Bulletin of the Chemical Society of Japan
Online ISSN : 1348-0634
Print ISSN : 0009-2673
ISSN-L : 0009-2673
Volume 50 , Issue 4
Showing 1-50 articles out of 57 articles from the selected issue
  • Mitsuaki Ohmori, Masanosuke Takagi
    1977 Volume 50 Issue 4 Pages 773-778
    Published: 1977
    Released: April 19, 2006
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    Phenylglyoxylic acid (I), phenylpyruvic acid (II), and pyruvic acid (III) were polarographically studied in buffer solutions and in DMF. Their reduction waves were reinvestigated in a wider pH range. Cyclic voltammetry showed that most electrode reactions of these acids in acidic pH are irreversible. pH-Dependence of E1⁄2 and limiting current was studied. The observed decrease of the limiting currents of II and III in the strongly alkaline region was attributed to the dissociation of their corresponding enol forms. The i-E curves of these acids in DMF showed successive poorly-defined reduction waves, while those of the corresponding tetraethylammonium salts (TEA salts) were found to be much simpler in shape. A small oxidation wave was also observed with TEA salts of II and III, suggesting the presence of the enol form in DMF. The reduction products of I and its salt in DMF were studied by means of controlled potential electrolysis and NMR-spectroscopy. The electrode reaction mechanism of α-keto acids in nonaqueous solution is discussed, emphasizing the role of the free acid form as a proton-donor and the formation of a radical anion followed by a disproportionation reaction.
  • Masatoshi Hirayama, Norio Ishida
    1977 Volume 50 Issue 4 Pages 779-782
    Published: 1977
    Released: April 19, 2006
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    The equilibrium constants, K1 and K2, between a series of o- and N-substituted anilines and Eu(fod)3 in CCl4 were evaluated using a four-parameter analysis of lanthanoid-induced shifts. It was found that the order of magnitudes of the values of K corrected for the effect of the pKa-value well corresponds to the accessibility of the nitrogen lone-pair to the Eu ion on the complexation.
  • Kenji Nakatani, Hiroshi Tsubomura
    1977 Volume 50 Issue 4 Pages 783-787
    Published: 1977
    Released: April 19, 2006
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    The electrode behavior of n-type TiO2 in acetonitrile solutions containing one of a variety of aromatic amines under illumination has been investigated. The onset potential of the anodic photocurrent leading to the oxidation of the amines changed from the most negative −0.51 V vs. SCE for N,N,N′,N′-tetramethyl-p-phenylenediamine to the least negative −0.27 V for aniline. These values parallel the change of the flat band potential by the amine and become more negative as the ionization potential of the amine decreases. The influence of the amine on the flat band potentials of ZnO, CdS, and GaP was also studied and found to be much less than in the case of TiO2. From these results, the reason for the change of the flat band potential in the case of TiO2 is attributed to a specific charge transfer interaction between the semiconductor and the amine.
  • Kazuo Sasaki, Yoshio Hirano, Seiji Tao
    1977 Volume 50 Issue 4 Pages 788-790
    Published: 1977
    Released: April 19, 2006
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    The relative performance of a new type thermal separation column has been reinvestigated. It was concluded that a column having a couple of vertical barriers is superior to an ordinary open column working under the same temperature gradient.
  • Fumio Kimura, Sachio Murakami, Ryoichi Fujishiro, Yoshio Toshiyasu
    1977 Volume 50 Issue 4 Pages 791-794
    Published: 1977
    Released: April 19, 2006
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    Enthalpies of mixing of some α,ω-alkanediol monoalkyl ether(ADAE)+heptane systems were measured at 298 K, and limiting partial molar excess enthalpies of ADAE at infinite dilution, x→0lim HEx(1−x), were estimated. The ADAE used were CH3O(CH2)nOH (n=2, 3, 4), C2H5O(CH2)nOH (n=2, 3), C3H7O(CH2)nOH (n=2, 3), and C4H9O(CH2)2OH. The values of x→0lim HEx(1−x), obtained were compared with those of normal alcohols, and discussed in the light of the intramolecular hydrogen bond contained in ADAE. The enthalpic contribution due to the intramolecular hydrogen bond in ADAE is estimated to be about 10 kJ mol−1.
  • Teruyuki Naito
    1977 Volume 50 Issue 4 Pages 795-797
    Published: 1977
    Released: April 19, 2006
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    The dimerization of 2-methylpropene by γ-irradiation occurred at a temperature of 300 °C and a 2-methylpropene density of 0.1 g/cm3, giving rise to the formation of 1,1,3-trimethylcyclopentane. The G value of this dimer was 50 at an absorbed dose rate of 4.3×1018 eV/g h and a total absorbed dose of 2.2×1019 eV/g. The G value of this dimer was inversely proportional to about 0.47 the power of the absorbed dose rate and was proportional to the 2-methylpropene density. The formation of this dimer was suppressed by the addition of oxygen or nitrogen monoxide. These facts led to the conclusion that the dimer was formed via chain reactions with the participation of the 2-methylallyl radical.
  • Tokio Yamabe, Kazuyoshi Tanaka, Akira Imamura, Hiroshi Kato, Kenichi F ...
