Bulletin of the Chemical Society of Japan
Online ISSN : 1348-0634
Print ISSN : 0009-2673
ISSN-L : 0009-2673
Volume 53 , Issue 6
Showing 1-50 articles out of 74 articles from the selected issue
  • Hidetoshi Karasawa, Rei Yugeta, Shin Sato
    1980 Volume 53 Issue 6 Pages 1479-1488
    Published: 1980
    Released: April 19, 2006
    JOURNALS FREE ACCESS
    The γ-ray induced oxidation of aromatic hydrocarbons has been studied in liquid dinitrogen oxide, mainly at −18°C. Various mixing ratios of dinitrogen oxide and four aromatic hydrocarbons have been examined. The main oxygen-containing products observed were the corresponding phenols and benzyl alcohols. The kinetic analysis showed that ionic species, probably N2O ions, are the main precursors at low mole fractions of dinitrogen oxide and that oxygen atoms become important with an increase in the mole fraction. 1-Butene was used as a scavenger of oxygen atoms. The following rate constant ratios were obtained for the reactions of oxygen atoms and N2O ions: k(O+toluene)/k(O+1-butene)=0.02, k(O+toluene)/k(O+benzene)=2.0, and k(N2O+1-butene)/k(N2O+toluene)=2.5. The relative rates for the formation of the corresponding phenols and benzyl alcohols through ionic reactions from aromatic hydrocarbons were obtained as follows: benzene, 1.0; toluene, 2.5; p-xylene, 2.2; 1,3,5-trimethylbenzene, 3.1. These values are quite different from the relative rate constants of the reactions of oxygen atoms with these aromatic hydrocarbons.
  • Hiroshi Yokoi, Masamoto Iwaizumi
    1980 Volume 53 Issue 6 Pages 1489-1492
    Published: 1980
    Released: April 19, 2006
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    The π-π interaction of octaethylporphyrincopper(II) (Cu(OEP)) with π acceptors has been investigated in solution and in magnetically-diluted crystals by ESR, and the perpendicular components of the ESR parameters for Cu(OEP) in various states have also been determined with considerable accuracy. It has been revealed that, upon the formation of charge-transfer complexes between Cu(OEP) and π acceptors, the g values decrease slightly, the copper hyperfine coupling constants remain almost unchanged, and the absolute values of the nitrogen superhyperfine coupling constants increase slightly. Accompanying changes in the electronic structure around the copper ion have been discussed. The ESR parameters of Cu(OEP) doped in Ni(OEP) have been noted to depend significantly upon the polymorphism of the diluent.
  • Masaharu Oguni, Takasuke Matsuo, Hiroshi Suga, Syûzô Seki
    1980 Volume 53 Issue 6 Pages 1493-1500
    Published: 1980
    Released: April 19, 2006
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    The heat capacities of pinacol hexahydrate and its deuterate analogue were measured in the temperature region between 13 and 260 K. A phase transition was found and the temperature of transition was determined to be 192.14 K for the hydrate and 191.17 K for the deuterate, respectively. The enthalpy and entropy of the transition were estimated to be 924 J mol−1 and 5.10 J K−1 mol−1 for the hydrate and 944 J mol−1 and 5.28 J K−1 mol−1 for the deuterate. The transition was interpreted as the order-disorder change of the orientations of the pinacol molecule. Besides the phase transitions, an additional anomaly was found around 150 K for the hydrate and two around 130 K and around 160 K for the deuterate, respectively. All of them are relaxational in their characteristics and interpreted as glass transitions due to freezing of reorientational motions of the water molecule and the pinacol molecule. The transition temperature and the activation enthalpy for the higher glass transition of the deuterate were estimated to be 167.2 K and (34±4) kJ mol−1, respectively.
  • Yuji Ohashi, Yoshio Sasada, Seiji Takeuchi, Yoshiaki Ohgo
    1980 Volume 53 Issue 6 Pages 1501-1509
    Published: 1980
    Released: April 19, 2006
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    The structure of [(S)-1-cyanoethyl][(S)(−)-α-methylbenzylamine]bis(dimethylglyoximato)cobalt(III) has been determined by X-ray analysis at 293 K and 173 K. The crystal is monoclinic, the space group being P21, Z=2, with a=8.768(2), b=13.356(2), c=9.538(3) Å, and β=96.73(3)° at 293 K, and a=8.617(4), b=13.222(4), c=9.517(7) Å, and β=96.26(7)° at 173 K. The structure was deduced by the heavy-atom method and was refined by the block-diagonal least-squares method to the final R values of 0.051 and 0.060 for 1878 and 1848 observed reflections at 293 K and 173 K respectively. The bis(dimethylglyoximato)cobalt moiety is twisted in the opposite way from that of [(R)-1-cyanoethyl][(S)(−)-α-methylbenzylamine]bis(dimethylglyoximato)cobalt(III). This supports the proposal that the asymmetry of the optically active amine is transferred into the substrate through the twist of the bis(dimethylglyoximato) cobalt moiety in the step of the σ-bond formation.
  • Norio Ohtomo, Kiyoshi Arakawa
    1980 Volume 53 Issue 6 Pages 1510-1513
    Published: 1980
    Released: April 19, 2006
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    The structure factor Sm(Q) for liquid acetyl chloride at room temperature has been determined in the range Q, 0.9–27 Å−1, by means of the time-of-flight (TOF) neutron diffraction method using the electron linear accelerator (LINAC). The structural parameters of CD3COCl, bond distances, bond angles, and rms amplitudes, in liquid phase have been determined by a comparison of calculated curves with observed data, and it has been concluded that a molecule within the liquid takes an essentially identical conformation as a rotational isomer with that in gaseous phase, which was determined by microwave spectroscopy.
