Bulletin of the Chemical Society of Japan
Online ISSN : 1348-0634
Print ISSN : 0009-2673
ISSN-L : 0009-2673
43 巻 , 1 号
選択された号の論文の77件中1~50を表示しています
  • Katsutoshi Ohkubo, Tokio Yamabe, Kenichi Fukui
    1970 年 43 巻 1 号 p. 1-8
    発行日: 1970年
    公開日: 2006/03/27
    ジャーナル フリー
    The homogeneous decomposition reaction of cumene hydroperoxide in cumene was studied by the use of triphenylsulfonium chloride over a low-temperature range (30–80°C). The hydroperoxide was decomposed remarkably in the presence of the sulfonium catalyst, whereas in the absence of the catalyst it was decomposed only a little. Among the homolytic decomposition products, acetophenone and dicumyl peroxide were found to be the main products, while α-cumyl alcohol was formed in only a small amount. Moreover, methyl alcohol was found in appreciable amounts. Traces of heterolytic reaction products, such as phenol and acetone, were also detected. After discussing the reaction mechanism and the nature of catalytic action, it is concluded that the partially-occupied d orbital of the sulfonium cation may play a role in breaking the oxygen-oxygen bond of the hydroperoxide homolytically. The counter chloride anion seems to take part in the heterolytic reaction to some extent.
  • Takeshi Ohno, Shunji Kato
    1970 年 43 巻 1 号 p. 8-12
    発行日: 1970年
    公開日: 2006/03/27
    ジャーナル フリー
    Excited states of some chromium(III) complexes were studied by a flash technique at −196°C. Transient species with strong absorption bands in visible and near UV regions were observed to decay at the same rate as their phosphorescence for CrIII(acac)3, K3[CrIII(NCS)6], NH4[CrIII-(NCS)4(NH3)2], and CrIII(exan)3. They are therefore 2E states (phosphorescent states). A strong absorption band for CrIII(acac)3 is assigned to a charge transfer transition from 2E state based on the intensity and energy of the transition. A transition to localized excited states in ligand with a small extinction coefficient was observed in near infrared region for CrIII(acac)3.
  • Hiroaki Baba, Chie Mugiya
    1970 年 43 巻 1 号 p. 13-19
    発行日: 1970年
    公開日: 2006/03/27
    ジャーナル フリー
    Fluorescence and absorption spectra and fluorescence polarization were measured at different temperatures, ranging from room temperature to 77°K, for 9,10-diazaphenanthrene, 2-naphthol and 2,3-naphthalenediol in polar solvents. At about 120°K, the fluorescence spectra shifted rapidly to the blue as the temperature was lowered. This observation is quantitatively interpreted on the basis of a kinetic scheme involving competitive rate processes, viz., radiative transition from the Franck-Condon excited state, as defined for the dipole orientation of the solvent, and relaxation of the Franck-Condon state into the equilibrium excited state. The Franck-Condon destabilization energies are evaluated from the observed blue shifts. Along with the fluorescence blues hifts, the degrees of polarization increased rapidly, but at a somewhat higher temperature of about 140°K. This phenomenon is related to the rotational relaxation of the solute molecule, and is discussed in comparison with the fluorescence blue shift.
  • Hirofumi Okabayashi, Toshizo Isemura
    1970 年 43 巻 1 号 p. 20-23
    発行日: 1970年
    公開日: 2006/03/27
    ジャーナル フリー
    The electronic excited states in L-proline oligopeptides were derived from molecular-exciton theory. The dipole-dipole approximation was used in the calculation of transition energies. The calculated absorption spectra related to the conformation of L-proline oligopeptides were compared with observed ones. A satisfactory agreement between the calculated and observed results was obtained.
  • Kazuo Fueki, Hideaki Inaba, Takashi Mukaibo
    1970 年 43 巻 1 号 p. 23-30
    発行日: 1970年
    公開日: 2006/03/27
    ジャーナル フリー
    The isotopic exchange between H2S and D2 has been followed in the temperature range 425–525°C on a cuprous sulfide specimen. At high sulfur activities of Cu2S, the predominant reaction is H2S+D2=H2+D2S, and at moderate sulfur activities the same reaction is predominant in the initial period. Analysis of kinetic data shows that the exchange reaction is first order. From the first-order rate constant, ki, the rate constant of sulfidation of Cu2S by “hydrogen sulfide”* and ki′, the rate constant of reduction of Cu2S by “hydrogen”* are determined. It is shown that ki is inversely proportional to the sulfur activity of Cu2S and that ki′ is independent of it. Dependence of ki and ki′ on sulfur activity is interpreted on the basis of a theory proposed by Kobayashi and Wagner. The formation of HD becomes remarkable as the sulfur activity of Cu2S decreases. This finding shows that the reaction, H2S+D2=HD+HDS, becomes appreciable with the decrease in sulfur activity.
  • Masahiro Kotani, Hideo Akamatu
    1970 年 43 巻 1 号 p. 30-33
    発行日: 1970年
    公開日: 2006/03/27
    ジャーナル フリー
    A vibrating-reed type cell for measuring contact potential difference was constructed and successfully applied for organic crystals. From the observed contact potential difference for violanthrene against graphite, the work function has been estimated as 4.50±0.1 eV. In association with the activation energy for electrical conductivity, 0.8–0.9 eV, the electronic energy diagram for violanthrene has been illustrated, which revealed the extrinsic nature of semiconduction and the energy gap, 2.3–2.5 eV, being comparable with the first excited singlet state of violanthrene molecule.