    1977 Volume 50 Issue 4 Pages 798-801
    Published: 1977
    Released: April 19, 2006
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    One-dimensional (SN)x and its isoelectronic system (SCH)x polymers are treated on the basis of the SCF-tight-binding MO theory. The Pennsylvania structure of (SN)x has been shown energetically favorable comparing the Lyon structure. Judging from the state density at the Fermi level of (SCH)x, it may be expected to be a metallic conductor under some favorable condition.
  • Osamu Haida, Hiroshi Suga, Syûzô Seki
    1977 Volume 50 Issue 4 Pages 802-809
    Published: 1977
    Released: April 19, 2006
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    Two kinds of glassy crystalline phases (I and III) of cyclohexene were realized by different thermal treatments. The heat capacities of the glassy and the supercooled crystal-I and -III, as well as the stable crystalline phases were measured by an adiabatic calorimeter in the temperature range 12–300 K. The glass transition temperature Tg, the heat capacity jump at Tg and the residual entropy were found to be 81 K, 11.4 JK−1 mol−1 and 11.7 JK−1mol−1 for crystal-I and 83 K, 3.6 JK−1 mol−1 and 2.6 JK−1 mol−1 for crystal-III, respectively. The glassy liquid state of cyclohexene was realized by vapor condensation technique, its Tg being 78 K as determined by DTA method. The results provide the first example of plural glass transition phenomena in one and the same lowmolecular-weight compound.
  • Akio Kosaki, Michio Sorai, Hiroshi Suga, Syûzô Seki
    1977 Volume 50 Issue 4 Pages 810-816
    Published: 1977
    Released: April 19, 2006
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    The heat capacity measurement for an organic free-radical salt, potassium p-chloranil, revealed a first-order phase transition at Tc=260.01 K. In spite of a first-order nature, the pre- and the post-transitional effects are remarkable. The enthalpy and the entropy of transition were determined to be ΔH=2796 J mol−1 and ΔS=11.06 JK−1 mol−1, respectively. The magnetic contribution to ΔS is only 2.23 JK−1 mol−1 when a dimeric configuration with a singlet-triplet spin equilibrium is assumed in the low temperature phase and a monomeric behavior of radicals with spin doublet is assumed above Tc. The present phase transition bears a close resemblance to a spin-Peierls transition in a linear chain system. The infrared spectrum at 120 K indicates a possible formation of dimers in the low temperature phase of this salt. A phenomenological model for the present phase transition is presented.
  • Akio Kosaki, Michio Sorai, Hiroshi Suga, Syûzô Seki
    1977 Volume 50 Issue 4 Pages 817-824
    Published: 1977
    Released: April 19, 2006
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    The heat capacities of stable organic free-radical salts [(C6H5)3PCH3]1−x+[(C6H5)3AsCH3]x+(TCNQ)2\ ewdot (x=0,0.159, 0.250, 0.449, and 1, and TCNQ=7,7,8,8-tetracyanoquinodimethane) have been measured with an adiabatic calorimeter in the temperature range between 12 and 370 K. The phase transitions are found for the former four cases at 315.65, 325.80, 333.05, and 357.92 K, respectively. The enthalpy and the entropy due to the phase transitions are determined. The transition temperature is raised by diluting the phosphonium salt with the arsonium one. This tendency is quite contrary to that found for usual solid solutions. The magnitude and the composition dependence of the transition entropy indicate that the phase transition of the solid solutions may be attributable to the changes in both the crystal structure and the magnetic spin state at the transition point. A plausible explanation for the present unusual tendency for the composition dependence is presented.
  • Masaharu Oguni, Takasuke Matsuo, Hiroshi Suga, Syûzô Seki
    1977 Volume 50 Issue 4 Pages 825-833
    Published: 1977
    Released: April 19, 2006
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    Thermal properties of normal and deuterated orthoboric acids were studied through the measurements of heat capacity in the temperature range from 13 to 370 K by using an adiabatic calorimeter and differential thermal analysis curves above room temperature. For both crystals, the heat capacity anomaly was found around 290 K in the heat capacity values dependent upon the thermal history of the specimen; i.e., the endothermic or exothermic enthalpy relaxation was observed in this temperature range. This behavior is of characteristic to the glass transition and is considered to be ascribed to the freezing-in phenomenon of the motion of rearrangement of the protons in hydrogen bondings. The enthalpy relaxation curves were analyzed with the exponential law and the characteristic time constant toward the equilibrium state was longer for enthalpy-excessive side than for enthalpy-deficient side. The glass transition temperature at which the endothermic relaxation time becomes 1 ks is 296.6 K for normal orthoboric acid and 298.2 K for deuterated orthoboric acid, respectively. The activation enthalpies were estimated to be 88±5 and 91±5 kJ mol−1 for the endothermic processes of normal and deuterated orthoboric acid, respectively. The melting points of normal and deuterated orthoboric acids were determined from the differential thermal analysis curves to be 169.9 and 167.4 °C, respectively.
  • Osamu Ohashi, Hisao Hara, Keiko Noji, Takeshi Sakaizumi, Masao Onda, I ...
