Bulletin of the Chemical Society of Japan
Online ISSN : 1348-0634
Print ISSN : 0009-2673
ISSN-L : 0009-2673
Volume 64 , Issue 3
Showing 1-50 articles out of 63 articles from the selected issue
  • Xing-Zheng Wu, Takehiko Kitamori, Norio Teramae, Tsuguo Sawada
    1991 Volume 64 Issue 3 Pages 755-759
    Published: 1991
    Released: June 07, 2006
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    Depth profiling for thin film sample using laser induced fluorescence spectroscopy under normal incidence conditions, based on the principle of reciprocity, was studied. A laminated Langmuir–Blodgett model film sample (187 nm in thickness) with a concentration depth profile which varies as a stair-like function with 20.8 nm steps was prepared. Using this model film sample, observation angle dependence of fluorescence intensity was compared with theoretical results based on the principle of reciprocity, and it was shown that the principle held for the thin film sample having a continuous concentration depth profile. Secondly, these data were used to reconstruct the concentration depth profile by the least square method. The quantitative concentration depth profiling results obtained for the model film sample were satisfactory. This method can be used for film samples thinner than the wavelength of the excitation light and its spatial resolution in the depth direction is estimated to be in the order of a nanometer.
  • Akio Yuchi, Motoo Shiro, Hiroko Wada, Genkichi Nakagawa
    1991 Volume 64 Issue 3 Pages 760-765
    Published: 1991
    Released: June 07, 2006
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    X-Ray crystallographic studies have been made for two Ti(IV) complexes with 4,4′-methylenebis(antipyrine) (so-called diantipyrylmethane, abbreviated to dam) used for spectrophotometry of Ti(IV). The crystal data and final R values are: [Ti(dam)3](ClO4)4 (1), triclinic, P\bar1, a=15.099(2), b=22.308(2), c=14.015(2) Å, α=100.00(1), β=116.68(1), γ=87.16(1)°, V=4151(1) Å3, Z=2, R=0.124 for 8060 reflections; [Ti(dam)3](ClO4)4·H2O (2), monoclinic, P21c, a=14.075(3), b=29.127(7), c=21.386(6) Å, β=122.42(1)°, V=7401(3) Å3, Z=4, R=0.105 for 6685 reflections. The reagent dam acts as a bidentate ligand to form eight-membered chelate rings. Between a pyrazolone moiety of one ligand and a phenyl ring of another prevails aromatic ring stacking, which gives extra stability to these complexes and is responsible for the characteristic charge transfer band around 385 nm.
  • Hidenori Okamoto, Shozo Kato
    1991 Volume 64 Issue 3 Pages 766-770
    Published: 1991
    Released: June 07, 2006
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    2-Aza-1,3-butadienes bearing alkoxyl substituent were obtained easily by the reaction of ketimines with orthoesters. The reaction proceeded smoothly by the addition of small amount of p-toluenesulfonic acid. When acetals were used in place of orthoesters, the corresponding 2-aza-1,3-butadienes were similarly prepared.
  • Hirofumi Nakano, Hatsue Tamura, Toshikazu Ibata
    1991 Volume 64 Issue 3 Pages 771-777
    Published: 1991
    Released: June 07, 2006
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    The Rh2(OAc)4-catalyzed decomposition of alkyl o-(diazoacetyl)benzoates in the presence of carbon disulfide gave two 2 : 1-adducts of the intermediate 1-alkoxy-2-benzopyrylium-4-olates with carbon disulfide together with a small amount of 5-(o-alkoxycarbonylphenyl)-1,3-oxathiole-2-thiones. The intramolecular carbene-carbonyl reaction of the carbenoid generated by the decomposition of the diazo ketones was clarified to be much faster than the intermolecular attack on carbon disulfide. The molecular structure of the major 2 : 1-adduct of 1-methoxy-2-benzopyrylium-4-olate with carbon disulfide was determined by means of X-ray crystallography. The crystals of the adduct are triclinic with space group P\bar1, and with the unit-cell dimensions of a=12.213(1), b=11.846(1), c=7.0403(2) Å, α=93.395(6), β=102.147(5), γ=109.536(7)°, and Z=2. The final R value is 0.044 for 2597 observed reflections. The structure was confirmed to be (S-endo, S′-endo).
  • Koji Kano, Tadashi Hayakawa, Shizunobu Hashimoto
    1991 Volume 64 Issue 3 Pages 778-784
    Published: 1991
    Released: June 07, 2006
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    The stability of the molecular complexes between 5,10,15,20-tetraarylporphyrins and quinones in organic solvents has been compared with that in water. 5,10,15,20-Tetrakis(mono-substituted phenyl)porphines (RTPPs) hardly form molecular complexes with p-benzoquinone (BQ), 2,3,5,6-tetramethyl-p-benzoquinone (DQ), and 2,3,5,6-tetrachloro-p-benzoquinone (CQ) in dichloromethane (K>60 mol−1 dm3). In contrast, the stability constants (K<60 mol−1 dm3) for the molecular complexes of cationic porphyrins (TMPyP and TAPP) with BQ in water are much larger than those in methanol. The thermodynamic parameters clearly indicate that complexation in water is an enthalpically favorable process, suggesting that the van der Waals interactions are the main binding forces and that hydrophobic interaction does not play an important role in complex formation in water. The larger stability of the molecular complexes in water can be interpreted in terms of the nature of water, as demonstrated by Smithrud and Diederich (D. B. Smithrud and F. Diederich, J. Am. Chem. Soc., 112, 339 (1990)). The microscopically hydrophobic porphyrin ring many hardly be hydrated and interact with BQ through the van der Waals interactions without an extensive dehydration process. The water molecules bound to BQ should be released upon complexation, and the released water molecules may be incorporated tightly into the hydrogen-bonding networks of water. Such complexation in water seems to be an enthalpically favorable process.