  • Tadashi Sasa, Yoichi Takahashi, Takashi Mukaibo
    1970 年 43 巻 1 号 p. 34-38
    発行日: 1970年
    公開日: 2006/03/27
    ジャーナル フリー
    Polycrystalline graphite was allowed to react with bromine vapor, and the change of its electrical conductivity during the course of bromination and debromination was studied. The graphite was found to behave in two different ways depending on the process of bromination. When the vapor pressure of bromine was changed stepwise, following the equilibrium line of bromine absorption of graphite, the electrical conductivity showed a reversible change. On the other hand, when a graphite sample was brominated with the saturated vapor, an increase of the electrical conductivity steeper than that of the former case was observed. These results were discussed in relation to the structural analysis of the brominated graphite. A metastable phase of graphite bromide, the electrical conductivity of which remained unchanged in spite of a considerable increase of absorbed bromine, was found. The electrical conductivity of the residue compounds was also investigated, and a steep decrease was observed at high concentrations of bromine.
  • Kunio Fukushima
    1970 年 43 巻 1 号 p. 39-41
    発行日: 1970年
    公開日: 2006/03/27
    ジャーナル フリー
    The far infrared spectra of potassium oxalate monohydrate and its deutero analog in their crystalline state were measured. Assignment of the infrared absorption bands was made on the basis of frequency shift associated with deuterium substitution of hydrogen atoms in water of crystallization and also on the basis of comparison of neutron scattering spectra of the compounds with the infrared spectra.
  • Nobuyuki Nishi, Ryoichi Shimada, Yoshiya Kanda
    1970 年 43 巻 1 号 p. 41-46
    発行日: 1970年
    公開日: 2006/03/27
    ジャーナル フリー
    The phosphorescence spectra of pyrimidine and 2-chloropyrimidine have been observed at 4.2°K. A detailed vibrational analysis of the pyrimidine spectrum suggests that the emission arises from two components of the emitting triplet state. The phosphorescence lifetimes of pyrimidine and 2-chloropyrimidine have been measured for the 0-0 band and the strongest “vibronic band” (the phosphorescence maximum), which involves various modes of vibrations, at different temperatures between 77 and 1.5°K. The decay curve observed for the 0-0 band has been resolved into two exponential components, and that for the vibronic band, into three exponential components, where the third component was extremely weak in intensity at a very low temperature. From the comparison of the observed and calculated lifetimes of the individual phosphorescence components and their relative intensities, it was deduced that: (1) the 0-0 band involves emissions arising from the B2 and A1 components of the 3B1(n*) state, while the vibronic band involves an additional, third emission which very likely arises from the A2 component; (2) the 1A2(n*) state is located below the 1B1(n*) state; (3) the 3A1(π,π*) state is located below the 1A2(n*) state, and (4) the major intersystem crossing takes place from both the 1A2(n*) and 1B1(n*) states to the 3A1(π,π*) state in pyrimidine and 2-chloropyrimidine.
  • Tsuneo Matsuda, Takashi Furukawa, Shigeyasu Togo, Toyosuke Tanaka
    1970 年 43 巻 1 号 p. 47-52
    発行日: 1970年
    公開日: 2006/03/27
    ジャーナル フリー
    The initial rate and the aging effect of ethylene polymerization with TiCl4- and TiCl3-AlEt3 catalyst were investigated. The initial rate, r, was expressed by the equation; r=k1PE+k2PE2, where pE is the ethylene partial pressure and where k1 and k2 are constants. The explanation of the equation is as follows:
    &(active site)+M\xrightarrowk_1(polymerization site), rate, k_1P_E
    &(polymerization site)+M^*\xrightarrowk_2(propagation), rate, k_2P_E^2
    M shows the ethylene monomer which is liberated by the catalyst formation or which is introduced into the system. M* is the monomer which is introduced into the system. The initial rate decreased in the TiCl4-AlEt3 system with the aging-time interval; on the other hand, in the TiCl3-AlEt3 system the rate showed its maximum at about half an hour’s aging. The optimum aging temperature was found to be 20°C. The decrease in the rates between the two systems may be ascribed to the reduction of the Ti atom in the initial valence state of the reaction to the lower valence.
  • Hiroshi Fujimoto, Yoshihiko Kitagawa, Hideyuki Hao, Kenichi Fukui
    1970 年 43 巻 1 号 p. 52-56
    発行日: 1970年
    公開日: 2006/03/27
    ジャーナル フリー
    The chemical reactivity of hydrogens in adamantane and substituted adamantanes has been calculated. The results of calculation have shown that the bridgehead hydrogens are most reactive toward electrophilic reagents or radicals. The chemical reactivity of hydrogens in diamantane, triamantane, and tetramantane has also been predicted. A discussion has been made of the stable configuration of the 1-adamantyl cation, radical, and anion and of the nature of the back-side conjugation between the two tertiary carbons in these species. A mode of the electrocyclic polymerization of p-quinodimethane to form polyamantane has been predicted on the basis of the symmetry properties of the frontier orbitals in the pi and sigma parts of p-quinodimethane.
  • Nobuko Sakai, Ichimin Shirotani, Shigeru Minomura
    1970 年 43 巻 1 号 p. 57-63
    発行日: 1970年
    公開日: 2006/03/27
    ジャーナル フリー
    The effect of pressure up to 7 kbar on the electronic absorption spectra of the crystalline TCNQ anion radical salts and Li(TCNQ) in PVA has been studied. For simple TCNQ salts such as Li(TCNQ), a blue shift with an increase in the pressure has been observed in the absorption band associated with the intramolecular transition. The magnitude of the blue shift is between 45 and 86 cm−1/kbar. The observed shift has been discussed in terms of the crystal-field effect of the cations. For N-MePhe(TCNQ) and M(TCNQ)2, composed of the formally-neutral TCNQ and its anion radical such as TEA(TCNQ)2, a pressure-induced absorption band has been observed at around 20 kK; it may be assigned to the charge-transfer band between the anion radicals.
  • Enzo Tachikawa
    1970 年 43 巻 1 号 p. 63-67
    発行日: 1970年
    公開日: 2006/03/27
    ジャーナル フリー
    The reactions of 80Br and 82Br excited by the isomeric transition processes with CH4 have been compared with each other. Similar reaction processes; energetic and thermal ionic, are involved in both cases. However, the isotope effect appears in the energetic process to form CH3Br, but not in the thermal ionic process to form CH3Br and CH2Br2. The difference in the γ-transitions of 80mBr and 82mBr to the ground states is responsible for the above results. It is concluded that at least a part of the recoil Br atoms enter chemical combinations with surrounding molecules within 10−8sec, the life-time of the excited 80Br atom. Furthermore, the yield of CH380Br, lower than that of CH382Br, is discussed on the basis of the different kinetic energies achieved on the Br atoms.