    1977 Volume 50 Issue 4 Pages 834-836
    Published: 1977
    Released: April 19, 2006
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    The microwave spectrum of anti-acetaldehyde oxime-d was investigated in the frequency region from 9 to 36 GHz. The rotational transition lines widely split into the A and E species due to the tunneling of the methyl group through the low potential barrier hindering the internal rotation. The transition lines belonging to the A species were fitted to the rigid rotor Hamiltonian, and the following effective rotational constants in MHz were obtained: AA=17250, BA=6284.33, and CA=4704.96. All the observed transition frequencies were fitted to the Hamiltonian containing perturbation terms to the fourth order in order to obtain the internal-rotation parameters using the principal axis method. The potential barrier, V3, hindering the internal rotation was determined to be 373 cal mol−1. The dipole moment was determined to be 0.828 D from the Stark effect of the transitions belonging to the A species.
  • Susumu Doi, Tamotsu Inabe, Yoshio Matsunaga
    1977 Volume 50 Issue 4 Pages 837-841
    Published: 1977
    Released: April 19, 2006
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    The electrical properties of the phenothiazine–iodine complex were examined in detail as a function of the composition. A shoulder in the resistivity-composition isotherm, a decrease in the activation energy for semiconduction by a factor of two, and a change in the sign of the Seebeck coefficient from negative to positive were observed at a composition of two molecules of phenothiazine to five atoms of iodine. These observations and the spectral behavior reported earlier indicate the formation of a complex cation radical salt, (phenothiazine)2+I5, which exhibits a resistivity of about 800 ohm cm at room temperature. By the incorporation of a half mole of iodine into this salt, the resistivity reaches a minimum of about 20 ohm cm at room temperature. Similar singularities in the resistivity-composition isotherms were observed with the complexes of the benzo[a]-, benzo[c]-, and N-methylderivatives.
  • Shigenobu Hayashi, Mitsuyuki Soma, Tamotsu Kondow, Takaharu Onishi, Ke ...
    1977 Volume 50 Issue 4 Pages 842-846
    Published: 1977
    Released: April 19, 2006
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    When alkali metals are brought into contact with silver or gold, catalytic activity for hydrogen activation reactions results which is higher than that for each of the constituent metals. The order of the activity per mole of alkali metal for the H2-D2 exchange reaction is Ag–C>Ag–K>Au–Cs>Ag–Na. The Ag–Cs and Ag–K systems absorb considerable amounts of hydrogen. The nature of the active sites and the contact effect of the IB metal with the alkali metal are discussed.
  • Tsuneo Fujii, Satoshi Suzuki, Michiyuki Fujishima
    1977 Volume 50 Issue 4 Pages 847-851
    Published: 1977
    Released: April 19, 2006
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    The method of configuration analysis has been applied to the interpretation of the ground and the excited states of disubstituted benzenes with two electron-donating groups, o-, m-, and p-benzenediols and o-, m-, and p-phenylenediamines, with particular attention paid to the dependence of the spectra on the positions of substitution and on the molecular symmetry. The wave functions calculated by the Pariser-Parr-Pople method are analyzed in terms of locally-excited states and intramolecular charge-transfer states. The characteristic changes in the location of the Lb, La, and Bb bands caused by substitution are adequately explained by the analysis. The intensification of the Lb band caused by the introduction of the substituents is interpreted as due to the mixing between the Lb, Bb, and Ba bands for the o- and m-substituted benzenes and between the Lb and Bb bands for the p-disubstituted benzenes. It was found empirically that the magnitudes of the spectral shift from benzene to the derivatives are determined primarily by the extent of charge-transfer contributions.
  • Minoru Sasaki, Tatsuya Yasunaga, Nobuhide Tatsumoto
    1977 Volume 50 Issue 4 Pages 852-857
    Published: 1977
    Released: April 19, 2006
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    A general theory for the propagation characteristics of the capillary wave on the gas-liquid interface, where the physicochemical equilibrium exists, is proposed. The theory is developed on the basis of the two-dimensional relaxation theory and the surface thermodynamics. The relaxation parameters in the equations are closely related to the dynamic behavior of the equilibrium. As an example, the theory was applied to the surfactant solution, taking account of the adsorption-desorption and diffusion processes of the surfactant. The derived equations revealed that the adsorption-desorption process plays an important role in the surfactant transfer between the surface and the bulk phase in a concentrated surfactant solution, while the diffusion process plays such a role in a dilute solution.
  • Minoru Sasaki, Tatsuya Yasunaga, Nobuhide Tatsumoto
    1977 Volume 50 Issue 4 Pages 858-861
    Published: 1977
    Released: April 19, 2006
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    The propagation characteristics of the capillary wave were studied in aqueous solutions of sodium dodecyl sulfate, octylamine hydrochloride, and dodecylamine hydrochloride. In most of the solutions, relaxation was observed both in the propagation velocity and the damping coefficient; it could be well interpreted by means of the theory for the propagation characteristics derived in Part I. The obtained relaxation parameters reveal the dynamic behavior of the adsorption-desorption of surfactants on the gas-liquid interface.
  • Yoshifumi Kato, Toshiyuki Nagai, Apollo Saika
    1977 Volume 50 Issue 4 Pages 862-872
    Published: 1977
    Released: April 19, 2006
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    The energy levels of the Nd3+ ion in Nd(C2H5SO4)3·9H2O and of the Er3+ ion in Er(C2H5SO4)3·9H2O are calculated within the 4fN configuration by the tensor operator method. The Hamiltonian containing a configuration interaction is diagonalized for the free ion levels and complete J-mixing is performed for the crystal field levels. The experimental “free-ion” energy levels of Nd3+ and Er3+ are fitted with a mean deviation of 70.8 cm−1 for 19 terms and 78.2 cm−1 for 22 terms, respectively. The crystal field parameters obtained for Nd(C2H5SO4)3·9H2O and Er(C2H5SO4)3·9H2O yield a mean deviation of 3.6 cm−1 for 43 levels and 3.6 cm−1 for 50 levels, respectively. The calculated Zeeman splitting factors (g values) in the direction along the crystal principal axis are in fair agreement with the experimental values.
