Bulletin of the Chemical Society of Japan
Online ISSN : 1348-0634
Print ISSN : 0009-2673
ISSN-L : 0009-2673
Volume 41 , Issue 5
Showing 1-50 articles out of 59 articles from the selected issue
  • Masaji Miura, Akinori Hasegawa, Masayuki Watanabe
    1968 Volume 41 Issue 5 Pages 1035-1038
    Published: 1968
    Released: March 27, 2006
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    A part of cation in polyphosphate was replaced with Mn2+ ion. Zero-field splitting parameter D due to the crystal field with axial symmetry was estimated according to Allen’s method from the ESR spectrum of Mn2+ ion. The value of D changes with the change in the state of polyphosphate, crystalline or glassy. As the degree of polymerization of sodium polyphosphate glass decreases, the value of D increases and approaches to the value corresponding to the crystalline state. These phenomena were interpreted as due to the disorderness of glassy state. The value of D was found to change with the variation of the kind of cation in polyphosphate. This was explained in terms of the effective cationic field.
  • Kumasaburo Kodera, Isao Kusunoki, Shinkichi Shimizu
    1968 Volume 41 Issue 5 Pages 1039-1045
    Published: 1968
    Released: March 27, 2006
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    Gases evolved during a vacuum heat treatment of various oxides were analyzed by means of an omegatron mass spectrometer. Carbon dioxide, carbon monoxide and water were detected as main gases evolved at lower temperatures. Oxygen due to thermal dissociation of ZnO, CdO, NiO, CuO, Cu2O, and WO3 was found at high temperatures. In the case of MoO3, however, evolution of oxygen was not observed. The equilibrium pressures of the evolved gases over these oxides have been measured with a McLeod gauge and a Knudsen gauge. The oxygen dissociation pressures of ZnO, CdO, NiO, CuO, and Cu2O were measured and compared with the calculated values.
  • Masumi Yamakawa, Tanekazu Kubota, Hideko Akazawa, Itaru Tanaka
    1968 Volume 41 Issue 5 Pages 1046-1055
    Published: 1968
    Released: March 27, 2006
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    The electronic spectra of 2,6-dimethylbenzonitrile N-oxide and its some derivatives were recorded in n-heptane and were compared with those of benzonitrile and phenylacetylene. The analyses of the electronic spectra of aromatic nitrile N-oxides were done by the following procedures. First, simple molecular orbitals (SMO) of benzonitrile and phenylacetylene were calculated using some parameters determined by the use of the overlap integrals and valence state ionization potentials. Then, by comparing the eigenvalues of the SMO thus obtained with the observed spectra the spectroscopic exchange integrals have been obtained for 1A1 and 1B1 bands, where interactions between two configurations were taken into consideration for the 1B1 bands. The SMO of benzonitrile N-oxide was next calculated on reference to the physicochemical nature of aromatic nitrile N-oxides studied before. The parameters were chosen so as to fit with the observed values of dipole moments of benzonitrile N-oxide and its some methyl derivatives. Electronic spectra of the nitrile N-oxides were then analyzed using the above SMO’s and spectroscopic exchange integrals. The substituent effect on the electronic spectrum of benzonitrile N-oxide was also discussed by the similar treatment. Characteristic strong band appearing in the near UV region was assigned to the 1A1 band having a change transfer (CT) nature, where the CT from the oxygen atom to the residual conjugated system makes a larger contribution than that of the reverse direction. In addition, the physicochemical nature and reactivity of nitrile N-oxides were discussed on the basis of their molecular diagrams, which were obtained from the SMO’s mentioned above.