  • Noriaki Hirayama, Kunikatsu Shirahata, Yuji Ohashi, Yoshio Sasada
    1980 Volume 53 Issue 6 Pages 1514-1518
    Published: 1980
    Released: April 19, 2006
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    Fortamine, L-3-amino-1-methoxy-6-methylamino-1,3,6-trideoxy-chiro-inositol, is a component of fortimicins which are potent aminocyclitol antibiotics. The space group is P21 with a=9.454(1), b=6.6957(8), c=7.622(1) Å, β=95.93(2)°, and two C8H18N2O4’s per unit cell. The structure was solved by direct methods, least-squares refinement using 932 reflexions giving the final R value of 0.033. The ring conformation of fortamine is closer to the ideal chair form than that of the fortamine moiety in fortimicin B. The strain caused by the intramolecular hydrogen bond and glycosidic bond in fortimicin B is released in fortamine.
  • Hisaharu Hayashi, Saburo Nagakura
    1980 Volume 53 Issue 6 Pages 1519-1522
    Published: 1980
    Released: April 19, 2006
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    The Norrish type II reaction of valerophenone was studied by the ns-laser photolysis technique, the fourth harmonic (266 nm) of a Q-switched Nd: YAG laser being used as an exciting light source. Transient absorptions due to the triplet state and 1,4-biradical of valerophenone were observed in both polar and nonpolar solvents. Quenching experiments with cis-1,3-pentadiene were also carried out. Transient absorptions due to the biradical were observed in the 350–300 nm region with the lifetimes of 103 ns (in methanol), 99 ns (in 2-propanol), 71 ns (in acetonitrile), and 31 ns (in 1,2-dichloroethane). Transient absorptions due to the triplet state were also observed in the 440–300 nm region.
  • Koichiro Miyajima, Hiromitsu Yoshida, Junko Maetani, Masayuki Nakagaki
    1980 Volume 53 Issue 6 Pages 1523-1529
    Published: 1980
    Released: April 19, 2006
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    The surface tensions of decyl-, tetradecyl-, and hexadecyl-trimethylammonium bromides were measured in the aqueous solutions of potassium bromide (KBr) and guanidinium bromide (GuBr). The critical micelle concentrations (CMC’s) of the above surfactants decreased with increase of the concentration of KBr, while the CMC’s showed minimum values in the aqueous GuBr solution, as the concentration of GuBr increased. The Langmuir coefficient, KC, increased with decrease of the CMC. The influence of the salts on the surface tension and the micellization were well described in terms of the activity of the surfactant calculated by combining the Debye-Hückel law and Setschenow’s equation.
  • Hajime Watanabe, Hiroyuki Horiguchi, Soji Tsuchiya
    1980 Volume 53 Issue 6 Pages 1530-1536
    Published: 1980
    Released: April 19, 2006
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    Distributions of vibrationally excited HF produced by Hg-photosensitized reactions of fluoroethylenes are determined by means of the IR emission measurement of HF fundamentals. The distributions are almost of Boltzmann type with temperatures of 11400, 13700, 7200, 5700, 5700, and 2200 K for respective parent molecules of CH2=CHF, CH3CF=CH2, CH2=CF2, cis-, trans-CHF=CHF, and CHF=CF2. The fractions of vibrational energy of HF among the energies available for distribution in various degrees-of-freedom of product molecules are 19, 23, 11, 7.6, 7.6, and 1.7% for the above molecules, respectively. The statistical calculation results in much less energy disposal in HF vibration in the decompositions of CH2=CHF, CH3CF=CH2, and CH2=CF2, while the distributions of HFt in CHF=GHF and CHF=CF2 are closer to those predicted by the statistical calculation. The deactivation rate of HF in CH2=CHF is about three times larger than that in CH2=CF2, and the latter values resemble those in HF.
  • Hiromitsu Sagae, Masamichi Fujihira, Henning Lund, Tetsuo Osa
    1980 Volume 53 Issue 6 Pages 1537-1541
    Published: 1980
    Released: April 19, 2006
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    The oxidation of o-, m-, and p-nitrotoluenes with electro-generated superoxide ion in dimethylformamide was studied using cyclic voltammetry and controlled potential macro-electrolysis. The electrochemical reduction of oxygen in the presence of o- and p-nitrotoluenes yielded the corresponding carboxylic acids because the methyl groups in these derivatives are activated by the nitro group. An intermediate in these oxidations should be the corresponding nitrobenzaldehyde. The reaction mechanism is discussed.
  • Hideki Masuda, Akira Fujishima, Kenichi Honda
    1980 Volume 53 Issue 6 Pages 1542-1546
    Published: 1980
    Released: April 19, 2006
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    Photoacoustic spectroscopy (PAS) was used for the study of electrode-electrolyte interfaces in situ. The design of the PAS cell and the experimental procedure are given. The change in absorption at the interface during electrochemical reaction at Au electrodes, as measured by PAS technique, is described.
  • Tatsuya Sekine, Teruyuki Tosaka
    1980 Volume 53 Issue 6 Pages 1547-1549
    Published: 1980
    Released: April 19, 2006
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    Adduct formation equilibria between bis(2-thenoyltrifluoroacetonato)-, bis(trifluoroacetylacetonato)-, and bis(hexafluoroacetylacetonato)copper(II) chelates and tributyl phosphate (TBP) in water-saturated carbon tetrachloride were studied spectrophotometrically at 25 °C. The chelates added one TBP molecule and decreased the absorption, but not very much. The formation constants obtained from the changes in the absorption, given as a function of the TBP concentration, agreed very well with those obtained previously by a solvent-extraction method.
  • Toshiro Yamashita, Hiroshi Nakamura, Makoto Takagi, Keihei Ueno
    1980 Volume 53 Issue 6 Pages 1550-1554
    Published: 1980
    Released: April 19, 2006
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    Crown ether dyes were synthesized in order to develop photometric reagents which are highly selective to alkali and alkaline earth metals. They contain dissociable protons attached to the chromophores of crown ether molecule. Their extraction behavior for alkali and alkaline earth metal ions as neutral complex was examined. The dyes extract potassium and alkaline earth metals, respectively. Dyes with picrylamino chromophore are effective for extractive photometric determination of potassium. A molecular design of colorimetric reagents is discussed on the basis of crown ethers.
