Bulletin of the Chemical Society of Japan
Online ISSN : 1348-0634
Print ISSN : 0009-2673
ISSN-L : 0009-2673
Volume 57 , Issue 8
Showing 1-50 articles out of 73 articles from the selected issue
  • Susumu Tsuchiya, Shinji Yamamoto, Hayao Imamura
    1984 Volume 57 Issue 8 Pages 2037-2039
    Published: 1984
    Released: June 27, 2006
    JOURNALS FREE ACCESS
    The catalytic isomerization of pentenes over KC24 has been investigated. The double-bond-migration and the cis-trans isomerization took place over KC24, but the skeletal isomerization was not observed. From the rates of reactions and the selectivity ratios, all six of the relative rate constants and the activation energies of reactions were determined. The reaction paths on the triangular graph calculated from the rate constants show the cis-convex type profile. The competitive isomerization of 1-pentene and 2-methyl-1-pentene has also been investigated. The rate of isomerization of 1-pentene was greater than that of 2-methyl-1-pentene, which can be explained on the basis that the amount of chemisorption of 1-pentene during the competitive reaction is greater than that of 2-methyl-1-pentene.
  • Yo-ichi Ishikawa, Shigeyoshi Arai
    1984 Volume 57 Issue 8 Pages 2040-2045
    Published: 1984
    Released: June 27, 2006
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    CO2 TEA laser-induced photolysis of C2H5F was studied by using a time-resolved infrared fluorescence technique. Molecular elimination of vibrationally excited hydrogen fluoride (HF*) from C2H5F* occurs in the process. Rotational temperatures and vibrational level populations of HF* are estimated from observed fluorescence spectra by computational fitting. Higher vibrational levels are populated to a less extent in the decomposition under a collisionless condition. When the pressure of C2H5F is increased, however, population inversion is allowed among some levels. Possible reaction mechanism is discussed for the production of HF* at extraordinarily high vibrational levels.
  • Yoshinori Kanno, Hisao Imai
    1984 Volume 57 Issue 8 Pages 2046-2050
    Published: 1984
    Released: June 27, 2006
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    The disproportionation reaction of NO was investigated on CaHY-type zeolite. The relation between pretreatment temperature and activity was determined by the pulse reaction technique, and the dependence of the initial formation rate of N2O on NO pressure was investigated with a gas circulation system. The rate of initial formation of N2O is third order in NO pressure in the lower pressure region (ca. 30 Torr, 1 Torr≈133.322 Pa) and 2.2th order in NO pressure in the higher pressure region (ca. 200 Torr). TPD spectra are composed mainly of three peaks: The first peak is assigned to the unreactive adsorbed NO, the second to the NO produced by the decomposition of N2O3 and left on the zeolite surface, and the third to the N2O remaining. On the basis of the reaction mechanism proposed by Chao and Lunsford, the rate equation for the initial formation of N2O has been derived as α=\bark2K1P3⁄(1+K1P2) where P, K1 and \bark2 are the pressure of NO, an equilibrium constant, and a rate constant, respectively. This equation is in good agreement with experimental results obtained with the gas circulation system.
  • Kohei Urano, Hisanao Kano
    1984 Volume 57 Issue 8 Pages 2051-2054
    Published: 1984
    Released: June 27, 2006
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    The adsorption isotherms of various aromatic compounds on an activated carbon or a polystyrene adsorbent in aqueous solutions and basic solutions were investigated. The adsorption isotherms of nonionic compounds and strong anionic electrolytes in the basic solutions were equal to the isotherms in the aqueous solutions. However, the adsorbed amounts of weak anionic electrolytes decreased with ionization in the basic solutions, and the adsorption isotherms of the non-ionized form and the ionized form of all these compounds except phenol could be expressed by the Freundlich equations with the same values of n. The amounts of those weak anionic electrolytes adsorbed at a desired pH could be calculated from the adsorption isotherms of the non-ionized form and the ionized form and the ionization constants.
  • Kohei Urano, Veerapan Chanyasak, Nobuhiko Fujii, Toshiaki Yukawa
    1984 Volume 57 Issue 8 Pages 2055-2059
    Published: 1984
    Released: June 27, 2006
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    Adsorption isotherms for single metal ions(Ca2+, Fe3+, Cu2+, Zn2+, Cd2+, or Pb2+) in acidic solutions at 25 °C on 9 types of commercial chelating resins were obtained. The results could all be expressed by the isotherm equation, Q=Qmax⁄(1+ACM−αCHβ), reported in the preceding paper. The parameters α and β, which indicate respectively the influences of concentrations of metal ion (CM) and hydrogen ion (CH) on the adsorption capacities (Q), were discussed in relation to the properties of the chelating resins and the metal ions.
  • Kohei Urano, Nobuhiko Fujii
    1984 Volume 57 Issue 8 Pages 2060-2063
    Published: 1984
    Released: June 27, 2006
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    Adsorption isotherms for the coexistence of two metal ions (combinations of Zn2+, Cd2+, and Pb2+) in acidic solutions on chelating resins were measured at 25 °C. They were analyzed in relation to the adsorption isotherm equation of a single metal ion, Q=Qmax⁄(1+ACM−αCHβ), as was reported in the preceding paper. It is found that the adsorption isotherms of two metal ions (i and j) in acidic solution on chelating resins can be generally expressed by the equation;
    Qi,j=Qmax⁄{1+AiCi−αiCHβi(1+Ki,jCjαjCH−βj)}
    over wide ranges of concentrations of the metal ion, C, and the hydrogen ion, CH (mol dm−3). Where Qi and Qi,j are the adsorption amounts (m mol/g-dry resin) of i metal ion in the absence and in the coexistence of j metal ion. Qmax is the maximum adsorption amount, α and β are parameters in the adsorption of single metal solution, A and K are correction factors, and subscripts i and j identifing i and j metal ions. The adsorption capacities of two metal ions in acidic solution can be obtained from the isotherms parameters Ai, αi, αj, βi and βj for an individual single metal ion and only one additional parameter Ki,j is needed.
