Bulletin of the Chemical Society of Japan
Online ISSN : 1348-0634
Print ISSN : 0009-2673
ISSN-L : 0009-2673
53 巻 , 2 号
選択された号の論文の68件中1~50を表示しています
  • Kazushi Arata, Kozo Tanabe
    1980 年 53 巻 2 号 p. 299-303
    発行日: 1980年
    公開日: 2006/04/19
    ジャーナル フリー
    The reaction of cyclohexene oxide over solid acids and bases at 108 °C gave five main products, 1,3-cyclohexadiene (1), cyclohexanone (2), cyclohexanol (3), 2-cyclohexen-1-one (4), and 2-cyclohexen-1-ol (5). SiO2–TiO2 and SiO2–TiO2–MgO were highly active for the isomerization, giving a large amount of 1. TiO2–ZrO2 mainly showed selectivity for the formation of 5, and other catalysts formed both 2 and 5. Of the alumina prepared in four different ways, two were highly active, giving 5 predominantly. The results were discussed in comparison with those for an oxide containing a methyl group on the oxide ring, 1-methylcyclohexene oxide. By the experiment using the deuterated epoxide, 1,2-epoxycyclohexane-3,3,6,6-d4, isotope effects for the formation of 2, 3, 4, and 5 over Al2O3’s, SiO2–TiO2 and solid H3PO4 were observed. It has been concluded that the epoxide is adsorbed on both acidic and basic sites, and that allyl alcohol is formed when both the opening of the epoxide ring and the hydrogen abstraction take place simultaneously, while ketone is formed when the former precedes the latter.
  • Kenjiro Kondo, Masuo Yagi
    1980 年 53 巻 2 号 p. 304-309
    発行日: 1980年
    公開日: 2006/04/19
    ジャーナル フリー
    The isomeric transition(IT)-activated 80Br and 82Br reactions in the gaseous H80mBr–CH3Br and H82mBr–CH3Br systems have been compared and the roles of the charge and kinetic energy imparted to 80Br and 82Br in recombina tion reactions studied using a Kr moderator. The products CH3Br, CH2Br2, CHBr3, and CH3CH2Br in both reactions are only formed via thermal ionic processes. This differs from the 82mBrBr–CH3Br system, in which the reaction products are only formed through excess kinetic energy processes. The difference between the two reactions has been explained on the basis of the cross sections for charge neutralization and ion molecule reactions of Br+ ions as a function of the kinetic energy initially imparted to the 80Br or 82Br atoms. An isotope effect has been observed between the IT-activated 80Br and 82Br reactions with CH3Br, and attributed to the difference in the decay modes of 80mBr and 82mBr. Furthermore, the analysis of product yields due to the successive internal conversion process in 80mBr suggested that the second Auger process from the excited 80Br occurs in a liquid-like condition such as ion-clusters.
  • Kiyoshi Otsuka, Kimiaki Tanaka, Akira Morikawa
    1980 年 53 巻 2 号 p. 310-314
    発行日: 1980年
    公開日: 2006/04/19
    ジャーナル フリー
    The reaction of butenes caused by the surface compounds formed from SO2 on Mg(OH)2 or MgO has been studied. It has been shown that the cis-trans isomerization of 2-butene is selectively induced by the sulfur compounds. This specific isomerization has been explained by the previously proposed mechanism that the reaction is accompanied by the copolymerization of 2-butene and SO2. The infrared spectroscopic study on the sulfur compounds formed on Mg(OH)2 or on MgO has demonstrated the presence of SO32−, SO42−, or sulfinato complexes. The formation of these surface species may cause a strong electrostatic field on the surface, resulting in the polarization of reactant molecules, which is necessary for the initiation of the copolymerization or of the cis-trans isomerization. It has been shown, however, that the presence of weakly adsorbed SO2 is essential for determining the catalytic activities of the solids in the SO2-induced isomerization.
  • Takeshi Suminaga, Sohachiro Hayakawa
    1980 年 53 巻 2 号 p. 315-318
    発行日: 1980年
    公開日: 2006/04/19
    ジャーナル フリー
    Temperature effect in electrochemiluminescenece (ECL) of pyrene was investigated in order to clarify the formation of excimers. The ratio of intensity of excimer to monomer emission was measured on solutions of pyrene in N,N-dimethylformamide (DMF) at various temperatures from the decay curves of excimer emission due to pulse excitation with a nitrogen laser. The temperature change of concentration dependence of the ratio was derived from the rate equations for the respective direct and indirect formation of excimers. The mechanism of direct excimer formation was confirmed in ECL of pyrene more clearly by analysis of the temperature effect than by that of the concentration effect at a certain temperature.
  • Akio Furusaki, Takeshi Matsumoto, Isami Tsujino, Isao Sekikawa
    1980 年 53 巻 2 号 p. 319-323
    発行日: 1980年
    公開日: 2006/04/19
    ジャーナル フリー
    The molecular structure of palythine, C10H16N2O5, has been confirmed by means of an X-ray crystal analysis of its trihydrate. The crystals are monoclinic, with two formula units in a unit cell with dimensions of a=10.499, b=12.812, c=5.322 Å, and β=98.53°; the space group is P21. 1377 unique intensity data were collected on a four-circle diffractometer with LiF-monochromated Cu Kα radiation. The structure was solved by the Monte Carlo direct method, using the 20 strongest reflections as a starting set, and was refined by the block-diagonal least-squares method. The final R value was 3.1%. The molecular structure thus obtained corresponds to that proposed by Tsujino et al. and Takano et al. on the basis of the chemical evidence. Palythine exists as a zwitter ion in the crystal. The palythine and water molecules are connected by twelve types of hydrogen bonds, forming a three-dimensional hydrogen-bonded structure.