  • Masao Koizumi, Yoshinori Ikeda, Hiroshi Yamashita
    1968 Volume 41 Issue 5 Pages 1056-1063
    Published: 1968
    Released: March 27, 2006
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    The effect of the addition of biacetyl on the quantum yield of photoreduction of acridine in methanol, ethanol, n- and iso-propanol has been studied under the aerated and deaerated conditions. From the analysis of the results, the quantum yields for four mechanisms ΦMS(S means that a reactive state is singlet excited states, S*, and M denotes a molecular mechanism), ΦMS (R denotes a radical mechanism), ΦMT (T indicates that a reactive state is a state other than S* and T(π–π*), most likely T(n–π*) and ΦRT have been decided, assuming that oxygen does not deactivate T(n–π*). The values are
    5&for methanol, & &Φ_M^S(0.027) & &Φ_R^S(0.039) & &Φ_M^T(0.006) & &Φ_R^T(0.057)
    &for ethanol, & &Φ_M^S(0.043) & &Φ_R^S(0.067) & &Φ_M^T(0) & &Φ_R^T(0.019)
    &for n-propanol, & &Φ_M^S(0.030) & &Φ_R^S(0.036) & &Φ_M^T(0) & &Φ_M^T(0.022)
    &for isopropanol, & &Φ_M^S(0.03) & &Φ_R^S(0.058) & &Φ_M^T(0) & &Φ_R^T(0)
    The quenching constants of biacetyl on the fluorescence of acridine have been found to agree with the ones on the reaction at S* in all alcohols; the rate constants approximate diffusion controlled. In addition it has been confirmed by a flash method that biacetyl does not attack the T(π–π*) nor the semi-reduced acridine; this justifies the present method of analysis.
  • Naomichi Iso, Daijiro Yamamoto
    1968 Volume 41 Issue 5 Pages 1064-1067
    Published: 1968
    Released: March 27, 2006
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    The viscometric behavior of a dilute aqueous solution of methylcellulose was studied by tilting capillary viscometers. The intrinsic viscosity was obtained by the extrapolation of Martin’s plots on the assumption that the plots were linear down to an infinite dilution. The intrinsic viscosity obtained increased with the rate of shear over the range of 200–1200 sec−1. Huggins’ constant, k′, the temperature coefficient of the intrinsic viscosity, d[η]/dT, and the energy of the activation of flow, Ev, decreased with the rate of shear. From the data of d[η]/dT and Ev thus obtained, it has seemed reasonable to assume that the methylcellulose chain has a relatively small flexibility and a strong tendency toward alignment with a flowing stream. This may be the main reason why the viscosity of the dilute aqueous solution of methylcellulose is non-Newtonian.
  • Taku Matsuo, Hideto Shosenji
    1968 Volume 41 Issue 5 Pages 1068-1073
    Published: 1968
    Released: March 27, 2006
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    The charge-transfer (CT) bands of complexes of alkylsubstituted pyrroles and chloranil or tetracyanoethylene (TCNE) were found to consist of two closely situated peaks. The peaks were assigned to transitions originated from the highest occupied, and second-highest occupied orbitals of the donor. The energy of the CT absorption band is hardly affected even by the presence of a bulky substituent such as a t-butyl group at the pyrrole nitrogen. Hence, the acceptor molecules were thought not to be close to the 1-position of the pyrryl group. In the case of 1-phenylpyrrole, the first CT bands are at almost the same positions as those of the corresponding complexes of 1-methylpyrrole. The bands show red shifts if methyl groups are introduced either on the pyrryl group or on the phenyl group, so that the planes of the two groups are twisted around the N–C bond between them. Thus the acceptor molecules were concluded to interact mainly with the pyrryl group.
  • Keiichiro Adachi, Hiroshi Suga, Syûzô Seki
    1968 Volume 41 Issue 5 Pages 1073-1087
    Published: 1968
    Released: March 27, 2006
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    It has been known that cyclohexanol has low-temperature form (crystal-II) and high-temperature form (crystal-I) and that the supercooled crystal-I shows in its heat capacity curve an anomalous jump resembled to that associated with glass transition. In order to clarify whether this anomaly arises from relaxation phenomenon or not, we have reinvestigated the heat capacity of this substance from 14°K to 320°K and obtained the values of 8827 J/mol, 265.31°K, 1782 J/mol and 299.09°K for heat of transition, transition point, heat of fusion and melting point respectively. Comparing the ideal gas entropy of cyclohexanol calculated from thermal data and that from statisticalmechanical data, we have estimated that the residual entropy of the crystal-II is of zero and that the potential barrier of internal rotation of OH group is 7.0 kj/mol. From these results, the residual entropy of the supercooled crystal-I amounts to 4.72 J/(mol deg K). We have discussed the glass transition of this crystal and proposed a new term glassy crystal. We have also studied the heat capacity of metastable phase (crystal-III) and obtained the results 244.8°K and 8640 J/mol for transition point and heat of transition. The residual entropy of the crystal-III has determined to be zero.
