Bulletin of the Chemical Society of Japan
Online ISSN : 1348-0634
Print ISSN : 0009-2673
ISSN-L : 0009-2673
Volume 56 , Issue 8
Showing 1-50 articles out of 72 articles from the selected issue
  • Akiko Kida, Mitiko Miura, Hiromu Murata
    1983 Volume 56 Issue 8 Pages 2193-2197
    Published: 1983
    Released: June 27, 2006
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    The lattice dynamical properties of MgO are studied using a model based on the Birman method, which is different from the conventional point-like atom model. The model includes three kinds of forces: the short-range, the long-range Coulomb, and the long-range polarization interactions. The long-range interactions are dependent on the magnitude of the expansion of the electron distribution. The degrees of the expansion for Mg and O (wMg and wO) are estimated from the X-ray data. The calculated phonon dispersion curves agree with the observed curves in the case of wMg=0.35 Å and wO=0.73 Å, which are nearly equal to the estimated values, 0.35 and 0.65 Å.
  • Shoji Tanaka, Masatoki Yokoi
    1983 Volume 56 Issue 8 Pages 2198-2202
    Published: 1983
    Released: June 27, 2006
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    Molecular motion in neat 3-methylsydnone and molecular interaction in 3-methylsydnone–water mixtures were studied by the multinuclear FT-NMR method. The estimated rotational correlation times of the methine carbon and the carbonyl oxygen atom in neat sydnone are 8.6 and 8.1 ps at 40 °C, respectively. According to shift variations of the 13C, 14N, and 17O nuclei of the sydnone molecule in sydnone–water mixtures, the sydnone forms a hydrogen bond with water at the carbonyl oxygen and not at the ring oxygen site. The effect of dissolved paramagnetic ions was investigated on the 13C spin-lattice relaxation time of the carbon atoms of sydnone, and a discussion was made on the possible relative configuration of cation and anion to the solvent sydnone molecule.
  • Akira Iimura, Yasunobu Inoue, Iwao Yasumori
    1983 Volume 56 Issue 8 Pages 2203-2207
    Published: 1983
    Released: June 27, 2006
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    The effect of hydrogen reduction on the composition, structure, and catalytic activity of dichromium(III) copper(II) tetraoxide (copper chromite), CuCr2O4, was investigated. In this oxide, the surface and the bulk CuII was reduced into CuI and further to Cu0 by heating in hydrogen. The methanol decomposition on fresh copper chromite proceeded in a manner similar to that on metallic copper formed as the result of strong reduction and dispersed on chromium(III) oxide. The contribution of CuII, CuI, and Cu0 species to catalytic activity was examined and the similarity in the character of reaction on these two samples with different surface states was discussed. The role of Cr2O3 interacting with zerovalent copper was postulated.
  • Yukihiro Yokoyama, Yukihide Yamashita, Kensuke Takahashi, Tyo Sone
    1983 Volume 56 Issue 8 Pages 2208-2211
    Published: 1983
    Released: June 27, 2006
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    Well-resolved 1H NMR signals of the cations formed from chlorothiophenes were observed in the HSO3F or AlCl3–HCl–CH2Cl2 system. Chlorothiophenes are protonated exclusively at the position adjacent to sulfur, either with or without substituents. The protonation of 2-chloro-5-methylthiophene occurs at the 5-position, and, in the HSO3F system, the cation 5H-2-chloro-5-methylthiophenium ion thus formed undergoes an irreversible 2,5-hydrogen shift.
  • Kazuhiko Seki, Hiroo Inokuchi
    1983 Volume 56 Issue 8 Pages 2212-2219
    Published: 1983
    Released: June 27, 2006
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    He I, Ne I, and Ar I ultraviolet photoelectron spectra were measured for solid hexane, 3-methylpentane, 2,2-dimethylbutane, neopentane, tetramethylsilane, cyclohexane, and 1-hexene deposited on a substrate at the temperature of liquid nitrogen. The spectra of all the compounds except hexane showed valence-band features. The threshold ionization potential was 7.6–8.9 eV, with a lowering of the threshold from the gas to the solid phase (polarization energy PS) of 1.2–1.8 eV. These PS values are in reasonable agreement with theoretical model calculations. To clarify the effect of intra- and intermolecular factors on PS, the observed PS values were compared with those of liquid-phase and solid-aromatic hydrocarbons. For compounds in which the bottom of the conduction band lies above the vacuum level, the polarization energy data showed that electrons with energies between these states are also emitted, possibly without any excitation of electrons to the conduction band in the bulk of the solid.
  • Shunichi Fukuzumi, Katsuhiko Hironaka, Nobuaki Nishizawa, Toshio Tanak ...
    1983 Volume 56 Issue 8 Pages 2220-2227
    Published: 1983
    Released: June 27, 2006
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    A new methodology for experimental determinations of redox potentials of oxidants or reductants in both reversible and irreversible systems is presented. The Rehm-Weller free energy relationship between the activation free energy ΔG and the free energy change ΔG for the electron transfer quenching of the excited states of oxidants or reductants by a series of reductants or oxidants is converted to a linear correlation between ΔG\ eweq−ΔG and (ΔG\ eweq)−1, which can be utilized in convenient determinations of redox potentials of oxidants or reductants. This methodology is established in various reversible systems where the redox potentials of oxidants or reductants determined based on the Rehm-Weller free energy relationship agree well with those determined independently by electrochemical methods. By using this method, one-electron oxidation potentials of two quite different compounds, one is an NADH model compound, 1-benzyl-1,4-dihydronicotinamide (BNAH), and the other [Rh2(dicp)4]2+ (dicp=1,3-diisocyanopropane), in MeCN have been determined as 0.60±0.10 and 0.38±0.10 V vs. SCE, respectively. The relation between the oxidation potential and the oxidation peak potential of BNAH measured by the cyclic voltammetry is discussed in the context of free energy relationships.
  • Kazuyoshi Sushida, Masahisa Fujita, Iwao Yamazaki, Hiroaki Baba
    1983 Volume 56 Issue 8 Pages 2228-2233
    Published: 1983
    Released: June 27, 2006
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    The rate constants of radiative decay (kF), internal conversion (kIC), and intersystem crossing (kISC) for single vibronic levels in the S1(n, π*) state of pyridine-d0 and -d5 vapors have been determined from measured fluorescence quantum yields (ΦF), intersystem crossing quantum yields (ΦICS), and picosecond fluorescence lifetimes. The ΦISC values are fairly constant in the region of lower excess vibrational energy (<1000 cm−1), while the ΦF values are particularly large for vibronic levels involving non-totally symmetric vibrations, ν16b and ν10a. The latter observation is attributed to both an increase of kF and a decrease of kIC and kISC (relative to the zero-point level) for the ν16b levels (16b2 and l6b26a1), and to an increase of kF for the ν10a levels. The relative values of kF are discussed using the Herzberg-Teller theory of vibronic coupling. The values of kF for 16b1 and 16b2 are significantly larger than that for the zero-point level, though no absorption band corresponding to 16b01 can be observed. In both pyridine-d0 and -d5, the value of kIC is as large as 1.7×1010s−1 even for the zero-point level, which is more than twice the kISC value for the same level.