  • Masayuki Nakagaki, Mihoko Yamamoto
    1977 Volume 50 Issue 4 Pages 873-878
    Published: 1977
    Released: April 19, 2006
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    A theoretical relation between the fractional adsorption amount, θ, and the concentration, C, taking account of the lateral interaction between the adsorbed molecules is used to integrate the Gibbs equation, and the relation between the surface pressure, F, and the molecular area, A, is derived. Since the equation does not contain the parameter, k0, related to the strength of adsorption, it is concluded that there is no substantial difference between the adsorption monolayers and the insoluble monolayers. The relation between F and C is also derived and compared with the experimental data for normal alcohols. The standard affinity of adsorption, −Δμ0, and the energy of lateral interaction, ε, increased linearly with the number of carbon atoms of the alcohols, n. Finally, it has been shown that the experimental data can be explained well with the theoretical equation presented here, but not with Szyszkowski’s, the latter being derived for negligible lateral interaction.
  • Koichi Kikuchi, Koji Uji-ie, Yoshikatsu Miyashita, Hiroshi Kokubun
    1977 Volume 50 Issue 4 Pages 879-882
    Published: 1977
    Released: April 19, 2006
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    The T1(π, π*)→T3(π, π*) absorption of acridine has first been observed at about 985 nm in ethanol. Temperature dependences of the fluorescence lifetime and the triplet yield of acridine were investigated in poly(vinyl alcohol) film, and it was found that the intersystem crossing from the first excited singlet state S1(π, π*) to T1(π, π*) occurs through both temperature dependent and independent processes. The activation energy of the temperature dependent process corresponds substantially to the energy difference between T3(π, π*) and S1(π, π*). The intersystem crossing from S1(π, π*) to T2(n, π*) followed by the internal conversion to T1(π, π*) was assigned to the temperature independent process.
  • Tadatsugu Yoshikuni, Ryokichi Tsuchiya, Akira Uehara, Eishin Kyuno
    1977 Volume 50 Issue 4 Pages 883-885
    Published: 1977
    Released: April 19, 2006
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    The thermal cis-to-trans isomerization of cis-[CrCl2tn2]Cl·0.5H2O in a solid phase was studied by means of derivatographic and isothermal measurements. It was found that cis-[CrCl2tn2]Cl·0.5H2O in which trimethylenediamine(tn) forms six-membered chelate ring with chromium undergoes isomerization to the trans-complex in contrast with the isomerization of trans-[MX2(diam)2]X·HX·nH2O (M=Co or Cr, X=halogen) to the cis-one in which the diamine (diam) forms five-membered chelate ring with metal M. The isomerization proceeded in anhydrous state. The activation energy of the isomerization of the complex was found to be 163 kJ mol−1 from the isothermal measurements, which is fairly greater than that of the trans-[CoCl2pn2](H5O2)Cl2 and cis-[CoCl2tn2]Cl·H2O. The difference was explained by whether or not water molecule involved as a lattice water contributes to the isomerization.
  • Yoshiaki Okajima, Yukiyoshi Aizawa, Katsumi Suzuki, Yasushi Sugawara
    1977 Volume 50 Issue 4 Pages 886-888
    Published: 1977
    Released: April 19, 2006
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    Quantitative analysis of hydrogen in titanium was investigated with an ion microanalyzer. Argon ions as primaries were accelerated at a voltage of 10 kV. The diameter and the current of the beam were 1 mm and 2 μA, respectively. A mass spectrum was measured at 2×10−7 Torr. It was found that the intensity ratio of me=49(48TiH+) and 46(46Ti+) can be used for the determination of hydrogen in titanium. A linear relation was obtained between the intensity ratio and hydrogen concentration determined by the standard vacuum fusion method. The present method was applied to determine the hydrogen concentration in the surface layer of a sample treated by cathodic polarization. It was observed that hydrogen concentrations in the surface layer were much higher than those in the bulk of the sample.
  • Kenzo Kitayama, Takashi Katsura
    1977 Volume 50 Issue 4 Pages 889-894
    Published: 1977
    Released: April 19, 2006
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    The phase equilibria in the Sm2O3–V2O3–V2O5 system was established at 1200 °C. In this system, Sm2O3, Sm10V2O20, SmVO3, SmVO4, V2O3, V3O5, V4O7, V5O9, V6O11 and VO2 were stable and Sm10V2O20, SmVO4, V2O3, and VO2 had the non-stoichiometry. On the basis of the phase equilibria, the Gibbs free energy for the reactions, SmVO3+1⁄2O2=SmVO4 and 4 Sm2O3+2 SmVO3+O2=Sm10V2O20, were determined to be −30.4±0.1 and −76.8±0.1 kcal, respectively. Also, standard Gibbs free energies of oxidation of various vanadium oxides were calculated.
