Bulletin of the Chemical Society of Japan
Online ISSN : 1348-0634
Print ISSN : 0009-2673
ISSN-L : 0009-2673
Volume 51 , Issue 12
Showing 1-50 articles out of 65 articles from the selected issue
  • Takeshi Sakaizumi, Yoshio Kohri, Osamu Ohashi, Ichiro Yamaguchi
    1978 Volume 51 Issue 12 Pages 3411-3417
    Published: 1978
    Released: April 19, 2006
    JOURNALS FREE ACCESS
    Microwave rotational spectra of five isotopic species of methyl selenocyanate (CH3SeCN with 82Se, 80Se, 78Se, 77Se, and 76Se) in the ground vibrational state, and two isotopic species of methyl selenocyanate-d3 (CD3SeCN with 80Se and 78Se) in the ground and first excited states of the methyl torsional mode have been assigned in the 8.0 to 35.5 GHz frequency range. For the most abundant species in the ground vibrational state, the rotational constants determined are AA=10147±2, BA=3483.57±0.04, and C=2631.58±0.04 MHz for CH380SeCN and A=8322.57±0.81, B=3308.06±0.02, and C=2436.92±0.01 MHz for CD380SeCN. The A-E splittings due to the methyl internal rotation were observed for the rotational transitions in the ground vibrational state for the normal species and in the first excited state of the methyl torsional mode for the deuterated species. Analysis of the splittings gave a barrier height to the methyl internal rotation of 1241±50 and 1228±50 cal/mol for the CH3 and CD3 species, respectively. Stark measurements yielded the principal axis dipole moments of μa=4.35±0.04, μb=0.76±0.10, and the total dipole moment of μ=4.42±0.05 D for CH380SeCN, and μa=4.31±0.04, μb=0.67±0.07, and μ=4.36±0.04 D for CD380SeCN. The direction of the dipole moment in the molecule is discussed.
  • Hiroo Ogura
    1978 Volume 51 Issue 12 Pages 3418-3425
    Published: 1978
    Released: April 19, 2006
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    The pyrolysis of acetylene in the presence of nitrogen oxide has been investigated by use of a single-pulse shock tube in the temperature range 1100–1650 K. The hydrocarbons produced in the presence of nitrogen oxide were quite the same as those obtained from the pyrolysis of acetylene by itself. The yield-temperature plots of 1-buten-3-yne showed that at temperatures below 1350 K the formation rate of 1-buten-3-yne is reduced by the addition of nitrogen oxide. The retarding effect of nitrogen oxide on the 1-buten-3-yne formation was interpreted in terms of the reactions of nitrogen oxide with 1-ethynylvinyl and 2-ethynylvinyl radicals to yield pro-pynenitrile and hydrogen cyanide, respectively. An illustrative radical chain mechanism was presented for the pyrolysis of acetylene in line with the experimental results obtained from the pyrolysis inhibited by nitrogen oxide. The radical chain is initiated by the bimolecular reaction of acetylene, viz. 2C2H2→C4H3+H, ethynyl and 2-ethynylvinyl radicals being the chain carriers, where C4H3 is 1-ethynylvinyl radical.
  • Tetsuo Higashihara, Ko Saito, Ichiro Murakami
    1978 Volume 51 Issue 12 Pages 3426-3429
    Published: 1978
    Released: April 19, 2006
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    The reaction of hydrogen chloride with nitrogen oxide in the temperature range 2670–3850 K and in the pressure range 2.5–3.5 atm has been studied behind reflected shock waves by monitoring the IR emission of HCl. When nitrogen oxide was added to the HCl–Ar system, the rate of HCl dissociation was found to be accelerated. For the early stage of reaction, the rate equation obtained was –d[HCl]/dt=1011.7exp (−33 kcal/RT)[HCl]1.3[NO]0.5 mol cm−3 s−1. As the initiation step, Reaction 1 was found to be more important than Reaction 2 under these experimental conditions:
    HCl+NO→HNO+Cl, (1)
    HCl+Ar→H+Cl+Ar. (2)
    The rate constant of Reaction 1 was determined to be k1=1013.2exp (−50.2 kcal/RT) cm3 mol−1 s−1.
  • Tetsuo Higashihara, Ko Saito, Ichiro Murakami
    1978 Volume 51 Issue 12 Pages 3430-3434
    Published: 1978
    Released: April 19, 2006
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    The reaction of hydrogen bromide with nitrogen oxide in the temperature range 2000–3300 K and in the pressure range 0.7–3.8 atm has been studied behind reflected shock waves by monitoring the IR emission of HBr. For the early stage of the reaction, the rate equation obtained was −d[HBr]/dt=koverall[HBr]1±0.3[NO]0.7±0.2[Ar]0±0.1, where koverall=1010.4±0.2exp{−(23.2±3.0) kcal/RT} cm2.1 mol−0.7 s−1. As the initiation step, Reaction 1 was found to be more important than Reaction 2:
    HBr+NO→HNO+Br, (1)
    HBr+Ar→H+Br+Ar. (2)
    The rate constant of Reaction 1 was determined to be k1=1012.8exp(−30kca⁄RT) cm3 mol−1 s−1.
  • Yutaka Kubokawa, Takehiko Ono
    1978 Volume 51 Issue 12 Pages 3435-3437
    Published: 1978
    Released: April 19, 2006
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    Adsorption of ethylene and propylene has been investigated volumetrically with various oxide catalysts. From the results together with those of oxidation of propylene adsorbed on oxides, it is concluded that the difference between the characteristics of oxidation of propylene adsorbed on the oxide catalysts for complete or selective oxidation is attributable to the difference in the oxygen species responsible for oxidation rather than that in the adsorbed state of propylene. A comparison of characteristics of the oxidation of adsorbed propylene in the presence of gaseous oxygen and in a vacuum suggests that on the catalysts for complete oxidation, adsorbed oxygen plays a significant role in the oxidation because of its higher activity as compared to that of lattice oxygen.
