Bulletin of the Chemical Society of Japan
Online ISSN : 1348-0634
Print ISSN : 0009-2673
ISSN-L : 0009-2673
Volume 57 , Issue 2
Showing 1-50 articles out of 74 articles from the selected issue
  • Ryozi Hino, Hiroyasu Aoi, Kenzi Toki
    1984 Volume 57 Issue 2 Pages 317-321
    Published: 1984
    Released: June 27, 2006
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    The mechanism of zeolite X crystallization was studied by using two kinds of silica sources, tetraethyl orthosilicate and silica sol. The adsorption of benzene and cyclohexane was subjected to a measurement to clarify the distribution of cation Na+ and the change in the pore structure and surface of solid phases with reaction progress. The relation between specific surface area and reaction time has been revealed by means of adsorption of nitrogen gas, benzene, and cyclohexane as follows: 1) In the early stage of reaction or in the amorphous solid state, N2≈C6H6≈C6H12 for tetraethyl orthosilicate and N2≈C6H6>C6H12 for silica sol; 2) for crystals in the early stage, N2>C6H12>C6H6 for tetraethyl orthosilicate and N2>C6H12≈C6H6 for silica sol; 3) for crystals in a sufficiently developed stage, N2>>C6H12>C6H6 for tetraethyl orthosilicate and N2≈C6H6>C6H12 for silica sol. In the case of silica sol, the crystallization mechanism is based on inhomogeneous nucleation; a number of critical nuclei may be generated but their dimension is small. In the case of tetraethyl orthosilicate critical nuclei are fewer in number and larger in size than in the case of silica sol; the mechanism of crystallization is based on homogeneous nucleation.
  • Hisaharu Hayashi, Saburo Nagakura
    1984 Volume 57 Issue 2 Pages 322-328
    Published: 1984
    Released: June 27, 2006
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    External magnetic field and magnetic isotope effects on the dynamic behavior of radical pairs in solutions have been studied theoretically, where the relaxation of their electron spins was taken into account. The decay observed with some radical pairs in micellar solutions under high magnetic fields is successfully interpreted in terms of the relaxation mechanism, and the magnetic field dependence of the relaxation rates is calculated for a model system.
  • Norio Ohtomo, Kazuo Tokiwano, Kiyoshi Arakawa
    1984 Volume 57 Issue 2 Pages 329-333
    Published: 1984
    Released: June 27, 2006
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    A formula for obtaining partial structure factors for fluid systems composed of molecular clusters with various sizes was derived according to the theoretical procedure proposed in the preceding papers (N. Ohtomo, K. Tokiwano, and K. Arakawa, Bull. Chem. Soc. Jpn., 54, 1802 (1981): 55, 2788 (1982)). The formula was applied to calculate partial structure factors of liquid water, and from the good agreement between the calculated and observed values the pentamer–monomer mixture model for liquid water was confirmed as reasonable.
  • Toshio Yoshioka, Masaharu Shimamura
    1984 Volume 57 Issue 2 Pages 334-337
    Published: 1984
    Released: June 27, 2006
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    To obtain a novel acid-base catalyst of high activity and easy treatment, we have prepared polystyrene-based fibrous ion exchange catalysts which have large surface areas per unit of weight and which can be utilized in various forms. They are excellent in chemical stability and mechanical strength due to their composite structures, reinforced with polypropyrene. The reactions of sucrose inversion and methyl acetate hydrolysis were carried out by using these cation exchange fibers and ordinary cation exchange resins. The fiber has about sixteen times as high a catalytic activity per equivalent acid as the resin in the case of sucrose inversion. The intrinsic rate constant in the fiber phase is evaluated to be 2.4 times larger than that in the resin phase in terms of the solid-catalysis theory considering the catalytic effectiveness factor and the absorption coefficient. On the other hand, the catalytic activity per equivalent acid of the fiber is almost equal to that of the resin in the case of methyl acetate hydrolysis. It is suggested that this different behavior is attributable to the different molecular sizes of the reactants.
  • Shoichi Okouchi, Sokichi Sasaki, Yoshio Harano
    1984 Volume 57 Issue 2 Pages 338-340
    Published: 1984
    Released: June 27, 2006
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    The volatilization rate of mercury was studied, together with the oxygen reaeration rate, in a laboratory scale under various mixing conditions. The rates of both mercury and oxygen were controlled by mass transfer in the aqueous phase. The obtained ratio of the mercury-volatilization rate constant to the oxygen-reaeration rate constant was 0.94 at temperatures ranging from 283 to 303. If the oxygen-reaeration rate constant is available in a real-water body or in a wastewater-treatment facility, multiplying its value by the ratio of 0.94 permits the determination of the volatilization rate constant of mercury without the direct measurement of the mercury.
  • Hiroyuki Uchimura, Akio Tajiri, Masahiro Hatano
    1984 Volume 57 Issue 2 Pages 341-348
    Published: 1984
    Released: June 27, 2006
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    The magnetic circular dichroism (MCD) and UV absorption spectra of 2,2′- and 4,4′-bipyridyl in cyclohexane and sulfuric acid were measured at room temperature. The MCD spectrum of 2,2′-bipyridyl is different from that of 4,4′-bipyridyl, reflecting the difference in molecular symmetry between them. The absorption and MCD spectral profiles of 2,2′-bipyridyl in cyclohexane are different from those of 2,2′-bipyridyl in mineral acids, in this system protonation taking place on the nitrogen atoms to give a mono- or di-cation with low symmetry. On the contrary, the MCD spectra of 4,4′-bipyridyl in cyclohexane and in acidic media at pH 0.98 exhibit a similar spectral profile to each other due to the D2 symmetry being retained in 4,4′-bipyridyl. Theoretical calculations were carried out on the basis of the PPP-SCF-CI method to get a reasonable explanation for the observed MCD spectra. The assignments of the MCD bands of these compounds are given and their dihedral angles are estimated.