  • Hiroyuki Koyama, Ichiro Murase
    1977 Volume 50 Issue 4 Pages 895-897
    Published: 1977
    Released: April 19, 2006
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    N,N′-Polymethylenebis(o-mercaptobenzylamine) ligands (polymethylene=ethylene 1,2-cyclohexylene, trimethylene, and tetramethylene) have been synthesized by the reduction of the corresponding amides, which were prepared by the condensation of 2,2′-dithiodibenzoyl chloride and polymethylenediamines, and then their nickel(II) complexes have been prepared and characterized. The elemental analyses and the magnetic and spectroscopic data indicate that all of the complexes are monomeric with metal-ligand ratio of 1: 1, and their geometries are essentially square-planar. When the bridging carbon chain was replaced from ethylene up to tetramethylene, the electronic spectra of the complexes exhibited pronounced change in the d-d bands.
  • Masaaki Kojima, Miho Fujita, Junnosuke Fujita
    1977 Volume 50 Issue 4 Pages 898-906
    Published: 1977
    Released: April 19, 2006
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    The circular dichroism spectra of a series of complexes of the type [Co(NH3)2n(RR-ptn)3−n]3+(n=0, 1,2), where the RR-ptn is (RR)-2,4-pentanediamine, were recorded in aqueous solutions with and without the addition of electrolytes such as chloride or sulfate, and in DMSO solutions. The circular dichroism spectra in the region of the first absorption band of Δ-[Co(RR-ptn)3]3+ and cis-Δ-[Co(NH3)2(RR-ptn)2]3+ were extremely sensitive to the environment of the complexes and showed a remarkable variation, while those of the corresponding diastereomers, Λ-[Co(RR-ptn)3]3+ and cis-Λ-[Co(NH3)2(RR-ptn)2]3+ were little affected by the given environment. The other complexes, trans-[Co(NH3)2(RR-ptn)2]3+ and [Co(NH3)4(RR-ptn)]3+ exhibited small variations in the circular dichroism spectra. These variations seem to be accounted for by the conformational change of the flexible sixmembered chelate ring brought about by ion-pair formation between the complex cations and anions.
  • Masaaki Okunaka, Gen-etsu Matsubayashi, Toshio Tanaka
    1977 Volume 50 Issue 4 Pages 907-909
    Published: 1977
    Released: April 19, 2006
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    2,2,6,6-Tetramethylpiperidine N-oxyl radical (CH3)4C5H6NO· (TMPNO·) reacts with palladium dichloride to give complexes of both anionic and cationic TMPNO; [PdCl(TMPNO)]2 (I) and [TMPNO+]2[Pd2Cl6]2− (II). I further reacts with dimethylsulfonium phenacylide or triphenylphosphine (L) to afford a mononuclear complex of the PdCl(TMPNO)(L) type. II undergoes a facile reaction with acetone to yield bis(N-acetonyl-N-hydroxy-2,2,6,6-tetramethylpiperidinium)hexachlorodipalladate, [(CH3)4C5H6\overset+N(OH)CH2COCH3]2[Pd2Cl6]2−. Configurations of these complexes are described.
  • Shinsaku Shiraishi, Satoru Ikeuchi, Manabu Sen\={o}, Teruzo Asahara
    1977 Volume 50 Issue 4 Pages 910-913
    Published: 1977
    Released: April 19, 2006
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    Cycloaddition reaction of aromatic nitrile N-oxides, such as benzonitrile N-oxide, 2,4,6-trimethylbenzonitrile N-oxide, and 2,3,5,6-tetramethylbenzonitrile N-oxide, with tetrahalo-p-benzoquinones was studied. The reaction gave 1:1- and/or 2:1-adducts of a nitrile N-oxide and a tetrahalobenzoquinone according to the conditions, especially the mole ratios of each reactant. The 2:1-adducts are formed via 1:1-adducts, each having two stereoisomers. The structures of these adducts were determined to be dioxazole derivatives formed by the addition of nitrile N-oxides to the carbonyl bonds of the tetrahalobenzoquinones.
  • Akira Omura, Tsutomu Nonaka, Toshio Fuchigami, Eiichi Ichikawa, Keijir ...
    1977 Volume 50 Issue 4 Pages 914-916
    Published: 1977
    Released: April 19, 2006
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    Methods for labeling the chemically non-equivalent nitrogen atoms of cyanoguanidine with 15N were established. 1-Cyanoguanidine-1-15N and 1-cyano-15N-guanidine were prepared, and their labeled positions were also confirmed by mass spectroscopic analysis. 15N FT-NMR spectra of cyanoguanidine enriched with 15N were measured.
  • Kiichiro Nakajima, Haruki Kawai, Michihiro Takai, Kenji Okawa
    1977 Volume 50 Issue 4 Pages 917-920
    Published: 1977
    Released: April 19, 2006
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    Oxazoline derivatives were mainly obtained from the O-tosyl-N-acyl-β-hydroxy amino acid peptides by β-elimination reaction. Dehydroalanine or hydantoin derivatives were isolated when the urethane type acyl groups were used.
  • Hidekazu Shirasaki, Takahiko Tsuyuki, Takeyoshi Takahashi, Robert Stev ...