  • Shigeo Fujita, Akio Takenaka, Yoshio Sasada
    1983 Volume 56 Issue 8 Pages 2234-2237
    Published: 1983
    Released: June 27, 2006
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    As a model for protein-nucleic acid interactions, crystals of the title complex were prepared from a water–ethanol (1 : 1) solution containing equimolar amounts of adenine and 1-(2-carboxyethyl)uracil. The space group is P21/c with the unit cell dimensions of a=12.567(1), b=13.358(1), c=8.032(1) Å and β=93.28(1)°. The crystal structure was determined by X-ray analysis. The final R value was 0.053. The adenine and uracil moieties form a reversed Hoogsteen base pair in which N(7) and N(6) of adenine are hydrogen-bonded with N(3) and O(2) of uracil, respectively. The carboxyl group is dissociated and hydrogen-bonded to the protonated N(1) of adenine in the adjacent base pair at a distance of 2.542(3) Å. It is suggested that the protonation of adenine–uracil reversed Hoogsteen base pair could occur to make the base pair more stable, and the dissociated carboxyl group may be hydrogen-bonded to it in the protein–nucleic acid interactions.
  • Hajime Ichimura, Toshiaki Shirakawa, Taneki Tokuda, Tsutomu Seimiya
    1983 Volume 56 Issue 8 Pages 2238-2240
    Published: 1983
    Released: June 27, 2006
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    Pressure-volume isotherms of 4-(trans-4-pentylcyclohexyl)benzonitrile were directly measured by means of piston-cylinder method at various temperatures. From the relation of the molar volume and the transition temperature which was determined by its clearing point, the parameter ∂lnTc⁄∂lnVc, was found to assume a value of −5.24, which should be closely related with the intermolecular potential energy. The value of this parameter increased correlatively with the alkyl chain length in the homologous series of 4-(trans-4-alkylcyclohexyl)benzonitriles.
  • Akira Ouchi, Yoshiyuki Sato, Yasuhiko Yukawa, Toshio Takeuchi
    1983 Volume 56 Issue 8 Pages 2241-2249
    Published: 1983
    Released: June 27, 2006
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    The crystal and molecular structure of tetrakis{(isopropylthio)acetato}bis(quinoline)dicopper(II) (1), bis(dibenzylamine)bis{(ethylthio)acetato}copper(II) (2), and bis{(isopropylthio)acetato}tris(isoquinoline)copper(II) (3) were determined by the X-ray diffraction method. The final R values obtained are 0.041, 0.055, and 0.078 for 1, 2, and 3 respectively. 1 is green in color and is orthorhombic with the space group Pcab. It has a dimer structure similar to that of the copper(II) acetate hydrate, where four (alkylthio)acetate liagnds bridge both copper(II) atoms. 2 is violet in color and is monoclinic with the space group A2/a. It has a square-palnar geometry, and no atoms are coordinated to the copper(II) atom from the axial direction, probably because of the steric effect of the large dibenzylamine molecules. 3 is blue in color and is triclinic with the space group P\bar1. It has potentially a hepta-coordinate geometry, where one nitrogen atom and two oxygen atoms ligate from the axial direction of the CuN2O2 plane.
  • Ryokichi Tsuchiya, Akira Uehara, Toshio Wazumi, Yoshinori Muramatsu
    1983 Volume 56 Issue 8 Pages 2250-2253
    Published: 1983
    Released: June 27, 2006
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    The enthalpy changes (ΔH) in the reaction of trans-[CoX2(AA)2]X·mHX·nH2O-type complexes with an alkaline sodium sulfide solution were calorimetrically measured at 25 °C, where AA is diamine and X is Cl, Br, or ClO4; m=0 or 1, and n=0, 0.5, 1, or 2. The thermal stabilities were found to decrease in the following orders for both dichloro and dibromo complexes: 1,2-ethanediamine>l- or d-1,2-propanediamine>racemic 1,2-propanediamine,d,l-2,3-butanediamine>meso-2,3-butanediamine>2-methyl-1,2-propanediamine, 1,2-ethanediamine>1,3-propanediamine, and meso-2,4-pentanediamine>d,l-2,4-pentanediamine. The complexes containing six-membered diamine chelate rings were less stable than those containing five-membered diamine chelate rings. The dibromo complex bromides were less stable than the corresponding dichloro complex chlorides.
  • Masaki Tachibana, Motohisa Furusawa
    1983 Volume 56 Issue 8 Pages 2254-2257
    Published: 1983
    Released: June 27, 2006
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    Trace amounts of carbazole and anthracene in dibenzofuran can be simultaneously determined by measuring the synchronous fluorescence intensities at 336 and 381 nm respectively. The determination limit is 2 ppm. For the application of this method to the practical samples containing interfering impurities, a zone-melting technique was applied successfully to remove the impurities prior to the determination. The recoveries of carbazole and anthracene were 99 and 92% respectively.
  • Susumu Kitagawa, Megumu Munakata, Noboru Miyaji
    1983 Volume 56 Issue 8 Pages 2258-2262
    Published: 1983
    Released: June 27, 2006
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    Binuclear copper(I) complexes [CuXL]2(X=Cl and I; L=2,2′-bipyridine, 1,10-phenanthroline, and their derivatives) have been synthesized in acetone, which react with CO reversibly to give crystalline carbonyl adducts [Cu2X2L2(CO)]. The cyclic voltammograms of [CuXL]2 and [Cu2X2L2(CO)] show two couples of coppercentered oxidation-reduction waves, indicative of binuclear structure. One couple of waves in [Cu2X2L2(CO)] alone shifts to the anodic region, exhibiting the formation of monocarbonylated complexes. All the half-wave potentials are primarily governed by the basicity of a ligand L, and the contribution of a coordinated CO to the stabilization of CuI state by π back-bonding is found. The equilibrium constants of the reaction, [CuXL]2+CO\oversetKco\ ightleftharpoons[Cu2X2L2(CO)], are lowered with the decrease in the transition energy of the ligand←metal charge transfer of [CuXL]2. On this basis, it is concluded that CO competes with L concerning π back-bonding with copper(I). The νco values of the coordinated CO exhibit apparent L-dependence, which is accounted for by the competition between Cu–L and Cu–CO π-bonding, and hence, νco values are useful probe to inquire into the nature of Cu–CO bonding among these copper(I) complexes.