  • Aritada Hatta, Chiaki Hirose, Kunio Kozima
    1968 Volume 41 Issue 5 Pages 1088-1090
    Published: 1968
    Released: March 27, 2006
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    The microwave spectrum of o-difluorobenzene has been studied in the 7.8- to 28-Gc/sec region, R- and Q-branch transitions of the a-type being assigned for the lowest vibrational state. The rotational constants obtained are A=3263.55 Mc/sec, B=2227.91 Mc/sec, and C=1323.87 Mc/sec. Four possible sets of structural parameters were obtained. seems probable that the angle made by two C–F bonds is larger than 60°. The value of the dipole moment obtained is 2.46±0.03 D.
  • Shigeya Niizuma, Masao Koizumi
    1968 Volume 41 Issue 5 Pages 1090-1096
    Published: 1968
    Released: March 27, 2006
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    Choosing two groups of solvent a) methanol, ethanol, isopropanol (glassy at liquid nitrogen temperature) and b) t-butanol, benzene, tetrahydrofuran (crystalline at liquid nitrogen temperature), ESR studies have been made on the irradiated solutions of A] acridine (A)+acridan (AH2) (1:1), B] A alone, and C] AH2 alone at 77°K. 1) 365 mμ irradiation of A] and B] in the solvents of a) group does not cause any photochemical reaction, whereas in the solvents of b) group, the A*+AH2→2AH· reaction occurs. A resultant singlet ESR line has been assigned to AH·. 2) Irradiation of A] and C] with the entire output from a superhigh pressure mercury lamp gives, for solvents of group a), the ESR spectra which can be attributed mainly to alcohol radicals (RCHOH) but gives electronic absorption spectra ascribed only to AH· ; for the solvents of group b) the results were almost the same as in 1).
  • Arata Kimoto, Haruka Yamada
    1968 Volume 41 Issue 5 Pages 1096-1104
    Published: 1968
    Released: March 27, 2006
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    The infrared spectra for the fundamental absorption bands, ν1, ν2, ν4 and ν5, of CHCl3 and CDCl3 have been measured in polycrystalline films. For the C–H or C–D bending band a triplet has been observed in the pure crystal. The spectra of a mixed crystal (CHCl3: CDCl3) have also been studied over the entire concentration range. The space group of crystalline chloroform has been determined to be D2h16. The intensity of the band changes, going from the gas to the solid, depending on the symmetry species to which the vibrational mode belongs; the A1 bands increase in intensity, while the E bands decrease. The C–H stretching band shows an especially remarkable increase.
  • Kenji Saito, Kazuhiko Ichikawa, Mitsuo Shimoji
    1968 Volume 41 Issue 5 Pages 1104-1109
    Published: 1968
    Released: March 27, 2006
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    Measurements of electric conductance as a function of temperature have been made for the pure liquids; I2, SbCl3, SbBr3 and SbI3, and the mixtures ; I2+SbI3 and SbBr3+SbI3, from 100 to 250°C. Furthermore, measurements of density by a pycnometric method as a function of temperature have also been made for these mixtures, from 100 to 300°C. The conductivities of these liquids lie in the range from 5×10−4 to 1×10−5 ohm−1 cm−1, and are about 10−4 times lower than those of alkali halide melts. In these poorly-conducting pure liquids, the molecules may be considered as constituting a solvent in which slightly dissociated ions are contained. The negative temperature coefficient of conductivity for iodine is in marked contrast to the antimony halide melts, and may be interpreted in terms of the ionic conduction and electron hopping mechanism rather than the metallic one.
  • Makio Morita, Masao Fujimaki
    1968 Volume 41 Issue 5 Pages 1109-1112
    Published: 1968
    Released: March 27, 2006
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    Radioactivity of water increased linearly with dose when aqueous solution of 3H-formate (2 μCi/ml and 2×10−8 M) was irradiated with γ-rays in the presence of oxygen. The increase of the radioactivity was found to be reciprocally proportional to the non-labeled formate concentration where the amount of 3H-formate was kept invariable. Addition of ferrocyanide and 2-propanol, effective OH-radicals scavengers, depressed the radioactivity increase to near zero. These facts show that the abstraction of tritium from 3H-formate by OH-radicals causes the increase of the radioactivity of water. A competition method to measure relative rate constants for reactions with OH-radicals was deviced on the present results. Some values obtained by this method were in agreement with published data.
  • Mamoru Yoshida, Tatzuo Ueki, Noritake Yasuoka, Nobutami Kasai, Masao K ...