  • Naokata Takeyama, Kimie Nakashima
    1984 Volume 57 Issue 2 Pages 349-354
    Published: 1984
    Released: June 27, 2006
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    Using titanium columns of 10 cm length and glass columns of different lengths, the vertical exponential distribution of the concentration of aqueous 1–1 electrolytes in each column has been ascertained at the steady state of convective thermal diffusion. The value of(a4L) In q is found to be characteristic of individual solutes, and possibly proportional to the thermal diffusion coefficients, where q is the quotient of the steady concentration of a solute at the bottom of column to that at the top, L is the effective column length, and a is the working column space. This fact has been also shown by jointed glass columns with and without top vessel, capable of multistep sampling from the top to the bottom through intermediate jointed parts along columns. The rate constants in processes to the steady state have been examined to be proportional to the square of temperature difference applied, and to decrease with increasing L. Although the enhancement of downward enrichment of solutes has been observed by attaching a large top vessel to the column top, the rate constants decrease inevitably and significantly thereby.
  • Yoshihiro Nakato, Motomu Yoshimura, Masahiro Hiramoto, Akira Tsumura, ...
    1984 Volume 57 Issue 2 Pages 355-360
    Published: 1984
    Released: June 27, 2006
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    The photooxidation of iodide ions on n-type silicon electrodes highly doped with boron from the surface in hydrogen iodide or hydrogen iodide/iodine solutions was investigated. Two doping methods were employed: thermal diffusion and ion implantation. The electrode was remarkably stabilized by coating with a 2 to 3 nm-thick platinum layer, followed by heat-treatment at about 400 °C for ca. 10 min. The photocurrent was stable for more than 500 h at a density of the order of 10 mA cm−2. The boron-doped and Pt-coated n-Si electrode also generated a photovoltage much higher than that for a Pt-coated n-Si electrode, showing an advantage of forming the p-n junction. Photoelectrochemical cells made of a boron-doped-Pt-coated n-Si electrode, a platinized Pt counter electrode, and a commercial cation exchange membrane were found to photoelectrolyze hydrogen iodide without externally applied voltage into hydrogen and iodine with a solar-to-chemical energy conversion efficiency (φchems) under simulated AM 1 solar radiation of 8.2%, probably the highest of the φchems values observed for the cells working without external voltage.
  • Makoto Isihara
    1984 Volume 57 Issue 2 Pages 361-365
    Published: 1984
    Released: June 27, 2006
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    A simple construction formalism of molecular orbitals is presented in the context of partitioning of the electronic Hamiltonian. As a consequence of the formalism, a variational method of determining molecular orbital energies is proposed. The method is illustrated with the numerical example for the helium atom, whose result is reasonably meaningful.
  • Naoki Sugimoto, Muneo Sasaki, Jiro Osugi
    1984 Volume 57 Issue 2 Pages 366-369
    Published: 1984
    Released: June 27, 2006
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    The proton tunneling has been examined for the reaction between 2,4,6-trinitrotoluene and 1,8-diazabicyclo[5.4.0]undec-7-ene in benzonitrile in view of the solvent effect on the rate ratio kHkD as well as on the various activation parameters. The reaction rate ratio kHkD diminishes from 18.3 at 15 °C to 14.5 at 35 °C. The difference in the activation energies EaDEaH is 8.8 kJ mol−1 and the ratio of Arrhenius preexponential factors is 2.5. All these values are greater than the semiclassical limits of the primary kinetic isotope effects. According to Bell’s equation the remarkable isotope effect is due to considerable contribution from tunneling in benzonitrile. The present results, being compared with those in other aprotic solvents, are discussed in relation with the effects of solvent polarity, specific acid–solvent interaction, and geometrical bulkiness in the vicinity of the reaction site.
  • Toshiyuki Osakai, Tadaaki Kakutani, Mitsugi Senda
    1984 Volume 57 Issue 2 Pages 370-376
    Published: 1984
    Released: June 27, 2006
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    The transfer of tetramethylammonium (TMA+) ion across the interface between a 0.1 mol dm−3 LiCl aqueous solution and a 0.1 mol dm−3 tetrabutylammonium tetraphenylborate nitrobenzene solution was investigated by means of phase-selective a.c. polarography. In recording the a.c. polarographic current a two-electrode cell system was used and the ohmic drop due to solution resistance in the cell was compensated for by positive feedback. The ion-transfer admittance vs. potential curves were determined in the a.c. frequency range between 10 and 100 Hz and the kinetic parameters of the TMA+-ion transfer across the water/nitrobenzene interface were determined.
  • Keishiro Shirahama, Masatoshi Tashiro
    1984 Volume 57 Issue 2 Pages 377-380
    Published: 1984
    Released: June 27, 2006
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    Binding of 1-decylpyridinium bromide onto poly(vinyl sulfate) in aqueous solution is measured by using a potentiometric titration method which employs propionyl-α-cyclodextrin as a neutral carrier in a 1-decylpyridinium selective electrode. Binding is highly cooperative and biphasic. The first step binding is reduced, while the second one increased on increasing added NaBr concentration. Temperaure dependence is very small giving an enthalpy of binding equal to −1.4 kJ mol−1.
  • Setsuko Kinoshita, Kikuo Miyokawa, Hisanobu Wakita, Isao Masuda
    1984 Volume 57 Issue 2 Pages 381-385
    Published: 1984
    Released: June 27, 2006
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    The title complexes with the [COIII(salen)L2] formula, where salen denotes N,N′-ethylenebis(salicylideneaminato) dianion and L2, bidentate 2,4-alkanedionato anions, like the pent, hex, hept, or non anions, underwent thermally induced, intramolecular one-electron transfer reaction from L2 to Co(III) in the solid state to give [CoII(salen)] in a stoichiometric amount. The gaseous products evolved on the pyrolysis included 1/2 mol of free 2,4-alkanedione, corresponding to the L2 of the complexes, per mole of the complexes. The pyrolysis reaction process was described by the contracting-disk equation for all the complexes. The rate constants increased in the following order of L2: pent<hex<hept<non. The activation enthalpy values were found to increase in the same order. These solid-state reactions are found to be predominantly controlled by the activation entropy.
  • Shigemi Iwasaki, Takashi Nagai, Eiichi Miki, Kunihiko Mizumachi, Tatsu ...