  • Yoshihiro Furukawa, Hideko Kiriyama
    1978 Volume 51 Issue 12 Pages 3438-3442
    Published: 1978
    Released: April 19, 2006
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    Nuclear spin-lattice relaxation times, T1 and T, have been measured above room temperature for 1H and 19F nuclei in powdered KHF2 and its deuterated analogue. Below 400 K and in the high-temperature β-phase (Tt=469.8 K), the magnetization recovery for both nuclei in KHF2 is strongly non-exponential owing to the heteronuclear H–F interaction. In the low-temperature α-phase the T1 vs. 1/T curves show broad minima ascribable to the 180°-flip motion of linear [FHF] anions. The activation energy Ea of this motion was determined to be 50.5±2 kJ/mol. The phase transition, which is defined by discontinuous changes in both T1 and T, is associated with diffusional disorder superimposed on rapid isotropic reorientation of the HF2 ion. The relaxational process in the β-phase is governed by self-diffusion of the anions with an Ea of 80±6 kJ/mol deduced from the T data. In contrast to the earlier suggestion from electrical measurements, the NMR results indicate that the dominantly mobile species in the conducting high-temperature β-phase are not single F ions but complex [FHF] anions.
  • Masaru Ohsaku, Akira Imamura, Kimihiko Hirao
    1978 Volume 51 Issue 12 Pages 3443-3448
    Published: 1978
    Released: April 19, 2006
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    The CNDO/2 and INDO calculations were performed on three azines: pyridazine, pyrimidine, and pyrazine. In order to check the validity of the lone-pair orbital energies, the calculated orbital energies were compared with those obtained by ab initio calculations. These molecules have two lone-pairs, which can be transformed into symmetric and antisymmetric combinations. In pyridazine and pyrimidine, the symmetric one is lower than the antisymmetric one in energy, while in pyrazine the reverse is true. These results were subjected to an analysis from the standpoint of the through-bond interaction. That is, we transformed the canonical molecular orbitals obtained by the CNDO/2 method into localized molecular orbitals. By the use of the localized molecular orbitals thus obtained, the variation in the lone-pair orbital energies of these molecules was estimated in terms of the through-bond (and/or the through space) interaction according to a method which selectively considered the particular interaction between the specified localized molecular orbitals in a molecule. As a result of this analysis, it was found that the relative order of the lone-pair orbital energies was determined by the different types of interactions from molecule to molecule, and the energy variation in the lone-pair orbitals was elucidated in terms of the specified through-bond and through-space interactions.
  • Masaharu Morita, Tohru Kishi, Masashi Tanaka, Jiro Tanaka, James Fergu ...
    1978 Volume 51 Issue 12 Pages 3449-3457
    Published: 1978
    Released: April 19, 2006
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    The absorption and the fluorescence spectra of four [2.2]anthracenophanes were investigated at low temperatures. A theoretical calculation of the energy levels was performed by including the charge resonance and the exciton type interactions. The fluorescence excitation polarization spectra were recorded for all absorption bands at low temperatures, the directions of the transition moment of the excimer type emission bands being estimated by the p-values and the established transition directions of anthracene chromophores. The assignments of the absorption bands are presented based on these results.
  • Jiro Tanaka, Masashi Tanaka, Masaharu Morita, Masazumi Nakagawa, Masah ...
    1978 Volume 51 Issue 12 Pages 3458-3461
    Published: 1978
    Released: April 19, 2006
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    Electronic absorption spectra of tetra-t-butylbisdehydro[14], [18], [22], [26], and [30]annulenes were investigated experimentally and theoretically. SCF MO calculations were carried out by the P-P-P method and random phase approximation (RPA). An assignment of spectra is presented. Fluorescence excitation polarization spectra of tetra-t-butylbisdehydro[14]annulene and the crystalline reflection spectra of tetra-t-butylbisdehydro[18]annulene were studied in order to determine the polarization of the spectra. The assignment was confirmed by these methods.
  • Naoto Yamamoto, Toshihiro Ohnishi, Masahiro Hatakeyama, Hiroshi Tsubom ...
    1978 Volume 51 Issue 12 Pages 3462-3465
    Published: 1978
    Released: April 19, 2006
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    Electric conductivities have been studied for Langmuir molecular layers of barium salt of fatty acids and for the layers of barium arachidate mixed with all-trans-β-apo-8′-carotenoic acid. These results have been interpreted based on an electron tunneling model taking account of the mirror image force. The conduction levels of the layers have thereby been estimated to be 1.00 eV for barium stearate, 1.31 eV for barium arachidate and 1.45 eV for barium behenate below vacuum level. The conduction level of the carotenoic acid has been derived to be 1.9 eV from these results. The structure of these layers has been discussed from the above mentioned experimental results, together with those on surface pressure, absorption spectrum and electric capacitance.
  • Hiroshi Kawazura, Hisao Tanaka, Koh-ichi Yamada, Toshio Takahashi, Yos ...
    1978 Volume 51 Issue 12 Pages 3466-3470
    Published: 1978
    Released: April 19, 2006
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    To elucidate the ligand conformation and the metal–olefin bonding nature in the binuclear palladium complex of dibenzylideneacetone, Pd2[(C6H5CH=CH)2CO]3, 1H NMR studies have been performed on the deuteriated complexes Pd2[(C6D5CH=CH)2CO]3, Pd2[(C6D5CD=CH)2CO]3, and Pd2[(C6D5CH=CD)2CO]3. Examination of the spectra has revealed that the three dibenzylideneacetone ligands which triply bridge the two Pd atoms are all in the s-cis,trans conformation. The most probable bonding scheme of the three ligands to the two Pd atoms is as follows: one Pd atom is ligated by one s-trans and two s-cis olefinic moieties and hence the other by one s-cis and two s-trans to yield a metal–olefin bonding stronger in the former combination than in the latter. A linear correlation between the couplings and the mean chemical shifts of the trans olefinic protons suggests a dominant role of metal between the couplings and the mean chemical shifts of the trans olefinic protons suggests a dominant role of metal to olefin π-back donation in differentiating the olefinic moieties in their bonding strength to the metal atoms and in retaining the characteristic rigid structure of the complex.
