Bulletin of the Chemical Society of Japan
Online ISSN : 1348-0634
Print ISSN : 0009-2673
ISSN-L : 0009-2673
Volume 58 , Issue 10
Showing 1-50 articles out of 70 articles from the selected issue
  • Yuriko Aoki, Akira Imamura, Hiroyuki Teramae
    1985 Volume 58 Issue 10 Pages 2737-2745
    Published: 1985
    Released: June 27, 2006
    JOURNALS FREE ACCESS
    The concept of the through space/bond interaction presented by Hoffmann et al. was extended to study electronic states of polymers. The band shape of lone pair orbitals was investigated by truncating converged Fock matrices and overlap integrals except for the terms corresponding to the through bond and particular through space interactions. This method was used by applying the ab initio tight-binding crystal orbital method to three isomers of one-dimensional polynitrilomethylidyne, for which the dependences of the lone pair orbital energy on the wave number vector differ significantly from one another. The band shape of the lone pair orbital is related intimately to the interaction with H atoms. The effect of each through space interaction on the band shape of the lone pair orbital may be reasonably interpreted in terms of the symmetry of crystal orbitals. This method seems expedient for analyzing qualitatively lone pair bands of various polymers at the ab initio level.
  • Iwao Satake, Tadashi Ikenoue, Tokuro Takeshita, Katumitu Hayakawa, Tam ...
    1985 Volume 58 Issue 10 Pages 2746-2750
    Published: 1985
    Released: June 27, 2006
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    The conductometric determination was made of the association constants of α-cyclodextrin (αCD) with ionic surfactants and their homologs. For 1-alkanesulfonate ions with carbon atoms (n) of 5–12, the association constant was found to increase regularly with n and become abruptly constant at n=10. The association constants for sodium 1-dodecanesulfonate, dodecylammonium chloride, dodecyltrimethylammonium chloride, and 1-dodecylpyridinium chloride were all similar in their magnitude. The effect of complexation on the micellar properties of sodium dodecyl sulfate and dodecyltrimethylammonium chloride were also studied potentiometrically by determining the counterion activities. In both cases, the critical micelle concentration increased regularly, while the degree of counterion association to the micelle decreased almost linearly with increasing αCD concentrations. It was suggested that the αCD-surfactant ion complex is solubilized in the hydrophilic surface region of surfactant micelle to give rise to a decrease in the surface charge density.
  • Hideo Horii, Yasuo Abe, Setsuo Taniguchi
    1985 Volume 58 Issue 10 Pages 2751-2755
    Published: 1985
    Released: June 27, 2006
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    Triose reductone (2,3-dihydroxy-2-propenal) was oxidized by Cl2−·, Br2−·, (SCN)2−·, and N3· to produce a triose reductone radical which had an absorption maximum at 398 nm, ε=5500 M−1 cm−1 (1 M=1 mol dm−3) and decayed by second-order kinetics. The rate constants for the reactions of triose reductone with these oxidizing inorganic radicals were obtained. The pKa of this radical was found to be 1.4.
  • Minoru Kimura, Hiroyuki Kawabe, Kiyoshi Nishikawa, Shigeyuki Aono
    1985 Volume 58 Issue 10 Pages 2756-2762
    Published: 1985
    Released: June 27, 2006
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    Electronic structure, especially the charge density or the spin density of the benzene anion (exactly dihydrophenylide ion) is investigated by the Hubbard Hamiltonian with vibronic interaction. Two limiting cases, i.e., I⁄β<<1 and I⁄β>>1 (I is the electron repulsion on site, β the absolute value of transfer integral.) are analytically examined. For whole range of this ratio, the numerical calculation has been performed. The actual system falls into the latter case, where the electron correlation produces a strong effect on the spin density distribution.
  • Minoru Kimura, Hiroyuki Kawabe, Kiyoshi Nishikawa, Shigeyuki Aono
    1985 Volume 58 Issue 10 Pages 2763-2768
    Published: 1985
    Released: June 27, 2006
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    Based on the spin density calculated in our previous paper, the ESR spectra of the benzene anion (exactly the dihydrophenylide ion) are analyzed by the Bloch equation. A hyperfine spectrum broader than those of usual aromatic radicals attributes to the chemical exchange process that the ion in question surrounded by solvent molecules undergoes a rotational motion characterized by the time τ which is the life time of chemical exchange. The line shape for each hyperfine spectrum is given in terms of 1⁄T2 and τ under the condition of τ⁄T2<<1.
  • Shigeya Niizuma, Nobuyoshi Sato, Hiroki Kawata, Osamu Murakami, Akihik ...
    1985 Volume 58 Issue 10 Pages 2769-2772
    Published: 1985
    Released: June 27, 2006
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    A Chemically Induced Dynamic Electron Polarization (CIDEP) signal of 1,4-naphthosemiquinone (NQH·) was examined by intermittent-light irradiation to a system of 1,4-naphthoquinone (NQ) and phenol (PhOH) in toluene–2-propanol (2:3), toluene–ethanol (2:3), and neat 2-propanol. The enhancement factors of the initial polarization and the F-pair polarization of the systems were determined separately. From the unusual pattern of a time profile of the ESR signal with a CIDEP phenomenon observed on the photoirradiated NQ–PhOH system in ethanol, it is concluded that in ethanol the photoexcited NQ first abstracts a hydrogen to give NQH· then NQH· releases a proton to form NQ\ ewdot.
  • Naohisa Kure, Thoru Nakatsuka, Takayuki Sano, Tatsuya Yasunaga
    1985 Volume 58 Issue 10 Pages 2773-2777
    Published: 1985
    Released: June 27, 2006
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    Both static and kinetic investigations have been carried out regarding the interaction between Cu2+ and human serum albumin (HSA). The static experiment, using a UV spectrophotometric technique, shows the presence of one primary binding site and other weaker binding sites at pH 5.2. The kinetic experiment, using stopped-flow apparatus, revealed a reaction process on the order of several seconds and a rapid absorbance change within the dead-time of the apparatus. These results are discussed from the viewpoint of the substitution effect of the second residue of the N-terminal position in the protein with reference to the previously reported results for a Cu2+–bovine serum albumin (BSA) system.