  • Hideo Sawada, Hideyo Ishigaki, Mitsukuni Kato, Masaharu Nakayama
    1991 Volume 64 Issue 3 Pages 785-788
    Published: 1991
    Released: June 07, 2006
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    The cobalt(II) naphthenate[Co(Nap)2] catalyzed decomposition of cumene hydroperoxide(CHP) gave a mixture of α-cumyl alcohol, acetophenone and di-α-cumyl peroxide in benzene at 25°C. All experimentally observed time courses of disappearing CHP and an increasing of three products compared well with theoretical values.
  • Yasuhide Nakayama, Koichiro Hayashi, Masahiro Irie
    1991 Volume 64 Issue 3 Pages 789-795
    Published: 1991
    Released: June 07, 2006
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    Non-symmetric diarylethenes with an indole ring on one end and a thiophene, a benzo[b]thiophene, or a pyrrole ring on the other end of the double bond were synthesized in an attempt to get thermally irreversible photochromic compounds having absorption bands at longer wavelengths. 2-(1,2-Dimethyl-3-indolyl)-3-(2,4,5-trimethyl-3-thienyl)maleic anhydride(8a) underwent photoinduced cyclization/ring-opening reactions with relatively high quantum yields (cyclization quantum yield: 0.15; ring-opening quantum yield: 0.40), and the both isomers were thermally stable. The closed-ring form had the absorption maximum at 595 nm with the edge extending to 760 nm. Cyclization/ring-opening reactions of 8a and 2-(1,2-dimethyl-3-indolyl)-3-(2-methyl-3-benzo[b]thienyl)maleic anhydride (9a) were induced by Ar ion (488 nm) and He–Ne (633 nm) lasers.
  • Tsutomu Inokuchi, Sigeaki Matsumoto, Mitsuhiro Fukushima, Sigeru Torii
    1991 Volume 64 Issue 3 Pages 796-800
    Published: 1991
    Released: June 07, 2006
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    A combination of 2,2,6,6-tetramethyl-1-piperidinyloxyl and tetraalkylammonium tribromides (R4NBr3), which are available from the corresponding tetraalkylammonium bromides via electrooxidation with potassium bromide, has proved to be useful for oxidations of primary and secondary alcohols to the corresponding aldehydes and ketones, respectively. The oxidation reaction proceeds smoothly even with a 0.5–1.0 mol% of N-oxyl compounds and 1.5–2.0 equivalents of tetraalkylammonium tribromides in an aqueous-organic two-phase solution buffered at pH 8.0–8.6. This recyclable oxidant/co-oxidant combination system may involve the formation of N-oxoammonium salts, actual oxidizing agents of alcohols, by the action of hypobromite species generated from R4NBr3 in the binary solution. Utility of the method is highlighted by the selective oxidation of benzylic alcohols bearing electron-releasing groups on the aromatic nucleus to the corresponding aldehydes or ketones without any bromination and overoxidation.
  • Tamotsu Inabe, Isabelle Gautier-Luneau, Naomi Hoshino, Kaoru Okaniwa, ...
    1991 Volume 64 Issue 3 Pages 801-810
    Published: 1991
    Released: June 07, 2006
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    Two kinds of N-salicylideneaniline derivatives, N-tetrachlorosalicylideneaniline (CL4SA) and N-tetrachlorosalicylidene-1-pyrenylamine (CL4SPY), have been prepared and subjected to structural and optical studies in the crystalline state. A thermochromic-type behavior of the former crystal has been observed as a shift of the absorption edge, while that of the latter crystal is much less pronounced. Fairly short O–H···N hydrogen bonds have been found in both compounds through crystallographic studies, which may be mainly due to a steric effect of chlorine substituents. The difference in the proton transfer behavior of CL4SA and CL4SPY should presumably be caused by an intermolecular charge-transfer interaction in the latter crystal.
  • Yusei Maruyama, Tamotsu Inabe, Lin He, Toshifumi Terui, Kokichi Oshima
    1991 Volume 64 Issue 3 Pages 811-813
    Published: 1991
    Released: June 07, 2006
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    Single crystals of a new material, black phosphorus doped with germanium, have been prepared by a bismuth-flux method. Germanium atoms are incorporated into the black phosphorus in 2 to 4 atomic percent. The resistivity is reduced by two to three orders (ρ=6×10−3 Ω cm) compared with the pure black phosphorus, and its temperature dependence is metallic at low temperatures. There is no magnetoresistance up to 12 T at 0.6 K in striking contrast to the pure black phosphorus which shows negative magnetoresistance in this region. The crystal lattice constants decrease with germanium doping, especially in the interlayer direction. These facts indicate the enhanced three dimensionality with germanium doping.
  • Yukio Kubota, Naofumi Omura, Kiyofumi Murakami
    1991 Volume 64 Issue 3 Pages 814-820
    Published: 1991
    Released: June 07, 2006
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    Stopped-flow method has been used to investigate the kinetics of the solubilization of Acridine Orange (AO, 3,6-bis(dimethylamino)acridinium chloride) and its 10-alkyl derivatives into the micelle of sodium dodecyl sulfate (SDS). The reaction curves of the SDS–AO and SDS–10-alkyl AO systems were characterized by single and double exponential functions, respectively. It was found that all the time constants are concentration dependent and approach limiting values at high reactant concentrations. The data were fitted by a minimal mechanism in which a rapid bimolecular step is followed by one (AO) or two (10-alkyl derivatives of AO) sequential isomerizations. All the rate constants determined for this mechanism markedly decrease with an increase in the length of the introduced alkyl chain. The equilibrium constants for the bimolecular and first isomerization steps do not highly depend on the size of the alkyl chain, while the equilibrium constant for the second isomerization step progressively increases with increasing it. The spectral changes with time indicate that the bound dye gradually migrates to more hydrophobic environment inside the micelle. These results lead to the conclusion that the steps in the proposed mechanism correspond to rapid adsorption of the dye to the micelle surface site, followed by reorientation of the dye and then migration of its alkyl chain into the hydrophobic region of the micelle.