  • Takahide Saito, Naomichi Iso, Haruo Mizuno, Ichiro Kitamura
    1978 Volume 51 Issue 12 Pages 3471-3474
    Published: 1978
    Released: April 19, 2006
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    The self-association of phycocyanin in a buffer solution of pH 5.4 with an ionic strength of 0.1 has been studied by sedimentation equilibrium measurements in the temperature range from 5.0 to 25.0 °C. The thermodynamical treatment is also presented. The self-association of phycocyanin molecules proceeds with a decrease in the temperature. The concentration dependence of the apparent weight-average molecular weight of phycocyanin is interpreted in terms of a monomer\ ightleftharpoonshexamer equilibrium system. It is clear from the thermodynamic parameters, ΔG0, ΔH0, and ΔS0, that the self-association reaction is spontaneous in the solution of pH 5.4. In the association process, the formation of hydrophobic bonds is suggested by the large positive entropy change accompanying association reaction of phycocyanin molecules.
  • Keiji Kamogawa
    1978 Volume 51 Issue 12 Pages 3475-3481
    Published: 1978
    Released: April 19, 2006
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    Spectra of depolarized Rayleigh wings were observed for the liquids and CCl4 solutions of C6H6, CH3CN, and CHCl3. The spectral band shape can be reproduced very well by a Lorentz function for the low frequency wing component and a Gauss function for the far wing component. The functions for neat liquids gave the relaxation times for orientational motion, which support free rotation models. The relaxation times of the solutions were found to be independent of concentration, the integrated intensities showing a linear dependence on concentration. The results for the wing component are in marked contrast to those found for the central component of the spectra. The difference is discussed in terms of dynamical structure of the liquids.
  • Chikatoshi Utsunomiya, Tsunetoshi Kobayashi, Saburo Nagakura
    1978 Volume 51 Issue 12 Pages 3482-3484
    Published: 1978
    Released: April 19, 2006
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    The angular distributions for the He I photoelectron spectra of pyridine, pentafluoropyridine, and 2,6-lutidine have been measured in order to solve the ambiguities on the band assignment of pyridine. It has been concluded that the first band of pyridine is assigned to the a1n orbital and the fifth band to the lowest occupied b1π orbital.
  • Yoshitsugu Hasegawa, Motomasa Kuwayama
    1978 Volume 51 Issue 12 Pages 3485-3488
    Published: 1978
    Released: April 19, 2006
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    The ammonium–hydrogen ion-exchange on α-zirconium phosphate prepared by the direct precipitation method has been investigated by means of pH titration and X-ray diffractometry. In the forward process (α-zirconium phosphate to the ammonium form) the ion-exchange reaction took place in one stage at the equilibrium pH of 5.9–6.0 and the α-zirconium phosphate exchanger was directly converted into the ammonium form. In the reverse process (the ammonium form to α-zirconium phosphate) the reaction proceeded in three stages, that is, the ammonium form→ a half-exchanged form→ an intermediate form→α-zirconium phosphate. The chemical composition of the half-exchanged form has been represented as Zr(NH4PO4)(HPO4nH2O (n>0.5). A small amount of ammonium ions in the exchanger could not be easily replaced with protons in the solution.
  • Yoshinori Yamamoto, Akira Miura, Akira Kawamata, Masayoshi Miura, Shin ...
    1978 Volume 51 Issue 12 Pages 3489-3495
    Published: 1978
    Released: April 19, 2006
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    The title ligand, which contains two 8-quinolinol (oxine) functions in one molecule, and the Ni(II) and Cu(II) chelates have been synthesized and characterized. Visible and ultraviolet spectra of the chelates and the ligand in several solvents have been measured. Square-coordination of the ligand to the metal has been revealed by a comparison of the d-d bands between the chelates and quadridentate Schiff base chelates in the literature. Intraligand transition bands of the title chelates and the solvent effects on the frequency shifts have been compared with those of the ligand, 8-hydroxy-1-methylquinolinium hydroxide, bis(8-quinolinolato)palladium(II), -copper(II), and -nickel(II), and have been discussed.
  • Satori Utsumi, Tadao Okutani, Akio Sakuragawa, Akira Kenmotsu
    1978 Volume 51 Issue 12 Pages 3496-3499
    Published: 1978
    Released: April 19, 2006
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    A new photometric method has been developed for determining nitrite ions. This method is based on the kinetic effect of nitrite ions on the color-fading of the iron(III) thiocyanate complex in dilute nitric acid solution in the presence of iodide ions. The reaction is initiated by adding an ammonium iron(III) sulfate solution to the sample solution containing a mixture of potassium thiocyanate and potassium iodide at 25 °C. A concentration of nitrite ions, ranging from 0.0005 to 10 ppm can be determined by measuring the absorbance at 460 nm at a given time after the initiation using four appropriate calibration curves. Silver, mercury(II), iron(II), sulfide, sulfite, thiosulfate, chromate and cyanide ions in the concentration range from 0.1 to 1 ppm level interfered with the determination.