  • Yoji Tachibana, Makoto Ando, Hiroyoshi Kuzuhara
    1983 Volume 56 Issue 8 Pages 2263-2266
    Published: 1983
    Released: June 27, 2006
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    The kinetics of the nonenzymatic transamination reaction from pyridoxamine analogs with a pyridinophane structure to α-keto acids catalyzed by Zn2+ were investigated by monitoring the changes in the absorption spectra in methanol. It was found that these reactions obeyed first-order kinetics for the formation of the Zn2+ chelate of an aldimine. No appreciable change in the reaction rate was observed when the concentration of the α-keto acid was increased, indicating that the isomerization of the ketimine chelate to the aldimine chelate is the ratedetermining step. There was a considerable enhancement of the reaction rate when the molar ratio of the zinc ion to the pyridoxamine analogs was reduced from 1/1 to 0.5/1. The reaction rates corresponding to the various α-keto acids employed in the presence of an amount of Zn2+ equimolar to the pyridoxamine analog decreased in this order; phenylpyruvic acid>pyruvic acid≈4-methyl-2-oxopentanoic acid>3-methyl-2-oxobutanoic acid, whereas those in the presence of half-molar equivalents of Zn2+ to the pyridoxamine analog decreased in this order; pyruvic acid>phenylpyruvic acid ≈4-methyl-2-oxopentanoic acid>3-methyl-2-oxobutanoic acid. Furthermore, the use of the pyridoxamine analog with a linear “ansa” bridge resulted in a larger reaction rate than the use of the one with a branched “ansa” bridge. The solvent isotope effect is also described.
  • Tadashi Hara, Motohiro Toriyama, Kazuhiko Tsukagoshi
    1983 Volume 56 Issue 8 Pages 2267-2271
    Published: 1983
    Released: June 27, 2006
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    A synthesized metal-complex compound with catalytic activity for a chemiluminescence reaction has been used for the first time as a labeling reagent for immunoassay. Several complex compounds of iron(III) and cobalt(II) were synthesized, and their catalytic activities for the chemiluminescence reaction between 5-amino-2,3-dihydro-1,4-phthalazinedione (luminol) and hydrogen peroxide (H2O2) were examined. Iron(III) 4,11,18,25-tetracarboxyphthalocyanine (TCP-Fe(III)) showed the highest catalytic activity. The immunoassay of free albumin was carried out by a competitive method using albumin labeled with TCP–Fe(III) by means of the carbodiimide method; free albumin in the range of 2 to 1000 μg/tube could be determined with a coefficient of variation of from 6 to 16% in 5 analyses.
  • Kenji Nomiya, Ryoichi Kobayashi, Makoto Miwa
    1983 Volume 56 Issue 8 Pages 2272-2275
    Published: 1983
    Released: June 27, 2006
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    Tetrabutylammonium salt of the 12-tungstoheteropolyanion with central CoII as the heteroatom in a tetrahedral oxygen environment, [CoIIW12O40]6−, has been prepared by an improved manner. This manner remarkably shortens the total time needed for preparation, especially the time for purification, and gives a compound of a high purity. The corresponding CoIII compound has been obtained by oxidation with potassium peroxodisulfate from the potassium salt of the CoII compound; its spectroscopic data (IR, near-infrared, UV-vis, and MCD) are presented.
  • Satoshi Kaki, Kazuaki Yamanari, Yoichi Shimura
    1983 Volume 56 Issue 8 Pages 2276-2282
    Published: 1983
    Released: June 27, 2006
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    the chiral tetra-μ-hydroxo-trinuclear complexes, cis-[Co(CN)2{(OH)2Co(NH3)4}2]3+ and cis-[Co(CN)2{(OH)2Co(diamine)2}2]3+ have been prepared and separated into their optical isomers and/or diastereomers by column chromatography (diamine: ethylenediamine, (R)-1,2-propanediamine, and (S,S)-1,2-cyclohexanediamine). The absolute configurations of isomers have been assigned on the basis of their CD and 13C NMR spectra and the characterization of mononuclear complex produced by decomposition of the trinuclear isomers of ethylenediamine ligands. It has been proved that the main CD contributions due to the two chiral Co(OH)4(CN)2 and Co(N)4(OH)2 centers are additive for the present systems.
  • Kazuaki Yamanari, Yoichi Shimura
    1983 Volume 56 Issue 8 Pages 2283-2289
    Published: 1983
    Released: June 27, 2006
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    [2]-[[(en)2Co{NH2(CH2)2S(CH2)nS(CH2)2NH2}Co(en)2]Cl6]-[α- or β-CDX]-rotaxanes were prepared with partial stereoselectivity and characterized from their absorption and 13C NMR spectra, molar conductance, and elemental analysis (CDX=cyclodextrin; n=8, 10, and 12). The rotaxanes always showed apparently ΔΔ-rich. CD spectra, the highest selectivity (16% ΔΔ-rich) being found in the case of n=10 and α-CDX. The results are related to the direct preparation of [2]-[ΔΔ-[(en)2Co{NH2(CH2)2S(CH2)nS(CH2)2NH2}Co(en)2]Cl6]-[α-CDX]-rotaxanes (n=8, 10, and 12) in relatively higher yields than the corresponding ΛΛ rotaxanes: 3.5% for n=8, 21% for n=10, and 28% for n=12. Inclusion complexes of a new type [Co(en)2{NH2(CH2)2S(CH2)nBr}]Cl3·2(α-CDX) were also isolated (n=10 and 12).
  • Kazuaki Ito, Etsuro Iwamoto, Yuroku Yamamoto
    1983 Volume 56 Issue 8 Pages 2290-2292
    Published: 1983
    Released: June 27, 2006
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    The charge-transfer-to-solvent (c.t.t.s.) spectrum of the iodide ion in nitrobenzene was observed in the visible region, the intensity of the spectrum being lowered by addition of a small amount of water to the solution. From the spectral changes, the first, second, and third hydration constants, K1=3.5, K2=2.6, and K3=1.4 (mol−1 dm3) were determined. On the basis of 1H NMR of water in nitrobenzene solutions in conjunction with the hydration constants obtained from the spectra, it was suggested that a fraction of the water molecules bound to the iodide ion is hydrogen bonded to each other.