    1968 Volume 41 Issue 5 Pages 1113-1119
    Published: 1968
    Released: March 27, 2006
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    Low mp isomer of bis-(1,2-diethoxycarbonyl-ethyl)tin dibromide (mp 114–115°C) crystallizes in a monoclinic form: a=11.85, b=20.24, c=9.79 Å, β=101.3°; space group, P21/a; and four molecules are contained in a unit cell. Crystal structure was established by the heavy atom method. The coordination about the tin atom is nearly octahedral. Two bromine atoms attached to the tin atom are in cis-positions. Two ligands, 1,2-diethoxycarbonyl-ethyl groups, are both bound to the tin atom by carbon and oxygen, forming five-membered rings. These rings are rather puckered, and one is in d-form and another in l-form.
  • Yoshihiko Hatano, Shoji Shida, Shin Sato
    1968 Volume 41 Issue 5 Pages 1120-1125
    Published: 1968
    Released: March 27, 2006
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    The γ-radiolysis of liquid olefins was undertaken to obtain reliable evidence for a possible role of hot hydrogen atoms and superexcited states in radiation chemistry. The contribution of thermal hydrogen atoms may reasonably be excluded in this system. The effect of various electron or positive-ion scavengers on hydrogen formation in the radiolyses of liquid propylene and ethylene has been examined. The hydrogen formation is not appreciably affected by these additives, which indicates ionic species may not play an important role in the hydrogen formation. The liquidphase radiolyses of C3H6-C3D6 and C2H4-C2D4 mixtures have also been investigated and compared with those previously reported of C4H8-l - C4D8-l and trans-C4H8 - 2-trans-C4D8-2 mixtures. The data indicate that the hydrogen from the olefins except ethylene may be formed for the most part by bimolecular processes. A large part of the hydrogen from liquid ethylene may be interpreted in terms of the molecular detachment of a hydrogen molecule, while from the other olefins it may be interpreted in terms of the hydrogen-atom abstraction reaction of hot hydrogen atoms formed by direct excitation which must at least partially involve superexcitation. To attempt quantitative substantiation of the above viewpoint a simple calculation has been made based on the so-called optical approximation. Calculated yields of the hydrogen formation are apparently in good agreement with observed ones.
  • Yoshihiko Hatano
    1968 Volume 41 Issue 5 Pages 1126-1129
    Published: 1968
    Released: March 27, 2006
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    A simple calculation has been made based on the so-called optical approximation to obtain the yields of excitation from superexcitation of the hydrocarbons, methane, ethane, propane, n-butane, n-pentane, ethylene, propylene, butene-1, butene-2, 1,3-butadiene, acetylene, and cyclopropane. Their dipole-matrix-elements squared for excitation from superexcitation, Md2, have been found to be directly proportional to the number of carbon atoms in the hydrocarbons, and the ratio of Md2 to Mi2, the dipole-matrix-element squared for ionization, is about 0.2. Thus, the yields, per 100 eV energy absorbed, of excitation from superexcitation are nearly equal to 0.8 for all the hydrocarbons described here.
  • Takeshi Tomita, Eishin Kyuno, Ryokichi Tsuchiya
    1968 Volume 41 Issue 5 Pages 1130-1132
    Published: 1968
    Released: March 27, 2006
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    The formation constants of the chromium(III) complexes with maleic acid have been determined by the pH method to be logk1=5.4±0.1, logk2=3.0±0.1, and logk3=1.9±0.2 at an ionic strength of μ=0.1 and at 25°C. We also attempted to prepare the solid of the chromium(III) complex with maleic acid. Though it was an amorphous solid to X-ray diffraction measurement, its composition was presumed to be [Cr(mal)(OH)(H2O)3]. After it had been dried in a desiccator for a few days, when it was exposed to moist air we observed the curious phenomenon that the solid was made jumping due to the absorption of water vapor.