    1984 Volume 57 Issue 2 Pages 386-390
    Published: 1984
    Released: June 27, 2006
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    (Trichlorostannato)rhodate(III) complexes, [(CH3)4N]3[RhCln(SnCl3)6−n] (n=2, 3, and 4), reacted with tin(II) in hydrochloric acid solutions to form a purple species. This purple species is assumed to be [RhI(SnCl3)5]4−. The formation reaction of the purple species involved two independent paths, fast and slow paths. The main path was the fast one, in which the reactant mixture was in equilibria among [RhCl3(SnCl3)3]3−, [RhCl2(SnCl3)4]3−, [RhCl(SnCl3)5]3−, and probably [Rh(SnCl3)6]3−. The reaction orders in the formation of the purple species were 1, 2, and −2 with respect to the concentrations of the total rhodium(III) complexes, SnCl3, and Cl respectively. The absorpton spectra of the reactant mixture showed an interaction absorption between [RhCl2(SnCl3)4]3− and SnCl3.
  • Shin-ichi Ishiguro, Yoshihiro Oka, Hitoshi Ohtaki
    1984 Volume 57 Issue 2 Pages 391-394
    Published: 1984
    Released: June 27, 2006
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    Gibbs energies (or formation constants), enthalpies and entropies of formation of ethylenediamine complexes of copper(II) ions have been determined by means of potentiometric and calorimetric titrations at 25 °C in an aqueous solution and dioxane–water mixtures (dioxane contents are 0.1 and 0.2 mole fractions, which correspond to 35.2 and 55.0% w/w, respectively), all containing 3 mol dm−3 LiClO4 as a constant ionic medium. The thermodynamic quantities of the reactions CuLn−12++L=CuLn2+ (L=ethylenediamine and n=1 and 2) determined in the solutions were as follows: ΔG1°=−65.0 kJ mol−1 (dioxane content: 0.0 mole fraction), −66.8 kJ mol−1 (0.1 mole fraction), and −68.8 kJ mol−1 (0.2 mole fraction); ΔG2°=−56.9 kJ mol−1 (0.0), −58.8 kJ mol−1 (0.1), and −61.1 kJ mol−1 (0.2); ΔH1°=−67.7 kJ mol−1 (0.0), −68.6 kJ mol−1 (0.1), and −66.7 kJ mol−1 (0.2); ΔH2°=−71.0 kJ mol−1 (0.0), −70.2 kJ mol−1 (0.1), and −68.8 kJ mol−1 (0.2); TΔS1°=−2.7 kJ mol−1 (0.0), −1.8 kJ mol−1(0.1), and 2.1 kJ mol−1 (0.2); TΔS2°=−14.1 kJ mol−1 (0.0), −11.4 kJ mol−1(0.1), and −7.7 kJ mol−1 (0.2). In any solvent examined the enthalpies contribute predominantly to the Gibbs energies. On the other hand, for a given complex with varying solvent compositions, the entropies mainly contribute to the change in the Gibbs energies of the complex formation reactions. With an increase in the dioxane content of the solvent, the Gibbs energies of the complex formation reactions become more negative, while the enthalpies of the reactions remain practically unchanged or even become less negative. Consequently, the entropies of the reactions increase with increasing dioxane content of the solvent, which is explained in terms of weakening of the hydrogen-bonded structure of water in the bulk solvent by the addition of dioxane.
  • Seichi Okeya, Toshiko Miyamoto, Shun’ichiro Ooi, Yukio Nakamura, ...
    1984 Volume 57 Issue 2 Pages 395-404
    Published: 1984
    Released: June 27, 2006
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    Five-coordinate complexes [M(hfac)2L] (M=Pd, Pt; hfac=1,1,1,5,5,5-hexafluoro-2,4-pentanedionate anion) were produced by the reactions of [M(hfac)2] with equimolar amounts of tertiary phosphines, phosphites, and triphenylarsine. They were characterized by 1H, 13C, 19F, and 31P NMR spectra in solution and several complexes containing bulky phosphines as L were isolated, and structures of [Pd(hfac)2{P(o-tolyl)3}] and [Pt(hfac)2{P(cyclohexyl)3}] were determined by X-ray analysis. Both complexes have very distorted square-pyramidal structures, one of the two hfac anions in either of them spanning the apical and basal coordination sites. NMR spectra at various temperatures disclosed the fluxional behaviors of these complexes which retain the solid-state structures at such low temperatures as −60 °C. Two kinds of twist mechanisms were proposed.
  • Yukito Murakami, Yoshio Hisaeda, Akiro Kajihara, Teruhisa Ohno
    1984 Volume 57 Issue 2 Pages 405-411
    Published: 1984
    Released: June 27, 2006
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    The nuclear cobalt(II) ion in heptamethyl cobyrinate iodide, Cob(II)ester·I, was found to assume a distorted square-planar geometry of Co–N4 type with iodide as a counterion in a polar solvent (methanol) and a square-pyramidal one of Co–N4I type with the iodide ion coordinated at one of the axial positions in apolar solvents such as dichloromethane, benzene, and toluene. The redox chemistry of Cob(II)ester·I and heptamethyl cobyrinate perchlorate, [Cob(II)ester]ClO4, was investigated in various organic solvents by means of cyclic voltammetry and controlled-potential electrolysis. The Co(II)/Co(I) and Co(III)/Co(II) redox potentials for [Cob(II)ester]ClO4 exhibited cathodic shifts as either solvent basicity or polarity was raised, and were found to be in the anodic side relative to the corresponding potentials for CoII(tpp) under identical conditions. The medium effect on the redox behavior of hydrophobic vitamin B12 was discussed in connection with the microenvironmental effect on vitamin B12 placed in the enzyme active sites.
  • Masanobu Shiga, Hiroshi Nakamura, Makoto Takagi, Keihei Ueno
    1984 Volume 57 Issue 2 Pages 412-415
    Published: 1984
    Released: June 27, 2006
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    New crown ethers which have a benzeneazo group as a building block of a macrocyclic polyether ring. The complexation properties of these new azobenzo-crown ethers with alkali and alkaline earth metal iodide salts were investigated in acetonitrile solution spectrophotometrically. The complex formation constants were evaluated for alkali metal salts. The azo group is not particularly a favorable component of a crown ether macrocycle for stabilizing the metal complexes.