  • Kouzou Yoshitani
    1985 Volume 58 Issue 10 Pages 2778-2781
    Published: 1985
    Released: June 27, 2006
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    The volume changes and the equilibrium constants for the first protonation of [Co(edta)]2−, [Ni(edta)]2−, and [Cu(edta)]2− (H4edta=ethylenediaminetetraacetic acid) have been determined from density and pH measurements at 25 °C. In the case of [Cu(edta)]2−, a second protonation is assumed to successively occur. The volume change and the equilibrium constant for the second protonation have been estimated. The volume changes for the first protonation of Co(II)-, Ni(II)-, and Cu(II)-edta chelates were small and positive (3.5, 3.3, and 4.8 cm3 mol−1, respectively) and that for the second protonation of a Cu(II)-edta chelate was larger than the first one (8 cm3 mol−1).
  • Hisashi Kinoshita, Mamoru Shimoi, Akira Ouchi, Shoichi Sato
    1985 Volume 58 Issue 10 Pages 2782-2785
    Published: 1985
    Released: June 27, 2006
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    The new complex indicated in the title was synthesized and its crystal and molecular structures were determined by the use of a single-crystal X-ray diffraction method. The crystal is tetragonal, with the space group P\bar4, and the cell constants are a=12.124(5) and c=7.985(2) Å. The structure was solved using the heavy-atom method, and the final R value was 0.039. Two kinds of crystallographically independent mercury atoms in the unit cell are tetra-coordinated and they are in the tetrahedral geometry, where four sulfur atoms of the thiocyanate ions are ligated, respectively. The cobalt atom is hexa-coordinated, and is in an octahedral geometry, where four nitrogen atoms of the thiocyanate ions are coordinated equatorially, and two water oxygen atoms axially. Thiocyanate ions span mercury and cobalt atoms to form two-dimensional networks parallel to the (001) plane. The planar polymeric complexes are linked to the c-axis direction, through hydrogen bonds between coordinated water molecules and N,N-dimethylacetamide.
  • Kazuhiko Ozutsumi, Toshio Yamaguchi, Hitoshi Ohtaki, Kazuyuki Tohji, Y ...
    1985 Volume 58 Issue 10 Pages 2786-2792
    Published: 1985
    Released: June 27, 2006
    JOURNALS FREE ACCESS
    The EXAFS spectroscopy has been used to determine the structure of the bis(glycinato) complexes of nickel(II) and zinc(II) ions of low solubility (0.1–0.3 mol dm−3) in aqueous solution. The structural parameters were evaluated by the least-squares analysis both in the reciprocal and in the real spaces on the basis of various standard samples of known structures. Analysis of the EXAFS spectra of aqueous solutions containing the bis(glycinato) complexes of nickel(II) and zinc(II) ions has revealed that both complexes have two additional water molecules bound to the central metal ions to complete the octahedral structure. The structure of the nickel(II) complex is similar both in crystals and in solution, whereas the bis(glycinato)zinc(II) in solution is coordinated with two water molecules instead of two neighboring glycinato carbonyl oxygen atoms in the solid state.
  • Masamichi Atoh, Kazuo Kashiwabara, Junnosuke Fujita
    1985 Volume 58 Issue 10 Pages 2793-2797
    Published: 1985
    Released: June 27, 2006
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    New quadridentate phosphine ligands, 1,1,10,10-tetraphenyl-4,7-diaza-1,10-diphosphadecane (pp-PNNP) and 2,11-dimethyl-5,8-diaza-2,11-diphosphadodecane (mm-PNNP), were prepared from (ClCH2CH2NHCH2)· 2HCl and NaPR2 (R=C6H3, CH3) and purified through their Ni(II) complexes. Seven new cobalt(III) complexes containing the phosphine ligand were prepared: [CoX2(pp- or mm-PNNP)]n+(X2=(Cl)2, (NCS2), C5H7O2(2,4-pentanedionate ion), and CO32−). Four complexes of [CoX2(pp- or mm-PNNP)]+ (X=Cl, NCS) afforded only a trans(X,X) isomer, and [Co(acac)(pp- or mm-PNNP)]2+ and [Co(CO3)(pp-PNNP)]+ complexes yielded a cisβ isomer. The geometrical structures were assigned on the basis of the NMR and visible-ultraviolet absorption spectra.
  • Takemichi Nakamura, Hidemi Nagaki, Takeshi Kinoshita
    1985 Volume 58 Issue 10 Pages 2798-2800
    Published: 1985
    Released: June 27, 2006
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    Aromatic halogenated compounds and N-hydroxy nitrogen compounds were reduced to dehalogenated and deoxy analogs, respectively, in the fast atom bombardment ion source of a mass spectrometer. The reaction was found to occur in the liquid phase on exposure to a neutral fast atom beam.
  • Hiroki Kondo, Katsuhito Miura, Eiji Seki, Junzo Sunamoto
    1985 Volume 58 Issue 10 Pages 2801-2804
    Published: 1985
    Released: June 27, 2006
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    In order to delineate the mechanism of biotin-dependent carboxylation reactions, the following model experiments have been carried out. In reactions of carbonate derivatives such as methyl chloroformate with 2-ethoxy-2-imidazoline (1), a putative enolic biotin model, or 2-imidazolidinone (2), the former showed a much higher reactivity to provide the methoxycarbonylated 1 (3). Reactions of 3 with benzenethiolate, cyclohexylamine and carbanions have also been investigated as a model of transcarboxylation from N-carboxybiotin to an acceptor substrate. Only carbanions attack the carbonyl carbon of 3, leading to rupture of the C–O bond, but not of the N–C bond. A net “carboxyl” transfer was effected with 1-methoxycarbonylimidazole (9) as a donor substrate. Implications of these results in biotin catalysis are discussed.
  • Shoko Yoshimura, Yasutsugu Shimonishi
    1985 Volume 58 Issue 10 Pages 2805-2811
    Published: 1985
    Released: June 27, 2006
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    A peptide with the amino acid sequence Ser–Ser–Asp–Trp–Asp–Cys–Cys–Asp–Val–Cys–Cys–Asn–Pro–Ala–Cys–Ala–Gly–Cys of heat-stable enterotoxin (ST) produced by Yersinia enterocolitica was synthesized by a conventional method. The synthetic peptide was found to be identical with the corresponding natural peptide by chemical and physicochemical criteria, thus establishing the amino acid sequence of an ST of Yersinia enterocolitica.
  • Masanori Yamaura, Tsuneji Suzuki, Hironobu Hashimoto, Juji Yoshimura, ...