  • Tsutomu Sugiura
    1968 Volume 41 Issue 5 Pages 1133-1139
    Published: 1968
    Released: March 27, 2006
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    Samples were decomposed by fusion with Na2O2 and benzoic acid in a Parr-bomb, then halogens were separated from other elements by distillation and determined colorimetrically; chlorine by the thiocyanate method and bromine by the rosaniline method. The chlorine and bromine contents of rocks cover a very wide range with no relation to the type of rock. The Br/Cl ratio, however, is in a relatively narrow range from 1×10−3 to 16×10−3 by weight, mostly from 1×10−3 to 6×10−3, and evidently lower than those reported by previous investigators. The average Br/Cl ratio is (3±2)×10−3, about one-seventh of the value generally accepted for igneous rocks. The halogen content of quartz and feldspar is usually so small that it was not usually determined. The Br/Cl ratio in biotite seems to be rather small and Qertainly is smaller than 3×10−3 on the average. The Br/Cl ratios in volcanic rocks are similar to those in volcanic gases for any one volcano studied.
  • Kazuo Saito, Michihiko Takahashi, Yukio Miyakawa, Kazuyo Masuda
    1968 Volume 41 Issue 5 Pages 1139-1142
    Published: 1968
    Released: March 27, 2006
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    Rate of isotopic exchange between 8-quinolinol-14C and the 8-quinolinolato (oxinato) complexes of aluminum, gallium and indium has been studied in chloroform. Pure yellow complexes are precipitated by adding petroleum ether to the reaction mixture. The exchange rate decreased in the sequence In>Al>Ga, and a detailed kinetic study can be substantiated only with the gallium complex below 0°C. The rate is proportional to the concentration of the complex, but is independent of that of free 8-quinolinol (quinolH) and the Arrhenius activation energy is 18 kcal per mole. The reaction is accelerated by acid and presumably by water. It appears as if one of the ligands is present as unidentate under the given condition and the break of the remaining bond would be the rate determining step. Any reagent that can retard the recombination of the free end of unidentate ligand would catalyse the exchange reaction.
  • Nobuyuki Tanaka, Kenzo Nagase, Saburo Nagakura
    1968 Volume 41 Issue 5 Pages 1143-1146
    Published: 1968
    Released: March 27, 2006
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    Kinetics of the thermal decomposition reactions of hexammme-,halogenoammine- and oxalatoamminecobalt(III) complexes in solid state has been studied by following the change in the cobalt (III) contents with time. It was found that the decomposition of these complexes was initiated by the change of the valence state of cobalt(III) to cobalt(II), and that these electrontransfer reactions were kinetically of a first order. The first-order rate constants, the activation energies and the frequency factors of these electron-transfer reactions were obtained. The values of the activation energies were found to increase in parallel with the increase in the difference between t2g and eg orbitals of the cobalt(III) complexes investigated. (The notations, t2g and eg, are used in the expression of an Oh-symmetry approximation for halogenoammine- and oxalatoamminecobalt(III) complexes.)
  • Kenzo Kitayama, Takashi Katsura
    1968 Volume 41 Issue 5 Pages 1146-1151
    Published: 1968
    Released: March 27, 2006
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    The activity-composition relations in ortho-, and metasilicate solid solutions in the FeO-MgO-SiO2 system are determined at 1204°C on the basis of the measurement of equilibrium oxygen partial pressures. Both the olivine and the pyroxene solid solutions show significant deviations from ideality. Using the present data, the standard free energy change of formation of ferrosilite (hypothetical compound, FeSiO3) is calculated to be −41.7±0.2 kcal/mol on the basis of the equilibrium between metallic iron and silica, and to be −1.6±0.2 kcal/mol on the wüstite (“FeO”) and silica.
  • Kiyotada Matsui, Masatoshi Motoi, Tetsuro Nojiri, Kohtsuchi Wakabayash ...
    1968 Volume 41 Issue 5 Pages 1151-1153
    Published: 1968
    Released: March 27, 2006
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    The treatment of ethyl acetoacetate with terephthaloyl chloride in the presence of two equivalents of aluminum chloride in nitrobenzene at 55°C affords a polymer which may be designated as an aluminum chelate of the polymalonylphenylene derivative with some carbethoxy groups.