  • Megumu Munakata, Katsumi Yamada
    1978 Volume 51 Issue 12 Pages 3500-3504
    Published: 1978
    Released: April 19, 2006
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    The rate constants for the formation and dissociation of the binary Cu2+-acetylacetonate(acac) complex and the ternary 2,2′-bipyridyl(bpy)-Cu2+-acac complex have been determined by the temperature-jump method. For the reactions Cu2++acac\oversetk1b\undersetk-1b\ ightleftharpoonsCu(acac)+, Cu(acac)++acac\oversetk2b\undersetk-2b\ ightleftharpoonsCu(acac)2, and Cu(bpy)2++acac\oversetk1t\undersetk-1t\ ightleftharpoonsCu-(bpy)(acac)+, the rate constants are k1b=9.0×108 M−1 s−1, k-1b=3.2 s−1, k2b=7.0×107 M−1 s−1, k-2b=13 s−1, k1t=1.1×109 M−1 s−1 and k-1t=1.9 s−1. A comparison of the reactions shows that the forward rate for the Cu(bpy)-(acac)+ formation is larger than that for Cu(acac)+ and, subsequently, the rate of the complex formation between Cu(bpy)2+ and acac is enhanced by the coordinating bpy. On the other hand, the reverse rate for the ternary complexation reaction is smaller than for the binary. This illustrates that the dissociation of acac of Cu(bpy)-(acac)+ becomes more difficult owing to the coordination of the bpy. The above two effects of the bpy may be driving forces producing high stability, i.e., a positive value of ΔlogK\left(K=\frac[Cu(bpy)[L][Cu(bpy)][L]\ ight) for the ternary copper(II) complexes with bpy and other ligands containing O as donor atoms.
  • Satoru Muramoto, Kenji Kawase, Muraji Shibata
    1978 Volume 51 Issue 12 Pages 3505-3510
    Published: 1978
    Released: April 19, 2006
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    The [Co(O,O)2(N)2]-type complexes, [Co(ox)(mal)(en)], cis-[Co(CO3)(mal)(NH3)2], cis-[Co(ox)(mal)(NH3)2] and cis-[Co(mal)2(NH3)2], have been prepared and resolved. The CD spectra of various complexes of this type including these new complexes have been measured. The assignments of the absolute configurations have been carried out by means of the CD comparison. The CD patterns in the first absorption band region have revealed regular change with the varied O,O ligands (O,O=CO32−, ox2−, and mal2−), and from this fact a criterion for the assignments of the absolute configurations for the complexes of the present type has been established.
  • Akira Ouchi, Mamoru Shimoi, Fujio Ebina, Takashi Uehiro, Yukichi Yoshi ...
    1978 Volume 51 Issue 12 Pages 3511-3513
    Published: 1978
    Released: April 19, 2006
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    New stable trimethylantimony(V) complexes of some dithiocarbonate derivatives, (CH3)3SbL2, where HL=secondary amine-N-carbodithioic acid or O-alkyl dithiocarbonic acid, have been synthesized by the metathetical reaction between dibromotrimethylantimony(V) and the alkali salts of ligands. In these compounds, the antimony is kept quinquevalent. The 1H-NMR peak of the methyl protons of all of these compounds appears as a singlet even at −60 °C. Therefore, the most probable structure for these compounds is the trigonal bipyramidal one, where two unidentate dithiocarbonate derivative ligands bond to antimony from the apical directions.
  • Naohide Matsumoto, Masahiro Yamashita, Sigeo Kida
    1978 Volume 51 Issue 12 Pages 3514-3518
    Published: 1978
    Released: April 19, 2006
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    The crystal structures of Pt(II)–Pt(IV) complexes, [Pt(tn)2][PtCl2(tn)2](BF4)4 (1), [Pt(tn)2][PtBr2(tn)2](ClO4)4 (2), and [Pt(tn)2][PtBr2(tn)2](BF4)4 (3) have been determined by the single-crystal X-ray diffraction method, where tn denotes trimethylenediamine. The crystals of these complexes are isomorphous with one another and the space group is A222 with a=10.790(2), b=13.872(2), c=10.287(1) Å for 1, a=11.003(6), b=13.979(6), c=10.355(4) Å for 2, and a=10.925(3), b=13.862(3), c=10.291(1) Å for 3. The structures were determined by the heavy atom method and refined by the block-diagonal least-squares method to give the disagreement factor 0.082, 0.089, and 0.086 for 1, 2, and 3, respectively. Each crystal comprises infinite PtII…X–PtIV–X… chains running parallel to the a-axis. In the chain, tetragonal bipyramidal [PtIVX2(tn)2]2+ (X=Cl or Br) and square planar [PtII(tn)2]2+ units are stacked alternately. Two of the fluorine or oxygen atoms of the counter anion are hydrogen-bonded to the nitrogen atoms of the ligand, contributing to the formation of an infinite chain.
  • Katsuhiko Matsunaga, Hiroaki Tsujioku, Sigeru Fukasa, Kiyoshi Hasebe
    1978 Volume 51 Issue 12 Pages 3519-3521
    Published: 1978
    Released: April 19, 2006
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    Most of the mercury in coastal seawater polluted with waste water including mainly organic suspended matter is associated with suspended matter, especially particulate organic matter. The amount of mercury adsorbed on a given amount of particulate organic matter nearly obeys Freundlich’s adsorption isotherm at mercury concentrations less than 15 ppm in particulate organic matter. The mercury in suspended matter is not much reduced by the addition of tin(II) chloride. Thus, to get the total value of the mercury concentration, the water samples must be heated with the addition of a sulfuric and nitric acid mixture to decompose the suspended matter.
  • Yasuo Nakao, Akitsugu Nakahara
    1978 Volume 51 Issue 12 Pages 3522-3526
    Published: 1978
    Released: April 19, 2006
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    Nickel(II) complexes of Schiff bases derived from salicylaldehyde and glycylaspartate or glycylglutamate were prepared and their structures were determined on the basis of electronic absorption and 1H NMR spectra. The relationship between structure of the chelates and stability of fused-ring systems was discussed in some detail, and was applied to a selective hydrolysis reaction of dimethyl glycylaspartate and glycylglutamate. Nickel(II) complexes of Schiff bases derived from salicylaldehyde and β-methyl glycylaspartate or γ-methyl glycylglutamate were obtained by a reaction between dimethyl glycylaspartate or glycylglutamate and bis(salicylaldehydato)nickel(II) in methanol containing sodium or potassium hydroxide.