    1985 Volume 58 Issue 10 Pages 2812-2820
    Published: 1985
    Released: June 27, 2006
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    The title compound, the key intermediate for a total synthesis of bicyclomycin, was synthesized from N,N′-diacetyl anhydroglycine through twelve steps. The three-carbon branch for the construction of the bicyclic skeleton was introduced to the 2,5-piperazinedione ring as an alkylidene substituent, and then the olefinic function was converted into a diol function. The formation of bicyclic ring was achieved by treatment with N-bromosuccinimide followed by the intramoleculer substitution of the primary hydroxyl group in the side chain, and finally the secondary hydroxyl group was converted to the methylene function by an improved Peterson reaction.
  • Tsuneo Suzuki
    1985 Volume 58 Issue 10 Pages 2821-2825
    Published: 1985
    Released: June 27, 2006
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    Ethyl 3-alkyl-3-hydroxy-5-nitro-2,3-dihydro-2-benzofurancarboxylates were obtained from the reaction of ethyl 2-acyl-4-nitrophenoxyacetates with potassium hydroxide in dry dioxane. The relative ratios of the cis and trans isomers with respect to C-2 and C-3 stereochemistry varied according to the structure of the acyl group. When the acyl group was acetyl, propionyl, or isobutyryl group, the cis isomers (2-alkoxycarbonyl groups and 3-hydroxyl groups are cis) were exclusively obtained in high yields. On the other hand, a nearly equimolecular amount of the cis and trans isomers was obtained from the reaction of 2-formyl derivatives under the same conditions.
  • Hiromi Kitano, Helmut Ringsdorf
    1985 Volume 58 Issue 10 Pages 2826-2828
    Published: 1985
    Released: June 27, 2006
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    Three kinds of nucleic acid base-containing lipids were synthesized and the surface behaviors of these compounds in monolayer and bilayer systems were examined. In the monolayer systems, the addition of a complementary nucleoside to a subphase solution extended the monolayer much more efficiently than that of other nucleosides because of hydrogen bonding between a pair of complementary bases. In the monolayer and bilayer systems, the photodimerization reaction of a thymine ring was confirmed by the change in the surface pressure of the monolayer and the decrease in absorbance and the broadening of the phase-transition peak in the DSC curve of the liposome solution.
  • Masaki Matsui, Akihiro Konda, Katsuyoshi Shibata
    1985 Volume 58 Issue 10 Pages 2829-2831
    Published: 1985
    Released: June 27, 2006
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    In chlorinated solvents, 3-methyl-1-phenyl-4-phenylazo-5-pyrazolone (1) easily reacts with ozone to give benzene (2), phenol (3), chlorobenzene (4), o-chlorophenol (5), biphenyl (6), and 3-methyl-1-phenyl-2-pyrazoline-4,5-dione (7). The formation of these products is explained by an electrophilic ozone attack on the hydrazone tautomer 1′.
  • Kan-ichi Hasegawa, Yoshio Ueno
    1985 Volume 58 Issue 10 Pages 2832-2839
    Published: 1985
    Released: June 27, 2006
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    The 13C NMR chemical shifts of 3H-phenoxazin-3-one (1) and eighteen of its derivatives are reported. The chemical shifts of 1 can be explained in terms of a successive polarization of the π-conjugated framework by an electron-withdrawing carbonyl group and a π-donating ether oxygen. The principal factor solution for the chemical shifts of the 2-substituted 3H-phenoxazin-3-ones suggests that the first and the second factors collectively controlling the 2-substituent effect are electronic and steric effects, respectively. A dual substituent parameter analysis elucidated the transmission modes of the polar and resonance effects of the 2-substituents, and that the first and the fourth factor loadings multiplied by the corresponding standard deviation of the chemical shifts correlate with the CNDO/2 substituent-induced σ and π charge densities.
  • Hidetsugu Wakabayashi, Sumio Ishikawa, Harue Okai, Tetsuo Nozoe
    1985 Volume 58 Issue 10 Pages 2840-2843
    Published: 1985
    Released: June 27, 2006
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    Upon heating acetic acid containg a trace amount of coned sulfuric acid at 120 °C under nitrogen, 2-bromo-7-(2-hydroxyanilino)tropone (1a) gave 6-bromocyclohepta[b][1,4]benzoxazine (2a) as the main product and cyclohepta[b][1,4]benzoxazine, its 6,8-dibromo derivative and trace amounts of other mono-, di-, and tribromo compounds. This reaction became much more complex in the presence of oxygen. A similar bromine transfer was observed for 2-bromo-7-(dimethylamino)-, 7-(2-hydroxy-5-methylanilino)-, and 7-(2-methoxyanilino)tropone although the cite of the intermolecular bromine transfer depended upon the structures of the substrates and the reaction conditions. In contrast, 2a and 2-amino-5-bromotropone derivatives were completely stable towards the strong acid. Possible reaction pathways for this bromine transfer reaction are discussed.
  • Masayoshi Isobe
    1985 Volume 58 Issue 10 Pages 2844-2848
    Published: 1985
    Released: June 27, 2006
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    A series of 3-alkyl-1-methyl-1-nitrosothioureas with R=CH3, C2H5, cyclo-C6H11 (3), (CH3)2CH (4), C2H5(CH3)CH, and (CH3)3C were synthesized and their rates of acid catalyzed (pH<6.5) denitrosation measured. According to rate measurements in CH3COOD–D2O, the kinetic isotope effect kH:kD is 1.25 for 4. Except 3, a linear plot of logkRkMe for the denitrosation of RNHCSN(NO)CH3 vs. σ* provides ρ*=−0.98 (r=−0.997). The significant factor affecting the rate-determining step of the denitrosation of these N-nitrosothioureas at pH 4.6 is the electronic effect of the substituent at the N3 position.
  • Tsuyoshi Satoh, Takumi Kumagawa, Koji Yamakawa
    1985 Volume 58 Issue 10 Pages 2849-2854
    Published: 1985
    Released: June 27, 2006
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    Treatment of α,β-epoxy sulfoxides, prepared from 1-chloroalkyl phenyl sulfoxides and carbonyl compounds, with various kinds of alkane- or arenethiolates afforded α-sulfenylated ketones in good yields. This method also offered a novel procedure for a synthesis of α-sulfenylated aldehydes.