  • Tadashi Hata, Yasuo Hata, Takao Sato, Nobuo Tanaka, Saburo Neya, Noria ...
    1991 Volume 64 Issue 3 Pages 821-828
    Published: 1991
    Released: June 07, 2006
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    Sperm whale metmyoglobin reconstituted with 5,10,15,20-tetrapropylhemin was crystallized in the space group P212121, which was different from the space group P21 of the native. The crystal structure of the reconstituted metmyoglobin was determined by the molecular replacement method. The atomic coordinates were refined to R=0.209 at 2.0 Å resolution. The overall structure is essentially the same as that of the native. The pronounced structural change is observed in the side-chain orientation of Arg 45 moving to the surface of the molecule. This conformational change may reflect a side-chain fluctuation that allows the small ligands to approach the heme pocket from the outside of the protein. The porphyrin ring does not rotate freely about the Fe–Nε (His 93) bond in the crystalline state, although temperature-dependent NMR spectra suggest its free rotation in solution.
  • Hiroshi Saito, Takeo Imai, Kaori Wakita, Akio Urushiyama, Tatsuhiko Ya ...
    1991 Volume 64 Issue 3 Pages 829-836
    Published: 1991
    Released: June 07, 2006
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    Normal coordinate analyses were performed on three molecular models of the rubredoxin of Desulfovibrio vulgaris, Desulfovibrio gigas, and Clostridium pasteurianum. The total 1081, 1093, and 1148 internal coordinates were specified by the X-ray analyzed coordinates of the 390, 399, and 423 atoms, respectively, in a mass-group approximation. The appropriately assumed values of Urey–Bradley force constants as well as some diagonal values of out-of-plane bending and torsional forces gave 146, 146, and 148 normal modes, respectively, in 250–450 cm−1 region. These are the deformational vibrations within the peptide skeleton of the protein molecules. The Fe–S stretching displacements of the FeS4 core contribute to a limited number of these vibrations. The modes having a totally symmetric Fe–S stretching contribution confined within a frequency region of 290–330 cm−1 in which the principal resonance Raman band of rubredoxin has been reported, and the several minor resonance Raman bands reported in the higher frequency region of 330–420 cm−1 were assigned to noraml modes having a non-totally symmetric Fe–S stretching character. The PED values indicated that all of these modes are constructed mostly by the deformational displacements in the peptide skeleton widely spread into the molecule around the FeS4 core. This feature is very similar to the case of the blue-copper protein studied previously.
  • Kazuhiko Itaya, Takao Nasu, Jun Sakai, Mikio Katayama
    1991 Volume 64 Issue 3 Pages 837-841
    Published: 1991
    Released: June 07, 2006
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    The fifth overtone spectra of aryl C–H stretching vibrations of fluorobenzene, chlorobenzene, and bromobenzene in nonpolar solvents were observed using photoacoustic spectroscopy. In a nonpolar solvent, such as hexane, the three components of the overtones of the o-, m-, and p-C–H stretching vibrations could be easily decomposed owing to line-width narrowing. We could therefore obtain more detailed information concerning the chemical properties of these C–H bonds.
  • Hidemitsu Uno, Yasukazu Shiraishi, Yuji Matsushima, Ayumi Yayama, Hito ...
    1991 Volume 64 Issue 3 Pages 842-850
    Published: 1991
    Released: June 07, 2006
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    Treatment of 4-perfluoroalkyl-4-hydroxy-2,5-hexadien-1-one (4-perfluoroalkyl-4-quinol), prepared from the reaction of 1,4-benzoquinone with perfluoroalkyllithium, with acetic anhydride–sulfuric acid gave a mixture of 2,4-diacetoxy-1-perfluoroalkylbenzene and 1,2-diacetoxy-4-perfluoroalkylbenzene in a comparable ratio. When 4-perfluoroalkyl-4-quinols bearing a methyl group ortho to the perfluoroalkyl group were subjected to the rearrangement, acetoxymethyl compounds were obtained in addition to diacetoxybenzene derivatives. Only 1,3-migration was observed in the cases of 2,4-di-t-butyl-4-perfluorooctyl-4-quinol and 4-hydroxy-4-perfluoroalkyl-1(4H)-naphthalenone, while the reaction of 2,6-dimethyl and 2-methoxy derivatives gave only 1,2-shift products. Reaction routes to the apparent 1,2- and 1,3-acetoxyl migration products are discussed.
  • Katsunori Tsunoda, Mitsuyoshi Yamane, Hiroshi Nishino, Kazu Kurosawa
    1991 Volume 64 Issue 3 Pages 851-856
    Published: 1991
    Released: June 07, 2006
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    The reaction of methoxynaphthalenes with malonamide in the presence of magnanese(III) acetate gives 2-acetoxy-2-(1-naphthyl)propanediamides and 2-hydroxy-2-(1-naphthyl)propanediamides. It was found that the propanediamidation reaction did occur when naphthalenes have electron-donating substituents, such as a methoxyl group. The reactions of methoxynaphthalenes with ethyl 3-oxobutanoate, 2-cyanoacetamide, and malononitrile in the presence of manganese(III) acetate also yielded the corresponding substituted naphthalenes, ethyl 2-(acetoxymethyl)naphtho[2,1-b]furan-1-carboxylates, and/or a 4-methylene-1(4H)-naph-thalenone. The reaction mechanisms are discussed.