  • Toshio Ogawa, Kiyoshi Mizutani, Motoo Yasuda
    1984 Volume 57 Issue 8 Pages 2064-2068
    Published: 1984
    Released: June 27, 2006
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    The apparent molal volumes (φV), apparent molal adiabatic compressibilities (φKS), and relative viscosities (nr) at 25 °C have been obtained for the following amino acids in aqueous alkali-chloride solutions from measurements of the density, the ultrasonic velocity, and the flow time: glycine, L-alanine, β-alanine, α-aminoisobutyric acid, L-serine, and L-threonine. Viscosity measurements were also carried out in water for reference. The alkali chlorides used were lithium, sodium, and potassium chlorides. The limiting values φVo, φKSo and the extended Jones-Dole viscosity coefficients, B and D, were calculated by a linear extrapolation using the least-squares method. All the φVo, φKSo, and B values obtained in the mixed solvents were larger than the corresponding ones in water, except in a few cases of the B coefficient. The results are discussed in terms of the dehydration effect of the electrolytes upon the amino acids.
  • Yoshiya Kera, Hisateru Imori, Shigeharu Kida, Katsumi Degawa
    1984 Volume 57 Issue 8 Pages 2069-2074
    Published: 1984
    Released: June 27, 2006
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    Vanadium-oxide thin film, which was amorphous, brownish, and transparent, was prepared more conveniently by improving Sekiya-Matsushita’s method by, for instance, decomposing vanadium naphthenate thermally; that is, 10 wt% of a 1-butanol solution of vanadium naphthenate was dropped on slide glass, dried in air, decomposed at 600 °C for 20 min under 0.5 l/min of a N2 stream which was equilibrated with water at 21.5 °C, and then taken out rapidly into the air for cooling. The VO thin film thus prepared usually showed an abrupt change in electric conductivity from 2×10−5 to 1×10−4 Ω−1 at about 60 °C. The electrical feature was greatly affected by the addition of other metal oxides, such as Na2O, TiO2, Cr2O3, MoO3, and ZrO2. Both the conductivity and the gap tended to decrease in the cases of TiO2, Cr2O3, and MoO3, and to increase in ZrO2. On the addition of Na2O, however, the conductivity increased only at temperatures lower than the transition point; thus, the gap decreased greatly, almost disappearing. It was concluded from these facts that the electrical feature of the vanadium-oxide film must be controlled to a great extent by the addition of some compounds of vanadium oxide with the other metal oxides formed at the grain boundary of the VO2 amorphous particles. That is, the larger the conductivity of the compound in the boundary layer, the more clearly the intrinsic feature of the VO2 particles appears, and vice versa.
  • Nobuo Kamiya, Masaaki Matsushima, Hiromu Sugino
    1984 Volume 57 Issue 8 Pages 2075-2081
    Published: 1984
    Released: June 27, 2006
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    The three-dimensional structure of plasminostreptin, a bacterial protein protease inhibitor from Streptomyces antifibrinolyticus, was determined at 2.8Å resolution by the multiple isomorphous replacement technique. A dimer with the molecular weight of 11,402×2 was included in an asymmetric unit of the crystal. The monomer, composed of 109 amino acid residues, consisted of an antiparallel twisted β-sheet with five strands, two short helices, and irregular polypeptide-chain segments. The reactive site of plasminostreptin belonged to one of these irregular polypeptide-chain segments. The two monomers in the dimer were related by a non-crystallographic pseudo-two-fold axis, and the two β-sheets were arranged face-to-face with each other. The averaged angle between the strands of the two β-sheets was approximately 30° clockwise. In spite of 37 amino acid substitutions including the reactive site residues, the tertiary and quaternary structures of plasminostreptin were similar to those of Streptomyces subtilisin inhibitor (SSI). The main-chain conformations of the reactive site of plasminostreptin were similar to those of SSI and other protease inhibitors analysed previously. Moreover, the conformations of the side chain of the evolutionary conservative asparagine in the so-called “secondary contact region” resembled those found in the inhibitors of the pancreatic secretory trypsin inhibitor family.
  • Tsugio Sato, Takashi Goto, Taijiro Okabe, Frank Lawson
    1984 Volume 57 Issue 8 Pages 2082-2086
    Published: 1984
    Released: June 27, 2006
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    The oxidation of iron(II) sulfate with SO2/O2 (sulfur dioxide and oxygen mixtures) was carried out using an air-lift percolator in the temperature range of 25–50 °C and over the pH range of 0–3. Under conditions in which sulfur dioxide is immediately oxidized, the rate of the oxidation of iron(II) is proportional to the flow rate of sulfur dioxide and independent of the flow rate and partial pressure of oxygen, and the concentration of iron(II). The molar ratio of Fe2+ oxidized/SO2 oxidized is 1.3–2 in the pH range of 0.5–2.0. A free-radical chain reaction in which HSO5 oxidizes iron(II) is proposed as the reaction mechanism.
  • Makoto Watanabe, Yoshio Morii, Shoji Sato
    1984 Volume 57 Issue 8 Pages 2087-2090
    Published: 1984
    Released: June 27, 2006
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    Magnesium phosphoramidate–water (1/7) was made by adding an aqueous magnesium chloride solution to an aqueous potassium hydrogenphosphoramidate solution at pH 9.0–9.5. The product was stable at room temperature, while it decomposed on heating. The product decomposed to produce polyphosphates when it was heated in air. The decomposition product heated above 600 °C was magnesium diphosphate. A small amount of imidodiphosphate was made when the phosphoramidate was heated in dried N2.