  • Shigenobu Funahashi, Tetsuo Nishimoto, Pradyot Banerjee, Kiyoshi Sawad ...
    1980 Volume 53 Issue 6 Pages 1555-1559
    Published: 1980
    Released: April 19, 2006
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    Kinetics of reactions of tetra-μ-acetato-dicopper(II) (copper(II) acetate dimer: Cu2(OAc)4) with lithium chloride and hydrogen chloride (XCl where X denotes Li or H) in acetic acid have been studied spectrophotometrically by using a stopped-flow technique with a computer-assisted averaging device. The rate of decomposition of copper(II) acetate dimer to the monomeric chloro complex is expressed as −d[Cu2(OAc)4]/dt=kXCl[Cu2(OAc)4][XCl]. At 25 °C kLiCl=(3.5±0.6)×105 mol−1 kg s−1H\ eweq=50±10 kJ mol−1 and ΔS\ eweq=30±20 J mol−1 K−1) and kHCl=(4.8±1.0)×105 mol−1 kg s−1H\ eweq=23±10 kJ mol−1 and ΔS\ eweq=−60±20 J mol−1 K−1). Mechanisms are proposed for the decomposition of copper(II) acetate dimer and some discussions are made on the difference in reactivities of LiCl and HCl.
  • Akio Yuchi, Hiroshi Muranaka, Shinkichi Yamada, Motoharu Tanaka
    1980 Volume 53 Issue 6 Pages 1560-1563
    Published: 1980
    Released: April 19, 2006
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    Dissociation of dimeric vanadium(V) complexes with 8-quinolinol(Hox) and 4-isopropyltropolone(Hipt), V2O3(ox)4 and V2O3(ipt)4, in organic solvents was studied spectrophotometrically. The equilibrium is found to be
    V_2O_3L_4+H_2O\ ightleftarrows2VO_2L+2HL
    with the following logarithmic equilibrium constants: logK=−12.9 for L=ox and −12.8 for L=ipt in chlorobenzene. VO2L was synthesized and characterized by IR, UV, and visible spectroscopy for these ligands and also for 2-methyl-8-quinolinol.
  • Yasuo Nakao, Masaaki Demichi, Akitsugu Nakahara
    1980 Volume 53 Issue 6 Pages 1564-1570
    Published: 1980
    Released: April 19, 2006
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    Copper(II) complexes of the Schiff bases derived from salicylaldehyde and dibenzyl aspartate or glutamate have been prepared for the first time. Upon refluxing the solution of these complexes in methanol for 30 min, bis(α-methyl β-benzyl N-salicylideneaspartato)copper(II) and bis(α-methyl γ-benzyl N-salicylideneglutamato)copper(II) were obtained. The mechanism of these selective ester-exchange reactions in the metal-coordination sphere has been discussed. Several Schiff bases were obtained and characterized.
  • Mihoko Kunimatsu, Hideaki Kanno, Masaaki Kojima, Kazuo Kashiwabara, Ju ...
    1980 Volume 53 Issue 6 Pages 1571-1576
    Published: 1980
    Released: April 19, 2006
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    The (lel3), (lel2ob), and (lelob2) isomers of [Co(rac-cptn)3]3+ were obtained by the reaction of trans-[CoCl2(pyridine)4]+ with rac-cptn, where cptn denotes trans-1,2-cyclopentanediamine. No indication for the formation of the (ob3) isomer was found. The isomers were resolved into optical isomers by SP-Sephadex column chromatography. The circular dichroism spectra of these optical isomers were measured and the results compared with those of the related complexes. The anomalous circular dichroism pattern of the (lel3) isomer in the region of the first absorption band was found to result from the contribution of the strong vicinal effect of the chiral cptn chelate ligand as compared with that of the configurational effect.
  • Shinichi Matsumoto, Shinichi Kawaguchi
    1980 Volume 53 Issue 6 Pages 1577-1583
    Published: 1980
    Released: April 19, 2006
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    The reactions of bis(acetylacetonato)palladium(II), Pd(acac)2, with alkylamines (L) such as butyl-, cyclohexyl-, diethyl-, and dipropylamines in methanol to afford [Pd(acac)L2](acac) obey the usual two-term rate law, rate=(k0+k1[L])[Pd(acac)2]. On the other hand, the rate of reaction of Pd(acac)2 with diethylamine in THF and benzene is expressed by rate=(k1+k2[L])[L][Pd(acac)2]. A mechanism is proposed which presumes the hydrogen-bonding interaction of Pd(acac)2 with methanol and amine. Intermediacy of Pd(acac)(acac-C3)L in these reactions was denied on the basis of the kinetic studies, and the carbon-bonded complex was concluded to be produced via [Pd(acac)L2](acac). The equilibrium constants for the reactions, Pd(acac)2+2Et2NH\ ightleftarrows[Pd(acac)(Et2NH)2(acac) and Pd(acac)(acac-C3)(Et2NH)+Et2NH\ ightleftarrows[Pd(acac)(Et2NH)2](acac) were determined in dichloromethane and methanol.
  • Hideo Imoto, Motoshige Sasaki, Taro Saito, Yukiyoshi Sasaki
    1980 Volume 53 Issue 6 Pages 1584-1587
    Published: 1980
    Released: April 19, 2006
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    The pressure isotherms of the ZrCr2–H system (20–200 °C, 10–700 Torr) and powder X-ray diffraction have shown the occurrence of two phases, cubic ZrCr2Hx (x<1.0) and hexagonal ZrCr2Hx (2.5<x<3.5). From the gradual change in the diffraction pattern with x, it has been concluded that samples with a low hydrogen concentration (x<0.8) contain another hexagonal phase. All these phases have Laves-type structures (C14 and C15). At 106 K, ZrCr2H2.66 has a much smaller second moment (7.2 G) of 1H-NMR than the value calculated from the random-distribution model (77.9 G), which shows that the nearest sites can not be filled by hydrogen atoms at the same time. The system of TiCr2–H has also been studied for comparison.