  • Shuji Okada, Kikuko Hayamizu, Hiro Matsuda, Atsushi Masaki, Hachiro Na ...
    1991 Volume 64 Issue 3 Pages 857-863
    Published: 1991
    Released: June 07, 2006
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    Structures of the polymers obtained by solid-state polymerization of diyne, triyne, and tetraynes substituted by long chain alkyl groups were investigated by solid-state 13C NMR spectroscopy. Assignment of all peaks in the spectra were made successfully, referring to those of the monomers and the polydiacetylenes of known structures. It was clearly shown that the backbone of these polymers has always the same structure of (Remark: Graphics omitted.). This fact suggests that only 1,4-addition polymerization takes place in the similar way for the diyne, the triyne and the tetraynes, excluding many other possible addition schemes, and the tetraynes give an interesting polydiacetylene with butadiynyl substituents. This exclusive 1,4-addition can be explained in terms of topochemical control.
  • Tyo Sone, Yasuhiro Umetsu, Kazuaki Sato
    1991 Volume 64 Issue 3 Pages 864-868
    Published: 1991
    Released: June 07, 2006
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    3,4′-Diaryl-, and 4,4′-diaryl-2,2′-bithienyls, new classes of mixed thiophene–arene oligomers, were synthesized from 2,5-dichlorothiophene via 4-aryl-2-chlorothiophene in three and two steps, respectively. Namely, a Friedel–Crafts type self-condensation of 4-aryl-2-chlorothiophene, followed by catalytic dechlorination, yielded unsymmetrical bithienyls. Homocoupling of 4-aryl-2-chlorothiophene using a nickel–phosphine catalyst gave symmetrical bithienyls.
  • Tadashi Hanaya, Hiroshi Yamamoto, Takeshi Ohmae, Heizan Kawamoto, Marg ...
    1991 Volume 64 Issue 3 Pages 869-876
    Published: 1991
    Released: June 07, 2006
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    1,2-O-Isopropylidene-3-O-methyl-6-O-tosyl-β-D-arabino-hexofuranos-5-ulose (9a) and its 3-O-benzyl congener (9b) were prepared from 1,2:5,6-di-O-isopropylidene-β-D-altrofuranose in 4 steps. Addition of methyl phenylphosphinate to 9a and 9b in the presence of DBU, followed by reduction with Raney Ni, afforded (5R and 5S)-5,6-dideoxy-1,2-O-isopropylidene-5-[(methoxy)phenylphosphinyl]-3-O-methyl-β-D-arabino-hexofuranose(11a) and 3-O-benzyl congener (11b), respectively. The latter compound (11b) was debenzylated to 3-O-unsubstituted hexofuranose 11d. By reduction with sodium dihydrobis(2-methoxyethoxy)aluminate, followed by acid hydrolysis, these key intermediates 11a, 11b, and 11d provided the title L-fucoses 13 (together with a minor proportion of D-altropyranoses 14) having as phenylphosphinylidene group in place of the ring oxygen. Compounds 13 and 14 were converted into per-O-acetyl derivatives for structural and conformational analysis by spectroscopy.
  • Yoshiharu Nakano, Yuzo Yoshikawa, Shigeo Masuhara, Shoichi Sato
    1991 Volume 64 Issue 3 Pages 877-881
    Published: 1991
    Released: June 07, 2006
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    3-Formylcamphor Co(III) complexes of a tripod-like ligand, tren, were prepared and the two possible geometrical isomers were separated successfully. The crystal structure of one of them was determined by X-ray diffraction. A red plate-like crystal was monoclinic, space group P21, a=12.401 (2), b=9.9400 (7), c=10.932 (1) Å, β=108.44 (1)°, and Z=2. The structure was refined to R=0.047 on 2818 reflections. The geometrical isomers were compared sepectroscopically.
  • Hisanori Imura, Hiromi Takahashi, Nobuo Suzuki
    1991 Volume 64 Issue 3 Pages 882-887
    Published: 1991
    Released: June 07, 2006
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    The extraction equilibrium of the inert hexaaquarhodium(III) ion has been studied. Rhodium(III) was quantitatively and rapidly extracted from 0.10 mol dm−3 trichloroacetate (TCA) or 0.010 mol dm−3 pentadecafluorooctanoate solutions to heptane containing 0.10 mol dm−3 trioctylphosphine oxide (TOPO) at pH 3–5. The extraction equilibria were achieved within 1 min at 298 K. From the equilibrium study in the TCA-TOPO system, the rhodium(III) species extracted into heptane was found to be Rh·3TCA·4TOPO, and the extraction constant was 1012.29. The rhodium(III) species in the organic phase was suggested to be the hexa-aquarhodium(III) complex associated with TCA and TOPO.
  • Eishun Tsuchida, Etsuo Hasegawa, Teruyuki Komatsu, Taisaku Nakata, Kei ...
    1991 Volume 64 Issue 3 Pages 888-894
    Published: 1991
    Released: June 07, 2006
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    The synthesis and characteristic ligation behaviors of new “double-sided porphyrinatoiron(II) complexes” having two pockets of different spacing-size on each side of a ring plane and a larger sized one on both sides of a macrocycle, are described. The equilibrium constants for the imidazole derivatives to the four-coordinated porphyrinatoiron(II)s were increased in proportion to the size of the pocket-space, which is reflected by the ΔH term. The five-coordinated complexes of the porphyrinatoirons, obtained by the addition of 1,2-dimethyl-imidazole (1,2-dmin) in a toluene solution, formed stable and reversible dioxygen adducts at 25°C. The oxygen affinities for the iron(II) complexes increased as the steric bulk on the rear side of the porphyrin plane was relieved. These changes in the oxygen affinity are attributed to the strength of the π-electron donation from the imidazole to the central iron ion.