  • Araki Masuyama, Kikuo Tsuchiya, Mitsuo Okahara
    1985 Volume 58 Issue 10 Pages 2855-2859
    Published: 1985
    Released: June 27, 2006
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    The title N-ammonioamidates (aminimides) were prepared in satisfactory yields from lactones or α-hydroxy carboxylates. By the thermolysis of these aminimides in mesitylene, some types of urethane compounds were formed, depending on the structure of the aminimide and on the concentration of the solutions.
  • Akira Kai, Hitoshi Kitamura
    1985 Volume 58 Issue 10 Pages 2860-2862
    Published: 1985
    Released: June 27, 2006
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    The influence of the concentration of a brightener on the structure of cellulose from an Acetobacter culture in the presence of a fluorescent brightener was examined. At a brightener concentration above 0.05 wt%, the X-ray diffraction diagram of cellulose from an incubated medium was observed. Except for the intensity of the diffraction corresponding to the (020) plane of cellulose I, the intensity of diffraction of the (110) plane became very weak and diffraction of the (1\bar10) plane disappeared. A new diffraction, not corresponding to cellulose I or II, occurred inside. The position of each diffraction pattern was constant and independent of the concentration of the brightener. As the brightener concentration of the medium became lower, in the X-ray diagram of the dyed cellulose that was produced, the diffraction intensity of both the (1\bar10) and (110) planes of cellulose I increased, and a new diffraction pattern gradually disappeared. In the case of an extraction of dyed cellulose from an incubated medium with a brightener (above 0.05 wt%), the same result was obtained. The above results suggest that the monomolecular layer of a brightener is included between the (1\bar10) planes of the produced cellulose.
  • Yasuo Kubo, Takeo Araki, Kazuhiro Maruyama
    1985 Volume 58 Issue 10 Pages 2863-2869
    Published: 1985
    Released: June 27, 2006
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    Photoreactions of N-methylbiphenyl-2,2′-dicarboximide and N-ethylnaphthalene-1,8-dicarboximide (2) with 1,1-diphenylethylene (3) in methanol gave methanol-incorporated 1 : 1 : 1-adduct (7) and 2,2-diphenylethyl methyl ether (6), an anti-Markovnikov adduct of methanol to 3. The ratio of the two types of products largely depends on the structure of the aromatic imides. Probably the spin densities of the radical anions of the aromatic imides seem to play an important role to determine the reaction courses after the photochemical electron-transfer process. Similar results were obtained in the photoreaction of N-(2-phenylallyl) aromatic imides; elimination induced by methanol-incorporation vs. anti-Markovnikov addition of methanol. Photoreactions of N-(trans-3-phenylallyl) aromatic imides in methanol gave methanol-incorporated O-cyclized products (20 and 27) and C-cyclized products (21 and 28). A tentative mechanism for the O-cyclization is proposed; i.e., intramolecular electron transfer followed by anti-Markovnikov addition of methanol to the radical cation of the double bond moiety, nucleophilic attack of the aromatic imide radical anion moiety, secondary electron-transfer, and then polar addition of methanol.
  • Toshiro Ootubo, Shunsaku Kimura, Yukio Imanishi
    1985 Volume 58 Issue 10 Pages 2870-2874
    Published: 1985
    Released: June 27, 2006
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    The effect of the hydrophobic interaction on the association in aqueous media of tyrosine-containing cyclic dipeptides and 1-acyl-4-bromobenzenes having various lengths of acyl chain was investigated by quenching of the fluorescence of the former compounds by the latters. In ethanol, the change of fluorescence intensity (I0I) was linearly related to the quencher concentration according to the Stern-Volmer’s plot, which was attributed to a dynamic quenching. In this case, structures of fluorophores and quenchers did not affect the quenching constant. However, in a buffer solution, I0I was linearly related to the quencher concentration according to the Perrin’s plot, which was attributed to a static quenching. Perrin’s quenching constants depended on the structure of fluorophores and quenchers. In some cases, a quencher molecule was bound to a fluorophore by hydrophobic interaction in a favorable arrangement for fluorescent quenching. In aqueous solution, fluorophores and quenchers formed comparatively large aggregates with nonspecific arrangement for fluorescent quenching. In this case, Perrin’s quenching constants were independent of the nature of quenchers and related with the size of formed aggregates.
  • Tadamitsu Sakurai, Hidenori Sukegawa, Hiroyasu Inoue
    1985 Volume 58 Issue 10 Pages 2875-2881
    Published: 1985
    Released: June 27, 2006
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    Quantum yields (Φ) were determined for benzophenone-sensitized and direct photolysis of the title hydroxylamine (NT). Analysis of linear Stern-Volmer plots of the reciprocal of Φ against the reciprocal of NT concentration reveals that the sensitized decomposition of NT takes place via its first triplet excited state (T1) produced by triplet-triplet energy transfer from benzophenone to NT. The fact that the quantum yields for the direct photolysis are independent of NT concentration indicates no occurrence of both self-quenching and induced decomposition of NT by the photochemically generated radicals. Closer examination of the micellar and solvent viscosity effects on the quantum yields for the direct photolysis with 313-nm light shows the existence of at least two spin-correlated (singlet) radical pairs: One is a contact radical pair whose recombination eventually yields 1,3-toluoyloxyl-migrated product and the other a solvent-separated radical pair from which 1,5-toluoyloxyl-migrated product is derived in competition with diffusive escape from the solvent or micelle cage. Exclusive occurrence of the direct photolysis from the first singlet excited state (S1) was explained on the basis of the large energy gap between S1 and T1 (31 kcal mol−1) which is likely to make intersystem crossing from S1 to T1 very inefficient.
  • Takao Saito, Michio Nakane, Toshihiko Watanabe, Shinichi Motoki, Kimik ...
    1985 Volume 58 Issue 10 Pages 2882-2888
    Published: 1985
    Released: June 27, 2006
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    The Wittig-type reactions of N-sulfinyl-p-toluenesulfonamide with (1) O=C–, (2) C=C–, and (3) N=C-conjugated phosphorus ylides were investigated. In the reaction with (1), N-sulfinyl-p-toluenesulfonamide reacted at both the ylide and the carbonyl moiety to form TsN=C-conjugated thione S-imide, which underwent intramolecular 1,3-dipolar cycloaddition of the CSN group with the aromatic C=C bond of the tosyl group giving a structurally unique spiro-fused tricyclic adduct. The structure of the adduct was determined by means of X-ray diffraction. In the reactions with (2) and (3), 1-azadiene and sulfobetaines were obtained instead of the expected conjugated thione S-imides.