  • Akihiro Yamaguchi, Kunio Ohzeki, Tomihito Kambara
    1983 Volume 56 Issue 8 Pages 2293-2295
    Published: 1983
    Released: June 27, 2006
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    The fractional determination of ethylenediaminetetraacetate(EDTA) and nitrilotriacetate(NTA) was carried out by use of hydrogen- and sodium-form ion exchange resin columns. After the conversion of free and complexed EDTA and NTA to the corresponding iron(III) complexes, two aliquots of the sample solution were separately passed through the columns. The iron(III)–EDTA complex was stable in both columns but iron(III)–NTA complex was completely decomposed in the hydrogen-form resin column, therefore, both of iron(III)–EDTA and –NTA were found in the effluent of sodium form resin column but only iron(III)–EDTA was found in the effluent of hydrogen-form resin column. The complexes in the respective effluents were determined spectrophotometrically at 255 nm. The recovery tests of EDTA and NTA from the synthetic sample solutions containing various metal ions were examined and the results observed were satisfactory.
  • Satoru Onaka, Yoshinori Kondo, Nobuhiro Furuichi
    1983 Volume 56 Issue 8 Pages 2296-2299
    Published: 1983
    Released: June 27, 2006
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    Photochemical reactions of RMn(CO)3L2 (R=H and CH3; L=P(OC6H5)3) and CH3Mn(CO)4L in benzene gave several kinds of orthometalated products, (Remark: Graphics omitted.) (x=0, 1, and 2). The reactions have been shown to proceed via ligand dissociation, CO and/or L, from the parent compounds and the resulting 16-electron intermediates activate a C–H bond of phenyl groups in triphenyl phosphite intramolecularly to yield orthometalated products. The results of photochemical reactions for MeMn(CO)3L2 and MeMn(CO)4L are compared with those of thermal reactions for these compounds. HMn(CO)4L was left intact by photochemical and thermal reactions.
  • Toshikazu Takata, Mayumi Yamazaki, Ken Fujimori, Yong Hae Kim, Takashi ...
    1983 Volume 56 Issue 8 Pages 2300-2310
    Published: 1983
    Released: June 27, 2006
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    Stereochemistry of enzymatic oxygenations of various diaryl, dialkyl and aryl alkyl sulfides to the corresponding sulfoxides with hepatic microsomes obtained from phenobarbital pretreated rabbit was investigated in comparison with those of nonenzymatic oxidations. Relative reactivity of the sulfides in the enzymatic oxygenation, based on the yields of the sulfoxides and the amount of oxygen absorption, depends upon the steric demand of the substituent in the oxygenation of 2-substituted thiochroman derivatives. However, such a trend was not observed in the enzymatic oxygenations of various acyclic sulfides. A substantial asymmetric induction on the sulfur atom was always observed (e.g., 54% e.e. for benzyl t-butyl sulfide). Formation of the sulfoxide with R-configuration predominated over that with S-configuration. The enzymatic oxygenation of all the unsymmetrical sulfides examined proceeded via the same steric course. Diastereomeric ratios of the sulfoxides formed in the enzymatic oxygenations of various racemic sulfides bearing alkyl substituents at α-position are markedly favoured more for the trans isomers than for the cis ones, while the ratio was nearly fifty-fifty in the nonenzymatic oxidations with both MCPBA and NaIO4. These results suggest that the enzymatic oxygenation takes place at the less hindered side of the sulfide. Both enzymatic and nonenzymatic oxidations of rigid six-membered cyclic sulfides, trans-thiadecalins and 4-(p-chlorophenyl)thiane, similarly occurred at the less hindered side to give mainly equatorial sulfoxides. The yields of the four stereoisomeric sulfoxides were nicely determined in the enzymatic oxygenation of racemic 2-methyl-2,3-dihydrobenzothiophene to elucidate the steric course of the oxygenation. Dependency of this microsomal oxygenation upon cytochrome P-450 enzyme was proved by several inhibition experiments and also by the identical stereochemical results of the oxygenation of a few selected sulfides to those with a reconstituted system with purified cytochrome P-450 and co-factors.
  • Shinji Kurokawa
    1983 Volume 56 Issue 8 Pages 2311-2318
    Published: 1983
    Released: June 27, 2006
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    2-(4-Azulenyl)ethanamine derivatives, nonbenzenoid analogs of the biologically active amine, were synthesized by the action of methyleneammonium salts on sodium 4-methylazulenide, sodium 4,6,8-trimethylazulenide, and sodium guaiazulenide. These compounds, as well as their hydrochlorides, were characterized by UV, IR, 1H NMR, 13C NMR, and MS data. The reaction of sodium guaiazulenide and N-ethylidenemethylamine also yielded the corresponding 2-(4-azulenyl)ethanamine derivatives, but the low yield of the product showed that the electrophilicity of azomethine carbon atom to 4-methylene carbanion was insufficient. The enzyme activity for some of those products was investigated. Negligible effect was found on prostaglandin 15-hydroxydehydrogenase, and considerable inhibition to cyclic AMP-phosphodiesterase, in vitro.
  • Seiichiro Ogawa, Hiroyuki Ito, Takao Ogawa, Shinichi Iwasaki, Tetsuo S ...
    1983 Volume 56 Issue 8 Pages 2319-2325
    Published: 1983
    Released: June 27, 2006
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    Synthesis of the 2-deoxy analogs of DL-hydroxyvalidamine and DL-valienamine starting from DL-1,2-di-O-acetyl-(1,3,5/2)-5-bromo-3-bromomethyl-1,2-cyclohexanediol is described.
  • Seiichiro Ogawa, Hiroyuki Ito, Tetsuo Suami
    1983 Volume 56 Issue 8 Pages 2326-2329
    Published: 1983
    Released: June 27, 2006
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    DL-2-Deoxyvalidoxylamine B and its diastereomer have been synthesized by the reaction of the protected DL-valienamine and the anhydro derivative of (hydroxymethyl)cyclohexanetetrol followed by removal of the protecting groups.
  • Yuji Hiraki, Toshihiko Oda, Akira Tai
    1983 Volume 56 Issue 8 Pages 2330-2337
    Published: 1983
    Released: June 27, 2006
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    A pair of primary amines was competitively acylated with acid anhydride in water–dioxane mixed solvents. Based on the product distribution, the mode of differentiation of hydrocarbon residues in the competing substrates with a reagent was studied. In solvents with a low water content, where both reactants and products were completely soluble, no appreciable differentiation of the alkyl-chain length of alkylamines occurred. On the other hand, the differentiation of a phenyl group from an alkyl group occurred. From the dependency of the product distribution on the water content in reaction media, an attractive interaction induced by water was postulated between alkyl and phenyl groups, but no such interaction was observed between alkyl and alkyl groups. The differences in functions of the phenyl and alkyl groups in the differentiation process are discussed. In solvents with a very high water content, the acylation proceeded under heterogeneous conditions, since acid anhydrides became insoluble and provided an organic phase in the reaction mixture. In this case, the differentiation was controlled by the hydrophobicity of hydrocarbon residues of amines indexed by the partition coefficients of amines between the aqueous phase and the organic phase.