  • Kiyohiko Yoshida, Takayuki Kitada, Naomi Odano, Mayumi Kashiwagi, Kazu ...
    1991 Volume 64 Issue 3 Pages 895-900
    Published: 1991
    Released: June 07, 2006
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    Syntheses of the title new complex compounds of Rh(III) were successful. Single, sharp IR peaks of ν (C≡N) were observed at 2130 cm−1 (trans-[Rh(CH)2(NH3)4]Cl·H2O) and 2170 cm−1 (trans-[RH(CN)2(en)2]Cl), respectively. The values of the ligand field tetragonal parameter Dt were estimated to be −366 and −377 cm−1, respectively, based on the 1Ega (D4h)←1A1g Aig transition (37100 cm−1: trans-[Rh(CN)2(NH3)4]+; 37000 cm−1: trans-[Rh(CN)2(en)2]+). The X-ray crystal data are: for trans-[Rh(CN)2(NH3)4]Cl·H2O, orthorhombic, Cmcm, a=7.961(3), b=17.295(2), c=7.436(3) Å, Dc=1.79, Dm=1.79 g cm−3, Z=4; for trans-[Rh(CN)2(en)2]Cl, monoclinic, P21n, a=9.665(4), b=9.107(3), c=6.779(3) Å, β=109.68(2)°, Dc=1.85, Dm=1.83 g cm−3, Z=2. The N≡C–Rh–C≡N sequence of trans[Rh(CN)2(NH3)4]+ lies in a line of m2m Symmetry in the crystal. The central Rh atom of trans-[Rh(CN)2(en)2]+ occupies the special position of inversion symmetry. The important geometrical data of the complexes are Rh–N=2.07(1), Rh–C=2.02(3) Å, N–Rh–N=88.0(5)° (trans-[Rh(CN)2(NH3)4]+) and Rh–N=2.080(3), 2.072(3), Rh–C=2.047(4) Å, N–Rh–N (within chelate ring)=82.7(1)° (trans-[Rh(CN)2(en)2]+).
  • Shoji Imai, Masayoshi Ichinoseki, Yasuko Nishiyama, Yasuhisa Hayashi
    1991 Volume 64 Issue 3 Pages 901-907
    Published: 1991
    Released: June 07, 2006
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    The atomic absorption signals for lead were measured in various chloride matrices at a charring temperature of 700 K. A typical double-peak signal was observed with iron(III) chloride, while a single peak was observed with iron(III) nitrate. At a charring temperature of 1440 K, the first peak disappeared and only the second peak remained; the atomization temperature of the latter was in agreement with that in the iron matrix. The larger content of the chloride ion increased the first peak absorption and decreased the second peak absorption without any shift of the peak temperatures, showing that one species for the second peak was converted to the same species for the first peak by the addition of a chloride ion. The appearance temperature of the first peak signal in the X–Fe3+ matrix system increased in the order Cl<Br<I. It was concluded that the appearance of the first peak is caused by the dissociation of lead halide.
  • Keiichi Tsukahara, Yuuko Wada, Masaru Kimura
    1991 Volume 64 Issue 3 Pages 908-915
    Published: 1991
    Released: June 07, 2006
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    Hydrogen peroxide was efficiently produced by the irradiation of visible light on aqueous acid solutions containing ascorbic acid, molecular oxygen, and ruthenium(II) complexes: [Ru(bpy)x(bpz)3−x]2+ (x=0–3, bpy=2,2′-bipyridine, and bpz=2,2′-bipyrazine). The formation of hydrogen peroxide and the decay of ascorbic acid were followed by polarography during continuous irradiation by visible light of the solution. The rate constants of the quenching reaction of the excited triplet state of the ruthenium(II) complexes by ascorbate and molecular oxygen obtained from the initial rate method were in good agreement with those obtained from luminescence quenching experiments. The initiation reaction in the photo-induced reaction mechanism changes from the oxidative quenching of *[Ru(bpy)3]2+ by molecular oxygen to the reductive quenching of *[Ru(bpy)2]2+, *[Ru(bpy)(bpz)2]2+, or *[Ru(bpz)3]2+ by ascorbate. Such a change in the mechanism arises from a difference in the redox potentials, E0(Ru3+/*Ru2+) and E0(*Ru2+/Ru+), for each ruthenium(II) species containing bpy and bpz. The detailed mechanisms are discussed.
  • Kazuo Sueoka
    1991 Volume 64 Issue 3 Pages 916-920
    Published: 1991
    Released: June 07, 2006
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    A sensitive viscometer method is presented for precise measurements of the magnetic susceptibility of liquids. This method can be applied to a determination of the diamagnetic susceptibilities of various materials and the temperature dependence of the susceptibility for water. Measurements show that this method has a sensitivity of ±0.005% and a reproducibility of ±0.02%.
  • Taro Someno, Taketoshi Hoshizaki, Kozo Kozawa, Tokiko Uchida, Hakuro H ...
    1991 Volume 64 Issue 3 Pages 921-925
    Published: 1991
    Released: June 07, 2006
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    One-dimensional metallic conductance was observed along the c axis of a single crystal of benzo[b]phenothiazine–iodine complex, (B[b]PT)2(I3)(I)2, the crystal structure of which was preliminarily determined by X-ray analysis. Its metal-insulator transition was observed around 235 K, and the sign of the carriers seemed to be positive above 250 K. From the reflection spectra, with polarized light parallel to the c axis, a plasma-edge-like dispersion was observed in near IR region. Several parameters were evaluated by assuming a tight binding band model. The EPR spectra of this complex consist of only one broad signal (peak-to-peak width at room temperature 250×10−4 T) in the temperature range from 4 K to 296 K (g=1.998±0.002).