  • Kanji Sakata, Fumio Ueda, Makoto Misono, Yukio Yoneda
    1980 年 53 巻 2 号 p. 324-329
    発行日: 1980年
    公開日: 2006/04/19
    ジャーナル フリー
    The reactivity and mobility of the lattice oxygen of iron oxide, in particular γ-Fe2O3, has been investigated by 18O-exchange with CO2 and CO oxidation by 18O2. The low mobility of the lattice oxygen is in agreement with the reduction-oxidation mechanism of γ-Fe2O3 bulk, which proceeds by Fe ion migration without diffusion of the lattice oxygen. The rapid diffusion of the Fe ion makes the redox cycles of γ-Fe2O3 easy and explains, together with the cation deficient structure, the high reactivity and selectivity of lattice oxygen. Thus, γ-Fe2O3may be regarded as a new prototype of selective catalyst for allylic oxidation.
  • Tadashi Okamoto, Atsuyoshi Ohno, Shinzaburo Oka
    1980 年 53 巻 2 号 p. 330-333
    発行日: 1980年
    公開日: 2006/04/19
    ジャーナル フリー
    The reaction of 1-propyl-1,4-dihydronicotinamide with hexacyanoferrate(III) in 20% aqueous methanol follows a second-order rate law with first order with respect to each reactant concentration. Kinetic parameters are ΔH\ eweq: (8.8±0.4)×103 J mol−1 and ΔS\ eweq: −1.8×102 J mol−1 K−1, the observed kinetic isotope effect, kH/kD, being 1.51. The mechanism of the reaction is discussed.
  • Tooru Inoue, Claude Weber, Akira Fujishima, Kenichi Honda
    1980 年 53 巻 2 号 p. 334-338
    発行日: 1980年
    公開日: 2006/04/19
    ジャーナル フリー
    A heterogeneous electrochemical photovoltaic cell was constructed using the system of cadmium sulfide(CdS)/sulfides reducing agents//oxidizing agents/platinum. The output power characteristics were investigated focusing upon the redox potentials of the oxidizing agents in the cathodic half-cell and then discussed from the point of view of the solution-electrode junction. Though this type of cell intrinsically has a negative free energy for redox reactions of redox agents in an anodic and a cathodic compartment, it has a characteristic point that a larger open-circuit output than the intrinsical electromotive force determined by a redox couple was obtainable in operation under illumination. For example, in the CdS/S2−/S//Fe2+⁄3+/Pt system we found the open-circuit photovoltage of ca. 2.0 V, which is ca. 83% of a band gap (2.4 eV) of CdS. These measurements showed that a larger open-circuit photovoltage was obtained, though, of course, it was smaller than the band-gap energy of CdS, when the oxidizing agent of the more positive redox potential was dissolved in the cathodic compartment.
  • Kazutami Sakamoto, Masahiro Hatano
    1980 年 53 巻 2 号 p. 339-343
    発行日: 1980年
    公開日: 2006/04/19
    ジャーナル フリー
    An alcoholic solution of optically active acylamino acid (AAA) was found to show a circular dichroism (CD) band at 212 nm. The CD band should be inherent to the solution system, since AAA and alcohol per se have no absorption band at this wavelength. The CD band intensity decreased on addition of urea and rise in temperature. This is attributed to the formation of chiral aggregate through hydrogen bonds among AAA molecules. Hydrophobic interaction seems to be of minor importance for the formation of the chiral aggregate in alcoholic solution, since the variation of the chain length in the acyl group or addition of myristic acid did not affect the magnitude of profile of the CD band. In aqueous solutions, salts of optically active AAA formed micelles with hydrophobic interactions among the molecules, and only in the case of optically active monosodium salt of N-acylglutamic acid (AGS) showed a CD band at 220 nm resulting from the formation of chiral hydrogen bonds at concentrations above the critical micelle concentration (CMC). This type of chiral aggregation may be caused by the existence of free carboxyl group in the optically active AGS molecule.
  • Tetsuya Osaka, Robert de Levie
    1980 年 53 巻 2 号 p. 344-346
    発行日: 1980年
    公開日: 2006/04/19
    ジャーナル フリー
    Reduction of perbromate was used as a kinetic probe of double layer parameters for weak specific adsorption of double layer parameters for weak specific adsorption of alkaline earth cations at the mercury/electrolyte solutions interface. The results are interpreted as evidence for weak specific adsorption of Sr2+ and particularly Ba2+ in 10 mM solutions at negative electrode charge densities. The limitation of the use of an anionic probe for the quantitation of cation specific adsorption is discussed.
  • Ryuichi Ueoka, Hidehiko Matsuura, Syuji Nakahata, Katsutoshi Ohkubo
    1980 年 53 巻 2 号 p. 347-351
    発行日: 1980年
    公開日: 2006/04/19
    ジャーナル フリー
    The hydrolyses of anionic 3-nitro-4-acyloxybenzoic acid (S2–S16) and nonionic p-nitrophenyl carboxylate (S2–S16) substrates catalyzed by hydroxamic acids (C6–C12) and histidine derivatives (AcetHis and LauHis) were performed with and without alkyltrimethylammonium (DTAC, CTAB, and OTAC) surfactants at pH 7.45. The present reaction was characterized by the selectively efficient hydrolysis of the same substrate of S6 or S10 by the comicellar Cm (m=8, 10, or 12)–CTAB (or OTAC) or LauHis–CTAB (or OTAC) catalysts. Relevant factors to such a selective hydrolysis of a specific substrate by the comicellar catalysts were discussed by taking notice of the electrostatic-charge-attraction force, steric hindrance, and hydrophobic interaction. The investigation of the binding constants in the present micellar reaction system demonstrated the importance of an appropriate hydrophobic interaction between a substrate and micelles for the selective rate enhacement of ester-hydrolysis.
  • Tomoyuki Terada, Motohiko Koyanagi, Yoshiya Kanda
    1980 年 53 巻 2 号 p. 352-358
    発行日: 1980年
    公開日: 2006/04/19
    ジャーナル フリー
    The polarized emission spectra of anthracene, dibenzothiophene, and xanthone have been studied in stretched polyethylene films at 77 and 4.2 K. Applicability and advantage of this method are examined by virtue of conventional polarization technique and modulation technique. The latter leads us to finding of an important role of a nontotally symmetric vibration, the b3g ring vibration at 1655 cm−1, in the fluorescence spectrum of anthracene. An assignment for several prominent vibrational bands in the phosphorescence spectrum of dibenzothiophene is proposed from detailed analysis of the modulation polarization spectrum at 77 K. The phosphorescence properties of xanthone are also investigated.