  • Masaki Yamada, Kenji Okawa
    1985 Volume 58 Issue 10 Pages 2889-2890
    Published: 1985
    Released: June 27, 2006
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    β-Hydroxy-DL-norvaline(HyNva) was successfully separated into its diastereoisorners by fractional crystallization from 2-propanol as p-toluenesulfonic acid(TsOH) salts. The two racemic diastereoisorners were resolved into four stereoisomers by Vogler’s method, using diastereomers of the N-benzyloxycarbonyl DL-amino acid and L-tyrosine hydrazide.
  • Sukeya Kodama
    1985 Volume 58 Issue 10 Pages 2891-2899
    Published: 1985
    Released: June 27, 2006
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    The photolysis of HN3 vapor in the presence of CH4 was studied at 313 nm, 30 °C, and a low light intensity. The reaction products were N2, H2, NH4N3, CH3NH2·HN3, and CH3N3. CH3 radicals were also detected as intermediates. The quantum yields of these products were measured as a function of the CH4 and HN3 pressures. The following mechanisms for the main reactions were proposed: HN3+hν(313nm)→N2+NH(a1Δ); NH(a1Δ)+HN3→2N2+2H(2a); NH(a1Δ)+HN3→N3+NH2 (2b); NH(a1Δ)+HN3→N2+N2H2* (2c); NH(a1Δ)+ CH4→CH3NH2* (3); NH(a1Δ)+CH4→NH(X3Σ)+CH4 (4); CH3NH2*→H+CH2NH2 or CH3NH (5); CH3NH2*→CH3+NH2 (6). The rate-constant ratios at 30°C were: k3k2=0.175; k4k2=0.177; k6k5=0.133. The collisional deactivation of CH3NH2* was not found in the total pressure range, from 6.4 to 24.3 kPa.
  • Sukeya Kodama
    1985 Volume 58 Issue 10 Pages 2900-2910
    Published: 1985
    Released: June 27, 2006
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    The photolysis of HN3 vapor in the presence of C3H8 was studied at 313 nm and 30°C. The main products were N2, H2, CH4, C2H6, C3H6, NH4N3, CH3NH2·HN3, C2H5NH2·HN3, and n- and i-C3H7NH2·HN3. The quantum yields of these products were measured as a function of the pressure of HN3 or C3H8. The following mechanisms for the main reactions was proposed: HN3+hν(313 nm)→N2+NH(a1Δ); NH(a1Δ)+HN3→2N2+2H, NH2+N3, and N2+N2H2* (2); NH(a1Δ)+C3H8→C3H7NH2*(n- and i-propylamine) (3); NH(a1Δ)+C3H8→NH (X3Σ)+C3H8 (4); C3H7NH2*→CH3+C2H4NH2 (5); CH4+C2H4NH (6), C2H4+CH3NH2 (7), C2H5+CH2NH2 (8), C2H6+CH2NH (9), H2+C3H6NH (10), and NH3+C3H6 (11); C3H7NH2*+HN3→C3H7NH2+HN3 (12); C3H7NH2*+ C3H8→C3H7NH2+C3H8 (13). The rate constant ratios are: k3k2=1.28; k4k2=0.262; k6k5=0.109; k7k5=0.050; k8k5=1.39; k9k5=0.040; k10k5=1.20; k11k5=4.72; k12k5=666 dm3 mol−1; k13k5=860 dm3 mol−1. The formation ratio of n-C3H7NH2/i-C3H7NH2 was 1.55, regardless of the total pressure. The half-life of 1.78×10−10 s for C3H7NH2* was obtained by using the collision theory. The relative and absolute rate constants were compared for the reactions of NH(a1Δ) with CH4, C2H6, and C3H8; it was found that the relative yield for the insertion of NH(a1Δ) into a C–H bond increases with a decrease in the C–H bond dissociation energy.
  • Yoshiaki Hidaka, Hirokazu Takuma, Masao Suga
    1985 Volume 58 Issue 10 Pages 2911-2916
    Published: 1985
    Released: June 27, 2006
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    N2O decomposition and N2O–H2 reaction were studied behind incident and reflected shock waves in the temperature range 1450–2200 K and pressure range 0.6–3.5 atm using both single-pulse and time-resolve techniques. A computer-simulation study was performed to determine the rate-constant expressions of important elementary reactions. Computer calculations showed that the values of the rate constant for N2O+O\xrightarrowk2N2+O2 and N2O+O\xrightarrowk2NO+NO (cited in current papers) are too low. The rate-constant expressions were found to be k2=7.0×1014exp(−28 kcal/RT) cm3mol−1 s−1 and k3=5.6×1014exp (−28 kcal/RT) cm3 mol−1 s−1. The rate constant expression for N2O+H\xrightarrowk2N2+OH, was found to be k4=1.5×1014exp (−15 kcal/RT) cm3 mol−1 s−1.
  • Hiroyasu Nomura, Shinobu Koda
    1985 Volume 58 Issue 10 Pages 2917-2922
    Published: 1985
    Released: June 27, 2006
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    The conformational changes in isobutyl halides (i-BuX) and s-butyl halides (s-BuX) in hexane and methanol have been analyzed by Raman spectroscopy as a function of temperature and pressure. The enthalpy and volume differences in the conformational changes from PC (trans) to PH (gauche) of i-BuX and from SHH(trans) to SHH′(gauche I) and to SCH(gauche II) of s-BuX in the dissolved state have been obtained. The enthalpy and volume differences, ΔH and ΔV, of all the conformational changes depended on the solvents and the concentration in solution. In the solution of hexane, the ΔH (PC→PH) of i-BuCl and i-BuBr both increased with a decrease in the concentration of i-BuX. The ΔV (PC→PH) of i-BuCl increased with an increase in the contents of the solvents, hexane, but that of i-BuBr decreased. The concentration dependences of ΔH and ΔV were discussed on the basis of the intermolecular interactions. The relation between ΔH and ΔV was also discussed on the basis of thermodynamic consideration.
  • Kazunori Maruyama, Hiroshi Akahoshi, Michio Kobayashi, Yoshié T ...
    1985 Volume 58 Issue 10 Pages 2923-2928
    Published: 1985
    Released: June 27, 2006
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    Absorption, emission and excitation spectra of heat-treated PVA film have been interpreted as corresponding to mixtures of –(CH=CH)n– and –(CH=CH)n–CO–, which are distinguishable from each other according to whether spectrum is accompanied with fine structures or not. The former shows fine structures and has had n determined to be 2–14 by analysis of peak locations on the basis of linearity for Lewis-Calvin’s plot. For the latter, n has been determined to be 1–7, and Lewis-Calvin’s plot between the wavelength of band maximum and n also shows a good linearity.