  • Tomikatsu Kudo, Yoichi Shimura
    1980 Volume 53 Issue 6 Pages 1588-1594
    Published: 1980
    Released: April 19, 2006
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    Eight, six, and four optical isomers of diamine hexols [Co{(OH)2Co(diarnine)2}3]6+ containing meso-2,3-butanediamine, (R)-1,2-propanediamine, and (R,R)-1,2-cyclohexanediamine, respectively, were separated by column chromatography. The absorption and CD (circular dichroism) spectra were measured in the visible and ultraviolet regions in 0.01 mol dm−3 HCl, the absolute configurations being determined mainly on the basis of the CD spectra. Assuming that the configurational chiralities are identical to those of the corresponding ethylene-diamine hexol isomers, it has been established that the lel and ob orientations of the (R)-diamine ligand show different vicinal CD curves due to the asymmetric carbon atom in the ligand.
  • Hiroshi Nakazawa, Ushio Sakaguchi, Hayami Yoneda
    1980 Volume 53 Issue 6 Pages 1595-1599
    Published: 1980
    Released: April 19, 2006
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    The effect of added malonate upon the chemical shift and the exchange rate of amine hydrogens of acetylacetonatobis(ethylenediamine)cobalt(III) ion, [Co(acac)(en)2]2+, have been investigated by 1H and 13C NMR spectroscopy. In the absence of malonate, the amine groups give rise to two signals in the 1H spectra and two rate constants of amine exchange due to trans and cis (to coordinated oxygen) amine groups. Upon addition of malonate, the trans NH2 undergoes a down-field shift, the cis NH2 resonance splitting into two peaks. In the presence of malonate, all of the four kinds of amine hydrogens of [Co(acac)(en)2]2+ exhibit different exchange rates. The following conclusion was obtained from the results coupled with 13C NMR data, (i) The malonate ion works in two ways in amine exchange, as a general base catalyst and to form an exchange-inert ion-pair, (ii) The two trans hydrogens that are directed approximately parallel to the two-fold axis of the complex ion hydrogen-bond simultaneously to the two carboxyl groups of malonate, leading to a retardation of amine exchange rates. (iii) The rates of the other trans hydrogens and cis hydrogens are determined by a compromise between acceleration due to general base catalysis and deceleration due to forming ion-associated species, (iv) The conformation of coordinated ethylenediamine is fixed as either (δδ) or (λλ) in the hydrogen-bonded species.
  • Byong-Tae Chang, Jae-Gun Oh, Suk-Ja Om
    1980 Volume 53 Issue 6 Pages 1600-1604
    Published: 1980
    Released: April 19, 2006
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    Effects of sodium tetraborate as an additive in the reaction of α-alumina with molten sodium carbonate have been studied mainly in a N2 atmosphere. Addition of sodium tetraborate accelerates the reaction, the α-alumina reacted increasing from 31.7% to 99.3% by addition of sodium tetraborate corresponding to the initial B2O3/Na2O molar ratio of only 1/15 under the other same conditions. By means of the Jander equation the activation energy was found to be 53 kcal/mol for the α-Al2O3–Na2CO3–Na2B4O7, system, which was lower by 10 kcal/mol than that for the α-Al2O3–Na2CO3 system. X-Ray diffraction and thermal data were analyzed in relation to the phase equilibrium of the melt.
  • Kikuo Terada, Kumiko Morimoto, Toshiyasu Kiba
    1980 Volume 53 Issue 6 Pages 1605-1609
    Published: 1980
    Released: April 19, 2006
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    A solid chelating material, 2-mercaptobenzothiazole supported on silica gel (MBT-SG), was prepared and used for the preconcentration of inorganic and organic mercury compounds from a sea-water sample. The chelating capacity of the material was 12 μeq. Hg/g. The mercury (II) ion, the methylmercury ion, and the ethylmercury ion were quantitatively retained on the MBT-SG at pH values of 1.0, 5.0, and 4.0 respectively from an aqueous solution, and at pH values of 4.0, 4.5, and 5.0 respectively from a sea-water. A column packed with the material provided a quantitative recovery of these ions from a sea-water sample at a high flow rate (1–3 1 h−1). Mercury was eluted by the use of a acetone–hydrochloric acid mixture (25: 1) or a 1% thiourea solution in 0.1 mol dm−3hydrochloric acid. The latter effluent was submitted atomic-absorption spectrometry after reductive vaporization for the determination of mercury.
  • Naoyuki Torihara, Masahiro Mikuriya, Hisashi Okawa, Sigeo Kida
    1980 Volume 53 Issue 6 Pages 1610-1613
    Published: 1980
    Released: April 19, 2006
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    Binuclear manganese(III) complexes with 3-salicylideneamino-1-propanol and its homologues, MnL(ac) and MnLXH2O (L=Schiff base dianion; ac=acetate ion; X=Cl, Br, N3), were synthesized. It was shown that manganese(III) ions were bridged by the deprotonated alcoholic oxygen of the Schiff base in the equatorial plane and coordinated by bidentate acetate ion or X and H2O groups in apical positions to form six-coordination. Cryomagnetic measurements indicated that an antiferromagnetic spin-exchange interaction operates between a pair of manganese(III) ions; exchange integral being evaluated at −13.5–−20.4 cm−1.
  • Yoshinori Ihara, Ryokichi Tsuchiya
    1980 Volume 53 Issue 6 Pages 1614-1617
    Published: 1980
    Released: April 19, 2006
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    Thermal reactions of the complexes, [Ni(abi)4]X2·nH2O (abi, 2-aminobenzimidazole; X, Cl, Br, I, NO3, ClO4, or 1/2SO4; n, 3 for chloride and bromide, 1 for nitrate, and 0 for others) were investigated. Distinct color changes from orange to green were observed in the three complexes of chloride, bromide, and nitrate upon heating. It was found from the changes in absorption and far-IR spectra and magnetic susceptibilities under the thermal reactions that the complexes undergo transformation from square planar to tetragonally distorted octahedral structures, involving an increase in the coordination number from four to six. No such transformation could be found in the corresponding iodide, perchlorate, and sulfate. The effect of the introduced amino group on the structural conversion reactions of the abi complexes is discussed as compared with the corresponding benzimidazole complexes, [Ni(bimd)4]X2, which underwent transformation from square planar to octahedral structure upon heating when X is I or NO3.