  • Hideaki Matsuura, Yasushi Kai, Noritake Yasuoka, Nobutami Kasai
    1980 年 53 巻 2 号 p. 359-361
    発行日: 1980年
    公開日: 2006/04/19
    ジャーナル フリー
    The molecular structure of the sole photocycloaddition product of α-naphthonitrile with phenyl vinyl ether, C19H15ON was determined by means of X-ray diffraction. The crystals are monoclinic, space group P21/c, unit-cell dimensions are a=11.563(2), b=9.826(1), c=14.324(2) Å, β=113.46(1)°, Z=4. The structure was solved by the direct method, the final R value being 0,042 for 2022 non-zero reflections. The molecule has an endo-configuration, and the cyclobutane ring is puckered.
  • Hitofumi Taniguchi, Tatsuo Masuda, Kazuo Tsutsumi, Hiroshi Takahashi
    1980 年 53 巻 2 号 p. 362-365
    発行日: 1980年
    公開日: 2006/04/19
    ジャーナル フリー
    Heats of adsorption of ammonia on specifically poisoned silica–alumina were measured by use of a twin-conduction-type calorimeter in order to elucidate the adsorption energy and acid strength distributions for both Brönsted (hereafter referred to as B) and Lewis (L) acid sites. Infrared spectra of adsorbed pyridine and cumene cracking activity for the poisoned sample were also examined. Sodium alcoholate–alcohol solution was used as the reagent poisoning only B sites. The use of sodium 2-propanolate–2-propanole dilute solution of which sodium contents was approximately equal to the expected amount of proton on silica–alumina surface caused a large portion of B sites to be poisoned without the decrease in the number of L sites. The following conclusions could be drawn from the experimental results that i) above 115 kJ/mol of the differential heat of adsorption of ammonia no B acid sites were present but only L acid sites, and ii) B acid sites existed chiefly in the vicinity of the adsorption energy distribution of 110 kJ/mol.
  • Yoshio Fukuda, Toshiro Fukushima
    1980 年 53 巻 2 号 p. 366-371
    発行日: 1980年
    公開日: 2006/04/19
    ジャーナル フリー
    Tartaric acid does not produce uniform films on A6063 alloy (Al–Mg–Si). Uniform films are formed when oxalic acid is added to the tartaric acid bath, but hardness above Hv 400 cannot be obtained at a voltage below 100 V. When 1 mol dm−3 tartaric acid–0.4–0.6 mol dm−3 oxalic acid baths were adjusted with triethanolamine (0.26–0.54 mol dm−3) to pH 1.00 and 1.25, crack-free films with hardness above Hv 430 were formed at 40 °C in the range 65–85 V. The hardness of the film is independent of the anion content of the film, increasing with increase in the thickness of cell wall and lowering in porosity.
  • Takeo Yamaguchi, Akira Yamauchi, Eiji Kimoto, Hideo Kimizuka
    1980 年 53 巻 2 号 p. 372-376
    発行日: 1980年
    公開日: 2006/04/19
    ジャーナル フリー
    Nitroxide spin labeled surfactant, sodium salt of 2-ethyl-2-[9-(hydroxysulfonyloxy)nonyl]-4,4-dimethyloxazolidin-3-yloxyl, was synthesized and some properties of the compound were studied by means of ESR and conductivity measurements. From conductivity measurements it was found that the critical micelle concentration of the compound was 21.6 mmol kg−1 at 25.0±0.1 °C and the micelle consisted of a small number of labeled surfactant ions. The ESR spectra of the labeled surfactant were measured as a function of concentration and temperature. These spectra showed a typical pattern interpreted in terms of spin exchange. Regarding spin exchange as chemical reaction, second order rate constant was determined from the analysis of line width and compared with the values obtained by diffusion controlled model.
  • Noriko Tani, Asako Kawamori, Haruka Yamada
    1980 年 53 巻 2 号 p. 377-382
    発行日: 1980年
    公開日: 2006/04/19
    ジャーナル フリー
    When 1,1-diphenylethylene (DPE) was adsorbed on porous Vycor glass (PVG) or silica–alumina, some unstable reaction intermediates, blue, green, and yellow species, were formed. The blue species produced on the silica–alumina showed a characteristic band at 1525 cm−1, assigned to the shifted C=C stretching band, which disappeared in the green and yellow samples; it also showed an ESR signal. This indicates that the unstable blue species is probably a cation radical (Remark: Graphics omitted.). The infrared spectra of the green and yellow species on the silica–alumina showed new bands, ascribed to the –CH3 and –CH2– vibrations, which were in good agreement with the resonance Raman bands of the carbonium ions formed on the PVG. The green and yellow intermediates, therefore, should be two kinds of carbonium ions. The structures, formation mechanisms, and surface coverages of these intermediates are discussed.
  • Akio Takenaka, Masuhiro Kato, Yoshio Sasada
    1980 年 53 巻 2 号 p. 383-387
    発行日: 1980年
    公開日: 2006/04/19
    ジャーナル フリー
    The crystal structure of 5-methylcytosine hemihydrate has been determined by an X-ray analysis to investigate the substitution effect on the cytosine moiety. The space group is C2/c, with unit-cell dimensions a=17.832(4), b=8.261(2), c=10.641(3) Å, β=125.12(1)°, and Z=8. The hydrogen bonding scheme is quite different from that of cytosine, its monohydrate, 5-bromocytosine, and its dioxane hemi-solvate. This is ascribed to the packing effect of the methyl group. A comparison with the cytosine structure indicates some deviations in bond lengths and angles, which are due to the steric and electronic effects caused by methylation. The similar values of the C(2)–N(3)–C(4) angle in cytosine and 5-methylcytosine can be related to a resemblance of their pKa values.