  • Haruo Shizuka, Motonobu Kato, Toshio Ochiai, Kohji Matsui, Toshifumi M ...
    1970 年 43 巻 1 号 p. 67-74
    発行日: 1970年
    公開日: 2006/03/27
    ジャーナル フリー
    The photochemical reactions of N-acetyl diphenylamine and N-acetyl carbazole in solution have been studied. N-Acetyl diphenylamine and N-acetyl carbazole undergo the photo-Fries-rearrangement by means of 2537Å irradiation. The reaction products consist of the ortho- and para-isomers, plus corresponding amines transformed through the deacetylation of the original compounds. The quantum yields in the early stages of the rearrangement were measured under various conditions by spectrophotometry. The reaction mechanism has been discussed on the basis of the relation between the rate constants of the rearrangement and the odd π electron densities obtained from simple Hückel MO calculations.
  • Teijiro Yonezawa, Takashi Kawamura, Hiroshi Kato
    1970 年 43 巻 1 号 p. 74-80
    発行日: 1970年
    公開日: 2006/03/27
    ジャーナル フリー
    The isotropic hyperfine coupling constants of cyclopropyl, vinyl, formaldiminoxy, formyl, and hydrogen cyanide anion radicals are calculated by a method which corresponds to the extension of the McLachlan procedure. These hyperfine coupling constants are then studied, and the contributions from the spin delocalization and spin polarization mechanisms are estimated. The role of one-center exchange integrals in the estimation of these hyperfine coupling constants is also studied; it is shown to be important in the claculation of the hyperfine coupling constants of the nuclei of the radical-center atom and of the atoms bonded to it.
  • P. S. Radhakrishnamurti, G. P. Panigrahi
    1970 年 43 巻 1 号 p. 81-84
    発行日: 1970年
    公開日: 2006/03/27
    ジャーナル フリー
    The reactions between benzyl bromide and various bases as well as p-nitrobenzyl bromide and various bases have been studied in nitrobenzene-ethanol mixtures (80:20 v/v). The reaction is total second order as stated earlier. Comparison is made with the previous work on the same reaction with benzyl chloride and p-nitrobenzyl chloride.
  • Mutsukazu Kamo, Shigeru Ohashi
    1970 年 43 巻 1 号 p. 84-89
    発行日: 1970年
    公開日: 2006/03/27
    ジャーナル フリー
    The thermal decomposition of uranyl dihydrogen orthophosphate trihydrate was studied by means of paper chromatography, X-ray diffractometry, differential thermal analysis, thermogravi-metric analysis, infrared spectroscopy and chemical analysis. From these studies, it was revealed that in the thermal decomposition of the uranyl salt the following reactions take place. 1) The formation of condensed phosphates with relatively small polymerization degrees such as di- and triphosphates takes place below 300°C, accompanied by the elimination of water. 2) A uranyl salt of long-chain metaphosphate, [UO2(PO3)2]n is produced bewteen 300 and 840°C. 3) The metaphosphate is melted at about 900°C, while uranium(VI) is reduced to uranium(IV) at the same time. 4) As a result of the reduction, the formation of uranium(IV) diphosphate, UP2O7, starts. 5) Finally, almost pure uranium(IV) diphosphate is produced at 1200°C.
  • Mitsuo Hara
    1970 年 43 巻 1 号 p. 89-94
    発行日: 1970年
    公開日: 2006/03/27
    ジャーナル フリー
    The method for preparing Am(V) in various solutions was investigated by utilizing the difference in extractability between Am(V) and Am(III) in an TTA-isobutanol extraction system; Am(III) was quantitatively extracted with 0.1M TTA in isobutanol from a 1M acetate buffer solution at a pH greater than 3, while the percentage of Am(V) extracted into the organic phase was increased substantially with an increase in the pH from 3 to 5. When the organic phase containing Am(V) was shaken with an aqueous phase having a proper pH value and composition, Am(V) was selectively stripped into the aqueous phase. The stability of the valency state of Am(V) in the perchlorate, the acetate, and the sulfate solutions was then studied by examining the variation in the percentage of americium extracted as a function of the standing time. The rate of change in the valency state in the acetate and the perchlorate media is very slow, while it is rather rapid in the sulfate medium. This difference may be attributable to the faster rate of the disproportionation reaction of Am(V) in the last medium than in the former two. By applying the above results, the chemical behavior of Am(V) in the aqueous solution was investigated by TTA extraction; it was found that Am(V) would be in the form of AmO2+ in the absence of a complexing reagent. By the addition of acetate ions, the step-by-step formation of the acetate complex of Am(V) was observed. The stability constants of [AmO2Ac] and [AmO2Ac2] were determined to be (25.0±3.1) (mol/l)−1 and (12.8±1.2) (mol/l)−2 respectively.
  • Kazushi Hirota, Takashi Katsura
    1970 年 43 巻 1 号 p. 94-96
    発行日: 1970年
    公開日: 2006/03/27
    ジャーナル フリー
    The equilibria between the molten Na2CO3 and the Au-Na alloys were determined at 1400°K under CO+CO2 gaseous mixtures. The activity coefficient of Na in the Au-Na alloys was constantly 0.0392±0.0028 at concentrations ranging from 0.2 to 0.02 wt% Na.