  • Yuzo Saeki, Ryoko Matsuzaki, Seiki Fujiwara
    1978 Volume 51 Issue 12 Pages 3527-3529
    Published: 1978
    Released: April 19, 2006
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    The product formed by heating FeCl2 in an oxygen stream has been examined in detail. The reaction processes of gaseous FeCl3 and FeOCl, formed during the reaction between FeCl2 and oxygen, with oxygen were also examined. The reaction process between FeCl2 and oxygen can be represented as follows: FeCl2 reacts with oxygen above about 250 °C to form FeOCl and gaseous FeCl3, 2FeCl2(s)+1/2O2(g)→FeOCl(s)+1/2Fe2Cl6(g). Subsequently, the resulting FeOCl reacts with oxygen to form α-Fe2O3 and chlorine, 2FeOCl(s)+1/2O2(g)→Fe2O3(s)+Cl2(g). Above about 320 °C, the decomposition of the FeOCl to α-Fe2O3 and gaseous FeCl3, 3FeOCl(s)→Fe2O3(s)+1/2Fe2Cl6(g), also occurs. Above about 370 °C, the reaction between gaseous FeCl3 formed and oxygen to form η-Fe2O3 and chlorine, Fe2Cl6(g)+3/2O2(g)→Fe2O3(s)+3Cl2(g), occurs in addition to the above reactions.
  • Hidetoshi Kita, Kazuyuki Itoh, Koji Tanaka, Toshio Tanaka
    1978 Volume 51 Issue 12 Pages 3530-3533
    Published: 1978
    Released: April 19, 2006
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    Kinetics of the reaction of bis(μ-dibutyldithiocarbamato-S,S′)-digold(I), [Au(n-Bu2dtc)]2, with I2, IBr, and Br2 in dichloromethane was studied by the stopped-flow technique. A 1 : 1 charge-transfer (CT) complex, [Au(n-Bu2dtc)]2·X2 (X2=I2, IBr, and Br2), formed in the initial process of reaction was identified spectrophotometrically at −50 °C. The rates of reaction were almost the same for I2, IBr, and Br2, and independent of the both [Au(n-Bu2dtc)]2 and halogen concentrations. The reaction has been interpreted to proceed via the charge-transfer complex, [Au(n-Bu2dtc)]2·X2, which decomposes in a rate-determining step to give the final product, [AuIII(n-Bu2dtc)2][AuIX2]. The activation parameters for the reactions were determined: ΔH\ eweq(kJ/mol)=43.7 (I2), 26.0 (IBr), and 12.3 (Br2); ΔS\ eweq(J/mol K))=−91.5 (I2), −156 (IBr), and −201 (Br2).
  • Ken-ichi Okamoto, Tomitake Tsukihara, Jinsai Hidaka, Yoichi Shimura
    1978 Volume 51 Issue 12 Pages 3534-3539
    Published: 1978
    Released: April 19, 2006
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    The crystal structure of (+)546-cis(O)-triammine(sarcosinate-N-propionato)cobalt(III) (+)546-ethylenediaminetetraacetato)cobaltate(III) monohydrate was solved by single crystal X-ray diffraction techniques. The crystal is orthorhombic, space group P212121, with a=10.792, b=26.816, c=8.203 Å, and Z=4. The final R value was 0.054. The absolute configurations of two complex ions were determined by means of anomalous dispersion using Cu Kα radiation. The coordinated asymmetric nitrogen atom of sarcosinate-N-propionate ligand takes an R configuration, and the (+)546-(ethylenediaminetetraacetato)cobaltate(III) ion Δ one.
  • Jun-ichi Aihara
    1978 Volume 51 Issue 12 Pages 3540-3543
    Published: 1978
    Released: April 19, 2006
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    Resonance energies of 30 conjugated hydrocarbons and their molecular ions have been calculated on the basis of the graph-theoretical theory of aromaticity. No difficulty was found in extending the aromaticity theory to ionic conjugated species. In general, the resonance energies obtained correlated well with typical chemical features of the compounds.
  • Seiji Shinkai, Yumiko Kusano, Toyoko Ide, Takaaki Sone, Osamu Manabe
    1978 Volume 51 Issue 12 Pages 3544-3548
    Published: 1978
    Released: April 19, 2006
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    Nonenzymatic dihydronicotinamide reduction of carbon-carbon double bonds occurs with the aid of Mg2+ ion or acetic acid. The role of Mg2+ ion and acetic acid is discussed on the basis of spectral studies, kinetic measurements, and product analyses. The addition of Mg2+ ion caused the shift of the NMR peak of substrate α-proton to lower field, and the magnitude was parallel to the yield of reduced methylene derivatives. Kinetic studies suggested that the dihydronicotinamide reduction in the presence of Mg2+ ion is most reasonably understood by assuming a competitive complexation of dihydronicotinamide and substrate with Mg2+ ion. On the other hand, acetic acid aids the reduction by means of general acid catalysis, but an alternative mechanism is suggested for the reduction of benzylidenemalononitrile.
  • Ikuko Wakeshima, Yoshihiro Saitoh, Ichiro Kijima
    1978 Volume 51 Issue 12 Pages 3549-3552
    Published: 1978
    Released: April 19, 2006
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    Reaction of organic tin(II) compounds, Sn(OR)2[R=C2H5, CH2CH2N(CH3)2, C6H5, o-CH3C6H4], with phenyl isothiocyanate and carbon disulfide have been investigated. The reaction of di(ethoxo)tin(II) with phenyl isothiocyanate in benzene at room temperature gave the corresponding addition product. The reaction at 80–81 °C however gave diethyl N-phenylcarbonimidate. Phenyl isothiocyanate reacted exothermically with bis[2-(dimethylamino)ethoxo]tin(II) to yield the 1 : 1 addition product. In the reaction with bis(2-methylphenoxo)tin(II), a compound containing one molecule of phenyl isothiocyanate per two molecules of the tin(II) compound was isolated, but the reaction with di(phenoxo)tin(II) did not occur. Di(ethoxo)tin(II) reacted with carbon disulfide to give diethyl thiocarbonate, diethyl carbonate, and tetraethyl orthocarbonate. Bis(o-methylphenoxo)tin(II) and di(phenoxo)tin(II) however did not react with carbon disulfide.