  • Nobuatsu Watanabe, Kazuo Ueno
    1980 年 53 巻 2 号 p. 388-390
    発行日: 1980年
    公開日: 2006/04/19
    ジャーナル フリー
    Graphite fluoride, (CF)n, was photolyzed in alcohols and hydrocarbons. Hydrogen fluoride was formed in each case. Alcohols were partially converted into the corresponding carbonyl compounds by the reaction 2(C–F)+RR′CHOH\oversethν→2(C)+2HF+RR′C=O. ESCA measurement revealed that the fluorine at the surface decreases more rapidly than that of the inner region of (CF)n particle, the inner region being also photolyzed. Results of DTA measurement indicate that the irradiation reduces the thermostability of (CF)n.
  • Seiji Kawamoto, Yu Yokoyama, Shigero Ikeda
    1980 年 53 巻 2 号 p. 391-394
    発行日: 1980年
    公開日: 2006/04/19
    ジャーナル フリー
    Photoacoustic spectrometry was applied to the determination of michroamount of Hg diphenylcarbazone complex. The photoacoustic spectrum and diffuse reflectance spectrum almost agree with each other, showing an absorption maximum at 560 nm, as in the absorption spectrum of the complex in benzene solution. Determination of Hg was performed by measuring the intensity of photoacoustic signal at 560 nm. The normalized signal intensity increased linearly with the amount of mercury ion up to 100 ng, deviating from linear relationship downwards above 100 ng. The photoacoustic signal saturation caused by strong absorption of radiation was investigated.
  • Yukihiro Yamamoto, Yoichi Shimura
    1980 年 53 巻 2 号 p. 395-401
    発行日: 1980年
    公開日: 2006/04/19
    ジャーナル フリー
    Several chromium(III) and cobalt(III) complexes with (S)-N,N′-bis(2-pyridylmethyl)propylenediamine (S-picpn) were prepared and their structures assigned. The [CoCl2(S-picpn)]+ complex was reassigned to have cis-α configuration. The Δ and Λ diastereomers of [CrX2(S-picpn)]+ of cis-α. configuration were obtained (X=Cl and Br) and their absorption and circular dichroism spectra were discussed.
  • Shuzo Tokunaga, Jiro Shiokawa
    1980 年 53 巻 2 号 p. 402-406
    発行日: 1980年
    公開日: 2006/04/19
    ジャーナル フリー
    The characteristics and mechanism of the adsorption of orthophosphate on a commercial synthetic silica–alumina, Neobead D, were studied. The adsorption rate increased with decrease in pH and increase in the dose of silica–alumina below the concentration of 4 g dm−3. The adsorption almost terminated in 24 h, but a very slow reaction was observed even after 3 d. The adsorption isotherm follows the Freundlich equation, the inflection in the log-log plot indicating difference in the adsorption mechanism between low and high phosphate concentrations. The adsorption capacity increased with decrease in pH, being the highest at an initial pH of 3.0. The silica–alumina exhibited buffer action, phosphate-free solutions of pH 4–10 showing pH of ca. 6 after 24 h. In coincidence with and in proportion to the adsorption, release of hydroxide, sulfate and silicate ions occurred in the reaction of initial pH of 4.7. The sum of the equivalents of the three anions released could well account for the moles of phosphate adsorbed. The adsorption thus proceeds mainly through the ion-exchange process between phosphate in solution and the anions on the solid, univalent phosphate ions taking part in the reaction.
  • Kazutoyo Endo, Michiaki Furukawa, Hideo Yamatera, Hirotoshi Sano
    1980 年 53 巻 2 号 p. 407-410
    発行日: 1980年
    公開日: 2006/04/19
    ジャーナル フリー
    The lifetimes of ortho-positronium (o-Ps) have been measured in benzene solutions of β-diketonates of iron(III) and cobalt(III). A trend in substituent effect on the acceleration of o-Ps decay has been found. A substituent such as trifluoromethyl, that tends to withdraw electrons from the chelate ring, greatly accelerated o-Ps decay; the greatest rate constant observed was 33.8×109 M−1 s−1 for tris(hexafluoroacetylacetonato)iron(III). An electron-releasing substituent such as t-butyl accelerated o-Ps decay to a lesser extent, e.g. 10.5×109 M−1 s−1for tris(dipivaloylmethanato)iron(III). The extent to which a complex accelerated o-Ps decay was largely related to the redox potential, which was observed by cyclic voltammetry. Complexes with phenyl substituents in the ligand showed slightly smaller effects than that suggested by their redox potentials.
  • Hiroto Watanabe, Takashi Ueda
    1980 年 53 巻 2 号 p. 411-415
    発行日: 1980年
    公開日: 2006/04/19
    ジャーナル フリー
    A selective enrichment procedure for copper, cadmium, and lead is described. This method is based on precipitating the three elements with 6-anilino-1,3,5-triazine-2,4-dithiol (ATD) or with a combination of ATD and benzyldimethyltetradecylammonium chloride (BMTAC), filtering the precipitates to form a suitable X-ray sample, and then analyzing the sample by means of X-ray fluorescence. Microgram amounts of the three elements were precipitated quantitatively with ATD from 50 cm3 or less of aqueous solutions of pH 7. Several to several tens mg amounts of such other elements as aluminium, iron(III), vanadium(V), zinc, arsenic(III, V), nickel, cobalt, and manganese(II) do not form any precipitates in the presence of citrate. Quantitative recoveries of the three elements from aqueous solutions ranging from 200 to 500 cm3 were also possible when BMTAC was present as a coagulant aid. ATD was used for the determination of the three elements in reference materials (Orchard Leaves and Pepperbush Leaves). The results agreed with the certified values and with those obtained by isotope-dilution mass-spectrometry, and the precisions were satisfactory. The three elements in hot-spring water at levels from several to several tens ppb were determined by using a combination of ATD and BMTAC.