  • Masashi Tashiro, Takashi Itoh, Gouki Fukata
    1984 Volume 57 Issue 2 Pages 416-420
    Published: 1984
    Released: June 27, 2006
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    Reaction of 4-halocyclohexadienones such as 4-bromo-(1a), 4-chloro-2,4,6-tri-t-butyl-(1b), 2,4-dichloro-4,6-di-t-butyl-2,5-cyclohexadien-1-one, and 2,4-dichloro-2,6-di-t-butyl-3,5-cyclohexadien-1-one with phenols in the presence of α-picoline was carried out under various conditions. The reaction of 1a and 1b with phenols afforded the corresponding 2-aryloxy-4,6-di-t-butyl phenols together with various by-products. The AlCl3-catalyzed trans-t-butylation of 2-aroxy-4,6-di-t-butyl-phenols, which were obtained by the above reaction, afforded the corresponding 2-hydroxyphenyl aryl ethers. The similar reaction of 4-aroxy-2,4,6-tri-t-butyl-2,5-cyclohexadien-1-ones also afforded the corresponding 4-hydroxyphenyl aryl ethers.
  • Masaru Sato, Masao Kubo, Seiji Ebine, Sadatoshi Akabori
    1984 Volume 57 Issue 2 Pages 421-425
    Published: 1984
    Released: June 27, 2006
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    Polyoxadithia[n]ferrocenophanes and polyoxatetrathia[n.n]ferrocenophanes were prepared by treatment of 1,1′-ferrocenedithiol with α,ω-dibromo polyethers. The ferrocenophanes formed efficiently a complex with a silver ion, but not with alkali and alkali-earth metal ions. The spectral data of the silver ion-complexed ferrocenophanes suggested the presence of a partial electron-transfer interaction between the iron atom and the complexed silver ion.
  • Syuichi Matsui
    1984 Volume 57 Issue 2 Pages 426-434
    Published: 1984
    Released: June 27, 2006
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    Dianion derived from ethyl mercaptoacetate undergoes aldol type reaction with a carbonyl compound to give an adduct, which exhibited low diastereoselectivity. However, the adducts obtained by the reaction with a variety of aldehydes were subsequently treated with ethyl chloroformate in the presence of trivalent phosphorus compound to give (E)-isomers of α,β-unsaturated esters in high yields with greater than 85% stereoselectivity regardless of the stereochemistry of the diastereomers of the adducts. The stereochemical mechanism and application of this reaction were studied in detail.
  • Yoshihisa Watanabe, Yasushi Tsuji, Jun Shida
    1984 Volume 57 Issue 2 Pages 435-438
    Published: 1984
    Released: June 27, 2006
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    Nitroarenes are reductively converted into quinoline derivatives with aliphatic alcohols in the presence of a catalytic amount of ruthenium compound at 180 °C. Ruthenium(III) chloride is the most effective catalyst. The reaction of nitrobenzene with 1-propanol and 1-butanol gave 2-ethyl-3-methylquinoline and 3-ethyl-2-propylquinoline in 65 and 70% yields respectively. p-Methoxynitrobenzene gave 3-ethyl-6-methoxy-2-propylquinoline in 70% yield with 1-butanol. The reaction appears to include the redox reaction between the nitroarenes and the alcohols, that is, a catalytic hydrogen transfer reaction which generates the aminoarenes and aldehydes. Thus, the alcohol plays roles as both a reductant and an aldehyde precursor.
  • Masanao Oya, Toshiyuki Negishi
    1984 Volume 57 Issue 2 Pages 439-441
    Published: 1984
    Released: June 27, 2006
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    N-Peptidyl-D-glucosamines were synthesized by the stepwise reaction of N-carboxy α-amino acid anhydrides (4-alkyl-2,5-oxazolidinediones) with D-glucosamine hydrochloride in the presence of equimolar sodium methoxide in a mixture of acetonitrile and methanol, or in methanol, at a low temperature. Polymerization reaction of N-carboxy α-amino acid anhydrides (NCAs) did not occur at −50 °C. The mechanism of the reaction was then studied.
  • Seiji Yamaguchi, Satoru Yamamoto, Shoichi Abe, Yoshiyuki Kawase
    1984 Volume 57 Issue 2 Pages 442-445
    Published: 1984
    Released: June 27, 2006
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    Orientation in acylation reactions of 2,2-dimethyl-2H-chromenes was studied. Five acetylchromenes were obtained with two methods and six formylchromenes were obtained with a third method. Demethylation of four acyl-methoxy-substituted chromenes gave the corresponding acylchromenols. 2,2-Dimethyl-2H-chromene-6-carboxylic acid (anofinic acid) was also obtained by oxidation of 6-formylchromene.
  • Kazuhiko Takai, Ichiro Mori, Koichiro Oshima, Hitosi Nozaki
    1984 Volume 57 Issue 2 Pages 446-451
    Published: 1984
    Released: June 27, 2006
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    Organoaluminium compounds, R3Al, promote the Claisen rearrangement of allyl vinyl ether derivatives at room temperature under transfer of R or H as a nucleophile to the aldehydic carbon. Treatment of 1-butyl-2-propenyl vinyl ether with a hexane solution of Me3Al (1.0 M, 2.2 equiv) in CH2ClCH2Cl at 25 °C afforded 5-decen-2-ol (91% yield, EZ=47⁄53), which was produced by the [3,3] sigmatropic rearrangement and successive methylation. The rearrangements with alkynylation, alkenylation, and hydrogenation are also achieved. The regular Claisen rearrangement products, or γ,δ-unsaturated aldehydes (ketones), are obtained at 25 °C in good to excellent yields with Et2AlSPh (2.5 equiv) or the combination of Et2AlCl (2.0 equiv) and PPh3 (2.2 equiv).