    1977 Volume 50 Issue 4 Pages 921-927
    Published: 1977
    Released: April 19, 2006
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    Photo-irradiation of friedelin (1) in diethyl ether gave a keto ether (2), a hydroxy ether (3), and an alcohol (4). A hydroxy ketone (5) was formed by the photo-irradiation reaction of 1 in diethyl ether containing acetone. In the latter case, labeled experiments showed that the photo-produced ketene (12) reacted with 1-hydroxy-1-methylethyl radical derived from acetone to give 5. The formation of 2 could be explained by an attack of an α-radical derived from diethyl ether to 12. Both 3 and 4 were shown to be derived from a norseco-aldehyde (11) which was produced from the ketene (12).
  • Eisuke Kaji, Haruo Kohno, Shonosuke Zen
    1977 Volume 50 Issue 4 Pages 928-932
    Published: 1977
    Released: April 19, 2006
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    The reaction of β-nitro alcohols (2-nitroethanol, 1-nitro-2-propanol, and 1-nitro-2-butanol) with acrylaldehyde in the presence of diethylamine-formic acid gave anomeric mixture of 4-nitro-DL-pento-, hexo-, and heptopyranoses (5) in reasonable yields. 5 were converted to the corresponding methyl 4-amino-DL-pento-, hexo-, and heptopyranosides (8) by O-methylation followed by reduction. Anomeric methyl DL-tolyposaminides and DL-forosaminides were synthesized in a good yield from anomeric methyl 4-nitro-2,3,4,6-tetradeoxy-DL-erythro-hexopyranosides (6b1 and 6b2). The configuration of methyl 4-nitro-DL-hexo-, and heptopyranosides (6b and 6c) and methyl 4-acetamido-DL-hexo- and heptopyranosides (8b and 8c) was established on the basis of PMR data.
  • J\={u}ro Ojima, Michiko Enkaku, Chikako Uwai
    1977 Volume 50 Issue 4 Pages 933-935
    Published: 1977
    Released: April 19, 2006
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    The Wittig reaction between o-ethynylcinnamaldehyde (II) and α,α′-bis(triphenylphosphonio)-o-xylene dibromide (III) gave the corresponding acyclic compound (IV and V) in a good yield, while that between o-ethynylbenzaldehyde (VII) and α,α′,α″,α'″-tetrakis(triphenylphosphonio)durene tetrabromide (VIII) similarly afforded an acyclic compound (IX) in a moderate yield. The title compounds, VI and X, were obtained by the oxidative coupling of V (or, IV and V) and IX, respectively. The examination of the NMR spectra indicated that VI and tribenzo-fused, fourteen-membered periphery on the sides of the benzene nucleus of X are atropic.
  • Fuminori Akiyama
    1977 Volume 50 Issue 4 Pages 936-938
    Published: 1977
    Released: April 19, 2006
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    2-Isopropyl-5-methyl-1-cyclohexenyl alkyl sulfides were obtained in about a 60% yield by the reaction of 2-isopropyl-5-methylcyclohexanone with thioacetals or thiols in the presence of aluminum chloride. 1-Cycloalkenyl ethyl sulfides, (Remark: Graphics omitted.) (n=4, 5, or 6, R=H or alkyl) were obtained in good yields by the reaction of cycloalkanones with ethanethiol in the presence of diphosphorus pentaoxide. However, an attempt to apply this method to acyclic vinyl sulfides was unsuccessful.
  • Hiroyuki Nakazumi, Teijiro Kitao
    1977 Volume 50 Issue 4 Pages 939-944
    Published: 1977
    Released: April 19, 2006
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    The physical properties of 4H-1-benzothiopyran-4-ones (thiochromones) and related compounds were characterized by means of mass, NMR, and UV spectra in order to distinguish thiochromones from 2H-1-benzothiopyran-2-ones (thiocoumarins). In the mass spectra, the fragmentation due to the retro-Diels-Alder reaction directly from the molecular ion is the most useful for differentiation. In the NMR spectra, thiochromones show the characteristic deshielding effect of benzenoid proton in 5-position and in the UV spectra a very strong absorption band in the region 250–270 nm. It was found that in the reaction of S-phenyl 3-oxobutanethioates with PPA, most of these compounds afford thiochromones through rearrangement giving an intermediate (IVa). The effect of the substituent of the S-phenyl 3-oxobutanethioate on the formation of the thiocoumarin was also discussed.
  • Munehiro Nakatani, Tadao Kamikawa, Tsunao Hase, Takashi Kubota
    1977 Volume 50 Issue 4 Pages 945-947
    Published: 1977
    Released: April 19, 2006
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    The racemic and meso bis(1-mesitylethyl) ethers were synthesized. The optical resolution of the dicarboxylic acid derivative showed that the high-melting compounds were racemic in form and the low-melting isomers meso in form.
  • Hiroshi Imaizumi, Shizen Sekiguchi, Kohji Matsui
    1977 Volume 50 Issue 4 Pages 948-952
    Published: 1977
    Released: April 19, 2006
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    Aromatic amines underwent dimerization in a molten salt consisting of a mixture of AlCl3–NaCl–KCl. The reaction is an oxidative cationic polymerization but, in contrast with the reactions of the ordinary aromatic compounds which gave the corresponding polyaryls, in the cases of aromatic amines the reaction was regiospecific and stopped at the stage of biaryl to yield benzidine derivatives.