  • Masakatsu Ueno, Noriaki Tsuchihashi, Kiyoshi Shimizu
    1985 Volume 58 Issue 10 Pages 2929-2934
    Published: 1985
    Released: June 27, 2006
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    The molar conductances of KCl in 5, 10, 15, 20, and 30 mol% ethanol–water mixtures were measured in the dilute concentration range of (2–8)×10−4 M (1 M=1 mol dm−3) at 25 °C up to 1500 kgf cm−2 (1 kgf cm−2=0.9807×105 Pa). The Fuoss-Onsager conductance equation for unassociated electrolytes was used to determine the limiting molar conductance, Λ°, of KCl in 5 and 10 mol% of ethanol. In 15, 20, and 30 mol% of ethanol, where the ionic association takes place, the Shedlovsky equation was employed to obtain Λ° and the association constant KA of KCl. The limiting ionic molar conductances of the K+ and Cl ions were determined by combining Λ° with the limiting transference number for KCl. The Walden products of both K+ and Cl ions decrease with an increase in the pressure in 5 mol% of ethanol, but in 15 mol% of ethanol and above they increase with an increase in the pressure. These facts indicate that the breaking effect of these ions appears prominently in about 5 mol% of ethanol.
  • Jun Shiraishi, Yuichi Fujimura, Takeshi Nakajima, Masahiro Kawasaki, K ...
    1985 Volume 58 Issue 10 Pages 2935-2942
    Published: 1985
    Released: June 27, 2006
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    Mechanisms of resonant two-photon transitions via repulsive intermediate states are experimentally and theoretically studied. Polarization ratios, Ω⁄σ↑↑ (where σ and σ↑↑ are the cross section of the two-photon transitions obtained by the circularly polarized light and that by the linearly polarized light, respectively) of the two-photon excitation of iodine vapor have been measured in the wavelength range of 420–510 nm. An expression for the polarization ratio for the two-photon absorption in which both simultaneous and sequential processes take place has been presented. The polarization ratios calculated by using the δ-function approximation for the repulsive intermediate states as a function of the laser frequency for the iodine molecule system explain qualitatively the experimental result. This indicates that both the simultaneous and the sequential process take place in the frequency region measured.
  • Noritake Yasuoka, Yasushi Kai, Nobutami Kasai
    1985 Volume 58 Issue 10 Pages 2943-2946
    Published: 1985
    Released: June 27, 2006
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    The title compound crystallizes in monoclinic form, space group P21/c with a=20.810(1), b=16.000(1), c=18.131(1) Å, β=107.77(1)°, Z=8. The structure was established by the direct method and refined including all hydrogen atoms by the blockdiagonal least-squares procedure, R=0.062 for 4609 observed reflections. The heterocyclic spiran skeletons in two independent molecules have the same structure; however, four phenyl rings out of five take different conformations to the hetero rings to which they attached.
  • Atsushi Kubo, Ryuichi Ikeda, Jose Antofnio Sampedro, Motomichi Inoue, ...
    1985 Volume 58 Issue 10 Pages 2947-2950
    Published: 1985
    Released: June 27, 2006
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    The temperature variation of 1H and 19F nuclear spin-lattice relaxation times T1 in [Cu4(CF3COO)4]·2C6H6 was observed at different resonance frequencies. From the NMR experiments, it was found that this complex undergoes a first order phase transition at 130 K, which was confirmed by DTA measurements. In the room-temperature phase, 1H gave normal exponential magnetization recovery curves and logT1 linearly decreased with increasing 103T−1 whereas 19F gave nonexponential magnetization recovery curves, from which long- and short-T1 components could be derived. This indicates that the C3 reorientation of CF3 groups about their respective symmetry axis is responsible for 19F T1 and for 1H T1 as well through 1H-19F cross relaxation. This was confirmed from the coincidence of the logT1 vs. 103T−1 curve of the long component and that of 1H T1. A very small activation energy of 5.5 kJ mol−1 was obtained for the CF3 reorientation. For the low-temperature phase, both 1H and 19F yielded nonexponential magnetization decay curves.
  • Yutaka Tamaura
    1985 Volume 58 Issue 10 Pages 2951-2954
    Published: 1985
    Released: June 27, 2006
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    When solutions containing FeII, ZnII, and SO42− ions were oxidized by a mixed gas of air and nitrogen at pH 6.7 (25 °C), a ZnII-bearing green rust II (GR-II), which is a uniform crystalline precipitate with a definite chemical composition, was formed. The mol ratio of ZnII/FeIIin the ZnII-bearing GR-II increased linearly with an increase in the ZnII/FeII mol ratio in the reaction solution. The distribution coeffient of ZnII between the solid (ZnII-bearing GR-II) and the solution phase is 3.3 times higher than that of FeII. The ZnII-bearing GR-II was spontaneously transformed into ZnII-bearing ferrite. In this reaction, Zn2+ ions in the ZnII-bearing GR-II are preferentially incorporated into the ferrites.
  • Yasushi Inoue, Hiromichi Yamazaki, Kazushi Okada, Kazuhiko Morita
    1985 Volume 58 Issue 10 Pages 2955-2959
    Published: 1985
    Released: June 27, 2006
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    In order to elucidate the fundamental properties of hydrous niobium(V) oxide as a cation exchanger, the stoichiometry of cation exchange and the selectivity for various cations were studied. As the reversibility and the equivalent exchange between the cations were confirmed, this material showed an ideal cation-exchange reaction. The affinity series for alkali metal ions and alkaline earth metal ions were Cs+>>K+>>Li+ and Ba2+>>Sr2+≥Ca2+>Mg2+ respectively; the values decreased in the order of the increase in the hydra ted ionic radii of the cations. For transition metal ions, the distribution coefficients had a strong correlation with the first hydrolysis constants of the cations and/or the first stability constants of their acetato complexes. Based on this finding, the transition metal ions are considered to be adsorbed on the exchanger by a bond partially covalent in character, rather than by a pure ionic bond. The pH-dependency of the distribution coefficients of the cations was discussed in terms of the effects of the dissociation of the exchange sites on the overall ion-exchange equilibrium.