  • Hiroshi Ogino, Shigeru Kobayashi, Nobuyuki Tanaka
    1970 年 43 巻 1 号 p. 97-99
    発行日: 1970年
    公開日: 2006/03/27
    ジャーナル フリー
    Synthesis of new complexes of cobalt(II), cobalt(III), nickel(II) and copper(II), [Co2hdta]·6.5H2O, K[Co tdta]·3H2O, [Ni2 hdta]·6.5H2O, Na2[Cu tdta]·6H2O, [Cu2 tdta]·1.5H2O and [Cu2 hdta]·6.5H2O, has been carried out, where tdta and hdta represent (OOCCH2)2N(CH2)4N(CH2-COO)24− and (OOCCH2)2N(CH2)6N(CH2COO)24−, respectively. The infrared, nuclear magnetic resonance and visible and ultraviolet absorption spectra were measured. The infrared and the NMR spectra of the Co(III) complex with tdta indicate that a quadrivalent tdta anion behaves as a hexadentate in this complex.
  • Hiroto Watanabe
    1970 年 43 巻 1 号 p. 100-104
    発行日: 1970年
    公開日: 2006/03/27
    ジャーナル フリー
    The distribution of metal ions between phases of dilute sulfuric acid and carbon tetrachloride containing long-chain primary amine (Primene JM) and di-2-ethylhexylphosphoric acid (D2EHPA) has been investigated. The degree of the extraction of bi- and tervalent metal ions, such as zinc, iron (III), indium, lanthanum, and cerium(III), is found to be the lowest when the organic phase contains 5 g/l of Primene JM and 7–8 g/l of D2EHPA, while a minimum extraction of thorium occurs at a different composition of the organic phase. Thus, thorium can be quantitatively separated from most other metals by extraction from a 0.1N sulfuric acid medium with carbon tetrachloride containing 5 g/l of Primene JM and 7–8 g/l of D2EHPA. Under these extraction conditions, a single extraction is sufficient for the quantitative separation of thorium from high concentrations of lanthanide metals. Contrary to the usual method of extraction using long-chain amines, which involves a tedious multiple extraction, the mixed-extractant technique described is simple and will find many uses in the determinations of thorium in a variety of samples.
  • Toshiaki Nomura
    1970 年 43 巻 1 号 p. 104-108
    発行日: 1970年
    公開日: 2006/03/27
    ジャーナル フリー
    Mercury (II) complexes of EDTA, methylthymolblue, or cresolphthaleincomplexone form mixed-ligand complexes with cyanide, thiocyanate, or iodide ions. These anions can be determined with mercury(II) ethylenediaminetetraacetate, using the other mercury(II) complexes as indicators, because of the difference between the stability constant of the mixed-ligand complex of EDTA and that of the other complexes. The previously reported methods, however, require a calibration curve. The determination was simplified by Titer methods, using these mixed-ligand complexes as indicators. To the anion-sample solutions adjusted to a given pH value with a buffer solution, 5 ml portions of 1×10−4M mercury(II), an organic reagent, and anion solutions were added, these mixtures were then titrated with a 1×10−2M standard mercury (II) ethylenediaminetetraacetate solution. These solutions change in color from pale pink (PC) or yellow (MTB) to red-violet (PC) or blue (MTB) by the end point. The Titer values were determined by the use known of standard anion solutions.
  • Hidetake Kakihana, Masunobu Maeda
    1970 年 43 巻 1 号 p. 109-113
    発行日: 1970年
    公開日: 2006/03/27
    ジャーナル フリー
    The hydrolysis of Be2+ ion in heavy water containing 3M NaClO4 as an ionic medium was investigated at 25°C by potentiometric titrations, employing a technique of constant-current coulometry. The deuterium-ion concentrations was measured by the use of a commercial glass electrode. The emf data in the range of the total beryllium concentration from 2.5 to 10 mM can be explained on the basis of the following complex formation: Be2(OD)3+, −logβ1,2=3.28±0.04; Be3(OD)33+, −logβ3,3=9.399±0.007; Be(OD)2, −logβ2,1=11.89±0.07. The composition of the species formed in heavy water is the same as that in light water, but the values of the stability constants are smaller in heavy water than in light water.
  • Megumu Munakata, Masakazu Matsui, Masayuki Tabushi, Tsunenobu Shigemat ...
    1970 年 43 巻 1 号 p. 114-118
    発行日: 1970年
    公開日: 2006/03/27
    ジャーナル フリー
    The catalytic action of metal ions in the presence of various coordinating agents and a role of metal ions for the activations of an enzyme in a decarboxylation reaction were investigated. Many of the ligands studied decreased the catalytic activity of metal ions. However, α,α′-dipyridyl selectively enhanced the catalytic activities of divalent metal ions, except Cu2+. The activity of Cu2+ was specifically enhanced only with histidine and its derivatives. Histidine destroyed Ni2+ and Co2+ catalysis. The specific enhancement may be due to the increase in the electronegativities of the metal ions with dπ (metal)-pπ(ligand) back donation and to the stereo-configuration of the metal complexes. The catalytic behavior in these metal ion coordinating agent systems was different from that in the metal-enzyme systems. It was assumed that the activation of enzyme resulted from the change in the configuration of enzyme by the coordination of metal ions, and not from the catalytic action of metal ions enhanced by the coordination of enzyme. This was supported by the fact that the catalysis of compounds containing amino groups, active sites of enzyme, remarkably depended on the stereo-configuration. In the enzyme-model system, Mn2+ was generally preferable to Cu2+ and Ni2+. The catalytic actions of Cu2+ and Ni2+ were lowered by the complex formation with the active sites. This may solve the question why, in enzymatic reactions, Mn2+ having small complex-forming ability is more selective and effective than Cu2+ and Ni2+ with large complex-forming abilities.