  • Taitiro Fujinaga, Yukio Nagaosa
    1980 年 53 巻 2 号 p. 416-420
    発行日: 1980年
    公開日: 2006/04/19
    ジャーナル フリー
    A selective and sensitive method is presented for the determination of cadmium(II), based on polarography after salting-out extraction into acetonitrile. The effect of nonaqueous solvents, salting-out agents, and the concentration of reagents has been studied. Under the conditions established, the cadmium(II) iodide complex extracted into the solvent gives a well-defined d.c. wave and a sharp a.c. peak, with E1⁄2 and Ep=−0.72 V vs. SCE respectively. Down to 0.50 ppm of cadmium(II) in the original aqueous solution can be determined by the proposed method. Lead(II) and In(III) do not interfere up to a 1000-fold amount relative to Cd(II). Interference from Fe(III) and Tl(III) can be eliminated by the addition of ascorbic acid.
  • Fumio Wada, Tsutomu Matsuda
    1980 年 53 巻 2 号 p. 421-423
    発行日: 1980年
    公開日: 2006/04/19
    ジャーナル フリー
    Among twelve crown ethers of 12, 15, 18, and 21 rings only benzo-15-crown-5 and those with an electron-releasing substituent formed the complexes with aluminium chloride which were stable in methanol.
  • Hiroaki Kido, Kazuo Saito
    1980 年 53 巻 2 号 p. 424-428
    発行日: 1980年
    公開日: 2006/04/19
    ジャーナル フリー
    Tris(acetylacetonato[2-14C])iron(III) undergoes ligand exchange in acetylacetone at 4–16 °C without side reactions. The exchange rate is expressed by Rate=(ka+kb[H2O])[complex]([complex]≈0.01 M, [H2O]≈0.05 M), and the rate constant (10.2 °C) and activation parameters are ka=(8.9±1.2)×10−4 s−1, ΔH\ eweq=14.4±0.9 kcal mol−1, ΔS\ eweq=−22±3 cal K−1 mol−1 and kb=(2.22±0.20)×10−2 M−1 s−1, ΔH\ eweq=16.9±0.4 kcal mol−1, ΔS\ eweq=−6.1±1.3 cal K−1 mol−1 (1 cal=4.18 J, 1 M=1 mol dm−3). No deuterium isotope effect on the rate. The rate-determining steps seem to correspond to the formation of intermediates containing a one-ended acac and an Hacac molecule (the ka path), and the anion and a water molecule (the kb path), by the SN2 mechanism.
  • Tomio Shimizu, Yoshiyuki Hayashi, Yoshio Nagano, Kazuhiro Teramura
    1980 年 53 巻 2 号 p. 429-434
    発行日: 1980年
    公開日: 2006/04/19
    ジャーナル フリー
    The reaction of the p-tolyl(or phenyl)sulfonylhydrazones of some 2-(alkenyloxy)benzaldehydes with lead tetraacetate leads, via the nitrile imide intermediates, Ar–\overset+C=N–\overset−N–SO2–C6H4–X-p, to intramolecular 1,3-dipolar cycloadducts and 1-acetyl-2-aroyl-1-[p-tolyl(or phenyl)sulfonyl]hydrazines in 20–65% and 7–70% yields respectively, while the intermolecular reactions of the benzaldehyde p-tolylsulfonylhydrazone with a dipolarophile such as acrylonitrile or styrene in the presence of lead tetraacetate gives only 1-acetyl-2-benzoyl-1-(p-tolylsulfonyl)hydrazine. The treatment of the N-(p-tolylsulfonyl)-o-(allyloxy)benzohydrazonoyl chloride (10) with triethylamine or by refluxing a benzene solution of 10 also gives an intramolecular 1,3-dipolar cycloadduct in a good yield.
  • Kentaro Okuma, Hiroshi Minato, Michio Kobayashi
    1980 年 53 巻 2 号 p. 435-437
    発行日: 1980年
    公開日: 2006/04/19
    ジャーナル フリー
    The optically active methoxymorpholino-p-tolylsulfonium salt has been synthesized by the reaction of optically active N-p-toluenesulfinylmorpholine with methyl trifluoromethanesulfonate. The sulfonium ion methylated benzylethylphenylamine and benzyl ethyl sulfide with asymmetric induction to give the optically active benzylethylmethylphenylammonium ion and benzylethylmethylsulfonium ion respectively. The optically active methoxymorpholino-p-tolylsulfonium salt and diaminosulfonium salts have been prepared in a one pot reaction between N-p-toluenesulfenyImorpholine and 1-chlorobenzotriazole with methanol in the presence of 1-menthol at −80 °C.
  • Seizi Kozuka, Ikuya Naribayashi, Jun-ichi Nakagami, Kenji Ogino
    1980 年 53 巻 2 号 p. 438-441
    発行日: 1980年
    公開日: 2006/04/19
    ジャーナル フリー
    The mechanism for the process giving trimethyl(benzoyloxy)stannane by the reaction of benzoyl peroxide with trimethylphenylstannane or tetramethylstannane has been investigated. The kinetic results exclude the possibility that the decomposition of the peroxide is induced by the stannanes. The addition of dicyclohexylcarbodiimide as a trapping agent for benzoic acid markedly depressed the yield of the benzoyloxystannane by the reaction of trimethylphenylstannane, suggesting that the benzoyloxystannane is mainly or exclusively produced by the protodestannylation reaction of trimethylphenylstannane with benzoic acid. In the reaction of tetramethylstannane with benzoyl peroxide, trimethyl(benzoyloxy)stannane was formed only when a large excess of the stannane was used, and dicyclohexylcarbodiimide showed no significant effect upon the formation of the benzoyloxystannane. A homolytic process has been suggested for the reaction giving the benzoyloxystannane from tetramethylstannane.
  • Takeshi Kinoshita, Hiroko Watanabe, Sadao Sato, Chihiro Tamura
    1980 年 53 巻 2 号 p. 442-445
    発行日: 1980年
    公開日: 2006/04/19
    ジャーナル フリー
    The reactions of α-aminoacetonitriles with isothiocyanates gave 1-cyanomethyl-1,3-disubstituted thioureas or 1,3-disubstituted 4-amino-4-imidazoline-2-thiones depending upon the reaction conditions. In the presence of polar organic solvents such as methanol the former products were easily cyclized to the latter. 1,3-Disubstituted 4-amino-4-imidazoline-2-thiones were autoxidized in methanol affording 1,3-disubstituted 5-imino-2-thiohydantoins.