  • Yasushi Inoue, Osamu Tochiyama
    1980 Volume 53 Issue 6 Pages 1618-1624
    Published: 1980
    Released: April 19, 2006
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    The back extraction of methyltrioctylammonium chloride (MTOACl) from ten kinds of organic solvents was investigated as a function of the MTOACl concentration. The chemical species of the ammonium salt in the organic phase were found to be in the form of dissociated ions, of ion pairs, or of dimeric ion pairs, according to the dielectric constant of the solvent. MTOACl was better extracted into more polar and acidic solvents, such as nitrobenzene, 3-methyl-1-butanol, and chloroform. The selectivity coefficients (KX/Cl) of MTOA for the exchange of Br, I, ClO4, vs. Cl were obtained from the study of the distribution of several organic color reagents; they were found to increase with the anion size, irrespective of the organic solvent used. For all but acidic solvents, the values of KX/Cl were similar to each other. Such acidic solvents as 3-methyl-1-butanol and chloroform, however, reduced the selectivity of the extraction for anions.
  • Mitsuji Yamashita, Mitsumasa Kojima, Hiroshi Yoshida, Tsuyoshi Ogata, ...
    1980 Volume 53 Issue 6 Pages 1625-1628
    Published: 1980
    Released: April 19, 2006
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    The Arbuzov reaction of trimethyl and triethyl phosphites with acyl chlorides gave 1-oxoalkylphosphonates in 57–80% yields. The Wittig reaction of the phosphonates with methylenetriphenylphosphorane gave vinylphosphonates in 25–59% yields. Hydroboration of vinylphosphonates in oxolane gave 2-hydroxyethylphosphonates in 50–65% yields. The procedure seems to be a good synthetic method to afford 1-alkyl-substituted 2-hydroxyethylphosphonates which have one more carbon atom than the starting 1-oxoalkylphosphonates.
  • Mitsuki Yasuhara, Kazuko Inanaga, Takashi Kumae, Hemat Rysona Brahmana ...
    1980 Volume 53 Issue 6 Pages 1629-1631
    Published: 1980
    Released: April 19, 2006
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    The structure, 3-hydroxy-2,3-didehydro-β,χ-caroten-4-one, assigned to tedanin, the main carotenoid pigment of the marine sponge “Tedania digitata (O. Schmidt),” has been confirmed by total synthesis starting with β,χ-carotene. An isomer, 3-hydroxy-2,3-didehydro-β,φ-caroten-4-one, was also synthesized from β,φ-carotene.
  • Takamasa Nonaka, Hiroaki Egawa
    1980 Volume 53 Issue 6 Pages 1632-1637
    Published: 1980
    Released: April 19, 2006
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    The polyampholytes were prepared by treating potassium polymethacrylate with (3-chloro-2-hydroxypropyl)trimethylammonium chloride. The solution viscosity behavior and the potentiometric titration of the polyampholytes were studied. The flocculating ability of the polyampholytes was also investigated by the use of kaolin suspensions. The amine/acid ratio could be varied as desired to some extent by means of changing the reaction temperature. However, the polyampholytes containing more amino groups than about 46% could not be obtained. The resulting polyampholytes showed characteristic viscosity behavior. The results of the flocculation of kaolin suspensions with the polyampholytes showed that the polyampholytes can be expected to become a new type of polymeric flocculants, in which the chain expansion and the charge sign can be varied by changing the pH values of the solutions.
  • Takashi Keumi, Hiroshi Saga, Hidehiko Kitajima
    1980 Volume 53 Issue 6 Pages 1638-1641
    Published: 1980
    Released: April 19, 2006
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    N-Benzoylimidazole in trifluoroacetic acid could benzoylate electron-rich aromatic compounds, such as durene, p-dimethoxybenzene, mesitylene, anisole, thiophene, and fluorene, to give the corresponding benzophenone derivatives in good yields. It was further elucidated, in the reaction of fluorene, that N-acylimidazoles composed of a variety of acyl groups also could be used for the ketone synthesis. Therein, the imidazolides of aliphatic carboxylic acids or substituted benzoic acids with an electron-donating group gave ketones in high yields. The above-mentioned aromatic compounds were also acylated with N-trifluoroacetylimidazole and free carboxylic acids in trifluoroacetic acid. The mechanism for these reactions was assumed to proceed via a mixed anhydride between trifluoroacetic acid and carboxylic acid.
  • Tohru Sakakibara, Yutaka Nomura, Rokuro Sudoh
    1980 Volume 53 Issue 6 Pages 1642-1646
    Published: 1980
    Released: April 19, 2006
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    The title compound was synthesized from 1,5-anhydro-D-glucitol via nitromethane cyclization. The reduction of the compound with sodium borodeuteride afforded a mixture of saturated nitro compounds having an axial and equatorial deuterium atom at C-2 in an approximate ratio of 2:1. On the other hand, the reaction with hydrogen cyanide gave predominantly the adduct with the manno configuration, together with small amounts of a cyano olefin. The reaction with hydrazoic acid yielded addition products with the gluco and manno configurations; the ratio was strongly affected by the solvent used.