  • Takashi Ikeda, Michitoshi Kitabatake, Masatomo Ito, Yoshitaka Noguchi
    1968 Volume 41 Issue 5 Pages 1154-1158
    Published: 1968
    Released: March 27, 2006
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    The effects of various metal compounds on the glycolysis of terephthalonitrile were studied in the presence of water at 185°C. The catalytically-active species were found to be metal ions. Their catalytic activities were correlated with the acid ionization constants, pKa, of metal ions. The active catalysts were limited to the metal ions with pKa values larger than 7. The study of the reaction mechanism suggests that, while one group of metal ions accelerates the formation of glycol and hydroxyl anions, the other involves catalytic acceleration through the coordination of metal ions. The metal ions with pKa values of less than 7 showed no catalytic activities. These results were interpreted in terms of the tendency of the metal ions to form too stable coordination intermediates. Most of these metal compounds also served to inhibit the reactions. For a series of salts derived from a given metal, the catalytic activities were found to decrease with a decrease in their solubilities in water. On the other hand, metal oxides and hydroxides had high catalytic activities.
  • Takashi Ikeda, Michitoshi Kitabatake, Masatomo Ito, Yoshitaka Noguchi
    1968 Volume 41 Issue 5 Pages 1158-1164
    Published: 1968
    Released: March 27, 2006
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    The kinetics of the lead ion-catalyzed glycolysis of benzonitrile were studied in the presence of water. The experimental results indicated that the rate of the formation of ammonia followed the first-order rate law with respect to the concentrations of benzonitrile and of water. For the concentration of the catalyst, the rate found was of a 0.44 order. It was observed that the product, β-hydroxyethyl benzoate, exhibited an inhibiting effect on the glycolysis. The effects of substituents on benzonitrile were found to fit the Hammett rule. The reaction was remarkably influenced by the type of glycol used. The reaction also proceeded through the hydrolysis of benzonitrile, followed by the glycolysis of the benzamide thus formed. The rate of the glycolysis of benzamide was about one-third that of benzonitrile, which is the main reaction in the system. The reaction of imidate formation possessed a small equilibrium constant at a high temperature, but it had a high reaction rate. The proposed mechanism for these glycolysis reactions is as follows: the addition of glycol to benzonitrile yields imidate, which then forms a chelate compound with a metal ion. The imidate activated by the formation of the chelate is easily hydrolyzed by water to form ester and ammonia. This ester tends to chelate to the metal ion and so inhibits the reaction.
  • Takashi Ikeda, Michitoshi Kitabatake, Masatomo Ito, Ryoji Ishioka
    1968 Volume 41 Issue 5 Pages 1165-1169
    Published: 1968
    Released: March 27, 2006
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    The kinetics of the lead ion-catalyzed glycolysis of terephthalonitrile have been studied in the absence of and in the presence of water. In the absence of water, scarcely any formation of β-hydroxyethyl p-cyanobenzoate is observed, but some orthoesters are formed. The reaction rate data obtained in the absence of water are found to fit a reversible consecutive reaction scheme in which some basic compounds are involved as the intermediates. In proportion to the increase in the concentration of water, such intermediates as the orthoesters and basic compounds are hydrolyzed more rapidly to form β-hydroxyethyl p-cyanobenzoate, but simultaneously the hydrolysis of terephthalonitrile and the basic intermediates also takes place in the reaction mixture, thus yielding amide.
  • Tsuyoshi Shishibori
    1968 Volume 41 Issue 5 Pages 1170-1174
    Published: 1968
    Released: March 27, 2006
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    The nature of intramolecular hydrogen bonding in diastereoisomeric pairs of 10-nor-8-oxomenthols (VIII and IX) and 10-nor-8-oxocarvomenthols (X and XI) has been studied by infrared spectroscopy. It was found that 10-nor-8-oxoneomenthol (IX) contains the OH···O type intramolecular hydrogen bond, while 10-nor-8-oxomenthol (VIII) contains the OH···π interaction in addition to the OH···O hydrogen bond. 10-Nor-8-oxocarvomenthols (X and XI) were internally unbonded. In addition, the extent and the limitation of the intramolecular OH···π interaction has been investigated for the diastereoisomeric pairs of a series of p-menth-8-enols: p-menth-8-en-4-ols (I and II), isopulegols (III and IV), dihydrocarveols (V and VI), and trans-β-terpineol (VII). Thus, the hydroxyl group in α- or β-unsaturated alcohols I, II, III and IV was found to be internally bonded to the π-electrons on the double bond; the other isomers are internally unbonded.