  • Yukito Murakami, Yoshio Hisaeda, Teruhisa Ohno
    1984 Volume 57 Issue 8 Pages 2091-2097
    Published: 1984
    Released: June 27, 2006
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    The incorporation of hydrophobic vitamin B12 derivatives into the single-compartment vesicles of N,N-didodecyl-Nα-[6-(tyimethylammonio)hexanoyl]-L-alaninamide bromide (N+C5Ala2C12) was found to be primarily concerned with the extent of insolubility of the cobalt complexes in the aqueous bulk phase, while such incorporation into the single-walled vesicles of N,N-ditetradecyl-Nα-[6-(trimethylammonio)hexanoyl]-L-histidinamide bromide (N+C5His2C14) was enhanced by the coordination interaction between the cobalt complex and the imidazolyl group of the lipid. In molecular aggregates formed with hexadecyltrimethylammonium bromide, α-[4-(1,1,3,3-tetramethylbutyl)phenyl]-ω-hydroxypoly(oxyethylene), or N+C5Ala2C12, the alkylation rates of a hydrophobic vitamin B12 with 1-bromo-2-methylpropane and methyl 2-methyl-3-bromopropanoate were much enhanced relative to those in methanol. In the N+C5Ala2C12 vesicle, a two-step mechanism was observed for the alkylation with the latter reagent. The possible origin of such rate enhancement was discussed.
  • Takashi Toki, Masahiro Mikuriya, Hisashi Okawa, Ichiro Murase, Sigeo K ...
    1984 Volume 57 Issue 8 Pages 2098-2105
    Published: 1984
    Released: June 27, 2006
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    1:1 Copper(II) complexes with N,N′-bis(2-hydroxyethyl)malonamide (abbreviated as H4maae), MCu(maae) (M=Ca, Sr, Ba), and 2:1 copper(II) complexes with N,N′-bis(5-amino-3-hydroxypentyl)malonamide and N,N′-bis(5-amino-3-hydroxypentyl)oxamide (abbreviated as H4madpl and H4oxdpl, respectively),[Cu2(madpl)]·3H2O and [Cu2(oxdpl)]·2H2O, were prepared and characterized by elemental analyses, infrared and electronic spectra, and magnetic susceptibilities. The 2:1 complexes exhibit a band at 23.3–27.0×103 cm−1 characteristic of alkoxo-oxygen bridged structure and show a very strong antiferromagnetic interaction, whereas the 1:1 complexes show no such band and their magnetic moments fall in the range of those for ordinary mononuclear copper(II) complexes. The crystal structures of [Cu2(madpl)]·3H2O and BaCu(maae)·7H2O were determined by the single-crystal X-ray diffraction method. The structure of [Cu2(madpl)]·3H2O consists of alkoxo-oxygen bridged binuclear molecules, where madpl4− functions as a sexadentate binucleating ligand with an N2O2N2 donor set. In BaCu(maae)·7H2O, the basic unit is a hetero-metal tetranuclear entity (H2O)2{Ba(H2O)4Cu-(maae)}2 in which the two Ba2+ are linked sharing two H2O and are also bound to alkoxo oxygens of Cu(maae)2−. On the basis of the crystal structures, their spectral properties were discussed.
  • Masanori Sawano, Hideki Yoshifuji, Akira Uehara, Ryokichi Tsuchiya
    1984 Volume 57 Issue 8 Pages 2106-2110
    Published: 1984
    Released: June 27, 2006
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    The photochemical reactions of trans- and cis-[CrX2(AA)2]X in methanol were investigated under the ligand-field band irradiation, where X is Cl or Br ion and AA is en, pn or tn. In the earlier step of irradiation, only trans-to-cis photoisomerization was observed irrespective of diamines. The process of the photoisomerization was reasonably explained in terms of the bond indices calculated on the basis of VC theory. The quantum yields for dichloro complexes were larger than those for dibromo complexes, and the yields increased in the order of pn<en<tn complexes. The photochemistry of cis-[CrCl2(pn)2]Cl was also studied and the difference of the photochemical reactions from the thermochemical reactions was discussed.
  • Takeshi Negoro, Yoshitsugu Ikeda
    1984 Volume 57 Issue 8 Pages 2111-2115
    Published: 1984
    Released: June 27, 2006
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    In the reaction of styrene with chlorine, the added bromide ions were mostly incorporated into the adduct, giving a bromo chloro compound. Tetrabutylammonium dichlorobromate(1–) was found to be an efficient bromochlorinating agent. The reactions of 2-butenes and stilbenes were completely anti stereospecific.
  • Takeshi Negoro, Yoshitsugu Ikeda
    1984 Volume 57 Issue 8 Pages 2116-2120
    Published: 1984
    Released: June 27, 2006
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    The bromochlorinations of 1-phenylpropenes with tetrabutylammonium dichlorobromate(1–) in aprotic solvents (dielectric constants 5–36) were found to be completely anti stereospecific and nonregiospecific, although Markownikoff adduct was mainly formed. In marked contrast, addition of molecular bromine chloride to the same alkenes was found to give nonstereospecific and regiospecific adducts. These results suggest that the addition of bromine chloride in the form of (n-C4H9)4NBrCl2 involves a rate- and product-determining attack of a chloride ion to a three-center bound π complex.
  • Noriyuki Kishii, Koji Araki, Shinsaku Shiraishi
    1984 Volume 57 Issue 8 Pages 2121-2126
    Published: 1984
    Released: June 27, 2006
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    The reaction of 6,6′-dibromo-2,2′-bipyridine with ammonia in an autoclave gave 6,6′-diamino-2,2′-bipyridine (DABP) in more than 80% yields. DABP behaved as a diacidic base in the pH range of 0 to 10 with the conformational changes. DABP formed complexes with Cu(II), Ni(II), Co(II), and Zn(II). The amino groups at 6 and 6′ positions play a role as strong electron-donationg groups and not as coordination sites. pKa values and complex formation constants were estimated.