  • Morihide Higo, Sinichi Mizutaru, Satuo Kamata
    1985 Volume 58 Issue 10 Pages 2960-2967
    Published: 1985
    Released: June 27, 2006
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    The vibrational spectra of phthalic, isophthalic and terephthalic acid adsorbed onto the alumina surface have been measured by using inelastic electron tunneling spectroscopy. The tunneling spectra of these acids were obtained by liquid-phase doping with water or various alcohol solutions. The detailed assignments for these spectra are given, together with a comparison of their infrared and Raman spectra. It has been found that both phthalic and isophthalic acid are adsorbed onto the alumina surface mainly as the dicarboxylate ions. However, a comparison between the tunneling spectra of terephthalic and p-acetylbenzoic acid shows that terephthalic acid is adsorbed predominantly as the monocarboxylate ion onto the surface when doped with alcohol solutions. Hydrogen bonding is observed among the adsorbed hydrogen terephthalate ions. These results show a difference in their orientation and different probabilities of chemical interaction between the alumina surface and the carboxyl groups of the adsorbed isomeric phthalic acids.
  • Yoshiyuki Ohki, Yasuo Suzuki, Masao Nakamura, Mamoru Shimoi, Akira Ouc ...
    1985 Volume 58 Issue 10 Pages 2968-2974
    Published: 1985
    Released: June 27, 2006
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    Eight isomorphous 2-naphthalenesulfonato complexes of lanthanoids(III) (Pr, Nd, Sm, Eu, Gd, Dy, Er, and Yb) were synthesized, and the structures of five of them were determined by the single-crystal X-ray-diffraction method. They are monoclinic, with the space group of P21; the cell constants of the PrIII complex, for example, were a=18.228(8), b=7.498(4), c=14.177(9) Å, β=107.75(4)°, Z=2, and its final R value was 0.043. The unit-cell size of the complex decreases with the increase in the atomic number of the metal atom. The central metal atom is in a square-antiprism geometry and is octa-coordinated with two unidentate 2-naphthalenesulfonato ligands and six water–oxygen atoms. Nonligated oxygen atoms of the sulfonato ions form hydrogen-bonds with the coordinated and lattice water molecules to form a double-layered network along the ab-plane. All the naphthalene rings stand together to form hydrophobic sheets between the hydrogen-bonding networks.
  • Hidekazu Doe, Toyokichi Kitagawa
    1985 Volume 58 Issue 10 Pages 2975-2980
    Published: 1985
    Released: June 27, 2006
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    The ionic association constants of M(ClO4)2 (M=Co, Ni, Cu, Zn) were determined by conductometric measurements in methanol–ethylene glycol mixtures of 100, 80, 60, 40, 20, and 0 wt% methanol compositions at 5, 15, 25, 35, and 45 °C. The conductometric data were analyzed using a modified Fuoss and Edelson method. The association constant of an ion pair M2+ClO4, K1A, was studied and thermodynamic functions, ΔH1A\ominus and ΔS1A\ominus, for that association were determined at 25 °C. Free-energy changes, ΔG1A\ominus (=–RTlnK1A), at 25 °C which slowly decreased with an increase in the ethylene glycol content in a solvent, are in good agreement with estimates from Fuoss’ theory regarding ionic association. Values of both ΔH1A\ominus and ΔS1A\ominus were positive in many systems: i.e., unfavorable enthalpy and favorable entropy changes, and those were obtained near to estimates from the Fuoss’ theory in pure methanol, 100 wt%. However, there have been a few systems with a negative ΔH1A\ominus (Co, Ni, and Zn at 40 and 20 wt%, and Co at 0 wt%), contrary to theoretical expectations. These results are discussed from the standpoint of a changing solvation between M2+ and MClO4+. In all the solvents, moreover, the ΔH1A\ominus and ΔS1A\ominus values have been in a sequence according to Co<Ni<Cu>Zn. The results of limiting molar conductances, Λ0, are discussed regarding Walden products.
  • Yoshihisa Matsui, Kohji Kinugawa
    1985 Volume 58 Issue 10 Pages 2981-2986
    Published: 1985
    Released: June 27, 2006
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    Copper(II) forms a 1 : 1 complex (CuCD), as well as a 2: 1 complex (Cu2CD), with cyclodextrin (CD) in an alkaline solution. An equilibrium constant (Kdsp) for the disproportionation reaction of Cuα-CD to Cu2α-CD and α-CD was determined by spectrophotometry and polarimetry to be ca. 17 in 1.0 mol dm3 NaOH at 25 °C. The Kdsp value gradually decreased with increasing NaOH concentration. A ligand-exchange reaction of CU2CD with ethylenediaminetetraacetic acid (EDTA) to give Cu(edta)2− and CD was also examined by means of spectrophotometry and polarimetry. The equilibrium constants (Klex) for the ligand-exchange reaction was evaluated to be ca. 2.1 for an α-CD system and ca. 1.2 for a β-CD system in 1.0 mol dm−3 NaOH at 25 °C. The Klex value decreased rapidly with increasing NaOH concentration. The role of OH in the complexation of Cu(II) with CD is discussed on the basis of these results.
  • Akira Takeuchi, Shoichiro Yamada, Hiroshi Yokoi
    1985 Volume 58 Issue 10 Pages 2987-2989
    Published: 1985
    Released: June 27, 2006
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    Twelve of the title complexes including color isomers show powder ESR spectra of various line shapes. These complexes are a novel series of copper(II) complexes which have very weak intermolecular spin-exchange interactions in crystals. Brown complexes and most green complexes show monomer and dimer ESR spectra, respectively. It is demonstrated by ESR measurements that the above green complexes are transformed into the brown ones only by grinding those green crystals finely and forcefully with agate mortar and pestle.
  • Hiroshi Yokoi, Akira Takeuchi, Shoichiro Yamada
    1985 Volume 58 Issue 10 Pages 2990-2994
    Published: 1985
    Released: June 27, 2006
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    Ten of the title complexes in frozen toluene solutions and occasionally in other solutions have been studied by the ESR method. Most of the complexes showed both monomer and dimer ESR spectra simultaneously, and the equilibrium constant for 2 monomer\leftrightarrowsdimer has been determined by analyzing the concentration dependence of the intensity ratios of dimer and monomer ESR signals. The results indicate that the equilibrium constants of the complexes are dependent in a marked but subtle way, not upon the bulkiness of N-substituents, but upon both kind and position of the substituents introduced into the ligand benzene rings, and that the equilibrium constants are solvent-dependent. All the observed dimer ESR spectra were similar to each other, and computer simulation analysis of the spectra has revealed that the dimers formed in toluene have the same structures as that in green crystals of bis(N-cyclohexylsalicylideneaminato)copper(II). On the other hand, monomers of the title complexes have been found to show various degrees of tetrahedral distortion in the coordination geometry.