  • Kazuo Saito, Kazuyo Masuda
    1970 年 43 巻 1 号 p. 119-124
    発行日: 1970年
    公開日: 2006/03/27
    ジャーナル フリー
    The kinetic study concerning isotopic exchange of acetylacetone (acacH) and trisacetylacetonatoaluminum [Al(acac)3] (Bull. Chem. Soc. Jap., 41, 384 (1968)) has been extended to solutions in various organic solvents. Similar catalytic actions of water and acid were observed, and the concentration of acacH did not affect the rate, so that the kinetic formula is expressed by
    R=[complex](k_1+k_2[H_2O]+k_1’[acid]+k_2’[acid][H_2O])
    The rate constants and activation parameters are listed in Table 1. The k1 values are zero in non-polar solvents such as toluene and xylenes, whereas the k2 values are greater in these solvents than in polar solvents such as tetrahydrofuran and ethylacetate. The activation enthalpy is practically constant in these solvents, regardless of the participation of catalysts. The third and the fourth term seem to represent acid-catalysed reaction paths involving different proton carriers. The whole result appears to support our previous tentative conclusions that the exchange proceeds via an intermediate in which one of the acetylacetonate ligands is present as unidentate, and that the ease with which the free end recombines with the aluminum ion is responsible in determining the reaction rates.
  • P. B. Talukdar, S. Banerjee, A. Chakraborty
    1970 年 43 巻 1 号 p. 125-129
    発行日: 1970年
    公開日: 2006/03/27
    ジャーナル フリー
    Kinetic studies of the compound given in the title were conducted in aqueous alcohols over a wide range of pH. The observed rate constants are dependent on the hydroxide-ion concentration as well as polarity of the medium. Hydrolytic decomposition is characterised by a small magnitude of entropy (ΔS*) and negative salt-effect. Mechanism consistent with these facts has been suggested.
  • Seizi Kozuka, Hideo Takahashi, Shigeru Oae
    1970 年 43 巻 1 号 p. 129-134
    発行日: 1970年
    公開日: 2006/03/27
    ジャーナル フリー
    The mass spectra of diaryl disulfides, diaryl thiolsulfinates and diaryl thiolsulfonates have been studied by analyzing metastable peaks and mass numbers. The main fragmentation observed for the disulfides was the cleavage of the S–S bond while the fragmentation of thiolsulfinates was similar to that of disulfides after elimination of oxygen. In the case of thiosulfonates, however, no such deoxygenation was observed, formation of sulfonium ion and one oxygen migration from the sulfone sulfur to the thiol sulfur were observed. Formation of thiabenzonium ion was observed in the mass spectra of sulfinates and sulfonates.
  • Takumi Ishiwaka, Mitsuru Sano, Kakuzo Isagawa, Yasaburo Fushizaki
    1970 年 43 巻 1 号 p. 135-138
    発行日: 1970年
    公開日: 2006/03/27
    ジャーナル フリー
    2-Aminobenzophenone semicarbazones (II) or 2-aminobenzophenone phenylhydrazones (III) were cyclized to 3,7-disubstituted 5-phenyl-2,3-dihydro-1H-benzo[e]-1,3,4-triazepines (IV) by treating them with paraformaldehyde. On the other hand, 3,7-disubstituted 2-oxo-5-phenyl-2,3-dihydro-1H-benzo[e]-1,3,4-triazepines (V) were prepared by the fusion of II at 190–195°C or by the treatment of III with phosgene. In the latter reactions, 1-carboxy derivatives (VI) of V were obtained by using two equimolar amounts of phosgene. Vf was treated with sodium ethoxide to give a ring-cleavage product, 5-chloro-2-ethoxycarbonylaminobenzophenone phenylhydrazone (VIIIf), which was then fused to afford 6-chloro-1,2-dihydro-2-oxo-4-phenylquinazoline (VIIb).
  • Iwao Tanimoto
    1970 年 43 巻 1 号 p. 139-142
    発行日: 1970年
    公開日: 2006/03/27
    ジャーナル フリー
    Kinetic investigation of the Baudisch reaction indicates that the reaction follows first-order kinetics, and the isokinetic temperature lies at −11°C. Both kinetic studies and product studies require the formation of a phenol-copper-hydroxylamine-hydrogen peroxide complex during the course of the reaction. It was found that the yield of o-nitrosophenol which is the main product of the Baudisch reaction is counterbalanced by that of catechol according to the pH of the reaction system. Maximum yield of o-nitrosophenol is attained in the lower pH region (pH=2.5–3.5). Catechol which is the main product in the higher pH region (pH>4) seems to be produced through the same complex.
  • Yasuhiro Yamamoto, Hiroshi Yamazaki
    1970 年 43 巻 1 号 p. 143-147
    発行日: 1970年
    公開日: 2006/03/27
    ジャーナル フリー
    Isocyanides were treated with π-C5H5Mo(CO)3R (R=CH3, CH2Ph) in benzene at room temperature to give π-C5H5Mo (CO)2 (isocyanide)COR (A), which exist as a trans-isomer in the solid state and as a mixture of trans- and cis-isomers in solutions, based on the NMR spectra. The structures of the compounds (A) are discussed on the basis of the spectroscopic studies. Studies on trans to cis isomerization were also carried out kinetically.
  • Heimei Yuki, Yoshio Okamoto
    1970 年 43 巻 1 号 p. 148-151
    発行日: 1970年
    公開日: 2006/03/27
    ジャーナル フリー
    The anionic copolymerization of butadiene (M1) and 1,1-diphenylethylene was investigated in tetrahydrofuran (THF) and benzene, using n-butyllithium (n-BuLi), Na-naphthalene, and Na-and K-dispersions as initiators. An alternating copolymer was formed in THF, where the reaction proceeded without termination and chain-transfer reactions. The monomer reactivity ratios, r1 were 0.13 (Li+), 0.09 (Na+), and 0.09 (K+) in THF at 0°C. The r1 values in benzene at 40°C were 54 (Li+), 0.71 (Na+), and 0.10 (K+). The order of rate constants in THF was k12>k11>k21; the last of these was 0.27M−1 sec−1, with n-BuLi at 0°C.
  • Kazuhiro Maruyama, Masaharu Yoshida, Katsuya Murakami
    1970 年 43 巻 1 号 p. 152-155
    発行日: 1970年
    公開日: 2006/03/27
    ジャーナル フリー
    Phenylxanthyl, phenylthioxanthyl, phenylselenoxanthyl, 9-phenylfluorenyl, dioxadehydrocoranthryl, and their derivatives were studied by the electron spin resonance (ESR) technique, and the odd-electron distribution in the radicals was examined. From the results, the angle between the plane of the phenyl group and the plane of the rest of the molecule was estimated at about 63°. Since these radicals are in equilibria with their dimers, heat of reaction in the system was also determined on two of them. Some discussion of the correlation between the heat of reaction and the molecular shape was undertaken.