  • Ryuichi Arakawa, Yozaburo Yoshikawa
    1984 Volume 57 Issue 2 Pages 452-455
    Published: 1984
    Released: June 27, 2006
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    The abundances of C6H5+, C6H4, C4X4, and C3X3+ (X=H, D) fragments occurring in the metastable transition of benzene and perdeuterio benzene have been measured by means of electron-impact ionization. The isotope effects on the relative intensities were reproduced by the simple model calculation on the basis of the RRKM theory. The vibrational frequencies of the transition states for the deuteriated and the nondeuteriated were obtained by a vibrational analysis for the assumed geometries and force fields. The transition states for the C6H5+ and C6H4 channels preferred a benzene structure while those for the C4H4 and C3H3+ has a propargylcyclopropene structure. The calculated decay rates for the C6H5+, C4H4 and C3H3+ fragmentation were compared with those of the photoion photoelectron coincidence (PIPECO) results.
  • Hiroshi Tanaka, Kiyoshi Isobe, Shinichi Kawaguchi, Seichi Okeya
    1984 Volume 57 Issue 2 Pages 456-464
    Published: 1984
    Released: June 27, 2006
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    A novel type of palladium(II) complexes, [Pd(β-dik)(pyridyl)(PPh3)] and [Pd(β-dik)(pyridyl)]2 containing a chelating acetylacetonate, trifluoroacetylacetonate, or hexafluoroacetylacetonate anion and 2-, 3-, or 4-pyridyl radical as the coexisting ligands were prepared and characterized by elemental analysis and molecular weight determination as well as 1H and 13C NMR spectroscopy. [Pd(acac)(C5H3(6-Cl)N–C2)(PPh3)] is stereochemically rigid in solution but undergoes the coordination-site exchange reaction catalyzed by nitrogen and phosphorus bases and donor solvents. Similar reaction of [Pd(acac)(C5H4N–C2)(PPh3)] is catalyzed by triphenylphosphine liberated by the dinuclear-complex formation reaction (autocatalysis). Intact molecules of [Pd(acac)(C5H4N–C3 and –C4) (PPh3)] catalyze mutually their own coordination-site exchange (self-catalysis).
  • Etsuro Kobayashi, Shigemitsu Shin
    1984 Volume 57 Issue 2 Pages 465-469
    Published: 1984
    Released: June 27, 2006
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    The synthesis of microcrystalline compounds with the formula of Zr(RNH)xH2−x(PO4)2·yH2O (R=(CnH2n+1)3, C5H5, n=1–6, x=0.1–0.6, y=1–3) and their characteristics have been investigated. The compounds were formed by means of a hydrothermal reaction between RNH·H2PO4 and ZrOCl2 in the mole ratio of 4:1 at 130–180 °C. The layer-spacings of the trimethyl-, triethyl-, tripropyl-, tributyl-, tripentyl-, trihexylamine, and pyridine phosphates were 9.9, 13.0, 13.6, 17.0, 16.5, 18.4, and 10.9 Å respectively. In the thermal decomposition of each phosphate, the water of crystallization was eliminated at 105–130 °C. The organic base group in the alkylamine phosphates was burned in the presence of air at 330–360 °C, but this combustion was imperfect in the case of pyridine phosphate. The phosphates condensed at 400–450 °C. Zr(RNH)xH2−x(PO4)2·yH2O was also obtained by means of an ion-exchange reaction between γ-Zr(HPO4)2·2H2O and the corresponding tertiary amine. In these products, the layer-spacings of the trimethyl-, triethyl-, tripropyl-, tributyl-, tripentyl-, and trihexylamine phosphates were 17.6, 16.4, 16.7, 21.0, 21.5, and 23.2 Å respectively, while those of pyridine and piperidine phosphates were 12.4 and 18.4 Å respectively. The layer-spacings of the products increased roughly with the size of the guest molecules. When Zr(RNH)xH2−x(PO4)2·yH2O was treated with HCl, the products from the hydrothermal reaction changed to α-Zr(HPO4)2·H2O, while the products from the ion-exchange reaction returned to γ-Zr(HPO4)2·2H2O the raw material.
  • Yoshimori Omote, Atsushi Tomotake, Hiromu Aoyama, Takehiko Nishio, Cho ...
    1984 Volume 57 Issue 2 Pages 470-472
    Published: 1984
    Released: June 27, 2006
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    The intramolecularly bridged N,N′-azelaoylindigo (3) and N,N′-sebacoylindigo (4) have been synthesized from indigo and the corresponding dichloride. The intermolecularly bridged N′,N″-sebacoylbis(N-acetylindigo) (5) has been synthesized from N-acetylindigo and sebacoyl dichloride. The relative rates of the cis-to-trans thermal isomerization of 3, 4, and 5, compared with that of N,N′-diacetylindigo (1c), were as follows: 3, 0.77; 4, 3.9; 5, 1.4; 1c, 1.0.
  • Hajime Satonaka
    1984 Volume 57 Issue 2 Pages 473-479
    Published: 1984
    Released: June 27, 2006
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    The 1H NMR spectra and IR C=O stretching frequencies of methyl [trans-β-(3-, 4-, and 5-substituted 2-thienyl)acrylate]s are reported. The chemical shifts of the ring protons in methyl [trans-β-(4- and 5-substituted 2-thienyl)acrylate]s are correlated linearly with those of the corresponding protons in substituted thiophenes and methyl (substituted 2-thiophenecarboxylate)s. The substituent effects on the chemical shifts of α-protons in methyl [trans-β-(3- and 5-substituted 2-thienyl)acrylate]s have been interpreted by the mesomeric effect of the substituentes. The plots of the coupling constants in methyl [trans-β-(substituted 2-thienyl)acrylate]s against those in substituted thiophenes and methyl (substituted 2-thiophenecarboxylate)s gave good linear correlations. The IR C=O stretching wave numbers showed a narrow range of variation. The coupling constants in methyl [trans-β-(substituted 2-thienyl)acrylate]s were found to vary linearly with the electronegativity of the substituents.
  • Munetaka Akita, Hajime Yasuda, Akira Nakamura
    1984 Volume 57 Issue 2 Pages 480-487
    Published: 1984
    Released: June 27, 2006
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    A series of 1-alkynes (RC≡CH where R=Et, n-Pr, n-Bu, n-C6H13, cyclohexyl, Ph, Me3Si, Me3SiCH2, and Me3SiOCH2) was found to dimerize regioselectively (>99%) to 2,4-disubstituted 1-buten-3-ynes in 92–99% yields by catalysis of (η5-C5Me5)2TiCl2/i-PrMgBr at 30 °C in 1–3 h. The catalyst system is also effective for the regioselective codimerization of various 1-alkynes with 1-ethynylcyclohexene or ethynylbenzene.