  • Kazushi Arata, Makoto Hino
    1980 年 53 巻 2 号 p. 446-449
    発行日: 1980年
    公開日: 2006/04/19
    ジャーナル フリー
    The acetylations of toluene and benzene with acetyl halides and acetic anhydride were studied over catalysts prepared by heat-treating FeSO4 in air, followed by activation on exposure to benzyl chloride in toluene or benzene at 40–80 °C for 1 h, together with FeCl3 and AlCl3. The sulfates treated at 700 and 800 °C showed high activity. The former, activated at 60 °C, gave 68% methylacetophenones, and the latter, more than 90%, with an isomer distribution of 2% ortho-, 1% meta-, and 97% para-form in the reaction of toluene with acetyl halides at room temperature, while the maximum yield was 24% with FeCl3 and 29% with AlCl3. A high yield of acetophenone, 77%, was obtained over the FeSO4 (700 °C) catalyst in the reaction of benzene with acetyl bromide at 60 °C for 1 h. The present catalysts were also highly active for the acetylation of toluene with acetic anhydride; e.g., 55% methylacetophenones were obtained over the FeSO4 (800 °C) catalyst at 100 °C for 5 h. FeCl3 and AlCl3 gave quite low yield compared with the present catalysts.
  • Kazushi Tokita, Tetsuo Takemura, Shoichi Kondo, Nobuo Mori
    1980 年 53 巻 2 号 p. 450-454
    発行日: 1980年
    公開日: 2006/04/19
    ジャーナル フリー
    The relationships between the aryl carbon chemical shifts and the CNDO/2 electron densities for several [2.2]cyclophanes are reported. Plots of the chemical shifts against the excess total electron densities indicate additional downfield shifts of 6–9 ppm on the average for those aryl carbons that are in close proximity to other aryl carbons. A plot of the 13C shielding constant, calculated using the Karplus-Pople theory, against the chemical shift shows a downfield shift of a similar magnitude for the proximate carbons relative to the others. It is found that this difference can be essentially eliminated simply by adjusting the ΔE parameter in the Karplus-Pople equation from 10.0 eV to 9.7 eV for the proximate carbon atoms.
  • Seiichiro Ogawa, Tatsushi Toyokuni, Masaji Omata, Noritaka Chida, Tets ...
    1980 年 53 巻 2 号 p. 455-457
    発行日: 1980年
    公開日: 2006/04/19
    ジャーナル フリー
    New cyclitols, validatol and deoxyvalidatol, derived by hydrogenolysis of antibiotic validamycin A, were synthesized as the racemates from readily available tri-O-acetyl-(1,3/2,4,6)-4-bromo-6-bromomethyl-1,2,3-cyclohexanetriol.
  • Masashi Inoue, Keizo Chano, Osamu Itoh, Toshio Sugita, Katsuhiko Ichik ...
    1980 年 53 巻 2 号 p. 458-463
    発行日: 1980年
    公開日: 2006/04/19
    ジャーナル フリー
    The Friedel-Crafts reaction of toluene and anisole with 2-methyloxirane and 2,3-dimethyloxiranes was examined. The inter- and intramolecular selectivities of 2-methyloxirane were between those of conventional methylation and isopropylation. It was also found that all the positional isomers formed by the aluminum chloridecatalyzed reaction of toluene and anisole had almost completely inverted configurations of the epoxide carbons. These results are explained by a mechanism of the SN2 type. Diminished stereospecificities were observed in aluminum bromide-catalyzed reactions.
  • Yoshihiro Masui, Naoyoshi Chino, Shumpei Sakakibara
    1980 年 53 巻 2 号 p. 464-468
    発行日: 1980年
    公開日: 2006/04/19
    ジャーナル フリー
    The formation of a component, X, was observed when a reaction mixture of t-butyloxycarbonyl-tryptophan (Boc-Trp), trifluoroacetic acid (TFA), and 1,2-ethanedithiol was analyzed by cellulose TLC. The side product was isolated and further separated into two components by column chromatography on silica gel. The subsequent analysis of the NMR spectra of these components confirmed that they were Nin-But-Trp and Cin-But-Trp. The reaction of Boc-Trp with TFA and with anhydrous hydrogen fluoride (HF) was examined as model systems in order to determine conditions which would minimize the formation of the X component during the synthesis of peptides containing Trp. The addition of 10 molar equivalents of 1,2-ethanedithiol completely suppressed the formation of the X component in HF, but additives were less efficient in TFA. A combination of dimethyl sulfide and 1,2-ethanedithiol was the most effective method for suppressing the formation of the X component in TFA. The behavior of Nin- and Cin-But-Trp in acidic media was also investigated, and a possible pathway for the t-butylation of the tryptophyl residue will be proposed.
  • Hiroshi Yamaoka, Ikuhiro Mishima, Mitsuko Miyamoto, Terukiyo Hanafusa
    1980 年 53 巻 2 号 p. 469-477
    発行日: 1980年
    公開日: 2006/04/19
    ジャーナル フリー
    The monocyclopropanation of 4-pyrones with dimethyloxosulfonium methylide, using a dimethyl sulfoxide hexamethylphosphoric triamide medium in place of neat dimethyl sulfoxide, gave homo-4-pyrone derivatives, which were then rearranged into the 2-furylacetone derivatives, along with hydra ted triketones or the dehydrated naphtho[2,1-b]furan derivative, by means of strong acid catalysis at room temperature.