  • Koichi Honda, Hiroshi Nakanishi, Akira Yabe
    1983 Volume 56 Issue 8 Pages 2338-2340
    Published: 1983
    Released: June 27, 2006
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    1,8-Naphthalenediamine reacted with dimethyl and diethyl acetylenedicarboxylates, giving rise to tetrahydronaphtho[1,8-ef]diazepinones (2), dihydroperimidines (3) and bis(enamino)fumarates (4). The relative yields of 3 and 4 depended on the reaction conditions, while products 2 were always very minor. Products 4, the yields of which increased considerably in the presence of a large excess of the acetylenes, underwent cyclization at 230 °C leading to quinolinoquinolinediones.
  • Masakatsu Koshinuma
    1983 Volume 56 Issue 8 Pages 2341-2347
    Published: 1983
    Released: June 27, 2006
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    Single activities of the decyl sulfate (DeS), the calcium (Ca2+), and the sodium (Na+) ions in mixed surfactant solutions of varying mole ratios (Rm=Ca(DeS)2/NaDeS) were obtained at 30±1 °C by means of three kinds of EMF cells with ion-exchange membranes or Na+-selective electrode. The results showed that with increasing concentrations above the cmc, the activity of the DeS decreases gradually, while that of the Na+ increased linearly; the activity of the Ca2+ remained nearly constant in the solution of Rm=2, but it showed a minimum in the solutions of Rm=1, 0.5 and 0.2. From these activities, the counterion attachments of the Ca2+(rCa) and the Na+(rNa) and the degree of micellar charge (1−2rCarNa) were obtained. With increasing concentration, rCa diminished gradually and approached a constant value, while rNa and 1−2rCarNa changed reversely except in the solution of Rm=2 where they were nearly constant. The Ca2+ was bound preferentially to the micelle surface. The Na+, which almost diffused away for the solution of Rm=2, bound increasingly to lessen the electrical potential of the micelle as Rm decreased. The specific adsorption potentials and the electrical free energies of transfer of Ca2+ and Na+ from solution to micelle were calculated as 1.7 and −18.4 kJ mol−1, and 1.1 and −14.3 kJ mol−1 respectively at their cmcs. It was showed clearly that little dehydration from the counterion occured and the coulombic interaction played an important role in the counterion binding.
  • Sukeya Kodama
    1983 Volume 56 Issue 8 Pages 2348-2354
    Published: 1983
    Released: June 27, 2006
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    Photolysis of HN3 vapor was studied at 313 nm as a function of HN3 and Xe pressures, light intensity, and temperature. The photolysis of hydrazoic acid labeled with 15N was also studied. The quantum yields of N2, H2, and NH4N3 as a product were 4.85, 0.494, and 0.842 at 30 °C and 6.7 kPa of HN3, respectively. The mechanism for the main reactions was postulated as follows: HN3+hν(313 nm)→N2+NH(a1Δ); NH(a1Δ)+HN3→2N2+2H (2); NH(a1Δ)+HN3→N3+NH2 (3); NH(a1Δ)+HN3→N2+N2H2* (4). The rate constant ratios of k3k2=0.746 and k4k2=1.23 were obtained at 30°C. (k3+k4)⁄k2 decrease drastically with rising temperature. Xe is effective for the collisional deactivation, NH(a1Δ)+Xe→NH(X3Σ)+Xe (15), and k15⁄(k2+k3+k4)=0.187 was obtained at 30 °C.
  • Sukeya Kodama
    1983 Volume 56 Issue 8 Pages 2355-2362
    Published: 1983
    Released: June 27, 2006
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    Photolysis of HN3 vapor with C2H6 was studied at 313 nm and 30 °C. The products are N2, H2, CH4, NH4N3, CH3NH2·HN3, C2H5NH2·HN3, CH3N3, and CH3CN. The quantum yields of these products were measured as a function of pressures of HN3 and C2H6, and the light intensity. The following mechanism for the main reactions was proposed: HN3+hν(313 nm)→N2+NH(a1Δ); NH(a1Δ)+HN3→2N2+2H (2a); NH(a1Δ)+HN3→NH2+N3 (2b); NH(a1Δ)+HN3→N2+N2H2* (2c); NH(a1Δ)+C2H6→C2H5NH2* (3); NH(a1Δ)+C2H6→NH(X3Σ)+C2H6 (4); C2H5NH2*→CH3+CH2NH2 (5); C2H5NH2*→CH3CN+2H2 (6); C2H5NH2*+M→C2H5NH2+M (7). The rate constant ratios at 30 °C are: k3k2=0.334; k4k2=0.217; k6k5=0.038. The values of k7k5 for C2H6, HN3, CO2, and Xe are 36.5, 30.3, 29.0, and 14.5 dm3 mol−1, respectively. The values of k5=9.8×109 s−1, k6=3.7×108 s−1, τ (half life of C2H5NH2*)=6.8×10−11 s, η (collisional deactivation efficiency of C2H5NH2*)=1 for C2H6, HN3, and CO2, and η=0.60 for Xe were obtained by using the collision theory.
  • Sukeya Kodama
    1983 Volume 56 Issue 8 Pages 2363-2370
    Published: 1983
    Released: June 27, 2006
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    Photolysis of HN3 vapor in the presence of C2H4 was studied at 313 nm and 30 °C. The main products were N2, H2, CH4, C2H6, NH4N3, C2H5N·HN3 (salt of C2H5N (azomethines) with HN3), HCN, CH3CN, CH3N3, and C2H5N3. The quantum yields of these products were measured as a function of the light intensity and pressures of HN3 and C2H4. The following mechanism for the main reactions was infered: HN3+hν(313 nm)→NH(a1Δ)+N2; NH(a1Δ)+HN3→2N2+2H (2a); NH(a1Δ)+HN3→NH2+N3 (2b); NH(a1Δ)+HN3→N2+N2H2* (2c); NH(a1Δ)+C2H4→C2H5N* (aziridine and vinylamine) (3); C2H5N*→CH3+CH2N (4); C2H5N*→H2+CH3CN (5); C2H5N*→H+C2H4N (6); C2H5N*→C2H3+NH2 (7). The rate constant ratios at 30 °C are: k3k2=1.64; k5k4=0.102; k6k4=0.564; k7k4=0.734. The collisional deactivation from NH(a1Δ) to NH(X3Σ) by C2H4 was not found. The lifetime of C2H5N* is much shorter than 6.8×10−11 s for C2H5NH2*(←NH(a1Δ)+C2H6). The relative and absolute rates for the reactions of NH(a1Δ) with HN3, Xe, C2H6, and C2H4 are discussed.