  • Hidefumi Hirai, Shigeru Komatsuzaki, Naoki Toshima
    1984 Volume 57 Issue 2 Pages 488-494
    Published: 1984
    Released: June 27, 2006
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    Cyclopentadiene was hydrogenated to cyclopentene selectively by using colloidal palladium supported on chelate resin with iminodiacetic acid moieties as a catalyst. The catalyst, containing metal particles of 1–6 nm in diameter, was prepared by reduction of the palladium(II)–chelate resin complex with methanol. Cyclopentene was produced in 97.1% yield at 100% conversion of cyclopentadiene at 30 °C under 1 atm of hydrogen. This value in yield was also achieved on repeated uses of the catalyst. The hydrogenation rate was correlated to the polarity parameter, ET(30) values, of the solvents used in the reaction, except in the case of dimethyl sulfoxide. The hydrogenation rates of cyclopentadiene (RD) and cyclopentene (RE) were expressed as RD=kD[H2][catalyst] and RE=kE[H2][cyclopentene][catalyst], respectively, where kD and kE are the rate constants. The equilibrium constant for complex formation between cyclopentadiene and the catalyst, KD, was estimated to be over 400 times larger than that between cyclopentene and the catalyst, KE. A mechanism, including the coordination of olefins to the catalyst and the subsequent hydrogenation of the coordinated complexes, was proposed.
  • Kazuyuki Shimizu, Masayoshi Hasegawa, Masayasu Akiyama
    1984 Volume 57 Issue 2 Pages 495-499
    Published: 1984
    Released: June 27, 2006
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    Polymerization of N-benzyloxy DL-α-amino acid N-carboxy anhydrides (N-benzyloxy-NCAs) has been carried out in benzene for 30 d with cyclohexylamine as initiator. The N-benzyloxy-NCAs of glycine, alanine, 2-aminobutyric acid, and leucine give the corresponding polymers in good yields, while the starting material is recovered from those of valine and phenylalanine. The different behavior in the polymerization is discussed in terms of steric crowding. Catalytic hydrogenation of the N-benzyloxy polymers produces poly(N-hydroxy peptide)s. Complex formation of these polymers with iron(III) has been examined. Among the polymers, poly(N-hydroxyalanine) is further converted into poly(N-acetoxyalanine), which acts as an acyl active polymer. Treatment of poly(N-benzyloxyalanine) with B(CF3CO2)3 gives 1,4-dihydroxy-3,6-dimethyl-2,5-piperazinedione.
  • Hiroshi Matsuda, Hiroaki Nagamatsu, Tadashi Okuyama, Takayuki Fueno
    1984 Volume 57 Issue 2 Pages 500-505
    Published: 1984
    Released: June 27, 2006
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    Effects of boric acid on the rate of hydrolysis of a Schiff base derived from α-hydroxyisobutyrophenone and 2-methoxyethylamine were examined in the pH range 4.2–10.4 at 30 °C. The rate increased above pH 7 but decreased below pH 7 with increasing borate concentration following a saturation curve. This is consistent with a reaction sequence involving a preequilibrium formation of a borate–substrate complex followed by its rate-determining decay to the hydrolysis products. The formation constant of the complex showed a bellshaped change with pH but the rate constant for the complex decay was constant above pH 7, a small change being observed at lower pH. A mechanism involving an intramolecular transfer of the boron-coordinated hydroxide ion to the imine carbon within the complex is presented. Hydrazone formation from the hydroxy ketone was also examined in the presence of boric acid.
  • Atsuyoshi Ohno, Satoshi Ushida, Shinzaburo Oka
    1984 Volume 57 Issue 2 Pages 506-509
    Published: 1984
    Released: June 27, 2006
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    An amine reduces 1-benzyl-3-carbamoylpyridinium ion (BNA+) into 1-benzyl-1,4-dihydronicotinamide (BNAH) in aqueous solution. The mechanism of reduction has been elucidated. The covalently bound adduct of the amine and BNA+ at the 6-position is found to be the true reductant. The reduction with formate proceeds through the direct “hydride-transfer” mechanism. Selectivity of nucleophilic attack on the 4- and 6-positions of BNA+ is discussed in terms of hard-soft-acid-base (HSAB) principle.
  • Kan-ichi Hasegawa, Yoshio Ueno
    1984 Volume 57 Issue 2 Pages 510-517
    Published: 1984
    Released: June 27, 2006
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    The 13C NMR chemical shifts of 3H-phenothiazin-3-one (1) and eleven of its methyl derivatives are reported. The effect of including sulfur 3d orbitals is discussed in relation to the 13C chemical shifts. The chemical shifts of 1 can be explained in terms of both the successive polarization of the long π-conjugated framework promoted by the carbonyl group and the contribution of the sulfur d-orbitals. The 13C chemical shifts gave a better correlation with the CNDO/2 π- and total electron densities calculated by means of the sp-basis set than by means of the spd-basis set, but an improved correlation was obtained by reducing the extent of d-orbital participation on sulfur. From the correlation of the 13C chemical shifts with the CNDO/2 sp π- and the total electron densities of all the carbons of 1 and monomethyl derivatives, the proportionality constants of −300 and −180 ppm/e respectively were obtained.
  • Kunihiko Akutagawa, Naomichi Furukawa, Shigeru Oae
    1984 Volume 57 Issue 2 Pages 518-524
    Published: 1984
    Released: June 27, 2006
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    S,S-Diphenyl-N-(p-tolylthio)-, -N-(p-tolylsulfinyl)-, -N-(p-toluenesulfinimidoyl)-, -N-(p-tolylsulfonyl)-, and -N-(p-toluenesulfonimidoyl)sulfoximines have been synthesized either by sulfenylation, sulfinylation, sulfinimidoylation, sulfonylation, and sulfonimidoylation or by oxidation of the N-substituted sulfoximines with sulfur groups of lower oxidation states, i.e., the N-sulfenylated sulfoximine. Similar attempts have been made on similarly substituted sulfonediimines. Sulfenylation and sulfonylation of N-unsubstituted N-(p-tolylsulfonyl)sulfonediimine were unsuccessful but its sulfinylation underwent nicely. An attempt to disulfonylation of the N,N′-unsubstituted sulfonediimine ended up in the monosulfonylation. N,N′,-bis(p-Tolylsulfonyl)sulfonediimine was successfully prepared by oxidation of the N-(p-tolylsulfinyl)-N′-(p-tolylsulfonyl)sulfonediimine with m-chloroperbenzoic acid.