  • Takeshi Nakai, Yoshio Ueno, Makoto Okawara
    1970 年 43 巻 1 号 p. 156-162
    発行日: 1970年
    公開日: 2006/03/27
    ジャーナル フリー
    The equimolar reaction of 1,2-dichloroethane with sodium N,N-dimethyldithiocarbamate was studied in various solvents. As major products, ethylene bis(N,N-dimethyldithiocarbamate) and 2-dimethylamino-l,3-dithiolanylium salt (the perchlorate or the tetraphenylborate) were obtained in yields, largely varying with the solvent used. On the basis of the solvent effect on the product ratio, and kinetic experiments it has been verified that neighboring-group participation of the N,N-dimethyldithiocarbamate function would be involved through the intermediacy of the isolated anchimeric carbonium ion, and that such participation is more predominant in nonpolar aprotic solvents such as dioxane and tetrahydrofuran. The mechanism of the reaction between 2-dimethylamino-l,3-dithiolanylium ion and the dithiocarbamate anion was established.
  • Yoshio Ueno, Takeshi Nakai, Makoto Okawara
    1970 年 43 巻 1 号 p. 162-167
    発行日: 1970年
    公開日: 2006/03/27
    ジャーナル フリー
    Thermal ring-isomerization and reactions with epoxides of 2-substituted imino-1,3-dithiolanes (I) were studied. The methylimino (Ia) and ethylimino derivatives (Ib) were found to be ringisomerized to the corresponding 3-alkyl-1,3-thiazolidine-2-thione (V) at about 200°C, while the phenylimino compound (Ic) was not isomerized even under more drastic conditions. The influence of various additives including Lewis acids was also examined. In contrast to the oxygen analog of I, these imino compounds were not polymerized with Lewis acids, and catalysis of any additives on isomerization was not observed. The possibility that I thermally dissociated into methyl isothiocyanate and ethylene sulfide followed by their recombination to V would be excluded by the observation that the reaction of alkyl isothiocyanate with ethylene sulfide at 150°C afforded I in good yield. Reactions of I with epoxides were carried out regarding the isomerization mechanism. All these imino compounds reacted with epoxides to give the 2-oxazolidone derivatives (III) in good yield. Mechanisms of the ring-isomerization and formation of III have been suggested, and the difference in reactivity between I and its oxygen analog has been discussed.
  • Yoshio Ueno, Takeshi Nakai, Makoto Okawara
    1970 年 43 巻 1 号 p. 168-172
    発行日: 1970年
    公開日: 2006/03/27
    ジャーナル フリー
    The reactions of propylene oxide (PO) with various thione-compounds containing two α-hetero atoms including dithiocarbamates, thioncarbamates, trithiocarbonates and thioureas, and their cyclic analogs were studied in the presence of triethylamine or boron trifluoride etherate as a catalyst. It was found that most of these thione-compounds reacted with PO at 170–180°C to afford the corresponding one-compounds in good yields. This type of reaction may provide a new method for the transformation of the C=S bonds in thione-compounds into the C=O bonds. Boron trifluoride etherate appeared to be more effective than triethylamine as the catalyst. The mechanism which involves initial cycloaddition of PO to the C=S bond followed by elimination of propylene sulfide was proposed for the transformation. The reactivities of these thione-compounds were significantly affected by whether they are cyclic or open-chain and by the nature of the α-hetero atoms: the cyclic thione-compounds were more reactive then the open-chain analogs except for a pair of thioureas and the enhancement by the α-hetero atoms was in the order: N,O≈N,N>N,S>S,S. Both observations may be interpreted in terms of basicity of the thione-compounds. These results also support the proposed mechanism for the formation of 2-oxazolidones from 2-substituted imino-1,3-dithiolanes with epoxides in our preceding paper.
  • Miyuki Hagiwara, Hidemasa Okamoto, Tsutomu Kagiya
    1970 年 43 巻 1 号 p. 172-177
    発行日: 1970年
    公開日: 2006/03/27
    ジャーナル フリー
    The 60Co γ-ray induced polymerization of ethylene in a liquid carbon dioxide solvent was carried out under a pressure of 400 kg/cm2 at 30°C in the presence of such alkyl halides as CH2Cl2, CHCl3, CCl4, C2H5Cl, C2H5Br, C2H5I, C2H4Cl2, C2H2Cl4, C2Cl6, C2F6, C2F5Cl, C2F4Cl2, C2H3Cl3, and C2F2Cl4, and their effects on the polymerization rate and the molecular weight of the polymer formed were investigated. Both the rate and the molecular weight were increased by adding C2F4-Cl2, C2F5Cl, and C2F6. A study of the radiolysis of these three fluorocarbons by mass spectrometric analysis showed that bond scissions of these substances took place mainly at the C–G bond. When other halogen compounds besides the three fluorocarbons were added to the reaction mixture, the rate and the molecular weight were decreased and C–X (X: halogen) bond scission was predominant in those substances. On the basis of these results, the role of the additives in the polymerization was discussed in relation to their radiolysis reactions.
  • Sh\={o}suke S\={o}fuku, Mitsuo Mizumura, Akira Hagitani
    1970 年 43 巻 1 号 p. 177-181
    発行日: 1970年
    公開日: 2006/03/27
    ジャーナル フリー
    A new method for the syntheses of p-methoxybenzyl p-nitrophenyl carbonate, p-methoxybenzyl carbazate, and p-methoxybenzyloxycarbonyl amino acids has been devised. These compounds were obtained in satisfactory yield from sodium p-nitrophenolate, 85% hydrazine hydrate, and several amino acids with p-methoxybenzyl chloroformate prepared from anisyl alcohol and phosgene in the presence of dimethylaniline in dry ether at −5–−10°C. This direct p-methoxybenzyloxycarbonylation of amino acid with the chloroformate is more convenient than the usual Weygand method.