  • Hideo Kimizuka, Yoshihiko Nagata, Kozue Kaibara
    1983 Volume 56 Issue 8 Pages 2371-2379
    Published: 1983
    Released: June 27, 2006
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    A theory for the ion and solvent transports through membrane has been developed on the basis of nonequilibrium thermodynamics. The fluxes were represented as linear functions of the effective driving potentials. The theory is reduced to that of Katchalsky when the concentration ratio of two aqueous solutions is near unity and the solutions are dilute. The effect of solvent flow on the interionic correlations was discussed. It was pointed out that Despic and Hills’ theory of the electroosmotic effect on the membrane conductance is not valid with respect to both theoretical and experimental aspects. The comparison of the present theory with the previous one was also made. The six independent phenomenological coefficients (elements of the conductance matrix) were experimentally determined as a function of concentration with the concentration cell consisting of the amphoteric ion-exchange membrane and aqueous calcium chloride solutions. The membrane properties were discussed in terms of the conductance matrix. The diffusional ion conductance was much greater than the electrical ion conductance, as an indication of the failure of the Nernst-Einstein relation. The cation-anion coupling coefficient was close to unity whereas the ion-water coupling coefficients were less than 0.1. The solvent effects on the interionic conductance elements were found to be small in spite of the fact that the water permeability was extremely high. The distinction between the cationic and amphoteric ion-exchange membranes was explored in terms of the elements of the conductance matrix.
  • Shinji Sakanoue, Chiaki Murase, Mitsuo Endo
    1983 Volume 56 Issue 8 Pages 2380-2386
    Published: 1983
    Released: June 27, 2006
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    Computer simulations and a theoretical analysis of the Oregonator model of the Belousov-Zhabotinskii reaction are made based on Tyson’s equation. The behavior of the amplitudes of the unstable limit cycle near the transition point, pc, can be explained theoretically fairly well by the Landau theory. The global behavior of one stable limit cycle and one unstable limit cycle is examined by means of simulations. The existence of a triple point at which three different global states coexist has been suggested.
  • Takaaki Dohmaru, Yoshio Nagata
    1983 Volume 56 Issue 8 Pages 2387-2389
    Published: 1983
    Released: June 27, 2006
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    The addition of ·SiCl3 radicals to ethylene has been reinvestigated using a large conversion method. The amended values are log(k3k5)=−0.17±0.05−(0.80±0.10) kcal mol−1/2.303 RT and log{k−5k6(mol cm−3)}=3.4±0.3−(22.5±0.7) kcal mol−1/2.303 RT where the reactions involved are ·SiCl3+CH3COCH3\overset3→(CH3)2\dotCOSiCl3, ·SiCl3+C2H4\overset5\underset−5\ ightleftarrows·CH2CH2SiCl3 and ·CH2CH2SiCl3+HSiCl3\overset6→C2H5SiCl3+·SiCl3.
  • Kiwamu Yamaoka, Kazuyoshi Ueda
    1983 Volume 56 Issue 8 Pages 2390-2395
    Published: 1983
    Released: June 27, 2006
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    Electric birefringence was measured at 20 °C and at 535 nm for sodium poly(p-styrenesulfonate) (NaPSS), with and without added sodium chloride, and the 9-aminoacridinium (AA) complex in aqueous solutions. The field strength dependence of both the steady-state EB (Δn(∞)) the field-free decay time (⟨τ⟩EB) was examined. Charge suppression by added Na+ ions or neutralization by strongly bound AA decreased both Δn(∞) and ⟨τ⟩EB considerably, altering not only the optical factor Δg and electric moments, but also the backbone chain length. The weight-average values of chain length (lw), pseudopermanent dipole moment (μw), counterion-induced electric polarizability anisotropy (Δαw), and the length-independent values of Δg were estimated by analyzing the experimental data on the basis of the “classical” orientation function which takes into account the continuous distribution of chain length for the polydisperse NaPSS sample. The electric field orientation of NaPSS and the AA-complex could be described by the interaction between an applied field and the electric moment which transforms from counterion-induced type in the extremely low field region (<1.5 kV/cm) to saturated induced permanent type at higher fields.
  • Motosuke Naoki, Manabu Matsushita
    1983 Volume 56 Issue 8 Pages 2396-2401
    Published: 1983
    Released: June 27, 2006
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    Dielectric measurements have been made as a function of frequency, temperature, and pressure on a binary mixture of triphenylchloromethane and o-terphenyl in its supercooled liquid region. Since the distribution of relaxation time is independent of temperature and pressure in the present experimental range, the time-temperature-pressure superposition is accurately applied. The activation parameters such as the activation enthalpy at constant pressure, H*P, the activation enthalpy at constant volume, H*V, and the activation volume V* are obtained as a function of temperature and pressure. H*V is only half H*P unlike liquids and associated liquids such as alcohols. V* as well as the pressure coefficient of temperature at constant relaxation time τ, (∂T⁄∂T)τ, is similar in magnitude to that of polymer liquids and larger than that of associated liquids. These facts have revealed the contributions of inter- and intramolecular interactions to the molecular mobility in the supercooled liquid. (∂T⁄∂P)τ coincides with the pressure coefficient of the glass transition temperature, dTg/dP. This gives a statement that the glass transition temperature in simple normal liquids, as well as in polymer liquids, is an isorelaxation-time state.
  • Hidemi Iyota, Makoto Aratono, Michio Yamanaka, Kinsi Motomura, Ryohei ...
    1983 Volume 56 Issue 8 Pages 2402-2406
    Published: 1983
    Released: June 27, 2006
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    In order to investigate the effect of pressure on the adsorption at interfaces, the interfacial tension was measured as a function of pressure and composition for the systems of water and dilute solutions of 1-octadecanol in cyclohexane, benzene, and their equimolar mixture. The interfacial density of 1-octadecanol and the volume of interface formation were evaluated from the experimental data. Under atmospheric pressure, cyclohexane exhibits a significant adsorption of 1-octadecanol and a rapid decrease in the volume of interface formation, giving rise to the phase transition from the expanded to the condensed state in the adsorbed film, while benzene and equimolar mixture display only a small decrease in the thermodynamic quantities on the 1-octadecanol adsorption. Under high pressure, however, all the systems studied cause the phase transition. The effects of pressure and solvent on the phase transition of the adsorbed film were revealed on the basis of the thermodynamic quantities.