  • Tadayoshi Morita, Taira Fujita, Kahei Takase
    1980 Volume 53 Issue 6 Pages 1647-1651
    Published: 1980
    Released: April 19, 2006
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    The reaction of diethyl 2-chloroazulene-1,3-dicarboxylate (1a) with lithium acetylide in liq ammonia gave diethyl 4- and 6-ethynylazulene-1,3-dicarboxylates by an abnormal substitution reaction. In a similar manner, some 2-chloroazulenes, possessing alkoxycarbonyl and/or cyano substituents at the 1- and 3-positions of azulene nucleus, gave the corresponding 4 (or 8)- and 6-ethynylazulenes. The same type reaction proceeded when lithium phenylacetylide, sodium indenide, and sodium fluorenide were used as the reagents, 1a giving diethyl 4- and 6-(phenylethynyl)-, 6-(3-indenyl)-, and 6-(9-fluorenyl)azulene-1,3-dicarboxylates, respectively.
  • Yuzuru Masuda, Akira Arase, Akira Suzuki
    1980 Volume 53 Issue 6 Pages 1652-1655
    Published: 1980
    Released: April 19, 2006
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    The reaction of (1-halo-1-alkenyl)dialkylboranes with lead(IV) acetate or (diacetoxyiodo)benzene was studied. (1-Bromo-1-alkenyl)dialkylboranes gave 1-bromo-1,2-dialkylethylenes. When alkyl groups on the boron atom of vinylboranes were bulky or the reaction temperatures were low, Z-isomers were afforded, whereas when alkyl groups on the boron atom were small or the reaction temperatures were relatively high, E-isomers were afforded as the main products. (1-Chloro-1-alkenyl)dialkylboranes gave (Z)-1-chloro-1,2-dialkylethyienes regardless of the reaction conditions. (1-Iodo-1-alkenyl)dialkylboranes failed to give satisfactory yields of 1-iodo-1,2-dialkylethylenes.
  • Syun-ichi Kiyooka, Yoshinobu Ueda, Kojiro Suzuki
    1980 Volume 53 Issue 6 Pages 1656-1660
    Published: 1980
    Released: April 19, 2006
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    The UV-visible, IR, and 1H-NMR spectra of the sodium enolates of ethyl phenylacetates (substituents; p-CH3O, p-CH3, m-CH3, H, p-Cl, p-CH3CO, m-CH3CO, p-COOC2H5, p-CN, and p-NO2) in DMSO were measured at room temperature. The derivatives with electron-attracting groups at the para position exhibit their absorption maxima with ε>104 in visible regions above 400 nm. The visible spectra suggest the presence of a resonance between their electron-attracting groups at the para position and the enolate anion parts through the benzene ring. The carbonyl-stretching vibrations of the enolates in the IR spectra and the chemical shifts of the residual methine proton of the enolates in the 1H-NMR spectra can be well explained by using the substituent constants, σ and σ. The ρ values of the meta and para lines are extremely different. In the case of the p-NO2 derivative, the 1H-NMR spectra of the benzene-ring protons indicate that the free rotation of the partially double bond between the benzene ring and the enolate-anion part is fixed at room temperature.
  • Juzo Nakayama, Mimiko Imura, Masamatsu Hoshino
    1980 Volume 53 Issue 6 Pages 1661-1665
    Published: 1980
    Released: April 19, 2006
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    Reaction of 2-isopentyloxy-1,3-benzodithiole with indole in acetic acid gave a 93% yield of 3-(1,3-benzodithiol-2-yl)indole (4a) which was converted to 2-(3-indolyl)-1,3-benzodithiolylium tetrafluoroborate (5a) in a 77% yield by treatment with trityl tetrafluoroborate. 5a was also prepared by reaction of indole with 2 molar amounts of 1,3-benzodithiolylium tetrafluoroborate. Treatment of 5a with triethylamine afforded the title compound 6a in 93% yield. 6a was protonated, methylated, and benzoylated at its 6-position by tetrafluoroboric acid, methyl iodide, and benzoyl chloride, respectively. Reaction of 6a with dimethyl acetylenedicarboxylate gave a 1,6-dipolar intermediate which was trapped as an adduct with ethanol. 6a was smoothly reduced by sodium borohydride to give its 5,6-dihydro derivative.
  • Syoji Morimura, Hideo Horiuchi, Chihiro Tamura, Takao Yoshioka
    1980 Volume 53 Issue 6 Pages 1666-1669
    Published: 1980
    Released: April 19, 2006
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    Hindered piperidine derivatives with a new functional group (–S–N=S=S), 2,2,6,6-tetramethyl-1-(thiosulfinylaminothio)piperidines (4) were obtained from the corresponding piperidines 1, sulfur monochloride and ammonia. These compounds were also prepared from bis(2,2,6,6-tetramethylpiperidino) disulfides or bis(2,2,6,6-tetramethylpiperidino) trisulfides under similar reaction conditions. In much lower yields, unhindered 1-(thiosulfinylaminothio)piperidines (8) were also obtained. The photochemical and thermal stabilities of 4 and 8 were nearly the same. Reaction pathways were disucssed.
  • Hidetaka Yatagai
    1980 Volume 53 Issue 6 Pages 1670-1676
    Published: 1980
    Released: April 19, 2006
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    The reactions of alkenylboranes with palladium acetate were investigated. Alkenyldialkylboranes, derived from terminal alkynes, underwent intramolecular migration reaction in the presence of an equimolar amount of palladium acetate and triethylamine to give (E)-olefins. On the other hand, under the same conditions as above or even in the presence of catalytic amounts of palladium acetate, alkenyldialkylboranes derived from internal alkynes underwent protonolysis reaction to produce (Z)-olefins. An alkenylpalladium intermediate which was presumably involved in the latter reaction was trapped by allylic chloride to give 1,4-dienes.
  • Tetsuo Otsubo, Hisanori Horita, Yosuke Koizumi, Soichi Misumi
    1980 Volume 53 Issue 6 Pages 1677-1682
    Published: 1980
    Released: April 19, 2006
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    [m.m][n.n]Triple-layered paracyclophanes underwent bromination to give exclusively monobromo derivatives substituted to the inner benzene. The reactions were markedly accelerated by the transannular electronic interaction as compared to [n]- and double-layered paracyclophanes, and their enhanced reactivities were demonstrated by some competitive reactions. The relative rates of [2.2] and [3.3]systems are in reverse order for the triple-layered and double-layered series. Their reaction mechanisms were discussed.