  • Yoshiyuki Tanizaki, Masao Yamazaki, Sumiko Nagatsuka
    1985 Volume 58 Issue 10 Pages 2995-3002
    Published: 1985
    Released: June 27, 2006
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    Ultrafiltration and Millipore filtration techniques have been used in the speciation of trace elements in Tama River water. The size distribution was clarified for 32 elements by means of neutron-activation analysis in order to discuss their chemical or physical forms. Alkali and alkaline-earth elements were primarily found in the dissolved-size fraction (<0.45 μm). Their dissolved species were mostly distributed in the smallest-molecular-weight fraction (<MW 500), although the alkaline-earth elements were also recognized to a significant extent (20–30%) in the middle-molecular-weight fraction (MW 104–500). Transition elements were principally associated with the suspended-size fraction (>0.45 μm) in the upper reaches of the river, but in the lower reaches they were chiefly fractionated as the dissolved species, with the exception of Sc and Fe. The dissolved V and Mn were distributed in the smallest-molecular-weight fraction, while the Co, Ni, and Zn were divided between two smaller-molecular-weight fractions (MW 104–500 and <MW 500). Light rare-earth elements were mostly associated with suspended materials. Heavier rare-earth elements were, on the contrary, mainly found in the dissolved-size fraction, while their dissolved species were concentrated in the middle-molecular-weight fraction. The dissolved species for As, Se, Sb, and W were divided into two smaller-molecular-weight fractions, although As, Se, and W were predominantly found in the middle-molecular-weight fraction and Sb was mainly detected in the smallest-molecular-weight fraction. Aluminium and Ag were mainly associated with suspended materials. Furthermore, the dissolved Al was mostly distributed in the smallest-molecular-weight fraction, while the Ag was concentrated in the largest-molecular-weight fraction (>MW 104).
  • Katsumi Iwata, Masaaki Kojima, Junnosuke Fujita
    1985 Volume 58 Issue 10 Pages 3003-3009
    Published: 1985
    Released: June 27, 2006
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    Twelve new complexes, trans-[CoX2(dmae or dmap)2]+ (X=Cl, Br, I; dmae=1,2-bis(dimethylarsino)ethane, dmap=1,3-bis(dimethylarsino)propane), cis-[CoX2(dmap)2] (X=Cl, Br), [Co(CO3)(dmae or dmap)2]+, and [Co(acac)3−n(dmap)n]n+(n=0, 1, 2; acac=2,4-pentanedionate ion) were prepared and characterized. From a comparison of the 1A1g1Eg (D4h) d-d absorption bands of analogous trans-dichloro complexes of phosphines and amines, the order of spectrochemical series for the group 5B elements was suggested to be P>As>N. Largely reduced interelectronic repulsions between the crystal field levels were observed for the carbonato complexes. Isomerization of cis-[CoCl2(dmap)2]+ to the trans isomer was studied in methanol in the temperature range of 20.1–49.9 °C. The rate has a first-order dependence on the complex concentration. The rate constant at 54.9 °C, calculated from the ΔH\ eweq (115.2 kJ mol−1) and ΔS\ eweq (53.8 J mol−1 K−1) values, is 103 times as large as that reported for cis-[CoCl2(diars)2]+ (diars=o-phenylenebis(dimethylarsine)) at the same temperature.
  • Seiichi Kanda, Royce W. Murray
    1985 Volume 58 Issue 10 Pages 3010-3015
    Published: 1985
    Released: June 27, 2006
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    Electrochemistry of bilayer electrodes has until now been investigated mainly in the dark. For the further development of the photoelectrochemistry of bilayer electrodes and its application to optical-energy storage, a polymer of N-[4-[2-(trimethoxysilyl)ethyl]benzyl]-N′-methyl-4,4′-bipyridinium dibromide (BVSiBr2), a photoredox siloxane polymer, was employed as a photosensitive outer-layer, and bis(2,2′-bipyridine)bis(4-vinylpyridine)ruthenium(II) bis(hexafluorophosphate), [Ru(bpy)2(vpy)2](PF6)2, or tris(4-methyl-4′-viny-2,2′-bipyridine)iron(II) bis(hexafluorophosphate), [Fe(vbpy)3](PF6)2 was electrochemically polymerized as the inner layer on the surface of an SnO2 electrode. Direct and indirect photochemical reductions(trapping) of the outer layer siloxan polymer were attempted in the following ways: 1) the outer-layer, poly(BVSiBr2), was chemically trapped with a methylviologen radical, MV\underset.+, produced photochemically in an illumination cell and transferred to the electrochemical cell, 2) the outer-layer was photochemically trapped by UV irradiation in the presence of photosensitive alcohols (i-PrOH and EtOH) and 3) by photochemical trapping with tris(2,2′-bipyridine)ruthenium and triethanolamine. The 1st and the 2nd methods yielded results expressed by cyclic voltammograms showing an accumulation of poly(BVSi\underset.+), that is, a storage of optical energy in the outer-layer. The result of the 3rd method was negative.
  • Hirohide Furuya, Ryoichi Uwabe, Nobuyuki Sutoh, Akitsugu Okuwaki, Akir ...
    1985 Volume 58 Issue 10 Pages 3016-3020
    Published: 1985
    Released: June 27, 2006
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    Oxidation of 26 model compounds of low-ranked coal was performed to study the formation mechanisms of oxalic acid from coal. A mixture of 0.02 mol of the model compound, 4–60 g of NaOH, and 50 g of water was placed in a 300 cm3 autoclave and oxidized at 523 K and PO2=5 MPa for 120 min. Acetic acid was produced from phenols within 15 min and oxidized selectively to oxalic acid. The yield ratio(yield of oxalic acid(%)/yield of CO2 (%)) from most of the model compounds was higher than 1. These phenomena agreed well with those of low-ranked coal under the same oxidation conditions. The overall reaction rates, yields of oxalic acid, and yield ratios increased rapidly with an increasing concentration of NaOH as in the oxidation of coal. This behavior can be explained resonably well by an alkali-catalyzed oxidation mechanism regarding organic substances.
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