  • Yasuhiro Yamada, Shin-ichi Ohno
    1991 Volume 64 Issue 3 Pages 926-930
    Published: 1991
    Released: June 07, 2006
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    The emission and transient absorption spectra of solid europium irradiated with laser light at 308 nm were measured. EuCl3·6H2O in a KBr disk was photoreduced to form excited Eu2+, and the emission from excited Eu2+ was observed directly after a reduction of Eu3+. Since Eu2+ was not stabilized in the KBr disk sample, it oxidized rapidly to form Eu3+. From a discussion concerning the temperature dependence of the rate constants of the reduction and deexcitation, it is shown that the reduction rate increases at higher temperature.
  • Masakatsu Ueno, Kazuhito Matsukawa, Noriaki Tsuchihashi, Kiyoshi Shimi ...
    1991 Volume 64 Issue 3 Pages 931-937
    Published: 1991
    Released: June 07, 2006
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    The limiting molar conductances, Λ°, of hydrochloric acid and potassium chloride in 2,3,5,7,10, and 25 mol% t-butyl alcohol (TBA)–water mixtures were determined at 25°C as a function of the pressure up to 2000 kgf cm−2 (1 kgf cm−2=0.9807×105 Pa) from the conductances measured within a dilute concentration range. In each solvent mixture the value of Λ° (HCl) was about three- to five-times larger than that of Λ° (KCl) The anomalous excess proton conductance, λ°E, as estimated by the equation [λ°E=Λ° (HCl)−Λ°(KCl)], was found to increase with increasing pressure in 2,3,5,and 7 mol% TBA–water mixtures, but to decrease in 10 and 25 mol% TBA-water mixtures. The rate of increase with pressure of the excess proton conductance normalized to the molar concentration of water in the mixture was largest in a 2 mol% TBA mixture, and its magnitude decreased in the order: 2>3>0>5>>7>>10>>25 mol% of TBA. These results are compared with those obtained in ethanol–water mixtures and are discussed in relation to the effect of alcohol molecules on the water structure in the mixtures: the three-dimensional network of water in TBA–water mixtures is more stable at a lower mol% of alcohol, and collapses more rapidly with increasing alcohol content than in ethanol–water mixtures.
  • Takahiro Fujii, Kiyoshi Yukawa, Yasukazu Saito
    1991 Volume 64 Issue 3 Pages 938-941
    Published: 1991
    Released: June 07, 2006
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    Under boiling and refluxing conditions, cyclooctane has been dehydrogenated to cyclooctene and molecular hydrogen selectively with carbon- and alumina-supported Pd, Ph, and Ru catalysts. The activity order among these metal catalysts was Pd>Rh>Ru. The most active carbon-supported Pd catalyst was least sensitive to the rate retardation caused by cyclooctene adsorption. Desorption of molecular hydrogen from the Pd catalyst surface was deduced to proceed rapidly after the rate-determining step.
  • Toshihiro Tominaga, Satoshi Endoh, Hiroaki Ishimaru
    1991 Volume 64 Issue 3 Pages 942-948
    Published: 1991
    Released: June 07, 2006
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    Interactions between decyl-, dodecyl-, and tetradecyltrimethylammonium bromide (DeTAB, DTAB, and TTAB) and an anionic porphyrin, 5,10,15,20-tetrakis(4-sulfonatophenyl)porphine (H2TPPS4−), have been studied in water at 298.2 K. Precipitate formation constants between the surfactant cations and the H2TPPS4− anion have been obtained. The precipitates were resolubilized by a further addition of the surfactants at concentrations close to the critical micelle concentrations (cmc) in DeTAB, and below the cmc’s in DTAB and TTAB solutions. Surface tension and conductance measurements show that the effects of H2TPPS4− on the cmc’s are very small. The fluorescence of H2TPPS4− is quenched in both water and sodium dodecyl sulfate solutions by the methylviologen cation, but not in cationic surfactant solutions. The diffusion coefficients were measured in a system containing H2TPPS4− and TTAB; the results show the existence of large premicellar aggregates.
  • Kouji Yamagishi, Seitaro Namba, Tatsuaki Yashima
    1991 Volume 64 Issue 3 Pages 949-953
    Published: 1991
    Released: June 07, 2006
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    Aluminosilicates, gallosilicates, and indosilicates with the ZSM-5 type structure were prepared by the “Atom-Planting method”. The introduction of metal cations into the framework of highly siliceous ZSM-5 zeolites was confirmed by IR and unit cell volume measurements. The acidic properties of these metallosilicates were examined by pyridine-IR and NH3-temperature programmed desorption spectroscopies. The increasing order of the acid strengths of the metallosilicates is indosilicate<gallosilicate<aluminosilicate.
  • Yusuke Yasuda
    1991 Volume 64 Issue 3 Pages 954-961
    Published: 1991
    Released: June 07, 2006
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    The frequency-response (FR) method for studying an X\ ightleftharpoonsC system (Yasuda, 1982) has been extended to an X\displaystyle\mathop\ ightleftharpoonsIA\displaystyle\mathop\ ightleftharpoonsIIC system, where X denotes a molecule in the gas phase, A is an adspecies on the external surface of a porous adsorbent, and C is an adspecies within micropores. Based on the characteristic functions for a system derived analytically, it is shown that both rate constants for steps I and II can be determined separately from the FR data. According to actual data of CH4/5A zeolite systems, it has been confirmed that both the adsorption and desorption rate constants for step I, ka and kd, respectively, and also the Fickian diffusional time constant at step II, \ ildeD, can be evaluated. The present method is expected to provide quantitative information conerning the existence and intensity of surface barriers of zeolite crystals.