  • Toru Minami, Takenobu Yamanouchi, Shigehumi Tokumasu, Ichiro Hirao
    1984 Volume 57 Issue 8 Pages 2127-2131
    Published: 1984
    Released: June 27, 2006
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    The condensation of diethyl (ethoxycarbonylmethyl)phosphonate (1a) with cinnamaldehyde in the presence of piperidine gave a 1:1 mixture of diethyl (1E,3E)- (2a) and (1Z,3E)-(1-ethoxycarbonyl-4-phenyl-1,3-butadienyl)phosphonates (2b) in 82% yield, while a similar reaction using diethyl [cyanomethyl- (1b) and methylsulfonylmethyljphosphonates (1c) exclusively gave diethyl (1E,3E)-[1-cyano- (3) and 1-methyl-sulfonyl-4-phenyl-1,3-butadienyl]phosphonates (4) in 78% and 93% yields, respectively. The reaction of the butadienylphosphonates 2–4 with dimethyloxosulfonium methylide (5) gave mixtures of (E)- and (Z)-(1-substituted 2-styrylcyclopropyl)phosphonates 7–9 in good yields. Similar treatment of the butadienylphosphonate 2 with phosphonium ylides 16a–c led to (3-substituted 1-ethoxycarbonyl-2-styrylcyclopropyl)phosphonates 17a–c in moderate yields. Reduction and oxidation of 7 were studied. The reaction of the phosphonates, 2 and 4, with ketone enolates and ketones resulted in the formation of unexpected olefins 22–24 and dienes 20a, b. The reaction mechanism is discussed.
  • Yoshito Takeuchi, Takashi Bando, Shuji Tomoda, Yujiro Nomura
    1984 Volume 57 Issue 8 Pages 2132-2134
    Published: 1984
    Released: June 27, 2006
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    Carbon-13 chemical shifts for a series of 5-(4-substituted benzylidene)-2,3,4,5-tetrahydropyridines were determined. The substituent chemical shifts (SCS) were correlated with σI and σRo values by means of DSP and DSP-NLR analysis. It was found that as a substituent the C=C–C=N moiety is as mild as C=C and that the former can be approximated as a vinylogue of the C=N moiety. C-13 lanthanoid-induced shifts (LIS) of the parent compound were also discussed.
  • Masao Shiozaki, Noboru Ishida, Tetsuo Hiraoka, Hiroshi Maruyama
    1984 Volume 57 Issue 8 Pages 2135-2139
    Published: 1984
    Released: June 27, 2006
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    Treatment of (2R,3R)-N-(2,4-dimethoxybenzyl)-N-[bis(ethoxycarbonyl)methyl]-2-bromo-3-hydroxybutyramide (5) with DBU yielded the bicyclic β-actam 13 by a direct cyclization, and its diastereoisomer 14 and the γ-lactam 15 via the trans-epoxide 6. The same treatment of (2S,3R)-isomer (11) gave the direct cyclization product 14 in 93% yield. On the other hand, reaction of 5 and 11 with sodium hydride afforded the 2-azetidinone derivatives (mainly 14 (23%) from 5, and 19 (75%) from 11, respectively) via the corresponding epoxides 6 and 12.
  • Kuniaki Itoh, Hiroshi Yamada, Akira Sera
    1984 Volume 57 Issue 8 Pages 2140-2143
    Published: 1984
    Released: June 27, 2006
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    Irradiation of 1,4-dibromo-2,5-piperazinedione (1) with olefins in acetonitrile gave mixtures of addition products (1:1-adducts and 1:2-adducts). Addition of 1,2-epoxybutane (a hydrogen bromide scavenger) resulted in enhanced yields of the adducts. Structures of the adducts were elucidated and a reaction mechanism is discussed.
  • Seiji Shinkai, Yoshihiro Honda, Kaori Ueda, Osamu Manabe
    1984 Volume 57 Issue 8 Pages 2144-2149
    Published: 1984
    Released: June 27, 2006
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    Thiacrown ethers with a photofunctional azolinkage were synthesized to control their binding ability by an on-off light switch: They are the N2S4 crowns capped with 2,2′-azopyridine (1) or azobenzene (2). The cis-trans isomerism occurred reversibly by photoirradiation. The binding ability, evaluated by solvent extraction, showed that (i) the order of the affinity for Hg2+ is N,N′-dibenzoylated N2S4 crown (4)≈photoirradiated 1>trans-1>photoirradiated 2>trans-2, (ii) neither trans-2 nor 4 shows significant affinity toward heavy metal ions such as Cu2+, Co2+, Ni2+, and Pb2+, (iii) trans-1 has a slight affinity (Ex% 5.9%) for Cu2+,whereas photoisomerized 1 shows the remarkably enhanced affinity (Ex% 93.9%) with Cu2+, and (iv) such light-induced improvement is not seen for 2. The relatively poor binding ability of 2 and 4 is rationalized in terms of the unfavorable inside-out conformation of the N2S4 crown ring. The remarkable affinity change in cis-1 is probably due to the cooperative contribution of the thiacrown and the azopyridine cap constructing a new ligand site. 1 was used as a carrier for Cu2+ transport through a liquid membrane. It was found that the rate is efficiently accelerated by UV-light irradiation.
  • Seiji Shinkai, Kenichi Inuzuka, Kenzo Hara, Takaaki Sone, Osamu Manabe
    1984 Volume 57 Issue 8 Pages 2150-2155
    Published: 1984
    Released: June 27, 2006
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    Polyether ionophores with redox-functional thiol groups were synthesized: they are a diaza-18-crown-6 with a disulfide cap that exhibits redox-responsive interconversion between crown(1red) and cryptand(1ox) and tri- and tetra(oxyethylene)s having a mercapto and an 8-quinolyl group as their terminal groups that feature redox-responsive interconversion between monopodands (2red) and dipodands (2ox). For Na+ 1red and 1ox showed a similar ion affinity, but 1ox bound K+, Rb+, and Cs+ more efficiently than 1red because of the coordination of the cap oxygens to the complexed metal cations. The difference was rationalized by such that “K+ Rb+ and Cs+ also) perches on the crown ring whereas Na+ nests in it,” 2ox showed, in most cases, the ion affinity significantly higher than corresponding 2red, indicating the cooperative action of the two poly(oxyethylene) chains on the ion-binding. The rate of K+ transport with 2red across a liquid membrane was very slow but 2ox carried K+ more efficiently. It was found that the rate of K+ transport started with is efficiently accelerated by the addition of I2. This is due to the redox-switch of the carrier from 2red to 2ox. These results suggest that the redox-functionalized ionophores provide novel applications of ion-extraction and ion-transport.