  • Waichiro Tagaki, Yoshiharu Tamura, Yumihiko Yano
    1980 年 53 巻 2 号 p. 478-480
    発行日: 1980年
    公開日: 2006/04/19
    ジャーナル フリー
    Three thiazolium salts, 3-[2-(l-3-p-menthyloxy)ethyl]thiazolium bromide (1), 3-(l-3-p-menthyl)thiazolium halides (2), and 3-(l-3-p-menthyl)-4-methylthiazolium perchlorate (3) have been examined for the catalysis of benzoin condensation in micellar two-phase media. The catalytic activities on the chemical yields of benzoin were observed to be high for 1 and 2 but low for 3. On the contrary, for the asymmetric induction, 3 gave much higher optical purity of 35.3% than in the cases of 1 and 2 (0.8–3.5%). These results are discussed in terms of micellar and conformational effects.
  • Tadashi Mizuno, Yohji Nakatsuji, Shozo Yanagida, Mitsuo Okahara
    1980 年 53 巻 2 号 p. 481-484
    発行日: 1980年
    公開日: 2006/04/19
    ジャーナル フリー
    Alkyl-15-crown-5 and alkyl-12-crown-4 were prepared via polyethylene glycol β-haloalkyl ethers in two steps from terminal olefins, and their complexing ability with cations of alkali and alkaline earth metals was measured by using 1H NMR; it was found to be almost identified with that of the corresponding unsubstituted crown ether. A new type of alkyl crown ether with a chloro substituent could also be synthesized according to this method.
  • Otohiko Tsuge, Satoshi Urano, Takahiko Iwasaki
    1980 年 53 巻 2 号 p. 485-489
    発行日: 1980年
    公開日: 2006/04/19
    ジャーナル フリー
    Trimethylsilyl cyanide (1) and N-(trimethylsilyl)diphenylmethyleneamine (2) reacted with α-aryl-N-phenyl-nitrones to afford the corresponding 1: 1 adducts 4 and 5 respectively. Thermal decomposition of 4 in refluxing xylene gave azoxybenzene, stereoisomers of 2,3-diarylsuccinonitriles, α-iminonitriles and/or benzanilides, whose yields depended on the nature of substituents on phenyl group of 4. On heating in benzene 5 afforded a mixture of azoxybenzene and meso-N,N′-bis(diphenylmethylene)-1,2-diarylethylenediamines. On the other hand, reactions of 1 and 2 with N-(diphenylmethylene)aniline N-oxide or N-(9-fluorenylidene)aniline N-oxide did not give the corresponding 1: 1 adducts, but instead compounds arising from thermal decomposition of initial 1: 1 adducts were directly obtained. The reaction of 1 with N-(p-diethylaminophenyl)-α-phenylnitrone leading to the corresponding α-imino nitrile is also described.
  • Tetsuo Asakura, Atsuo Nishioka
    1980 年 53 巻 2 号 p. 490-493
    発行日: 1980年
    公開日: 2006/04/19
    ジャーナル フリー
    The 13C-NMR spectra of the N-acetyl-L-alanine methyl ester in solution were observed in order to clarity the solvent effect. The assignment of the two kinds of carbonyl groups was carried out on the basis of the difference in the long-range 1H–13C coupling patterns and the spectral change through the hydrolysis of the ester group in a D2O solution. The internal rotational angle around the N–Cα bond was estimated as −94° from the observed value of 3JC−N−C″−H, using Bystrov equation. In a trifiuoroacetic acid solution, the formation of strong hydrogen bonds accompanying partial protonation between the N-acetyl-L-alanine methyl ester and the solvent was suggested. Moreover, the acetyl C=O group tends to interact with trifiuoroacetic acid more strongly than the alanyl C=O group.
  • Takaaki Horaguchi, Reiko Yamazaki, Teishiro Abe
    1980 年 53 巻 2 号 p. 494-497
    発行日: 1980年
    公開日: 2006/04/19
    ジャーナル フリー
    Some electrophilic substitution reactions and hydrogenation of 4H-cyclopenta[def]phenanthrene (1a), phenanthro[4,5-bcd]furan (1b), and 4H-benzo[def]carbazole (1c) have been investigated. The bromination of 1a and 1b with bromine gave the corresponding 8-bromo derivatives. The bromination of 1c however gave the 1,3,5,7-tetrabromo derivative as the sole product. The benzoylation of 1a and 1b afforded the corresponding 1-benzoyl derivatives, but in the case of 1c, the 1,7-dibenzoyl derivative was obtained together with the 4-benzoyl derivative. It appears that ortho- and para-orientation of the nitrogen atom in 1c is much stronger than that of the methylene group or the oxygen atom in 1a or 1b. Hydrogenation of 1a, 1b, and 1c with palladium–charcoal catalyst afforded the corresponding 8,9-dihydro derivatives (4a, 4b, and 4c). The reduction of 1a and 1c with sodium–ethanol gave 4a and 4c. The reduction of 1b however gave the 3,3a,8,9,9a,9b-hexahydro derivative. It appears that facile hydrogenation of the carbon-carbon double bonds at the 8,9-positions in 1a, 1b, and 1c are due to strain in the fused ring system.
  • Tooru Yoshida
    1980 年 53 巻 2 号 p. 498-501
    発行日: 1980年
    公開日: 2006/04/19
    ジャーナル フリー
    The tautomerism of several solid hydroxy azo compounds has been examined by X-ray photoelectron spectroscopy. It has been found that the proportion of enol and keto tautomers may be readily estimated from the relative intensities of the two peaks in the O(1s) electron spectrum which corresponds to the protonated and deprotonated oxygen atoms. The resonance structures of the sodium salt of 1-phenylazo-2-naphthol and 5-phenylazo-8-quinolinol have been discussed on the basis of the N(1s) and O(1s) electron binding energies.
  • Masahide Yasuda, Chyongjin Pac, Hiroshi Sakurai
    1980 年 53 巻 2 号 p. 502-507
    発行日: 1980年
    公開日: 2006/04/19
    ジャーナル フリー
    The stereospecific photocycloaddition of 1-cyanonaphthalene to indene occured in cyclohexane, benzene, diethyl ether, tetrahydrofuran, and ethyl acetate, giving the endo head-to-head cycloadduct as the sole 1:1-adduct. The mechanism was discussed in terms of the exciplex intermediacy. In methanol or in acetonitrile in the presence of water, the photoreaction gave the dihydrocycloadduct (8), accompanied by the formation of 2-methoxyindan and 2,2′-dimethoxy-1,1′-biindanyl or 2-indanol and 1-hydroxy-2,2′-biindanyl. In these solvents, the reactions were suggested to be initiated by photochemical electron transfer; the methoxylated or hydroxylated compounds are formed by the nucleophilic attack of methanol or water on the indene cation. Anionic species, including the 1-cyanonaphthalene anion, were suggested to play important roles in the formation of 8.