  • Osamu Ito, Kiyohiko Hoteiya, Akira Watanabe, Minoru Matsuda
    1991 Volume 64 Issue 3 Pages 962-965
    Published: 1991
    Released: June 07, 2006
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    The reaction rate constants for halogen abstraction of Ph3Sn· and Ph3Si· have been determined by xenon-flash photolysis method. The absolute rate constants for the reactivity of Ph3Sn· with several alkyl halides have been compared with the relative ones; the agreement between the both methods was fairly good. For Ph3Sn·, the rate constant (in unit of mol−1 dm3 s−1) of n-BuCl (5.2×102) was smaller than that of n-BuBr (3.1×106) by a factor of ca. 1⁄104. With changing the alkyl halides, the rate constants for Ph3Si· and Ph3Sn· varied similarly, although the rate constants for Ph3Si· were larger than those for Ph3Sn· by factors of 50–100. The reactivity of alkyl halides increased with a decrease in the bond-dissociation energy of the R–X (X=Cl, Br).
  • Koji Chiba, Hideyuki Tagaya, Masa Karasu, Tsuyoyuki Ono, Kazumi Hashim ...
    1991 Volume 64 Issue 3 Pages 966-970
    Published: 1991
    Released: June 07, 2006
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    Active methylene compounds were effectively carboxylated with carbon dioxide in the presence of diphenylcarbodiimide (DPC) as a biotin model and potassium carbonate. Fluorene was carboxylated even under a nitrogen atmosphere in the presence of DPC, indicating that a carbonate ion was the carbon source. The reaction occurred even in the presence of water. It was considered that reaction intermediates are stable to water and that the concentration of the carbonate ion is important for carboxylation.
  • Shigeyasu Kuroda, Yoshinobu Kanbata, Yuriko Fukuyama, Syuzi Hirooka, H ...
    1991 Volume 64 Issue 3 Pages 971-982
    Published: 1991
    Released: June 07, 2006
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    The titled new non linear non benzenoid quinone compounds of cyclohepta[a]phenalene-6,10-, -6,12-, -7,10-, and -7,12-diones have been synthesized. The dicationic species formed from quinones by protonation in a strong acid were revealed as diatropic compounds instead of a 16-pi electron system by an examination of spectral measurements, such as the 1H NMR and UV spectra. The stability of these quinones, dicationic species, and dianonic species electrically derived from quinones depends upon the positions of carbonyl groups with both steric and electronic factors.
  • Choichiro Shimasaki, Hisashi Sanagi, Akira Unishi, Hisakimi Notoya, Ei ...
    1991 Volume 64 Issue 3 Pages 983-989
    Published: 1991
    Released: June 07, 2006
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    Thermal degradation of poly[1,3-phenylenebis(methylene) adipamide] (MXD-6) was investigated by DTA-TG, FT-IR, TG-GC/MS, and mass spectroscopy. The DTA-TG/DTG curve showed that the thermal decomposition of MXD-6 occurred in two stages. MXD-6 melted at about 235°C and decomposed to the oligomer or monomer with a weight loss of about 40% in the temperature region from 330 to 400 °C during the first stage. A TG effluent gas was collected in a cold trap and then directly injected into a GC for separation, the MS for an unequivocal identification. The eleven effluent compounds from the thermal degradation of MXD-6 were identified. The main fragmentation mechanism by electron impact for MXD-6 consisted of two processes: simple cleavage and a rearrangement reaction. The activation energy of the thermal decomposition was estimated to be 230 during the first stage and 150 kJ mol−1 during the second stage. From the value of the activation energy in each stage, the kinetic data for MXD-6 was elucidated.
  • Makoto Wada, Eiji Takeichi, Takashi Matsumoto
    1991 Volume 64 Issue 3 Pages 990-994
    Published: 1991
    Released: June 07, 2006
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    In the presence of a catalytic amount of bismuth(III) trichloride (5 mol%), silyl enol ethers react with aldehydes at room temperature in dichloromethane to give the corresponding aldols in good yields. Silyl enol ethers also have been found to react with α,β-unsaturated ketones at room temperature in dichloromethane to afford the corresponding 1,5-dicarbonyl compounds, the Michael adducts in good yields. The intermediate adducts of the aldol reaction (the silyl ethers) and the Michael reaction (the silyl enol ethers) were also obtained in good yields.
  • Masao Okamoto, Ken-ichiro Saito, Sadayuki Motoishi
    1991 Volume 64 Issue 3 Pages 995-999
    Published: 1991
    Released: June 07, 2006
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    A differential thermal analysis (DTA) of polymer blends of polyacrylonitrile (PAN) with poly (α-chloroacrylonitrile) (PCAN) and poly (vinyl chloride) (PVC), prepared by coprecipitation from a solution containing both polymers, was carried out under nitrogen. Even if a small amount of PCAN or PVC was added to PAN, the exotherm peak position due to violent polymerization of the cyano groups, which appears at ca. 260°C in pure PAN, shifts to the higher-temperature side by ca. 40°C and its intensity becomes lower. Moreover, a new generation of heat is observed above ca. 220°C and ca. 260°C in the case of PAN–PCAN and PAN–PVC, respectively. These results were associated with the HCl generated during the heating process, since the chlorine atom formed by the reaction of a thermally degraded PAN polymer radical with HCl can both initiate polymerization of the cyano groups in PAN and terminate progress in polymerization by combination. Namely, DTA behavior could be explained by the effect of initiation (in the case of PAN–PCAN) and termination (in the case of PAN–PVC) upon the polymerization of cyano groups both below and above the temperature, respectively, at which PAN begins to be subjected to a sharp transition.