  • Shigeru Murata, Seiichiro Kanno, Yo Tanabe, Mikio Nakamura, Michinori ...
    1984 Volume 57 Issue 2 Pages 525-528
    Published: 1984
    Released: June 27, 2006
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    Rates of some substitution reactions of 9-(2-bromomethyl-6-methylphenyl)fluorene rotamers with nucleophiles are compared. Methanolysis of the rotamers proceeded smoothly in the sp form but was sluggish in the ap. Reactions of the sp form with sodium methoxide afforded 6-methylspiro[benzocyclobutene-1(2H), 9′-[9H]fluorene] and sp-9-(2-methoxymethyl-6-methylphenyl)fluorene, the former being a minor product. In addition to these, isomerization to the ap was detected. In contrast, the ap form afforded the spiro compound as a major product and the ap form of the methoxy compound as a minor product. Menschutkin reactions with pyridine bases were much faster in the sp form than in the ap. These results are attributed to the steric effect in the transition states of the reactions: the sp form reacts much faster than the ap because of the presence of the fluorene moiety in proximity of the reaction site in the latter.
  • Kuniaki Tatsuta, Kohji Akimoto, Hideaki Takahashi, Takao Hamatsu, Masa ...
    1984 Volume 57 Issue 2 Pages 529-538
    Published: 1984
    Released: June 27, 2006
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    Apramycin and saccharocin (KA-5685) have been synthesized from previously synthesized neamine (3). Addition of allylmagnesium chloride to 4-O-[3′,4′-O-cyclohexylidene-2′-deoxy-2′-(tosylamino)-α-D-gluco-hexodialdo-1′,5′-pyranosyl]-5,6-O-cyclohexylidene-1,3-di-N-tosyl-2-deoxystreptamine which was derived from 3 through the 6′-N-oxide, gave 4-O-[3′,4′-O-cyclohexylidene-2′,7′,8′,9′-tetradeoxy-2′-(tosylamino)-L-glycero- and D-glycero-α-D-gluco-non-8′-enopyranosyl]-5,6-O-cyclohexylidene-1,3-di-N-tosyl-2-deoxystreptamines which were in turn converted into 4-O-[(8′S)-7′-N,6′-O-carbonyl-2′,3′,7′-trideoxy-8′-O-methyl-7′-(methylamino)-2′-(tosylamino)-D-glycero-α-D-allo-octodialdo-1′,5′:8′,4′-dipyranos-1′-yl]-5,6-O-cyclohexylidene-1,3-di-N-tosyl-2-deoxystreptamine (25), via azidonitration of 1-N-acetyl-4-O-[3′,6′-di-O-acetyl-4′,8′-anhydro-2′,7′-dideoxy-2′-(tosylamino)-L-glycero-α-D-gluco-oct-7′-enopyranos-1′-yl]-5,6-O-cyclohexylidene-1,3-di-N-tosyl-2-deoxystreptamine and epimerization of the 6′-hydroxyl group. Successive deprotection of 25 afforded aprosamine, from which 1,2′,3,7′-tetrakis(N-benzyloxycarbonyl)aprosamine (28) was prepared, and glycosidation of 28 with 4-azido-2,3,6-tri-O-benzyl-4-deoxy-β-D-glucopyranosyl fluoride or 2,3,4,6-tetra-O-benzyl-β-D-glucopyranosyl fluoride, followed by hydrogenolysis, completed the total synthesis.
  • Suketaka Ito, Yumo Tanaka, Akikazu Kakehi
    1984 Volume 57 Issue 2 Pages 539-543
    Published: 1984
    Released: June 27, 2006
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    N-(Phenylsulfonyl)- and N-methyl-N-(phenylsulfonyl)benzohydrazonoyl azides, prepared from the corresponding hydrazonoyl chlorides and sodium azide, undergo the cyclization to 5-phenyl-1-(phenylsulfonylamino)-1H-tetrazoles together with the competitive decomposition to benzonitriles and the Curtius-type rearrangement leading to semicarbazides when heated in benzene under reflux. The tetrazole formation of hydrazonoyl azides may be characteristic of such hydrazonoyl azides as those carrying an N-sulfonyl substituent, the strong electron-withdrawing nature of which probably promotes the cyclization.
  • Suketaka Ito, Yumo Tanaka, Akikazu Kakehi
    1984 Volume 57 Issue 2 Pages 544-547
    Published: 1984
    Released: June 27, 2006
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    3,4-Diaryl-4H-1,2,4-triazoles were obtained in good to comparable yields by the reaction of N-alkyl-N-phenylsulfonyl-N″-arylbenzamidrazones with sodium hydride. The reaction probably proceeds via the elimination of benzenesulfinic acid and the oxidative cyclization of N-alkylidene-N″-arylbenzamidrazones generated by the base-catalyzed isomerization of azo intermediates.
  • Akikazu Kakehi, Suketaka Ito, Shinji Murakami, Hiroaki Sano
    1984 Volume 57 Issue 2 Pages 548-552
    Published: 1984
    Released: June 27, 2006
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    Pyrano[3,2-a] and pyrano[2,3-b]indolizin-2-one derivatives were prepared in 12–86% yields by the acid-catalyzed deacetylation-cyclization of 2-acetoxy-1- and 3-[2-(ethoxycarbonyl)vinyl]indolizines with concentrated sulfuric acid at room temperature. On the other hand, similar reactions of 2-acetoxy-3-[1,2-bis(methoxycarbonyl)vinyl]indolizines did not give the initially expected pyrano[2,3-b]indolizinones at all, but, instead of them, afforded 3-(methoxycarbonylmethylene)furo[2,3-b]indolizin-2-one derivatives in fair yields. Formation mechanisms and some physical properties are also discussed.