  • Tadashi Teshima, Kunikazu Konishi, Tetsuo Shiba
    1980 年 53 巻 2 号 p. 508-511
    発行日: 1980年
    公開日: 2006/04/19
    ジャーナル フリー
    A cyclic guanidino amino acid, L-epicapreomycidine, isolated from hydrolyzates of protease inhibitors such as chymostatin and elastatinal was synthesized. This amino acid is a diastereomer of L-capreomycidine which is a component amino acid of tuberactinomycin N,O and capreomycin. A new synthetic route from β-hydroxy-DL-orni thine via an aziridine compound to DL-capreomycidine was applied to the synthesis of L-epicapreomycidine starting from erythro-β-hydroxy-L-ornithine. A convenient and one-step technique to obtain L-erythro form from a mixture of four diastereomers of β-hydroxyornithine by means of enzymatic reaction was newly exploited. The synthetic L-epicapreomycidine obtained was identical with natural one in all respects, thus confirming the proposed structure.
  • Tetsuo Otsubo, Takashi Kohda, Soichi Misumi
    1980 年 53 巻 2 号 p. 512-517
    発行日: 1980年
    公開日: 2006/04/19
    ジャーナル フリー
    A series of the title cyclophanes (m, n=2–4) were synthesized by the thermal- and photo-desulfurization methods from dithia intermediates. Their absorption and emission spectra were measured to examine the transannular electronic interaction. The absorption spectra of the title compounds and their TCNE complexes gave the same order of the interaction as seen in the case of double-layered system: [2.2]>[3.3]>[4.4] in neutral state and [3.3]>[2.2]>[4.4] in CT state. The emission spectra are discussed in terms of the existence of excited trimer.
  • Ryoka Matsushima, Ichiro Hirao
    1980 年 53 巻 2 号 p. 518-522
    発行日: 1980年
    公開日: 2006/04/19
    ジャーナル フリー
    On irradiation with light of λ≥365 nm, parent and methoxy-substituted 2′-hydroxychalcones undergo facile photocyclization to give corresponding 4-flavanones in high efficiencies in ethyl acetate or dioxane, whereas in low or nil efficiencies in benzene, chloroform, carbon tetrachloride, ether, acetonitrile, ethanol, or t-butyl alcohol. The low reactivity in benzene is, however, significantly increased by the addition of liquid paraffin to increase the solvent viscosity. 3′,4′-Benzo-2′-hydroxychalcone showed low reactivities in any solvents. The formation of 4-flavanones is neither quenched by triplet quenchers nor depressed by the addition of free radical scavengers. The reaction mechanism is discussed in terms of enolization.
  • Shafiullah, Islamuddin
    1980 年 53 巻 2 号 p. 523-524
    発行日: 1980年
    公開日: 2006/04/19
    ジャーナル フリー
    Pyridine promoted dehydrohalogenation of β-chloro-5-bromo-5α-cholestan-6-one resulting in ring-A aromatization with expulsion of C-10 angular methyl group to give 19-norcholesta-1,3,5(10)-trien-6-one along with 3a,5-cyclo-5α-cholest-7-en-6-one, cholesta-2,4-dien-6-one, and 5α-cholestane-3,6-dione. Similar treatment of 3β-chloro-5,7β-dibromo-5α-cholestan-6-one ends up with the aromatization of ring-A with migration of C-10 angular methyl group to give 1-methyl-19-norcholesta-1,3,5(10)-trien-6-one.
  • Eiichi Narita, Taijiro Okabe
    1980 年 53 巻 2 号 p. 525-532
    発行日: 1980年
    公開日: 2006/04/19
    ジャーナル フリー
    The properties of two kinds of hydrous manganese(IV) oxides (abbreviated as hydrous MnO2) prepared by the reduction of KMnO4 and by the disproportionation of K2MnO4 in alkaline solutions were investigated by means of chemical analysis, X-ray analysis, IR spectroscopy, wide-line NMR spectroscopy, thermal analysis, magnetic susceptibility measurement, etc. The chemical reactivity of the hydrous MnO2 was also evaluated from the extent of oxidation to K2MnO4 by the reaction with an alkaline KMnO4 solution at 80 °C. The properties and reactivity of the hydrous MnO2 predominantly depended on the pH of the suspensions. At a pH 8 or higher, amorphous ternary compounds of manganese(IV) oxide with an approximate composition of K2O·4MnOx·4H2O (x=1.97–2.00) were formed. The IR spectra and wide-line NMR spectra showed that the chemically bound water was in two different forms. The hydrous MnO2 had the greater chemical reactivity, being easily soluble as manganate(VI) ions by the reaction described above. The contents of the chemically bound water and alkali in the hydrous MnO2 decreased with a decrease in the pH of the suspensions and upon the acid-treatment of the precipitates. This variation in the chemical composition caused a decrease in the reactivity and a marked variation in the thermal behavior. The structure of the hydrous MnO2 was discussed on the basis of findings regarding the magnetic susceptibility and its temperature dependence.
  • Katsutoshi Ohkubo, Hiroyuki Sato
    1980 年 53 巻 2 号 p. 533-534
    発行日: 1980年
    公開日: 2006/04/19
    ジャーナル フリー
    A three-center interaction between the (πu)y of strained XC≡CX (X=H,F, or OCH3) and the (πg)y of 3O2 separated the two half-occupied πg MOs of 3O2 on an energy scale of 428–494 kJ/mol causing spin inversion in 3O2. A perepoxide-type 1O2–XC≡CX intermediate once formed is transformed into a stable dioxetene-type 1O2 complex from which the free generation of 2O2 was found to be difficult.
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