  • Masahiko Takahashi, Hideya Tan, Kunio Fukushima, Hiroaki Yamazaki
    1977 Volume 50 Issue 4 Pages 953-956
    Published: 1977
    Released: April 19, 2006
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    Three methods of cyclization of hydrazidines are described. The reaction of N4-arylhydrazidines (2) with dimethyl acetylenedicarboxylate in refluxing tetrahydrofuran afforded 6-alkyl and aryl-2-aryl-3-methoxycarbonyl-3-methoxycarbonylmethyl-2,3,4,5-tetrahydro-1,2,4,5-tetrazines (3). Oxidation of N4-aryl-N2-arylmethylenehydrazidines (6) with mercuric oxide in refluxing ethanol gave 3-alkyl and aryl-5-aryl-4-arylamino-1,2,4-triazoles (7). 3-Alkyl and aryl-4-arylamino-1,2,4-triazoles (7f, g) were obtained upon the heating of (2a, e) in formic acid.
  • Masahiko Takahashi, Noriyuki Sugawara, Kaoru Yoshimura
    1977 Volume 50 Issue 4 Pages 957-960
    Published: 1977
    Released: April 19, 2006
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    Amidrazones RC(NH2)=NNH2 (1a, b) (R=2-pyridyl, phenyl) reacted with EtOCH=CR1R2 (2ad) (R1R2=CN, CO2C2H5, COCO2C2H5) to give RC(NH2)=NNHCH=CR1R2 (3ag). 3,4-Disubstituted pyrazoles (4a, b) were obtained on the heating of 3a, b, e, and f (R=2-pyridyl, phenyl, R1=CN, R2=CN, CO2C2H5) in toluene. However, the heating of 3c (R=2-pyridyl, R1=R2=CO2C2H5) gave a dimer, the 2,3,7,9,10-pentaazadodeca-1,4,8,11-tetraene derivative (9), instead of 4. 5-Amino-6-ethoxycarbonyl-3-(2-pyridyl)-1H-1,2,4-triazepine (10) was obtained by the reaction of 3a (R=2-pyridyl, R1=CN, R2=CO2C2H5) with ethanolic hydrogen chloride. The treatment of 10 with alkaline gave 2,9-di-2-pyridyl-6,7,13,14-tetrahydro-4H,11H-[1,5]diazocino-[2,3-e:6,7-e′]di[1H-1,2,4]triazepine-6,13-dione (11). Triazepine (10) reacted with hydrazines to give 5-hydrazino-1H-1,2,4-triazepine derivatives (13a, b).
  • Yoshinobu Inouye, Yuji Uchida, Hiroshi Kakisawa
    1977 Volume 50 Issue 4 Pages 961-966
    Published: 1977
    Released: April 19, 2006
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    By unambiguous syntheses, the structures of maturinone and cacalol were shown to be 3,5-dimethylnaphtho[2,3-b]furan-4,9-dione (1) and 5,6,7,8-tetrahydro-3,4,5-trimethylnaphtho[2,3-b]furan-9-ol (2), respectively. 3,8-Dimethylnaphtho[2,3-b]furan-4,9-dione (1a), an isomer of maturione, was also synthesized.
  • Masayoshi Ito, Tetsuo Kanamoto, Koji Tanaka
    1977 Volume 50 Issue 4 Pages 967-971
    Published: 1977
    Released: April 19, 2006
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    The effects of morphology on γ-relaxation in 66-Nylon is investigated. The morphology of the samples was characterized mainly by thermal analysis. Information about the molecular motion of 66-Nylon is obtained from the temperature dependence of the spin-lattice relaxation times (T1). In order to compare the relaxation behavior of 66-Nylon with that of other semicrystalline polymers, the T1 of polyoxymethylene (POM) was also measured as a function of temperature. It was found that in 66-Nylon, both solution-grown crystals and bulk samples are composed of folded chain lamellae with fairly large amounts of less perfect crystalline regions. Both the magnitude and the temperature of the T1 minimum at about 30 °C (γ-region) for 66-Nylon are not sensitive to the sample history, in contrast to those for POM. In addition, the T1-temperature curve in the γ-region for 66-Nylon is much broader than that for POM. These NMR results for 66-Nylon are interpreted in terms of a rather wide variety of structural heterogeneities from the usual amorphous regions to fairly restricted regions, such as the less-perfect crystalline regions at the lamellar surface.
  • Isamu Watanabe, Tsutomu Tsuchiya, Sumio Umezawa
    1977 Volume 50 Issue 4 Pages 972-974
    Published: 1977
    Released: April 19, 2006
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    3′-Deoxybutirosin B and A (16, 17) were synthesized via condensation of 3,2′-bis-N-benzyloxycarbonyl-4′,6′-O-cyclohexylidene-3′-deoxyparomamine 1,6-carbamate (2) with tris-O-(p-nitrobenzoyl)-D-ribofuranosyl and -D-xylofuranosyl bromide, respectively, followed by 6′-O-tosylation of the decyclohexylidene derivative (8 and 9), cyclic 1,6-carbamate opening and amidation with (S)-4-benzyloxycarbonylamino-2-hydroxybutyric acid at the free C-1 amino group.
  • Hiroshi Sano, Tsutomu Tsuchiya, Shigeru Kobayashi, Hamao Umezawa, Sumi ...