  • Yayoi S. Yokoyama, Tan Inoue, Isao Kuwajima
    1984 Volume 57 Issue 2 Pages 553-556
    Published: 1984
    Released: June 27, 2006
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    In condensation reactions of 2,3,5-tri-O-benzoyl-D-ribofuranosyl acetate with various kinds of enol silyl ethers in the presence of tin(IV) chloride, the acetate behaves as an ambident electrophile to give two types of products arising from nucleophilic attack of the enol ether on C-1 carbon of the ribose derivative and on carbonyl carbon of 2-benzoyloxyl group, depending remarkably on the enol silyl ethers.
  • Takahiro Wada, Koji Matsunaga, Yoshihiro Matsuo
    1984 Volume 57 Issue 2 Pages 557-560
    Published: 1984
    Released: June 27, 2006
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    Influences of preheating temperature and time were studied on the crystallization of CH3CO2Na·3H2O from three kinds of CH3CO2Na aqueous solutions, whose concentrations were 58.0, 60.3, and 62.8 wt% and which contained a small amount of crystal nucleation catalyst, Na4P2O7·10H2O. In 60.3 wt% aqueous solution (CH3CO2Na·3H2O), the nucleation catalyst begins to get deactivated by preheating at about 81 °C, higher by 23 °C than the melting point of CH3CO2Na·3H2O. The temperature at which the catalyst begins to get deactivated is raised with increasing CH3CO2Na concentration of the solution; thus, in 62.8 wt% CH3CO2Na aqueous solution, the catalyst begins to get deactivated at 85 °C. One hundred samples, each consisting of 8 g of 60.3 wt% CH3CO2Na aqueous solution and 0.16 g of Na4P2O7·10H2O, all crystallized on cooling to 40 °C, even after they had been preheated at 80 °C for 39 h. These results are explained on the basis of the crystalline adsorption model proposed by Richards.
  • Takahiro Wada, Yoshihiro Matsuo
    1984 Volume 57 Issue 2 Pages 561-563
    Published: 1984
    Released: June 27, 2006
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    With particular reference to the use of Na2HPO4 as nucleation catalyst for crystallization of CH3CO2Na·3H2O, influences of preheating temperature and time were studied on the crystallization of CH3CO2Na·3H2O from three kinds of CH3CO2Na aqueous solutions, whose concentrations were 58.0, 60.3, and 62.8 wt%. In 60.3 wt% aqueous solution (CH3CO2Na·3H2O), the nucleation catalyst begins to get deactivated by preheating at 81 °C. The temperature at which the catalyst begins to get deactivated is slightly raised with increasing CH3CO2Na concentration of the solution. The results obtained are compared with those previously reported on the use of Na4P2O7·10H2O as nucleation catalyst, and are discussed on the basis of the crystalline adsorption model.
  • Hari Chand Bajaj, Madhu Phull, Prem Chandra Nigam
    1984 Volume 57 Issue 2 Pages 564-570
    Published: 1984
    Released: June 27, 2006
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    The kinetics of substitution reaction of cyanide ion with some bis complexes [NiL2]2−2n, where Ln is 4-(2-pyridylazo)resorcinolate, diethylenetriamine, or ethylenediamine, to form the square planar complex [Ni(CN)4]2− has been studied spectrophotometrically in aqueous solutions. The rate expression has the form:rate={kdNiL2+k′[CN]}[NiL22−2n], where k′ is a composite rate constant in case of par and dien and is equal to kCNNiL2 in case of en. These results indicate that these bis complexes are not directly converted into [Ni(CN)4]2− but first lose one ligand molecule and cyanide assists this loss. The backward reaction between [Ni(CN)4]2− and L is first order in each reactant and inverse first order in cyanide. Though the mechanism for the reactions appears to be same, there are kinetic differences in the behaviour of en and the other two chelates. The rate determining step for the three reactions have been identified. The activation parameters for the forward reaction have been evaluated to support the proposed mechanism. The temperature dependence of backward reaction has also been given.
  • Susumu Tsuchiya, Masahiro Mikami, Hayao Imamura
    1984 Volume 57 Issue 2 Pages 571-572
    Published: 1984
    Released: June 27, 2006
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    The relative rate constants and the activation energies of the isomerization of butenes over a graphite oxide have been measured, The reactivity of butenes and the selectivity ratios are in agreement with the characteristics of acid catalysts. The reaction profile shown on the triangular graph is of the rake-type.
  • Noriko Iwasaki, Minoru Kinoshita
    1984 Volume 57 Issue 2 Pages 573-574
    Published: 1984
    Released: June 27, 2006
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    The linear dependence of ODMR transition frequency on the T1→S0 transition energy of p-dichlorobenzene in various matrices was interpreted with the spin-orbit couplings of the lowest triplet state with the triplet and singlet manifold, by assuming that the matrix dependent shifts in the triplet and singlet state energy are correlated with each other.
  • Takayuki Sano, Hiroka Hori, Masako Yamamoto, Tatsuya Yasunaga
    1984 Volume 57 Issue 2 Pages 575-576
    Published: 1984
    Released: June 27, 2006
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    A relaxation obviously different from that due to the triiodide complex formation was observed by the temperature-jump experiments in the iodine–iodide solution. On the basis of the dependences of the relaxation time on the concentration of iodine and iodide and on the temperature, the relaxation was assigned to the complex formation of I62−. The rate constants of the reaction were estimated to be 2.2×105 M−1 s−1 and 5.3×105 s−1 for forward and backward processes, respectively.
  • Tsutomu Mizoroki, Mamoru Kioka, Masayasu Suzuki, Shiro Sakatani, Atsus ...
    1984 Volume 57 Issue 2 Pages 577-578
    Published: 1984
    Released: June 27, 2006
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    The title reaction was investigated to elucidate the reported disagreements on the kinetics. The concentration and the coordination stability of amine were found to affect the optimum pressure of carbon monoxide and the kinetics, and were suggested to control the reaction mechanism.
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