  • Masaaki Ueki, Kozo Shinozaki
    1984 Volume 57 Issue 8 Pages 2156-2161
    Published: 1984
    Released: June 27, 2006
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    Synthesis of bis[N,N-diallyl-[D-Ala2, L-Leu5]-enkephalyl]cystine, which is expected to be a selective opioid δ-receptor antagonist, was studied. The mercapto group of cysteine was protected by the dimethylphosphinothioyl(Mpt) group. For the removal of this group without damaging the allyl moiety, new mild removal conditions by use of KF/18-crown-6 in a solvent mixture of acetonitrile–methanol are proposed. Bis[D-Ala2, L-Leu5]-enkephalyl]cystine was also prepared in a similar manner.
  • Haruyo Sato, Shinzo Imamura, Yukishige Kitano, Teruo Kanda, Tamaichi A ...
    1984 Volume 57 Issue 8 Pages 2162-2166
    Published: 1984
    Released: June 27, 2006
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    The structure of the dimeric oxime compound obtained by the reaction of 2-chlorocyclohexanone oxime or 1-chloro-2-nitrosocyclohexane dimer with stoichiometrical ammonia was established to be 14-oxa-7,15,16-triazatetracyclo[11.2.1.01,6.08,13]hexadecan-16-ol by spectroscopic methods and X-ray crystallography; the result leads to a revision of the previously proposed structure, bis(2-hydroxyiminocyclohexyl)amine.
  • Toshio Sato, Kazuhisa Matsumoto, Toru Abe, Isao Kuwajima
    1984 Volume 57 Issue 8 Pages 2167-2170
    Published: 1984
    Released: June 27, 2006
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    Reactions of 2-chloroacyltrimethylsilanes with Grignard reagents have been examined. Thus, treatment with methylmagnesium iodide affords the corresponding 3-(trimethylsilyl)-2-alkanones through an initial addition followed by removal of chloride anion and 1,2-rearrangement of silyl group. In contrast, the reaction proceeds with 2 equiv of the Grignard reagents bearing β-hydrogen to give 2-(trimethylsilyl)-1-alkanols, where initial reduction of the silylcarbonyl group followed by such rearrangement and addition of the Grignard reagents to the resulting 2-(trimethylsilyl)alkanals have been proposed.
  • Sotaro Miyano, Masayoshi Nawa, Akira Mori, Harukichi Hashimoto
    1984 Volume 57 Issue 8 Pages 2171-2176
    Published: 1984
    Released: June 27, 2006
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    Axially dissymmetric bisphosphine ligands, (R)- and (S)-2,2′-bis(diphenylphosphinoamino)-1,1′-binaphthyl (BDPAB) and (R)-2,2′-bis[N-(diphenylphosphino)methylamino]-1,1′-binaphthyl (Me-BDPAB) were conveniently prepared from 2,2′-diamino-1,1′-binaphthyl. The rhodium(I)-catalyzed asymmetric hydrogenation of α-acylamidoacrylic acids and esters gave the corresponding amino acids of up to 95% optical purity. The sign of the centro-chirality of the product amino acids was always the same to that of the axial chirality of the ligand in both cases of BDPAB and Me-BDPAB.
  • Yukihisa Fujita, Yukinao Noda
    1984 Volume 57 Issue 8 Pages 2177-2183
    Published: 1984
    Released: June 27, 2006
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    The thermal denaturation of ribonuclease A(RNase A) and chymotrypsinogen A in aqueous solutions of ethylene glycol (EG) was investigated by differential scanning calorimetry at several pH values in the acidic region. The calorimetric enthalpies of denaturation, ΔHd, of these proteins increased monotonously with increasing the EG concentration under all the conditions studied. These proteins, however, differed from one another in the variation of the denaturation temperature, Td, with the addition of EG. The Td of chemotrypsinogen decreased slightly with an increase in EG concentration under all the conditions, producing a greater effect at high pH. The Td of RNase A, on the other hand, was almost independent of the EG content at pH 3.8, while at pH 2 and 3, the Td increased slightly with increasing the EG concentration and decreased slightly at pH 5. That is, EG stabilized or unstabilized these proteins against thermal denaturation, in a way which seemed to be dependent on temperature rather than the pH. The standard thermodynamic parameters for denaturation, ΔG°, ΔH°, and ΔS°, which were calculated using Td and ΔH° and assuming a constant heat capacity change, suggested that the slight increase or decrease in ΔG° induced by EG is attributed to whether ΔH° increases as much as ΔS° does or not. These results may be explained on the basis of the effect of EG on the solvation around hydrophobic groups of the protein. The EG effect may depends on the structural properties of proteins such as hydrophobicity and polarity, as well as on temperature.
  • Kiyoshi Tanaka, Hideyuki Masuda, Keiryo Mitsuhashi
    1984 Volume 57 Issue 8 Pages 2184-2187
    Published: 1984
    Released: June 27, 2006
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    The regio- and stereoselectivity of the cydoadditions of trifluoroacetonitrile oxide (1) with olefins and acetylenes were described. The oxide 1, generated in situ from trifluoroacetohydroximoyl bromide etherate in the presence of triethylamine, reacted with various monosubstituted olefins and acetylenes to give exclusively 5-substituted 3-trifluoromethyl-2-isoxazolines and -isoxazoles, respectively, whereas 1 cyclized with 1,2-disubstituted olefins and acetylenes to result in the formation of a mixture of two regioisomeric products. On the other hand, the cycloaddition of 1 with (Z)-β-methylstyrene afforded a mixture consisting of two regioisomeric isoxazolines retaining Z-configuration and one diastereoisomeric isoxazoline.
