-methylene-1,6,11-dodecatriene. As slightly higher boiling point fractions, two cyclic trimers 1,5,9-trimethyl-1,5,9-cyclododecatriene and 1,5,10-trimethyl-1,5,9-cyclododecatriene were detected. Factors that influence the reaction path leading to 1 were discussed. Sesqui- and diterpenoids, including farnesyl acetate, farnesylacetone and isophytol were synthesised starting from 1. A regioselective tail to tail coupling of 1 was achieved with a palladium catalyst to give the dimer C30H48 which, upon catalytic hydrogenation, gave perhydrosqualene in 85% yield.
  • Masahiko Kato, Yukio Okamoto, Takeji Chikamoto, Toshio Miwa
    1978 Volume 51 Issue 4 Pages 1163-1167
    Published: 1978
    Released: April 19, 2006
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    The benzyne reaction of cyclic olefins, in competition with that of cyclohexene has been studied. The relative reactivities for ene reaction and the stereoselectivity of the reaction with 4-t-butylcyclohexene, which afforded trans-5-t-butyl-3-phenylcyclohexene and cis-3-t-butyl-6-phenylcyclohexene, are consistent with the stereochemical requirements along the reaction pathway.
  • Hitomi Suzuki, Mamie Koge, Akiyoshi Inoue, Terukiyo Hanafusa
    1978 Volume 51 Issue 4 Pages 1168-1171
    Published: 1978
    Released: April 19, 2006
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    The reaction of tetramethylbenzenedicarbonitriles and tetramethylbenzonitriles with fuming nitric acid (d=1.5) has been investigated at room temperature in the dark. 2,4,5,6-Tetramethylbenzene-1,3-dicarbonitrile and 2,3,5,6-tetramethylbenzene-1,4-dicarbonitrile gave, after aqueous work-up, 4-cyano-5,6,7-trimethyl- and 5-cyano-4,6,7-trimethylphthalides, respectively, in high yields, while 3,4,5,6-tetramethylbenzene-1,2-dicarbo-nitrile produced appreciable amounts of two cyanonitro-3-cyclohexen-1-ones in addition to 7-cyano-4,5,6-trimethylphthalide. Similarly, 2,3,4,6- and 2,3,5,6-tetramethylbenzonitriles afforded 4-nitro-5,6,7-trimethyl- and 5-nitro-4,6,7-trimethylphthalides, respectively, along with the expected nitro compounds. In contrast, 2,3,4,5-tetramethylbenzonitrile underwent normal nitration, giving 6-nitro derivative as the sole product. The phthalide formation was found to proceed through 1,3-dihydroisobenzofuran-1-imines presumably derived from the initially formed o-cyanobenzyl nitrates. The reaction appears to provide potential utility in the synthesis of some substituted phthalides and 1,3-dihydroisobenzofuran-1-imines.
  • Hitomi Suzuki, Akiyoshi Inoue, Mamie Koge, Terukiyo Hanafusa
    1978 Volume 51 Issue 4 Pages 1172-1174
    Published: 1978
    Released: April 19, 2006
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    The reaction of 3,4,5,6-tetramethylbenzene-1,2-dicarbonitrile with fuming nitric acid at room temperature yielded appreciable amounts of 3,4-dicyano-5,6-dinitro-2,2,5,6-tetramethyl-3-cyclohexen-1-one and 3,4-dicyano-6-hydroxy-5-nitro-2,2,5,6-tetramethyl-3-cyclohexen-1-one in addition to the expected side-chain substitution products. 2,3,5,6-Tetramethylbenzonitrile similarly gave 3-cyano-5,6-dinitro-2,2,4,5-tetramethyl-3-cyclohexen-1-ones as minor products. The structures of these nitro ketones have been assigned by spectral methods and a probable mechanistic pathway to their formation is presented.
  • Kazu Kurosawa, Yoshihiro Ashihara
    1978 Volume 51 Issue 4 Pages 1175-1177
    Published: 1978
    Released: April 19, 2006
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    The oxidation of twelve 2-aryl-4H-1-benzopyrans with potassium permanganate in acetone gave the corresponding flavones in excellent yields.