  • Mamoru Ohashi, Kentaro Miyake, Kazuo Tsujimoto
    1980 Volume 53 Issue 6 Pages 1683-1688
    Published: 1980
    Released: April 19, 2006
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    Upon irradiation, p-dicyanobenzene reacted with primary, secondary, and tertiary aliphatic amines to give substitution products in which one of the cyano groups was replaced by the amine at α-CH position or by an alkyl group of the amine. o-Dicyanobenzene reacted similarly, but the meta-isomer did not react under similar conditions. The rates of the fluorescence quenching of p-dicyanobenzene with the amines are close to the diffusioncontrolled rate, but are somewhat dependent on the ionization potentials of the amines. When the substitution product was irradiated, the corresponding alkylation product was obtained. The mechanisms of these reactions have been investigated by the use of such proton donors as MeOH(MeOD); on the basis of those investigations, new photochemical reactions involving charge-transfer, followed by proton-transfer and then addition-elimination, are proposed, as well as a new type of photo-induced Birch reduction.
  • Ping-Lin Kuo, Norio Kawamura, Masaki Miki, Mitsuo Okahara
    1980 Volume 53 Issue 6 Pages 1689-1693
    Published: 1980
    Released: April 19, 2006
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    A new facile method of synthesizing crown ethers from oligoethylene glycols by treating them with arenesulfonyl or alkanesulfonyl chlorides in the presence of alkali metal hydroxide or alkoxide was described. 15-Crown-5 and 21-crown-7 were synthesized from pentaethylene glycol and heptaethylene glycol respectively in good yields, while 18-crown-6 was obtained from both hexaethylene glycol and triethylene glycol. Although the main product was 24-crown-8 in the reaction of tetraethylene glycol/TsCl/Na(K)OH in dioxane, 12-crown-4 was obtained in a moderate yield from the reaction of tetraethylene glycol/benzenesulfonyl chloride/t-BuOLi in t-BuOH. Furthermore, the analogous treatment of PEG 200 afforded a mixture of 15-, 18-, 21-, and 24-crown ethers. The reaction conditions were investigated, and the scope of the reaction was discussed.
  • Hajimu Kawa, Hamdy A. Hamouda, Nobuo Ishikawa
    1980 Volume 53 Issue 6 Pages 1694-1697
    Published: 1980
    Released: April 19, 2006
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    Reactions between hexafluoro-1,2-epoxypropane and 1,2-bifunctional ethanes were studied. Ethylenediamine, 2-aminoethanol and 2-aminoethanethiol gave corresponding N- and O-pentafluoropropionylated products, while ethylene glycol, 2-mercaptoethanol, and 1,2-ethanedithiol afforded ring closed products, such as 1,4-dioxanone, 1,4-oxathianone, and 1,4-dithianone compounds.
  • Kazuhiko Takai, Yuji Hotta, Koichiro Oshima, Hitosi Nozaki
    1980 Volume 53 Issue 6 Pages 1698-1702
    Published: 1980
    Released: April 19, 2006
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    Treatment of R1COR2 with a suspension prepared from diiodomethane, trimethylaluminum and excess zinc in tetrahydrofuran at room temperature affords olefins R1R2C=CH2 in fair (R1,R2=alkyl) to good (R1=alkyl, R2=H) yields. The ketone methylenation is better carried with another system consisting of CH2Br2–Zn–TiCl4. Ketones and aldehydes are transformed into α-chloro α,β-unsaturated esters or α,β-unsaturated esters in good yields on treatment with methyl trichloroacetate or t-butyl dichloroacetate (ethyl dibromoacetate) in the presence of diethylaluminum chloride and zinc.
  • Kazuhiko Chiba, Jun-ichi Aihara, Kotaro Araya, Yoshio Matsunaga
    1980 Volume 53 Issue 6 Pages 1703-1708
    Published: 1980
    Released: April 19, 2006
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    The first electronic absorption bands of the title compounds can all be assigned to the intramolecular charge-transfer transitions. The solvent effects on these bands are quite analogous to those on the absorption bands characteristic of binary charge-transfer complexes. Especially, when the title compounds are dissolved in trifluoroacetic acid, marked bathochromic shifts of the first bands are observed, in harmony with their charge-transfer character. Such solvatochromism is obviously due to the hydrogen-bond formation between the solute and the solvent molecules. When strong hydrogen bonding occurs, the electron affinity of the 2-methylene-1,3-indandione moiety increases by about 0.41 eV.
  • Yoshihiro Taniguchi, Keizo Suzuki
    1980 Volume 53 Issue 6 Pages 1709-1713
    Published: 1980
    Released: April 19, 2006
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    The rates of the hydrolysis of 2-valeryloxy(C5)- and 2-heptanoyloxy(C7)-benzoic acids catalyzed by α-chymotrypsin (α-CHT) were measured at pressures up to 2000 bar at 30 °C and pH 7.8 in a 0.05 M Tris buffer solution. The apparent Michaelis constant, Kmapp, was estimated to vary from 5.9 to 9.9 mM, and kcat from 11×10−3 to 52×10−3 s−1, for the C5 ester, and Kmapp, from 4.7 to 10 mM, and kcat from 37×10−3 to 200×10−3 s−1, for the C7 ester, between 1 and 2000 bar. From the pressure dependences of Kmapp and kcat, the volume changes accompanying the dissociation of the enzyme–substrate complex and the activation volume for the process of the product formation were calculated to be −6.3±2 and −20±2 cm3/mol for the C5 ester and −9.5±2 and −21±2 cm3/mol for the C7 ester. The effects of the pressure on the hydrolysis of p-nitrophenyl acetate (PNPA) catalyzed by α-CHT have also been measured up to 3000 bar at pH 7.8 in a 0.05 M Tris buffer solution and at 25 °C and 35 °C. The activation volumes were −3 cm3/mol at 25 °C and −4 cm3/mol at 30 °C and 25 °C. These results were discussed on the basis of the X-ray study of the enzyme-substrate complex.