  • Kin-ya Akiba, Yoshio Negishi, Naoki Inamoto
    1984 Volume 57 Issue 8 Pages 2188-2192
    Published: 1984
    Released: June 27, 2006
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    Dialkyl 2-(o-acylbenzoyl)-1,2-dihydro-1-isoquinolyl-phosphonates (1) were prepared by reactions of isoquinoline, o-acylbenzoyl chloride, and trialkyl phosphites. Treatment of 1 with lithium diisopropylamide gave 13-substituted 8H-dibenzo[a,g]quinolizin-8-ones by intramolecular Wittig-Horner reaction. Especially, 13-alkoxy and dimethylamino derivatives were obtained in good yields. A similar reaction of dimethyl 1-[o-(methoxycarbonyl)benzoyl]-1,2-dihydro-2-quinolylphosphonate was also described.
  • Kenjiro Tanimura, Tetsuo Kato, Michinori Waki, Sannamu Lee, Yasushi Ko ...
    1984 Volume 57 Issue 8 Pages 2193-2197
    Published: 1984
    Released: June 27, 2006
    JOURNALS FREE ACCESS
    (2R,3R)-Phenylalanine-2,3-d2 (D-Phe*) was synthesized through catalytic reduction of cyclo(-(Z)-2,3-dehydrophenylalanyl-D-alanyl-) under an atmosphere of 2H2 and successive acid hydrolysis in the yield of 80% in high chiral induction. The D-Phe* thus obtained was used for synthesis of [D-Phe*4,4′] gramicidin S (GS*). The 1H NMR spectrum of GS* in DMSO-d6 showed a sharp singlet at 2.98 ppm for the (3S)-proton of D-Phe* residue. It has been proposed that among rotamers of D-Phe aromatic side chain in GS the one with κ1=180° is predominant. The present observation provides sound evidence for assignments of D-Phe β-protons based on the proposal.
  • Hirohisa Tanaka, Gen-etsu Matsubayashi, Toshio Tanaka
    1984 Volume 57 Issue 8 Pages 2198-2202
    Published: 1984
    Released: June 27, 2006
    JOURNALS FREE ACCESS
    The [Cation]+ATCNQ type salts were prepared, where ATCNQ is (4-dicyanomethyl-1-pyridinio)dicyanomethanide anion, so-called AzaTCNQ anion, and [Cation]+ are N-alkylpyridinium, 4-cyano-N-alkylpyridinium, (4-methyl-1-pyrazinio)dicyanomethanide, N-alkylquinolinium (alkyl=Me and Et), N-methylacridinium, and N-methylphenazinium. Electrical resistivities of these salts as compacted samples fall in the range 106–109 Ωcm at 25 °C. The mixed ATCNQ/TCNQ\ ewdot salts (TCNQ\ ewdot=7,7,8,8-tetracyano-p-quinodimethan radical anion) of N-alkylpyridinium and -quinolinium cations also were prepared; [Cation]+ (ATCNQ)0.1(TCNQ\ ewdot)0.9([Cation]+=N-methylpyridinium, N-ethylpyridinium, and N-ethylquinolinium) and [N-methylquinolinium]+(ATCNQ)0.17(TCNQ\ ewdot)0.83 whose electrical resistivities (104–106 Ωcm at 25 °C) are somewhat smaller than those of the corresponding TCNQ\ ewdot salts. Stackings of ATCNQ and TCNQ\ ewdot anions are discussed on the basis of electronic reflectance and ESR spectra. The [Cation]+ATCNQ salts react with iodine in hexane to give [Cation]+ATCNQ·Ix ([Cation]+=N-methyl- and N-ethylpyridinium and -quinolinium; x=3.2–3.9). They exhibit electrical resistivities of 104–106 Ωcm at 25°C, which are lower by the 102–103 order than the resistivities of the undoped [Cation]+ATCNQ salts.
  • Masaru Shin, Ken Inouye, Hideo Otsuka
    1984 Volume 57 Issue 8 Pages 2203-2210
    Published: 1984
    Released: June 27, 2006
    JOURNALS FREE ACCESS
    Triostin A, a cyclic octadepsipeptide, was synthesized with Z–D-Ser[Boc–Ala–MeCys(Bzl)–MeVal]–OH and Z–D-Ser[H–Ala–MeCy(Bzl)–MeVal]–OTce as key intermediates. The synthetic antibiotic was compared with natural triostin A in terms of chromatographic behaviors, NMR spectra, and antimicrobial activity to establish their identity. The NMR data on S,S′-dibenzyldihydrotriostin A showed that this intermediate lacking the disulfide linkage also existed as two conformers in chloroform. This observation excludes the possibility that the conformer equilibrium known to occur with triostin A is a consequence of the reversed chirality of the disulfide bond.
  • Masaru Shin, Ken Inouye, Naoki Higuchi, Yoshimasa Kyogoku
    1984 Volume 57 Issue 8 Pages 2211-2215
    Published: 1984
    Released: June 27, 2006
    JOURNALS FREE ACCESS
    Nortriostin A, which is an analog of a cyclic octadepsipeptide antibiotic triostin A and contains one cystine and two valine residues substituted for the N,N′-dimethylcystine and N-methylvaline residues of the antibiotic, was synthesized with Z–D-Ser[Boc–Ala–Cys(MeBzl)–Val]–OH and Z–D-Ser[H–Ala–Cys(MeBzl)–Val]–OTce as key intermediates. The synthetic analog showed no antimicrobial activity at a concentration of 100 μg/ml and was found to exist as a single structure in solution as examined by 1H-NMR spectroscopy. The latter observation suggests that the conformer equilibrium known to occur with triostin A is a consequence of the presence of N-methyl peptide bonds in the antibiotic molecule.
  • Tohru Hayakawa, Koji Araki, Shinsaku Shiraishi
    1984 Volume 57 Issue 8 Pages 2216-2218
    Published: 1984
    Released: June 27, 2006
    JOURNALS FREE ACCESS
    The 1,3-dipolar cycloaddition reactions of nitrile oxides with methoxy p-benzoquinones are discussed in terms of FMO theory. The unusual reaction pattern of methoxy p-benzoquinones with nitrile oxides is interpreted by considering both antibonding secondary orbital interaction and SHOMO(quinone)–LUMO (nitrile oxide) interaction.