  • Shigenobu Kawakami, Shingo Iwaki, Masahiro Nakada, Tatsuaki Yamaguchi
    1991 Volume 64 Issue 3 Pages 1000-1004
    Published: 1991
    Released: June 07, 2006
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    Thermal reactions of p-xylene were investigated in two kinds of reactors, batch type and flow type, with a large temperature gradient. Excellent differences of the resulting products were observed between these two types of reactors. As for a batch type reactor, 4,4′-dimethylbibenzyl was produced in a high yield with [2.2]paracyclophane and toluene as by-products, and as for a flow type reactor, toluene was obtained as a major product with a low selectivity of 4,4′-dimethylbibenzyl, respectively. These results were different from those of the conventional fast flow pyrolysis method in which [2.2]paracyclophane or poly(3,6-dimethylene-1,4-cyclohexadiene) was formed as a major product. These differences can be accounted for by the partial separation of a reaction mixture caused by the thermal diffusion effect, which arises when the mixture is subject to a temperature gradient.
  • Satoshi Sato, Masahiro Tokumitsu, Toshiaki Sodesawa, Fumio Nozaki
    1991 Volume 64 Issue 3 Pages 1005-1007
    Published: 1991
    Released: June 07, 2006
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    A temperature-programmed desorption of adsorbed dimethylpyridine clarified the characteristic changes in acid type, acid strength, and acid amount of silica–alumina prepared by depositing silica on an alumina support. Lewis acid sites of the alumina changed into Brønsted acid sites together with a change in the acid strength with increasing silica deposition.
  • Hitoshi Koizumi, Takehito Yamaguchi, Hiroshi Yoshida
    1991 Volume 64 Issue 3 Pages 1008-1010
    Published: 1991
    Released: June 07, 2006
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    The free radicals generated from polycrystalline hexane at 77 K by photolysis with vacuum-ultraviolet light, sensitized photolysis, and γ-radiolysis were compared with each others using the ESR method. The selectivity of radical formation was found to depend on the excitation method.
  • Susumu Tsuchiya, Kenji Fujii, Tadashi Mitsuno, Yoshihisa Sakata, Hayao ...
    1991 Volume 64 Issue 3 Pages 1011-1012
    Published: 1991
    Released: June 07, 2006
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    The isomerization of 1,2,3- and 1,2,4-trimethylbenzene took place over a graphite–sulfuric acid to form 1,2,4- and 1,2,3-trimethylbenzene, respectively, but that of 1,3,5-trimethylbenzene was not observed.
  • Koe Enmanji, Kenzou Takahashi
    1991 Volume 64 Issue 3 Pages 1013-1014
    Published: 1991
    Released: June 07, 2006
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    Bis[1-(4-dimethylaminophenyl)-2-phenylethanedithione]nickel(0) was found to undergo photofading in the presence of dimethylformamide, by the action of photogenerated superoxide. Addition of a detergent suppressed the formation of superoxide, with an efficiency paralleling the fatty acid chain length.
  • Masao Tsukada, Naoki Inamoto
    1991 Volume 64 Issue 3 Pages 1015-1016
    Published: 1991
    Released: June 07, 2006
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    2,3-Butanedione and 2,3-pentanedione have been found to generate chemical oscillations in 2,3-dione/BrO3/Ce4+/H2SO4 system. The concentration range within which the oscillatory behavior can be observed for each reactant is reported.
  • Tohru Koike
    1991 Volume 64 Issue 3 Pages 1017-1018
    Published: 1991
    Released: June 07, 2006
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    The OH(2Σ) emissions from shock-heated mixtures of C2H2/O2, C2H2/C2H6/O2, and C2H6/O2 diluted in Ar were observed and the mixture dependences of the emissions were obtained. OH(2Σ) production, depending on the test gas mixture, could be in accordance with the view-point that the two oxidations of C2H2 and C2H6 progress by influencing each other.
  • Masaaki Muroya
    1991 Volume 64 Issue 3 Pages 1019-1021
    Published: 1991
    Released: June 07, 2006
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    Measurements have been made of the vibrational absorption bands of silica films. The results have been used to examine the importance of the polymerization of silica. Seven other absorption bands, which are related to the Si–O group, were clearly found in the region from 1300 to 400 cm−1. A band at a wave number of 1069 cm−1 increased with increasing the viscosity of the hydrosol. The band at 974 cm−1 was substantially sensitive in intensity to the heat-treatment and the rehydration of silica film, can be assigned to the Si–O stretching vibration of the surface silanol since the intensity of its band is influenced by both the heat-treatment(dehydration) and rehydration.
  • Ryuichi Arakawa
    1991 Volume 64 Issue 3 Pages 1022-1024
    Published: 1991
    Released: June 07, 2006
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    The ionization and appearance energies of hydroxyacetone (CH3COCH2OH) were obtained. The metastable dissociation of ionized hydroxyacetone involves the loss of a hydrogen atom and CHO. The results of the metastable-ion intensity and collisional activation indicate that the hydroxyacetone ion does not isomerize to the enol tautomers prior to dissociation.
  • Keiichi Kimura, Yoshiaki Kawasaki, Masaaki Yokoyama
    1991 Volume 64 Issue 3 Pages 1025-1027
    Published: 1991
    Released: June 07, 2006
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    The carrier density and thickness of both the semiconductor and ion-sensing membrane were found to significantly affect the sensitivity of ion-sensing devices with a junction of n-type SnO2 and cation-selective plasticized polymeric membranes. When an anion-selective membrane was employed instead, the resulting device responded in a different way from the corresponding cation-sensing device.
  • Ramasamy Ramaraj, Masao Kaneko, Akira Kira
    1991 Volume 64 Issue 3 Pages 1028-1030
    Published: 1991
    Released: June 07, 2006
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    The [Ru(NH3)6]3+ complex is shown to be a two-electron catalyst for homogeneous as well as heterogeneous water oxidation to evolve dioxygen. The oxygen evolution is proposed to proceed by two molecules of the complex through a peroxo-bridged intermediate involving higher oxidation state [Ruv(NH3)6]5+.
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