  • Gong-Wei Wang, Hideshi Hattori, Kozo Tanabe
    1983 Volume 56 Issue 8 Pages 2407-2410
    Published: 1983
    Released: June 27, 2006
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    The acid-base properties of ZrO2–SnO2 with different compositions have been measured by the indicator method and the adsorption with NH3 and CO2 and the catalytic activities studied. The ZrO2–SnO2 (atomic ratio=9 : 1) catalyst which was found to have the highest acid strength and the maximum acid amount exhibited the highest activities for the isomerization of cyclopropane and the dehydration of 2-butanol. The activities of the catalysts with different compositions for the two reactions correlated with the acidic properties. On the other hand, the activities for the isomerization of 1-butene and the decomposition of diacetone alcohol (4-hydroxyl-4-methyl-2-pentanone) correlated with the basic properties. The activity for the dehydrogenation of 2-butanol was found to increase with an increase of the SnO2 content. The active sites on the ZrO2–SnO2 catalysts are discussed.
  • Hiroyuki Kageyama, Kunio Miki, Yasushi Kai, Nobutami Kasai, Yoshio Oka ...
    1983 Volume 56 Issue 8 Pages 2411-2414
    Published: 1983
    Released: June 27, 2006
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    Crystals of t-BuMgCl–(−)-sparteine (1) belongs to orthorhombic system; P212121, a=25.689(6), b=10.030(2), c=7.942(2) Å, and Z=4; MgCl2–(−)-sparteine (2) also crystallizes in orthorhombic system; P212121, a=11.180(4), b=11.957(4), c=12.573(5) Å, and Z=4. Both structures were solved by the heavy atom method, and refined by the block-diagonal least-squares procedure; (1) R=0.098 for 1199 non-zero reflections and (2) R=0.091 for 1347 observed reflections. The Mg atom in each complex has a distorted tetrahedral geometry: (1) Mg–N=2.17(2) and 2.18(2), Mg–C=2.19(2), and Mg–Cl=2.332(7) Å and N–Mg–N=83.9(5)°; (2) Mg–N=2.150(9) and 2.160(9), and Mg–Cl=2.269(5) and 2.279(6) Å, and N–Mg–N=85.0(4)°.
  • Tadashi Sasamoto, Mitsuru Itoh, Toshiyuki Sata
    1983 Volume 56 Issue 8 Pages 2415-2419
    Published: 1983
    Released: June 27, 2006
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    Activities and heats of mixing for the molten KCl–MnCl2 system were determined mass-spectrometrically by the ion-current ratio method. Activities of components KCl and MnCl2 show large negative deviations from Raoult’s law, indicating a very strong interaction between KCl and MnCl2. Entropies of mixing calculated from measured activities and heats of mixing have minimum values in the vicinity of 33% MnCl2, and have been compared with those calculated on the basis of some molten structure models to infer possible chemical species in the molten salt.
  • Shuhei Fujinami, Akihiko Hattori, Muraji Shibata
    1983 Volume 56 Issue 8 Pages 2420-2425
    Published: 1983
    Released: June 27, 2006
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    Four complexes [Co(a)(gly)(NH3)3]+ (a=CN, NO2, NCS, and N3) and a related [Co(NO2)(β-ala)(NH3)3]+ complex have been prepared; they were characterized by the absorption spectra in the ultraviolet region. The fac(NH3) isomers of these complexes have been optically resolved by column chromatography. The CD spectra of fac(NH3)-[Co(H2O)(gly)(NH3)3]2+ and fac(NH3)-[Co(H2O)(β-ala)(NH3)3]2+ have also been measured. The absolute configurations of the fac(NH3) isomers have been determined by referring to the CD spectrum of fac(NH3)-(−)589[Co(NO2)(gly)(NH3)3]ClO4 which had been subjected to an X-ray analysis. Each isomer has exhibited a dominant Cotton peak at ca. 20000 cm−1 in the first absorption band region. The peak has been assigned to the electronic transition component which arises in the plane containing the glycinate chelate. The CD spectra fac(NH3)-[Co(a)(gly)(NH3)3]+ have been compared with those of the corresponding [Co(a)(gly)(1,4,7-triazacyclononane)]+ complexes, and the sources of the optical activities in these complexes have been investigated.
  • Shin-ichi Ishiguro, Yoshihiro Oka, Hitoshi Ohtaki
    1983 Volume 56 Issue 8 Pages 2426-2431
    Published: 1983
    Released: June 27, 2006
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    Equilibria between ethylenediamine and protons or nickel(II) ions have been investigated at 25 °C by means of potentiometric and calorimetric titrations in water and in dioxane–water mixtures (the dioxane contents are 0.1 and 0.2 mole fractions, which correspond to 35.2 and 55.0%w/w, respectively) containing 3 mol dm−3 LiClO4 as a constant ionic medium. Thermodynamic parameters (ΔG°, ΔH°, and ΔS°) referring to the formation of the species HL+, H2L2+, NiL2+, NiL22+, and NiL32+ (L denotes ethylenediamine) have been determined in the solutions. All the formation constants of the nickel(II)–ethylenediamine complexes increased with increasing dioxane content in the solvent mixtures, although the formation constants of the ethylenediammonium ions remained practically unchanged. On the other hand, enthalpies referring to the formation of the nickel(II)–ethylenediamine complexes became less negative, and thus entropies for the corresponding reactions increased remarkably with increasing dioxane content in the mixtures. The solvent effects on the thermodynamic parameters of the complex formation of nickel(II) ions with ethylenediamine are discussed in terms of enhancement of solvation of the complexes due to weakening of the hydrogen-bonded structure of the bulk water by the addition of dioxane.
  • Ikuo Hayashi, Keizo Ogihara, Kiyoshi Shimizu
    1983 Volume 56 Issue 8 Pages 2432-2437
    Published: 1983
    Released: June 27, 2006
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    Active esters (1) of glycine with o-hydroxybenzaldehyde oxime, o-hydroxyacetophenone oxime, o-hydroxybenzophenone oxime, and their 5-Cl and 5-NO2 derivatives were prepared by several methods. For aminolysis with benzylamine, esters 1 show higher reactivity than similar esters containing no hydroxyl group in the ortho position. It is suggested that esters 1 forms an intramolecular hydrogen bond between the hydrogen of the hydroxyl group at the ortho position and the hydroxyimino nitrogen so as to have its carbonyl group activated for the aminolysis; this mechanism of activation seems to be a sort of “intramolecular acid-catalysis.” Among the series of esters 1, esters of o-hydroxybenzaldehyde oxime and its 5-Cl and 5-NO2 derivatives are most reactive in the aminolysis. The reactivity of esters 1 is also discussed in relation to pKa values of aromatic o-hydroxy oximes.