  • Hideo Matsushima, Yasuki Mori, Kozo Kitaura
    1978 Volume 51 Issue 12 Pages 3553-3558
    Published: 1978
    Released: April 19, 2006
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    3′-Deoxyseldomycin 5 (2), 2′-deamino-3′-epiamino-3′-deoxyseldomycin 5 (14), and 2′,3′-epimino-2′-deamino-3′-deoxyseldomycin 5 (15) were prepared from seldomycin 5 (1). Treatment of hexa-N-ethoxycarbonyl (ecb)-3′-O-tosylseldomycin 5 with sodium borohydride in DMSO gave the corresponding N-ecb-derivatives of 2, 14, and 15. Removal of the ecb groups of these compounds with aq potassium hydroxide gave the free bases 2, 14, and 15, respectively. Structure determination of the products was performed by means of MS, CMR, PMR, and chemical reactions. It was found that 2 exhibits a more potent and broader antibacterial activity than the parent compound 1, and 14 shows unique antibacterial spectrum against resistant strains, whereas 15 has almost no activity.
  • Hiroshi Ozaki, Akira Tai, Shinzo Kobatake, Hironobu Watanabe, Yoshihar ...
    1978 Volume 51 Issue 12 Pages 3559-3563
    Published: 1978
    Released: April 19, 2006
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    Enantioface-differentiating hydrogenations of methyl acetoacetate over (S)-alanine-, (S)-2-aminobutyric acid, (S)-valine-, (S)-leucine-, (S) -malic acid-, and (R,R)-tartaric acid-MRNi were carried out under atmospheric pressure of hydrogen and the effects of the modifying reagent on the rates of the formation of enantiomer, vS and vR, were investigated. The rates of hydrogenation, v=vS+vR, were the same for all the amino acid-MRNi and also for all the hydroxy dicarboxylic acid-MRNi. However, the vRvs ratios were different. These results are explained in terms of the independence of the rate-determining and enantioface-differentiating steps in the reaction pathway of hydrogenation. The rate-determining step of hydrogenation was shown to be the hydrogen addition to the adsorbed substrate, while the enantioface-differentiating step was expected to occur prior to the rate-determining step.
  • Norikazu Takeda, Shohei Inoue
    1978 Volume 51 Issue 12 Pages 3564-3567
    Published: 1978
    Released: April 19, 2006
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    α,β,γ,δ-Tetraphenylporphinatoaluminium methoxide reacts reversibly with carbon dioxide in the presence of 1-methylimidazole, and this carbon dioxide is activated to react with propylene oxide to produce propylene carbonate under atmospheric pressure and at room temperature.
  • Sakae Uemura, Hajime Okazaki, Akira Onoe, Masaya Okano
    1978 Volume 51 Issue 12 Pages 3568-3570
    Published: 1978
    Released: April 19, 2006
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    The chlorination of norbornene and cyclooctadienes with sulfuryl chloride and phosphorus(V) chloride has been investigated mainly in carbon tetrachloride under various conditions. From the studies of the product distributions and the effect of radical scavengers, the following facts have been revealed for the first time in olefin chlorination: chlorination with sulfuryl chloride proceeds through an ionic pathway at room temperature or in the presence of silica gel and that with phosphorus(V) chloride through a radical pathway at elevated temperature, and an ionic chlorination with phosphorus(V) chloride in nonpolar solvents does not seem to involve C–P bond formation through the reaction.
  • Yoko Naya, Munio Kotake
    1978 Volume 51 Issue 12 Pages 3571-3573
    Published: 1978
    Released: April 19, 2006
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    The major volatile constituents present in different parts of a deciduous tree, Meratia praecox, have been identified by combination of GC-MS and spectral analysis of the isolated compounds. From the results, some biogenetic implications were discussed.
  • Yoshiaki Nakamura, Tatsuro Ouchi, Minoru Imoto
    1978 Volume 51 Issue 12 Pages 3574-3578
    Published: 1978
    Released: April 19, 2006
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    The polymerization of the vinyl monomer was carried out in water, using either dimethylbis(ethylthio)tin or triethyl(p-tolylthio)tin as an initiator. The polymerization required the coexistence of the iron(III) ion. The initiating species was concluded to be a thiyl radical. Macromolecular tin mercaptide was much more effective than monomeric tin mercaptide.
  • Kunihide Fujimori, Kameji Yamane
    1978 Volume 51 Issue 12 Pages 3579-3581
    Published: 1978
    Released: April 19, 2006
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    5,6,7,12-Tetrahydrobenzo[6,7]cyclohept[1,2-b]indol-7-ones were obtained by the oxidation of 5,6,7,12-tetrahydrobenzo[6,7]cyclohept[1,2-b]indoles with 2,3-dichloro-5,6-dicyano-p-benzoquinone (DDQ) in wet dioxane. The α,α-dibromo compound, obtained by bromination of 12-methyl-5,6,7,12-tetrahydrobenzo[6,7]cyclohept[1,2-b]indol-7-one with phenyltrimethylammonium tribromide (PTAB), was hydrolyzed to give the diketone (5). By treatment with alkali, compound 5 was converted to 6-hydroxy-12-methyl-7,12-dihydrobenzo[6,7]cyclohept[1,2-b]indol-7-one.