  • Taro Tachibana, Tomoko Mori, Kayako Hori
    1980 Volume 53 Issue 6 Pages 1714-1719
    Published: 1980
    Released: April 19, 2006
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    Thermally reversible jellies of optically active 12-hydroxyoctadecanoic acid (12HOA) with CCl4 or aromatic solvents form a lyotropic mesophase, which shows enantiomeric circular dichroism (CD) and induced CD due to achiral molecules added to the jellies, indicating that the jellies have a supramolecular helicoidal structure. The X-ray examination revealed that the jellies are composed of a number of small, ordered domains with such a lamellar structure as is observed in the crystalline solid. The supramolecular helicoidal structure was associated with the lamellar structure; as a result, it was suggested that the lyotropic mesophase has a chiral smectic structure and, furthermore, that the mesophase is present in thin, fibrous aggregates of 12HOA molecules within which the jellies are enmeshed.
  • Yasuyuki Takeda, Hisao Yano
    1980 Volume 53 Issue 6 Pages 1720-1722
    Published: 1980
    Released: April 19, 2006
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    The formation constants (KML+) for 1: 1 complexes of dibenzo-24-crown-8 (DB24C8) with alkali metal ions (Na+, K+, Rb+, and Cs+) in propylene carbonate (PC) and methanol have been determined conductometrically at different temperatures in order to obtain the values of the enthalpy (ΔH) and entropy changes (ΔS). The complexation reactions between DB24C8 and the alkali metal ions in PC and methanol are all exothermic, and the ΔS values of these systems are all negative. In the case of the PC system, there is no considerable difference in ΔS among the alkali metal ions (Na+, K+, Rb+, and Cs+); thus, the KML+ sequences depend entirely on the −ΔH sequences. Since, in methanol, the −ΔH and −ΔS values for K+ are nearly equal to those for Cs+, and since the largest −ΔH value for Rb+ is balanced by the largest −ΔS value, DB24C8 shows no selectivity for the alkali metal ions (K+, Rb+, and Cs+) in methanol.
  • Yoshio Kishimoto, Wataru Shimotsuma
    1980 Volume 53 Issue 6 Pages 1723-1727
    Published: 1980
    Released: April 19, 2006
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    To study the thermal stability of several metal cation–TCNQ salts (mainly alkali metal salts), the variation in the electrical resistivity and the characteristics of the chemical degradations by heating were measured. Most metal–TNCQ salts do not melt and are not sublimated, but have decomposition points at about 320 °C. Na(TCNQ) has a stable resistivity, even after heating for 500 hours at 200 °C, and is the most stable among the metal–TCNQ salts tested. Metal–TCNQ salts are gradually damaged from the surfaces of the crystalline powders by heating, and the TCNQ, molecule is oxidized, thus losing CN groups. The crystallization process of the TCNQ salts has a great influence upon their thermal stabilities. In the complex salt Cs2(TCNQ)3, the application of d.c. voltage gives rise to the polarization current at a temperature near 200 °C, and the TCNQ molecules tend to migrate in the electric field.
  • Neriyanuri Manohara Murthy, Saraswatula Venkata Subrahmanyam
    1980 Volume 53 Issue 6 Pages 1728-1731
    Published: 1980
    Released: April 19, 2006
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    The temperature dependence of structural propensity of 1-butanol has been studied by investigating its effect on the temperature of sound velocity maximum (TVM) in aqueous mixtures of glycerol and pyridine. The structural contribution to the shift in TVM of binary solution, [ΔTstr]exp was found to be positive at low concentrations of 1-butanol for aqueous pyridine solutions whose TVM are 37.6 °C and 23.7 °C. For aqueous glycerol solutions whose TVM is 43.3 °C, [ΔTstr]exp values, in the entire concentration range of 1-butanol studied, are found to be negative. The results indicate that below 40 °C 1-butanol behaves as a structure promoter while above 40 °C it behaves as a structure breaker.
  • Sudhir Kumar Saxena, Jagdish Prasad Shukla, Mahesh Chandra Saxena
    1980 Volume 53 Issue 6 Pages 1732-1735
    Published: 1980
    Released: April 19, 2006
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    Dielectric constants and losses have been measured at 9.8 GHz microwave frequency for ethyl and butyl acetates in benzene and benzene–paraffin oil mixtures at 18 °C. The data obtained has been analysed in terms of the two relaxation times τ(1) and τ2 using Higasi, Koga, and Nakamura method and their dependence on the viscosity has been examined. Since the observed values of τ(1)and τ(2) are significantly different, the systems studied represent two Debye type dispersions. It has been found that the relaxation behaviour giving rise to τ(1) in both the ester molecules is not effected to any appreciable extent by the increased macroscopic viscosity. The dielectric relaxation time τ(2) associated with the molecular process lengthens with the increasing macroscopic viscosity of the medium.
  • Raghunandan Singh Kharsan, Rajendra K. Mishra
    1980 Volume 53 Issue 6 Pages 1736-1738
    Published: 1980
    Released: April 19, 2006
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    A highly selective method for the extractive-spectrophotometric determination of molybdenum is described. Molybdenum is reduced with ascorbic acid in strongly acidic media (2.0–4.5 mol dm−3 HCl), and complexed with N1-hydroxy-N1-p-tolyl-N2-(3,4-dimethylphenyl)benzamidine in the presence of thiocyanate. The stoichiometry of mixed complex is found to be 1:2:2 (metal:reagent:thiocyanate). The red-orange molybdenum complex shows a sharp maximum at 470 nm having molar absorptivity 3800 dm3 mol−1 cm−1. All the metal ions associated with a matrix of molybdenum such as Ni(II), Co(II), Cu(II), Mn(II), Ti(IV), Zr(IV), V(V), Nb(V), Ta(V), and W(VI) do not interfere. The applicability of the method has been tested with an ore and various alloys.
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