  • Hiroshi Yoshida, Shingo Sogame, Yasunori Takishita, Tsuyoshi Ogata
    1983 Volume 56 Issue 8 Pages 2438-2441
    Published: 1983
    Released: June 27, 2006
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    N-Imidoyl sulfoximide (7) reacted with diphenylcyclopropenone (2) at 130 °C to yield a mixture of 1,2-disubstituted 5,6-diphenyl-4(1H)-pyrimidinone (6) and N-(4-oxo-2-pyrrolin-5-yl)sulfoximide (10), which might be formed by [3+3] and [2+3] cycloaddition reactions between 2 and 7. The yields of 6 and 10 depended on the electronic and steric effects of the substituents of 7.
  • Atsutaka Kunai, Junji Harada, Masayasu Nishihara, Yasuo Yanagi, Kazuo ...
    1983 Volume 56 Issue 8 Pages 2442-2446
    Published: 1983
    Released: June 27, 2006
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    Cathodic behavior of N-cyclohexylidenepyrrolidinium salt (1) and N-cyclohexylideneaniline (2) in acetonitrile has been studied by means of dc polarography, cyclic voltammetry and preparative electrolysis under controlled potential conditions. The compound 1 exhibits a reduction wave at about −1.8 V, which is accompanied by formation of a surface compound. The products obtained from the preparative electrolysis were neither saturated amines nor dimeric compounds but were mostly polymeric materials. However, when electrophilic olefins, such as acrylonitrile or methyl acrylate, were present in the solution, coupling products were produced. The compound 2, which cannot be reduced by itself below −2.7 V, is reduced at about −1.8 V when benzoic acid is in the solution. The reduction product in this case was N-cyclohexylaniline, which was replaced by a coupling product when acrylonitrile was present in the reaction system. The formation of the coupling products is considered to occur by a radical mechanism in both cases.
  • Masahiro Nakada, Sachio Fukushi, Hideaki Nishiyama, Keiji Okubo, Kotar ...
    1983 Volume 56 Issue 8 Pages 2447-2451
    Published: 1983
    Released: June 27, 2006
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    Photochemical dechlorinations and debrominations of C6HnX6−n (X=Cl, Br) isomers were carried out in hexane. The products and residual reactant were determined quantitatively by means of gas chromatography. From these experiments, the relative rates of dehalogenation were obtained. The different rates among unequivalent sites in a molecule were interpreted by the effect of steric acceleration by the neighboring halogen atom(s). The reactivity of the halogen atom in polyhalobenzene towards photochemical elimination reaction is dependent both on its position in the molecule when compared among isomers and on the number of halogen atoms in a molecule when compared among polyhalobenzenes of various degrees of substitution. The latter effect is more predominant in the series of polybromobenzenes.
  • Yoshihisa Watanabe, Yasushi Tsuji, Yukihiro Ohsugi, Jun Shida
    1983 Volume 56 Issue 8 Pages 2452-2457
    Published: 1983
    Released: June 27, 2006
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    Aminoarenes reacted with 2-propen-1-ol and 2-buten-1-ol at 180 °C to give quinoline derivatives in fairly good yields in the presence of a catalytic amount of a ruthenium complex. Dichlorotris(triphenylphosphine)ruthenium was the most effective catalyst. The aminoarenes with electron-releasing groups favored the formation of the quinolines. The N-heterocyclization also proceeded when aliphatic aldehydes were used in place of the allylic alcohols. The employment of allylic alcohols gave, however, higher yields in several cases. The reaction involves the isomerization of the allylic alcohols to the corresponding aldehydes. The aldehydes reacted with aminoarenes to give Schiff-base dimers which were then cyclized in the presence of the ruthenium complex to the quinolines. As a key intermediate in the reaction, the ortho-metallated species has been proposed.
  • Nanao Watanabe, Sakae Uemura, Masaya Okano
    1983 Volume 56 Issue 8 Pages 2458-2462
    Published: 1983
    Released: June 27, 2006
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    Treatment of olefins with a mixture of iodine and mercury(II) thiocyanate in benzene or diethyl ether gives vic-iodo(isothiocyanato)alkanes and vic-iodo(thiocyanato)alkanes in a high yield, the former being predominant. Similar results were obtained by using silver(I) and thallium(I) thiocyanates, though both the yield and the selectivity are slightly lower. By use of potassium thiocyanate and copper(I) isothiocyanate in place of mercury(II) thiocyanate, β-iodo thiocyanates were mainly formed. A reaction scheme involving initial formation of an iodonium ion from olefin and ISCN (formed in situ) and a subsequent attack of complex anion I(SCN)2 has been proposed to account for this predominant formation of β-iodo isothiocyanates.
  • Hajime Satonaka
    1983 Volume 56 Issue 8 Pages 2463-2468
    Published: 1983
    Released: June 27, 2006
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    The 1H NMR spectra and the IR carbonyl stretching frequencies of methyl (3-, 4-, and 5-substituted 2-thiophenecarboxylate)s have been reported. Good linear correlations between the chemical shifts of the ring protons in methyl (4- and 5-substituted 2-thiophenecarboxylate)s and those of the corresponding protons in substituted thiophenes were observed. The coupling constants in methyl (substituted 2-thiophenecarboxylate)s gave good correlations against the corresponding ones in substituted thiophenes. The IR carbonyl stretching frequencies in methyl (5-substituted 2-thiophenecarboxylate)s were correlated reasonably well with the chemical shifts of 5-protons in 2-substituted thiophenes. The coupling constants in methyl 2-thiophenecarboxylate series were found to vary linearly with the electronegativities of the substituents.
  • Junzo Sunamoto, Kiyoshi Iwamoto, Shinichi Nagamatsu, Hiroki Kondo
    1983 Volume 56 Issue 8 Pages 2469-2472
    Published: 1983
    Released: June 27, 2006
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    Decarboxylation reaction of 6-nitro-1,2-benzisoxazole-3-carboxylate (1) in cationic and anionic reversed micelles has been investigated with particular attention to the microenvironmental effect, such as microviscosity, micropolarity, and microactivity, in the specific and restricted reaction field as provided by reversed micelles. In 0.20 M CTAC/0.32 M H2O/CHCl3 reversed micelles, the reaction was accelerated about 1300-fold compared with that in bulk aqueous solution. Of various surfactant aggregate systems such as aqueous micelle, bilayer, and reversed micelle, the cationic reversed micelle could provide the most effective reaction field for the present decarboxylation reaction. This reaction is never accelerated in an anionic aqueous micelle. However, in the anionic AOT reversed micelle, the reaction was apparently accelerated by both lowering the micropolarity and increasing the microviscosity around the substrate. The unique rate enhancement for the decarboxylation reaction of 1 provided by reversed micelles was interpreted in terms of the “multiple field assistance.”
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