  • Kazuko Kohara
    1978 Volume 51 Issue 12 Pages 3582-3585
    Published: 1978
    Released: April 19, 2006
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    In the presence of selenium dioxide, guaiazulene and 4,6,8-trimethylazulene condensed with the active methylene compounds, ethyl acetoacetate and acetylacetone, to give ethyl α-(3-guaiazulenyl)acetoacetate (3a), α-(3-guaiazulenyl)acetylacetone, ethyl α-(4,6,8-trimethyl-1-azulenyl)acetoacetate (5a), and α-(4,6,8-trimethyl-1-azulenyl) acetylacetone. These α-substituted β-diketones exist exclusively in their corresponding enol forms, as evidenced by their NMR spectra. In the NMR spectra of 3a and 5a, the ethyl protons of the ester group show an ABX3 pattern; the observed nonequivalence of the methylene protons is attributable to the restricted rotation between azulene and the substituent carbon atoms. From an inspection of the chemical shifts of the methyl group of metal chelate compounds of azulene derivatives, it is now reasonably concluded that there is no aromaticity associated with the chelate ring, providing further support for Musso’s proposal.
  • Kazuhiro Maruyama, Tadashi Kozuka
    1978 Volume 51 Issue 12 Pages 3586-3589
    Published: 1978
    Released: April 19, 2006
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    Alkyl-substituted 2,5-dimethoxyacetophenones were oxidized with thallium(III) nitrate in methanol–trimethyl orthoformate (TMOF) to give methyl alkyl-substituted 2,5-dimethoxyphenylacetates in a good yield. A simple modification of separating method from the reacting mixture allowed us to obtain the corresponding methyl (alkylsubstituted 3,6-dioxo-1,4-cyclohexadienyl)acetates.
  • Sigeru Torii, Kenji Uneyama, Kaoru Okamoto
    1978 Volume 51 Issue 12 Pages 3590-3594
    Published: 1978
    Released: April 19, 2006
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    (±)-β-Vetivone was synthesized by the base-catalyzed spiroannelation of 2-[2-(4-hydroxy-2-methylphenyl)-ethyl]-3-methyl-3-butenyl p-toluenesulfonate followed by methylation and subsequent isomerization of the side chain double bond. The reactivities of the related tosylates, 4-(4-hydroxy-2-methylphenyl)-2-isopropylbutyl p-toluenesulfonate, 3-hydroxy-2-[2-(4-hydroxy-2-methylphenylethyl]-3-methylbutyl p-toluenesulfonate, and 2,3-epoxy-2-[2-(4-hydroxy-2-methylphenyl)ethyl]-3-methylbutyl p-toluenesulfonate have been discussed.
  • Mitsuhiro Kinoshita, Hiroshi Hamazaki, Masaki Awamura
    1978 Volume 51 Issue 12 Pages 3595-3598
    Published: 1978
    Released: April 19, 2006
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    The Grignard reaction of 3-O-benzyl-6-deoxy-1,2-O-isopropylidene-α-D-xylo-hexofuranos-5-ulose (5) with ethylmagnesium bromide yielded 3-O-benzyl-6-deoxy-5-C-ethyl-1,2-O-isopropylidene-α-D-glucofuranose (6) as a major product in 91% stereoselectivity. Hydrolysis of 6 followed by successive periodate oxidation and lithium aluminium hydride reduction gave 2-O-benzyl-5-deoxy-4-C-ethyl-D-arabinitol. Selective benzoylation of 9 followed by successive 3,4-O-isopropylidenation, debenzoylation, hydrogenolysis, and two-stage oxidation with periodate-hypoiodite afforded (4R,5S)-(+)-5-ethyl-2,2,5-trimethyl-1,3-dioxolane-4-carboxylic acid (15) in 24.6% overall yield from 5. Hydrolysis of 15 gave (2R,3S)-(−)-2,3-dihydroxy-3-methylpentanoic acid. The acetonide 15 is usefull as a synthon for pyridomycin synthesis.
  • Naomichi Furukawa, Mitsuo Fukumura, Takehiko Nishio, Shigeru Oae
    1978 Volume 51 Issue 12 Pages 3599-3605
    Published: 1978
    Released: April 19, 2006
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    Several N-acyl-S,S-arylphenylsulfilimines were prepared and subjected to thermal decomposition. They decomposed readily at 130–190 °C to give isocyanates together with diphenyl sulfide, quantitatively. However, N-tosyl-S,S-diphenylsulfilimine did not decompose even upon heating at 200 °C for 24 h. A kinetic study revealed that the rates of pyrolysis of N-aroyl-S,S-arylphenylsulfilimines (p-Y–C6H4(Ph)S→NCOC6H4–X-p) are nicely correlated with the Hammett σ-values, ρX=−1.2 and ρY=+0.92, respectively, being obtained. The activation enthalpies and entropies were ΔH\ eweq=38.7 kcal/mol and ΔS\ eweq=6.0 e.u. for Ph2S→NCOPh and ΔH\ eweq=32.3 kcal/mol and ΔS\ eweq=5.5 e.u. for (Remark: Graphics omitted.), respectively. The rearrangement was accelerated considerably by o-methyl substituent in the aryl group. The effect of solvent on the rate of pyrolysis was small. The results indicate that the pyrolysis of sulfilimine proceeds via a concerted migration of the R group from carbonyl carbon to imino nitrogen similar to the Curtius type rearrangement of acid azide.
  • Yasukazu Ohkatsu, Kazumi Kikkawa, Tetsuo Osa
    1978 Volume 51 Issue 12 Pages 3606-3609
    Published: 1978
    Released: April 19, 2006
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    Cumyl hydroperoxide has been decomposed using zinc O,O-diisobutyl dithiophosphate. The decomposition reaction consisted of three stages including the first homolytic decomposition and the last heterolytic decomposition. These decomposition modes depended considerably on the relative concentration of the complex to the hydroperoxide and the total concentration. From these results and on the basis of decomposition reaction in the presence of both zinc O,O-diisobutyl dithiophosphate and bis(O,O-diisobutoxyphosphonothioyl) disulfide, it has been shown that the formation of sulfuric acid was most important for heterolytic decomposition.