  • Gaku Yamamoto, Michinori Oki
    1984 Volume 57 Issue 8 Pages 2219-2223
    Published: 1984
    Released: June 27, 2006
    JOURNALS FREE ACCESS
    Energy barriers to rotation about the bridgehead-to-substituent bond in 9-ethyl-, 9-allyl-, and 9-benzyltriptycene derivatives with varying degrees of peri-substitution were studied by dynamic NMR and in one case by the classical kinetic method. In the singly peri-substituted series (1,4-dimethoxy derivatives) the barrier decreases in the order of 9-ethyl>9-allyl>9-benzyl. In the doubly peri-substituted series (1,8-dichloro derivatives) the barriers are alike irrespective of the 9-substituent, and in the triply peri-substituted series (1,4-dimethyl-8,13-dichloro derivatives) the barrier decreases in the order of 9-benzyl>9-allyl>9-ethyl. The reversal of the trend on the change in peri-substitution patterns may be explained on the basis of the change in the interaction between the peri- and 9-substituents in both the ground and the transition states.
  • Michinori Oki, Manabu Ohira, Yasuhiro Yoshioka, Toshiari Morita, Hiros ...
    1984 Volume 57 Issue 8 Pages 2224-2229
    Published: 1984
    Released: June 27, 2006
    JOURNALS FREE ACCESS
    Rates of proton exchange between p-substituted N,N-dibenzylanilinium ion and chloride ion in chloroform-d and acetonitrile-d3 were determined by the dynamic NMR technique. Comparison of the kinetic proton affinity of the anilines in the aprotic solvents with the proton affinity of anilines in the gas phase and the basicity in water revealed that they could be linearly correlated. The feature of the kinetic data was a large positive entropy of activation which can be ascribed to the change from an ionic ground state to a covalent transition state. The entropy of activation was somewhat smaller in acetonitrile-d3 than in chloroform-d. This was attributed to the change in the stage of the transition state for the exchange. A small amount of water which could not be removed easily from the aprotic solvents was proved not to harm the results.
  • Michikazu Yoshioka, Satoshi Aoki, Toshio Shimizu, Tadashi Hasegawa
    1984 Volume 57 Issue 8 Pages 2230-2233
    Published: 1984
    Released: June 27, 2006
    JOURNALS FREE ACCESS
    2-Benzoylalkanoates 1 undergo photoreduction with 2-propanol. The photoreduction products are classified into three types according to their origin: the homo-pinacol-type products 2, 5, 7, and 8, the mixed-pinacol-type product 3, and the β-hydroxy ester 6. The product distribution is affected by α-methyl substitution. The α-methyl substitution decreases the percentage of the homo-pinacol-type products and increases the percentage of the β-hydroxy ester.
  • Tadashi Shiraiwa, Akihiko Ikawa, Keiji Sakaguchi, Hidemoto Kurokawa
    1984 Volume 57 Issue 8 Pages 2234-2237
    Published: 1984
    Released: June 27, 2006
    JOURNALS FREE ACCESS
    An alkaline solution containing L-phenylalanine (L-Phe) and one of DL-valine, DL-leucine, and DL-isoleucine is allowed to selectively form a precipitate composed of L-Phe and the aliphatic D-amino acid by adjusting the pH of initial solution to around 5.5 with hydrochloric acid. 1H NMR spectra in deuterium oxide, elemental analyses, and infrared spectra of the precipitates indicate that they are adducts of the aliphatic D-amino acid and L-Phe in the molar ratio of 1:1. The free aliphatic DL-amino acids with high optical purity (84–100%) may be recovered from the adducts in 49–63% yield. An attempt was made to obtain both the aliphatic D- and DL-amino acids by using an aqueous solution containig the aliphatic DL-amino acid and L-Phe as an initial solution. The aliphatic L-amino acids obtained had optical purity of 47–85%.
  • Norio Takeuchi
    1984 Volume 57 Issue 8 Pages 2238-2242
    Published: 1984
    Released: June 27, 2006
    JOURNALS FREE ACCESS
    For the manufacture of sodium hydroxide and nitric acid a new thermochemical process of splitting sodium nitrate has been proposed which consists of (i) splitting of sodium nitrate by iron(III) oxide, (ii) hydrolysis of sodium ferrate, and (iii) absorption of nitrogen dioxide into water. Key reactions (i) and (ii) have experimentally been verified. The overall heat requirement for the process is discussed on the basis of a material and heat flow-sheet of the process constructed.
  • Kenzo Hiraoka, Masaji Nara
    1984 Volume 57 Issue 8 Pages 2243-2246
    Published: 1984
    Released: June 27, 2006
    JOURNALS FREE ACCESS
    The transmission of low-energy electrons (0–15 eV) through thin films of benzene, toluene, pyridine, aniline, styrene, and cyclohexene was studied. The electron transmission spectra of all the aromatic compounds studied are like each other in their forms. The energies of several prominent peaks in the electron transmission spectra are in good agreement with those of temporary anion states measured in the gas phase. It is suggested that vacant orbitals of free molecules form conduction bands in molecular crystals.
  • Susumu Kuwabata, Hiroshi Yoneyama, Hideo Tamura
    1984 Volume 57 Issue 8 Pages 2247-2253
    Published: 1984
    Released: June 27, 2006
    JOURNALS FREE ACCESS
    Polypyrrole films prepared by anodic polymerization of pyrrole on Pt or SnO2-coated glass show redox behavior in aqueous electrolyte solutions containing a supporting electrolyte alone. Transfer of electrolyte anions into and from the film is involved in the redox reaction similarly with acetonitrile solutions already reported. Insertion of divalent anions into the film occurs in two steps but that of monovalent anions in one step, as judged from corresponding cyclic voltammograms. The change in film color which occurs in the redox reaction of the film was investigated in detail as a function of electrode potential and the charge consumed in the redox reaction. Polypyrrole is a promising material for electrochromic display devices.