  • Hiroko Takesada (née Yamagami), Etsuko Saito (née Morigu ...
    1970 年 43 巻 1 号 p. 181-187
    発行日: 1970年
    公開日: 2006/03/27
    ジャーナル フリー
    The binding nature of acridine orange to DNA was studied by means of equilibrium dialysis and flow dichroism with spectrophotometric analysis. The adsorption isotherm of the acridine orange-DNA system was obtained by means of equilibrium dialysis. From the experiment, the binding constant (K) and the fractional amount of the binding site to the total number of nucleotides (f) were estimated for native- and heat-denatured DNA. Under a shear gradient, the acridine orange-DNA complex showed a negative dichroism in visible region as well as in the ultraviolet region. This implies that acridine orange is oriented on DNA rather perpendicularly to its main axis, like base pairs. The magnitude of the dichroism of the complex at 500 mμ, near the visible absorption peak of acridine orange, was larger than each value of the complex and that of the DNA itself (260 mμ). The transition moment corresponding to the absorption at 500 mμ may be oriented in a more orderly manner and/or more nearly perpendicularly to the main axis of DNA than that corresponding to 260 mμ.
  • Yozo Ohtsuka
    1970 年 43 巻 1 号 p. 187-191
    発行日: 1970年
    公開日: 2006/03/27
    ジャーナル フリー
    Several 2- and 5-substituted oxazolo[5,4-d]pyrimidines have been prepared from 5-amino-4-cyanooxazole derivatives via N-ethoxymethylene intermediates in order to compare them with purine derivatives. Spectroscopic data and some chemical properties of these compounds were examined. A convenient method for the preparation of a starting material was described.
  • Toshiyuki Shono, Yuko Yamashoji, Koichiro Shinra
    1970 年 43 巻 1 号 p. 192-195
    発行日: 1970年
    公開日: 2006/03/27
    ジャーナル フリー
    The present authors attempted the cyanoethylation of the methylene group in glycine by means of the reaction between acrylonitrile and copper, nickel, and palladium glycinates. The cyanoethylation of N-salicylideneglycinato-aquo copper (II) was also carried out. Four kinds of cyanoethylated complexes were obtained by changing the reaction conditions in the case of copper glycinate. In general, acrylonitrile reacted only with the hydrogen atoms of the amino group. In the case of N-salicylidene-glycinato-aquo copper (II), which has no hydrogen atom on the nitrogen atom, however, two methylene hydrogens were cyanoethylated with acrylonitrile.
  • Hideo Otsuka, Masaru Shin, Yasuhiko Kinomura, Ken Inouye
    1970 年 43 巻 1 号 p. 196-200
    発行日: 1970年
    公開日: 2006/03/27
    ジャーナル フリー
    The synthesis is decribed of an octadecapeptide, glycyl-tyrosyl-seryl-methionyl-glutamyl-histidyl-phenyl-alanyl-arginyl-tryptophyl-glycyl-lysyl-prolyl-valyl-glycyl-lysyl-lysyl-arginyl-arginine amide, corresponding to the first eighteen amino acid residues of corticotropin except for the amino end which has been replaced by a glycine for the serine in the native hormone. The protected end product was obtained by two different coupling procedures, the active ester and the catalyzed carbodiimide, from the amino-terminal decapeptide and the octapeptide of carboxyl end. The over-all yields of the peptide, for the final coupling, deblocking and purification steps, in the active ester and the carbodiimide procedures were approximately forty and thirty per cent, respectively. The synthetic octadecapeptide amide has been shown to possess a high adrenal corticotropic activity, which is comparable to that of the corresponding 1-serine octadecapeptide amide, and a lipolytic activity which is significantly lower than that of the 1-serine analog.
  • Kazuko Takahashi, Hiroshi Yamamoto, Tetsuo Nozoe
    1970 年 43 巻 1 号 p. 200-207
    発行日: 1970年
    公開日: 2006/03/27
    ジャーナル フリー
    The base-catalyzed proton migration (from the 7- to 2-position) and proton exchange (at the 7-position) of cycloheptatrienes carrying an electron-withdrawing group were studied in a medium of aqueous sodium hydroxide or alcoholic potassium hydroxide. The order of the effect of the various substituents upon the relative rates is approximately: CN>CONH2>COO, Ph. The base-catalyzed prototropic isomerization proceeds through: i) the abstraction of a proton of the 7-position by the base, ii) the migration of the resulting carbanion to the allylic position (the rate-determining step), and iii) the recovery of a proton from the solvent. The kinetic study of the isomerization of 7-carboxycycloheptatriene (Ia) discloses the rate of the isomerization (k[the cycloheptatriene][base]) and the parameters (Ea=22.6 kcal/mol, ΔH\ eweq=22.0 kcal/mol, ΔS\ eweq=−15.4 e.u. at 60°). The structure of the cycloheptatrienyl anions formed as intermediates is discussed.
  • Masafumi Moriya, Tadataka Yamashita
    1970 年 43 巻 1 号 p. 208-211
    発行日: 1970年
    公開日: 2006/03/27
    ジャーナル フリー
    The copolymerization of alkylene glycol nitrate acrylates (ANA) and methacrylates (ANMA) [M2] with styrene [M1] has been carried out at 60°C. The alkylene glycol mononitrates used were ethylene, propylene, and butylene glycol mononitrates, abbreviated as EGN, PGN, and BGN respectively. For their acrylates and methacrylates, the following abridged notations are used: ENA and ENMA, PNA and PNMA, and BNA and BNMA respectively. The monomer reactivity ratios, r1 and r2, and the Alfrey-Price Q2 and e2 values for ANA and ANMA were evaluated as follows: r1=0.48, r2=0.08, Q2=0.49, and e2=1.00 for ENA; r1=0.41, r2=0.20,Q2=0.69, and e2=0.78 for BNA; r1=0.35, r2=0.49, Q2=0.99, and e2=0.53 for ENMA; r1=0.36, r2=0.50, Q2=0.98, and e2=0.51 for PNMA and r1=0.37, r2=0.40, Q2=0.90, and e2=0.58 for BNMA. The polar and steric effects of the ester side chain containing the nitrate group were discussed. ANA was copolymerized with some other divinyl monomers, and the resulting crosslinked copolymer were subjected to the swelling test.