  • Heitaro Obara, Hiroshi Kimura, Masanobu Suzuki, Jun-ichi Onodera
    1978 Volume 51 Issue 12 Pages 3610-3611
    Published: 1978
    Released: April 19, 2006
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    The racemate of tetrahydroanhydroaucubigenone (3), one of the related compounds of aucubin, was synthesized by the photoirradiation of 6-[2-(nitrosooxy)ethyl]-3-oxabicyclo[3.3.0]octan-7-one. (±)-Tctrahydroanhydroaucubigenin was also obtained by reduction of (±)-3 with sodium in moist ether.
  • Kazu Kurosawa, Atsuko Hashiba, Hirobumi Takahashi
    1978 Volume 51 Issue 12 Pages 3612-3615
    Published: 1978
    Released: April 19, 2006
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    Lithium aluminium hydride (LAH) reduction of 4′-hydroxychalcones, followed by dehydration, yielded 4-cinnamylidene-2,5-cyclohexadien-1-ones in 19–42% yields. The LAH reduction of 4′-acetoxychalcones also gave the same products in improved yields.
  • Misuzu Namikawa, Tatsushi Murae, Takeyoshi Takahashi
    1978 Volume 51 Issue 12 Pages 3616-3621
    Published: 1978
    Released: April 19, 2006
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    6,7-Epoxyhumula-2,9-diene (2) was treated with 1.8 M sulfuric acid–acetone (1 : 1) to yield a new tricyclic diol, 5,9-dihydroxy-4,8,11,11-tetramethyltricyclo[6.3.0.02,4]undecane (9; diol B), together with tricyclohumuladiol (3; diol A), humulenol-II (4), a diol C (5b), a diol D (5a), and an acetonide (8a). The same reaction at 0° gave only 3. Tricyclohumuladiol (3) was shown to be a key intermediate in the reaction of 2 to form 4, 5a, 5b, 8a, and 9.
  • Minoru Kubota, Akio Yamamoto
    1978 Volume 51 Issue 12 Pages 3622-3626
    Published: 1978
    Released: April 19, 2006
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    Alkylcopper complexes, RCu(PPh3)2 (R=methyl, ethyl, propyl, isobutyl)reacted with sulfur smoothly at low temperatures to produce dialkyl disulfides. This indicates the insertion of sulfur to alkyl-Cu bond taking place followed by coupling of the two alkylthio–Cu bonds. Methylcopper complex, CH3Cu(PPh3)2·0.5Et2O reacted with thiols to produce alkylthio- and phenylthiocopper complexes having one or two triphenylphosphine ligands. The reactions of these alkylthiocopper complexes with acyl halides and acid anhydrides produced S-alkyl ethanethioates in high yields, whereas the reactions of alkylthiocopper complexes with alkyl halides produced dialkyl sulfides. Alkylthio- and phenylthiocopper complexes were found to catalyze the transesterification reactions between S-alkyl ethanethioates and thiols. The exchange reactions also take place between the alkylthiocopper complex and benzenethiol producing phenylthiocopper complex with liberation of alkanethiol.
  • Heitaro Obara, Jun-ichi Onodera, Yuji Kurihara, Fumitada Yamamoto
    1978 Volume 51 Issue 12 Pages 3627-3630
    Published: 1978
    Released: April 19, 2006
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    2′,3′,4,4′,6′-Pentahydroxychalcone (4), an aglycone of carthamin, was synthesized by the demethoxymethylation of 2′,3′,4,4′,6′-pentakis(methoxymethoxy)chalcone prepared by the condensation of 2,3,4,6-tetrakis(methoxymethoxy)acetophenone with p-methoxymethoxybenzaldehyde. 4 was converted into 4′,5,6,7- and 4′,5,7,8-tetrahydroxyflavanone (5 and 6) by boiling with methanolic hydrochloric acid. On the basis of the comparisons of the properties of 5 and 6 with those of carthamidin (A) and isocarthamidin (B) derived from natural product, the structures originally assigned for A and B should be reversed.
  • Yohji Nakatsuji, Yasuhiko Ikkaku, Masakatsu Nomura, Sh\={o}ichi Kikkaw ...
    1978 Volume 51 Issue 12 Pages 3631-3634
    Published: 1978
    Released: April 19, 2006
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    The hydrocracking of alkyl derivatives of polynuclear aromatic hydrocarbons (naphthalene, anthracene, dihydroanthracene, phenanthrene, and dihydrophenanthrene) over ZnCl2/CuCl molten salt was examined at 400 °C for 3 h in a batch autoclave system. The kinds of alkyl groups, the positions of the alkyl groups, and the types of condensed rings were changed in order to clarify the decomposition process of the polynuclear aromatic hydrocarbons. On the basis of the detailed product distribution obtained by using GC-MS, the behavior of the alkyl group attached to the condensed ring under these reaction conditions was found to be different. Generally, in this investigation, the alkyl group was not completely dealkylated in the initial stage and remained in the products as monocyclic aromatics; the extent of dealkylation was found to be dependent upon the type of starting materials. In the hydrocracking of 9,10-dihydroanthracene, dehydrogenation occurred in preference to the opening of the central ring.
  • Seiji Shinkai, Toyoko Ide, Osamu Manabe
    1978 Volume 51 Issue 12 Pages 3635-3636
    Published: 1978
    Released: April 19, 2006
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    The optical spectra of the picrate ion in a micellar solution indicate that slightly below the CMC of CTAB surfactant the anion is relatively free and exists as an ion pair above the CMC. The hydrophobic aggregate of TMAC invariably gives free ion. The polymer micelle of quaternized poly(4-vinylpyridine) results in a tight ion pair.
  • Yôichi Iida
    1978 Volume 51 Issue 12 Pages 3637-3638
    Published: 1978
    Released: April 19, 2006
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    Crystalline phenothiazine cation radical salts show charge-transfer transition between cation radicals in the low-energy region. These salts have antiferromagnetic exchange interaction between cation radicals. Their optical and magnetic properties were discussed in terms of onedimensional Hubbard model.
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