  • Akira Kitani, Jinko Izumi, Jun Yano, Yasuyuki Hiromoto, Kazuo Sasaki
    1984 Volume 57 Issue 8 Pages 2254-2257
    Published: 1984
    Released: June 27, 2006
    JOURNALS FREE ACCESS
    Basic behaviors and properties of polyaniline(PA) deposited anodically on platinum electrodes have been studied on the following points. 1) Effect of the mode of electrolysis and supporting electrolytes in the film forming process. 2) Characteristics of charging-discharging processes. 3) Electric conductivity and elemental composition of PA. The different modes of electrolysis do not affect the characteristics of the PA electrode obtained. The growth rate of PA film is 2.7–2.8 times faster in sulfuric acid than in perchloric, nitric or hydrochloric acid. It is indicated that there are two types of doping; one is associated with the acid-base equilibrium between amino or imino group in the film and proton in the solution and the other is associated with the excess charge in the film produced by anodic oxidation. The electric conductivity of PA markedly decreases by the immersion in alkali solutions. The release of doped anion from PA by treating with an alkali solution is confirmed by the elemental analysis. The amount of anions occluded by the electrochemical doping process is determined to be 0.25–0.29 per monomer unit.
  • Masashi Tanaka, Kohji Kamiya, Jiro Tanaka, Shizuaki Murata
    1984 Volume 57 Issue 8 Pages 2258-2260
    Published: 1984
    Released: June 27, 2006
    JOURNALS FREE ACCESS
    The polarized reflection spectra of (DBTTF)3·SnBr6 complex have been measured and the absorption spectra have been determined by the simulation of the observed reflection spectra. The 4000 cm−1 band polarized parallel to the stacking axis has been assigned to the charge resonance(CR) band. The theoretical analysis of the electronic structure of (DBTTF)3·SnBr6 complex has been made for the explanation of the energy and absorption intensity of the CR band.
  • Michiya Itoh, Yoshihisa Fujiwara
    1984 Volume 57 Issue 8 Pages 2261-2265
    Published: 1984
    Released: June 27, 2006
    JOURNALS FREE ACCESS
    The enhanced fluorescence of several 1,3-bichromophoric propanes in aqueous cyclodextrin solutions has been investigated by the steady-state fluorescence spectra and fluorescence lifetimes. 1-(9,10-Dicyano-2-anthryl)-3-(1- and 2-naphthyl)propanes exhibit the intramolecular charge transfer complex fluorescence generated in the ground state in the presence of γ-cyclodextrin. Two bichromophoric propanes, 1,3-di-2-naphthylpropane and 1-(1-naphthyl)-3-(2-naphthyl)propane, in the aqueous β- and γ-cyclodextrin solutions show not only the intramolecular excimer but also the ground state complex fluorescences, though the ground state complex formation of dinaphthylpropane has never been observed in the homogeneous solution even at low temperature. The intramolecular interactions in the ground and excited states seem to be attributable to their intramolecularly geometrical restriction in the extraordinary nonpolar cavity of the cyclodextrins.
  • Joji Kuniya, Kunishige Naito, Shinsuke Takei
    1984 Volume 57 Issue 8 Pages 2266-2270
    Published: 1984
    Released: June 27, 2006
    JOURNALS FREE ACCESS
    Organomercury(II)(RHg+, R; ethyl, n-propyl, n-butyl) forms two kinds of water-soluble complexes, RHgq and RHg(q)(OH), with 8-quinolinol(oxine Hq). These complex-formation reactions are studied by means of spectrophotometry, and the formation constants of these complexes, RHgOH, RHgOAc, and RHg(OH)(OAc), in 4%(v/v) ethanol at the ionic strength of 0.1 are determined. Reliable results are obtained for ethylmercury(II) and n-propylmercury(II) complexes.
  • Takao Sugimoto, Kunishige Naito, Shinsuke Takei
    1984 Volume 57 Issue 8 Pages 2271-2275
    Published: 1984
    Released: June 27, 2006
    JOURNALS FREE ACCESS
    The extraction of organomercury(II)(RHg+, R; ethyl, n-propyl, n-butyl, phenyl) with 8-quinolinol into benzene has been studied by means of spectrophotometry. This study confirmed that there was no co-extraction of electrically neutral species RHgOH by its investigation of the effect of the pH on the extraction of ethylmercury(II) chloride into benzene. Moreover, it was found that RHg+ forms 1:1 complexes with both HPO42− and PO43−. The formation constants of these complexes and of hydroxo complexes have been determined.
  • Akio Murai, Shingo Sato, Tadashi Masamune
    1984 Volume 57 Issue 8 Pages 2276-2281
    Published: 1984
    Released: June 27, 2006
    JOURNALS FREE ACCESS
    The synthetic procedure leading to preparation of representative compounds, (±)-solavetivone and (±)-hinesol, of two classes of spirovetivanes, is described. The procedure involves Diels-Alder reaction of 4-substituted 5,6-dihydro-3,5-dimethylanisoles with methyl acrylate and π-cyclization of 4-(2-mesyloxyethyl)-4-prenyl-2-cyclohexen-1-one as key steps (Scheme 1).
  • Akio Murai, Shingo Sato, Tadashi Masamune
    1984 Volume 57 Issue 8 Pages 2282-2285
    Published: 1984
    Released: June 27, 2006
    JOURNALS FREE ACCESS
    An alternative and efficient synthesis of the title compounds is described. The synthesis involves cycloaddition of 2-methylene-4-methoxy-6-methyl-4-cyclohexenylacetonitrile with methyl vinyl ketone as a key step.
  • Akio Murai, Shingo Sato, Tadashi Masamune
    1984 Volume 57 Issue 8 Pages 2286-2290
    Published: 1984
    Released: June 27, 2006
    JOURNALS FREE ACCESS
    The total synthesis of (±)-15-norsolavetivone, a key intermediate in the synthesis of oxygenated spirovetivane stress metabolites, is described.
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