    1977 Volume 50 Issue 4 Pages 975-978
    Published: 1977
    Released: April 19, 2006
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    2′-N-Acetyl-4′,6′-di-O-acetyl-3,3a-O-carbonyl-3′-deoxydihydrostreptobiosamine (15), a precursor in the synthesis of 3″-deoxydihydrostreptomycin, was prepared from benzyl α-dihydrostreptobiosaminide. The synthesis involves formation of L-allo compound (5) with inversion of the 3′-hydroxyl group of L-gluco derivative (2) in order to facilitate 3′-chlorination, dechlorination, of the 3′-chloro-L-gluco derivative (7 or 11) with tributyltin hydride, and utilization of cyclic 3,3a-O-carbonyl group instead of 3,3a-O-isopropylidene group which was unstable in the later reactions.
  • Jun Niwa
    1977 Volume 50 Issue 4 Pages 979-983
    Published: 1977
    Released: April 19, 2006
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    A semi-empirical equation for predicting the 1H chemical shift induced by substituents in an aromatic system (J. Niwa, Bull. Chem. Soc. Jpn., 48, 118, 1637 (1975)) has been applied to the ring protons of 1-substituted naphthalenes. The predictions of the equation are tested against the available experimental data for six representative substituents and are also compared with those of the electric-field model.
  • Shohei Inoue, Norikazu Takeda
    1977 Volume 50 Issue 4 Pages 984-986
    Published: 1977
    Released: April 19, 2006
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    Tetraphenylporphinatoaluminium ethyl reacts with carbon dioxide in the presence of 1-methylimidazole to produce tetraphenylporphinatoaluminium propionate in the presence of visible light but not in the dark.
  • Hiroshi Suginome, Terutoshi Mizuguchi, Tadashi Masamune
    1977 Volume 50 Issue 4 Pages 987-990
    Published: 1977
    Released: April 19, 2006
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    The irradiation of the title nitrone (5) with monochromatic light afforded a single isomeric oxaziridine (6), which reverted to the original nitrone (5) thermally at room temperature. The title nitrone was also converted into another oxaziridine (8) by treatment with benzoic anhydride.
  • Takayuki Mitaki, Yasutsugu Shimonishi
    1977 Volume 50 Issue 4 Pages 991-997
    Published: 1977
    Released: April 19, 2006
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    For elucidating one of the antigenic determinants of hen egg-white lysozyme close to its catalytic site, heneicosapeptide was synthesized by a conventional method. This peptide, phenylalanylglutamylserylasparaginylphenylalanylasparaginylthreonylglutaminylalanylthreonylasparaginylarginylasparaginylthreonylaspartylglycylserylthreonylaspartyltyrosylglycine, corresponds to positions 34–54 of the amino acid sequence of hen egg-white lysozyme.
  • Toshiaki Sodesawa, Eisuke Ogata, Yoshio Kamiya
    1977 Volume 50 Issue 4 Pages 998-1002
    Published: 1977
    Released: April 19, 2006
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    The disproportionation of propylene and 1-butene over MoO3–Al2O3 and Re2O7–Al2O3 catalysts was carried out in order to investigate the effects of reaction pressure in the range from 1.0 to 130 kg/cm2. The effects of the pressure on the reaction can be identified as two independent of the reaction phase; the catalytic activity increased with the reaction pressure, and the time needed to reach the maximum conversion (Tmax) as well as the time when the conversion falls to half the maximum value (τ1⁄2) decreased with the increase in the reaction pressure. It can be concluded that the catalytic activity by the polymers formed over the catalyst falls off rapidly with the increase in the pressure. In both phases, the disproportionation of olefins over the Re2O7–Al2O3 catalyst exhibits the following features as compared with that over the MoO3–Al2O3 catalyst: (1) a much higher activity at temperatures of 0–140 °C; (2) a much higher selectivity for disproportionation, and (3) a lower apparent activation energy.
  • Atsuyoshi Ohno, Kaoru Nakamura, Yasumasa Shizume, Sinzaburo Oka
    1977 Volume 50 Issue 4 Pages 1003-1004
    Published: 1977
    Released: April 19, 2006
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    Di-t-butyl thioketone reacts with phenyllithium affording both C-phenylated and S-phenylated products. The product distribution largely depends on the reaction temperature and solvent: the lower the temperature and the more solvated the counter cation, the larger the yield of the S-phenylated product. Steric effect is also important: 2,6-dimethylphenyllithium affords only S-arylated product. The result has been interpreted in terms of the charge-transfer-intermediate—radical-combination mechanism.
  • Nariyoshi Kawabata, Tetsuya Fujii, Michiharu Naka, Shinzo Yamashita
    1977 Volume 50 Issue 4 Pages 1005-1006
    Published: 1977
    Released: April 19, 2006
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    Ketocarbenoid was generated by the reaction of ω,ω-dibromoacetophenone with copper in aromatic hydrocarbon, and was trapped by cycloaddition to olefins. This is the first example of cyclopropanation of olefins by formally divalent carbon intermediate without use of diazoketones.
  • Tsutomu Okuda, Hideta Ishihara, Koji Yamada, Hisao Negita
    1977 Volume 50 Issue 4 Pages 1007-1008
    Published: 1977
    Released: April 19, 2006
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    The Zeeman effect of 127I NQR and the quadrupole effect of 11B NMR on a single crystal of BI3 were observed in order to investigate the principal axes of the EFG tensors. The frequencies of the torsional oscillations were determined from the temperature dependence of e2Qqiih.
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