  • Hiroo Tanaka, Isao Sakata, Ryoichi Senju
    1970 年 43 巻 1 号 p. 212-215
    発行日: 1970年
    公開日: 2006/03/27
    ジャーナル フリー
    On treatment in an aqueous solution with dichromate, p-cresol and creosol readily undergo nuclear oxidative coplig. The yields of dimeric and trimeric and trimeric cresols and of dimeric ketone are of the same order as the yields of the previously-recorded preparation by one-electron-transfer oxidants. When manganese sulfate is added, these yields are tripled. The probable mechanism of the coupling reaction of phenols with dichromate is discussed.
  • Michio Kobayashi, Hiroshi Minato, Eiichi Yamada, Nobumasa Kobori
    1970 年 43 巻 1 号 p. 215-219
    発行日: 1970年
    公開日: 2006/03/27
    ジャーナル フリー
    Substituted benzenes were phenylated with benzenediazonium tetrafluoroborate in homogeneous solutions with DMSO or acetonitrile. The distribution of substituted biphenyls and the partial rate factors indicated that this phenylation was an electrophilic substitution, but the selectivity was much smaller than those of nitration or sulfonylation. Experiments with chlorobenzene-4d, anisole-4d and chlorobenzene-d5 showed that both the orientation and partial rate factors did not change with deuterated compounds. Therefore, it was established that the rate-determining step was the addition of phenyl cation to an aromatic nucleus, and not the abstraction of proton from the phenylated intermediate.
  • Michio Kobayashi, Hiroshi Minato, Nobumasa Kobori
    1970 年 43 巻 1 号 p. 219-223
    発行日: 1970年
    公開日: 2006/03/27
    ジャーナル フリー
    The acid-catalyzed decomposition of phenylazo-p-tolylsulfone was studied in PhX, PhX-CH3CN and PhX-DMSO (X=OCH3, C2H5, CH3, Cl, CO2CH3, NO2). The decomposition was of first order but was faster with greater concentration of trifluoroacetic acid. The orientation and the partial rate factors for the phenylation of substituted benzenes were quite different from those for the radical phenylation but quite similar to those for the phenylation with phenyl cation generated from PhN2+BF4. Experiments with deuterated compounds indicated that the abstraction of proton from the phenylated complex was not rate-determining. A mechanism involving phenyl cation was proposed for the acid-catalyzed decomposition of azosulfone.
  • Nobumasa Kobori, Michio Kobayashi, Hiroshi Minato
    1970 年 43 巻 1 号 p. 223-225
    発行日: 1970年
    公開日: 2006/03/27
    ジャーナル フリー
    Naphthalene was phenylated with phenyl cation (from PhN2BF4) or phenyl radical (from PhN2BF4+NaNO2) in dimethyl sulfoxide. Partial rate factors for phenyl radical were somewhat larger than those reported with the phenyl radical generated from N-nitrosoacetanilide. Partial rate factors for phenylation with phenyl cation were smaller than those for free radical phenylation and those for common electrophilic substitution reactions. These small partial rate factors for phenyl cation were not compatible with the reaction scheme involving an ordinary σ-complex, and a mechanism involving a spiro cation appeared to be plausible.
  • Hajime Kanatomi, Ichiro Murase
    1970 年 43 巻 1 号 p. 226-231
    発行日: 1970年
    公開日: 2006/03/27
    ジャーナル フリー
    The compounds of a new type, 2,2′-bibenz-1,3-oxazine and its derivatives have been synthesized by the reactions of salicylamines with glyoxal or α-diketones in methanol at a temperature lower than 20°C. The oxazine structures were confirmed by infrared spectroscopy in solid state and by NMR spectroscopy in CCl4, CDCl3 and chlorobenzene. An oxazine-Schiff base equilibrium was observed in pyridine and in hot chlorobenzene by NMR spectra. It was found that hydrolytic decomposition of 2,2′-dimethyl-2,2′-bibenzoxazine leads to the formation of salicylidenesalicylamine through transamination. The mechanisms were investigated spectrophotometrically.
  • Takasi Mori, Kiyohide Matsui, Hitosi Nozaki
    1970 年 43 巻 1 号 p. 231-234
    発行日: 1970年
    公開日: 2006/03/27
    ジャーナル フリー
    Lead tetraacetate oxidation of 11, 12 and 13-membered cycloalkanols gives improved yields of 2,5-polymethylenetetrahydrofurans II in the presence of iodine. Oxidative cleavage of II furnishes 1,4-cycloalkanediones VII.
  • Michio Kobayashi, Hiroshi Minato, Yoshio Kohara
    1970 年 43 巻 1 号 p. 234-239
    発行日: 1970年
    公開日: 2006/03/27
    ジャーナル フリー
    p-Toluenesulfonylation of toluene, chlorobenzene and bromobenzene in the presence of aluminum chloride was investigated in methylene chloride at 0–20°C. The rate was equal to k3[TsCl][AlCl3][ArH]. Kinetic hydrogen isotope effects were found for p-deuteriotoluene (kHkD=2.8) and p-deuteriochlorobenzene (kHkD=1.98). Infrared studies indicated that not a sulfonyl cation but TsCl-AlCl3 complex was present in the medium. Substitution took place exclusively at para positions for halobenzenes, but 13.4% ortho and 86.6% para isomers were obtained for toluene. Partial rate factors for para positions were 52.5(PhCH3), 0.224(PhCl) and 0.164(PhBr). A plausible reaction mechanism was proposed, in which the abstraction of proton from the σ-complex was rate-determining.
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