  • Iwao Tabushi, Yoshinao Tamaru, Zen-ichi Yoshida
    1978 Volume 51 Issue 4 Pages 1178-1182
    Published: 1978
    Released: April 19, 2006
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    The electron donating ability of sulfur to a positively charged center through space was examined by means of ultraviolet spectroscopy. 7-Thiabicyclo[2.2.1]heptan-2-one and -2,5-dione exhibited finely separated charge transfer band (from divalent sulfide to carbonyl) at 260 nm in UV spectra, the longest wave-length for S–Cco charge transfer band so far reported. The assignment of these CT bands was confirmed by comparison with relevant reference compounds.
  • Tetsushi Yamashita, Hiroshi Yasueda, Noriyuki Nakatani, Nobuo Nakamura
    1978 Volume 51 Issue 4 Pages 1183-1185
    Published: 1978
    Released: April 19, 2006
    JOURNALS FREE ACCESS
    The asymmetric addition of methanol to phenylmethylketene was carried out in the presence of a chiral polymer obtained by the co-polymerization of N-benzyl-2-pyrrolidinylmethyl acrylate with methyl acrylate. The products obtained for the above co-polymer showed a correlation between logkRkS and 1⁄T deviating from linearity, while those for poly(N-benzyl-2-pyrroIidinylmethyl acrylate) exhibited a linear relationship. N-Benzyl-2-pyrrolidinylmethyl butyrate, hexanoate, and stearate were also used as catalysts; they showed asymmetric efficiencies intermediate between those of N-benzyl-2-pyrrolidinylmethyl propionate and poly(N-benzyl-2-pyrrolidinylmethyl acrylate). The use of several high- and low-molecular-weight catalysts derived from cinchonine was similarly attempted in order to examine the polymer effect with regard to the stereoselectivity.
  • Yoshihiko Ito, Yoshinori Inubushi, Toru Sugaya, Kazuhiro Kobayashi, Ta ...
    1978 Volume 51 Issue 4 Pages 1186-1188
    Published: 1978
    Released: April 19, 2006
    JOURNALS FREE ACCESS
    o-(Cyanomethyl)phenyl isocyanide and o-(methoxycarbonylmethyl)phenyl isocyanide were heated with a catalytic amount of Cu2O in benzene to give 3-cyanoindole and 3-(methoxycarbonyl)indole in 86 and 92% yields, respectively. Lithiations of o-(cyanomethyl)phenyl isocyanide and o-(methoxycarbonylmethyl)phenyl isocyanide with butyllithium at −78 °C followed by the reaction with alkyl halides such as methyl iodide, allyl bromide, butyl bromide, benzyl bromide and methyl α-bromoacetate afforded the corresponding o-(α-cyanoalkyl)phenyl isocyanides and o-[α-(methoxycarbonyl)alkyl]phenyl isocyanides. o-(α-Cyanoalkyl)phenyl isocyanides and o-[α-(methoxycarbonyl)alkyl]phenyl isocyanides thus obtained were also cyclized by Cu2O catalyst producing 3-alkyl-3-cyano-3H-indoles and 3-alkyl-3-(methoxycarbonyl)-3H-indoles, respectively, in moderate yields.
  • Tohru Sakakibara, Rokuro Sudoh, Toshio Nakagawa
    1978 Volume 51 Issue 4 Pages 1189-1192
    Published: 1978
    Released: April 19, 2006
    JOURNALS FREE ACCESS
    Treatment of methyl 4,6-O-benzylidene-2,3-dideoxy-3-nitro-β-D-erythro-hex-2-enopyranoside (1) with dimethyloxosulfonium methylide and dimethylsulfonium α-methylphenacylide afforded cyclopropane derivatives, whereas similar reactions with dimethylsulfonium phenacylide and dimethylsulfonium ethoxycarbonylmethylide gave stabilized ylides. In all cases the S-ylides enter the C-2 position of 1 from the side trans to the anomeric methoxyl group. The ylide structures were determined from IR and NMR data and confirmed by transformation into the desulfurized products. Anomalous stability of these ylides are attributed to the delocalization of the negative as well as positive charge over the carbonyl and the nitro group, respectively.
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