  • Takayuki Suga, Tsuyoshi Shishibori, Tamon Matsuura
    1968 Volume 41 Issue 5 Pages 1175-1179
    Published: 1968
    Released: March 27, 2006
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    The preferred rotational conformation of the acetyl group of (+)-10-nor-8-oxoneomenthol (I), (−)-10-nor-8-oxomenthol (II), (−)-10-nor-8-oxocarvomenthol (III), and (+)-10-nor-8-oxoneocarvomenthol (IV) has been examined by a combination of conformational analysis by a priori calculation and variable-temperature circular dichroism and infrared spectrum measurements. Compound I exhibited an inversion in the sign of the Cotton effect upon a change in the solvent. This phenomenon was interpreted as indicating the conformational change Ia\ ightleftarrowsIb. The cause of the change was ascribed to the formation and subsequent rupture of the intramolecular hydrogen bond. Compound II exhibited a solvent-depending circular dichroism curve similar to the curve of I; this was explained as indicating the existence of a conformational equilibrium between the free conformer, IIa, and the internally-hydrogen-bonded conformers, IIb, IIc, and IId. Furthermore, compounds III and IV were found to take preferentially the IIIa–IIIb and IVa–IVb conformations respectively.
  • Takayuki Suga, Tsuyoshi Shishibori, Toshifumi Hirata, Tamon Matsuura
    1968 Volume 41 Issue 5 Pages 1180-1184
    Published: 1968
    Released: March 27, 2006
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    The stereochemical structure of (+)-2-hydroxypinocamphone (II), which was obtained from (−)-α-pinene (I) by the permanganate oxidation, was examined by a combination of physicochemical methods. It was thus found that the C-2 methyl group is trans with respect to the C-6 bridge and that the preferred conformation is V having an axial hydroxyl group. In addition, the preferred conformation of cis-α-pinene glycol (IX) and trans-α-pinene glycol (X), which were produced from II by the lithium aluminum hydride reduction, was found to be IXa and Xa respectively.
  • Pu-Jun Kim, Nobue Hagihara
    1968 Volume 41 Issue 5 Pages 1184-1187
    Published: 1968
    Released: March 27, 2006
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    A series of acetylene-alcohol dicobalt hexacarbonyls was prepared from acetylene-alcohols and dicobalt octacarbonyl. The reactivity towards aqueous sulfuric acid in boiling methanol was investigated. From the ethynyl carbinol complexes, R1R2C(OH)C≡CH·Co2(CO)6, trinuclear cobalt complexes, R1R2CHCH2CCo3(CO)9, were obtained accompanying the reduction of C-OH to a C-H moiety. On the other hand, from the butynediol complexes, R1R2C(OH)C≡CC(OH)R1R2·Co2(CO)6, binuclear cobalt complexes, R1R2CHC≡CCHR1R2·Co2(CO)6, or 1,1,4,4-tetraphenyl-1,3-butadiene were obtained. The structures of all these compounds have been confirmed by analytical measurements and by a study of their absorption spectra.
  • Takeo Saegusa, Hiroyasu Fujii, Takashi Ueshima, Katsumi Tanaka
    1968 Volume 41 Issue 5 Pages 1188-1191
    Published: 1968
    Released: March 27, 2006
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    In reaction of AlEt3 with chloral hydrate has been investigated. The reaction system was examined by means of infrared and NMR spectra and by the vapor-phase chromatographic analysis of the acidolysis product of this system. The gas evolved during the reaction was also analyzed. The AlEt3-chloral hydrate system was proved to contain the linkages of >AlOCH2CCl3, >AlOCH(CCl3)OAl<, >AlOCH(Et)CCl3, >AlOAl<, >Al–Et and >Al–Cl. This system showed a very high catalytic activity for the cationic polymerization of i-butyl vinyl ether. Tetrahydrofuran, 3,3-bis(chloromethyl)oxacyclobutane, α-methylstyrene, and styrene were also polymerized by this catalytic system. The acid strength of the AlEt3-chloral [hydrate system was examined by two methods, the Hammett indicator method and shift of the infrared carbonyl band of xanthone caused by coordination to Lewis acid. It has been shown that the acid strength of this system is as strong as AlEt3–H2O (1:0.8) and Et2AlCl. The relation between the strong acid character of the AlEt3-chloral hydrate system and its structure was discussed.
  • Takeo Saegusa, Hiroyasu Fujii, Katsumi Tanaka
    1968 Volume 41 Issue 5 Pages 1192-1194
    Published: 1968
    Released: March 27, 2006
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    It has been found that the AlEt3-chloral hydrate system induces the random copolymerization of acetaldehyde with chloral. The homogeneity of the product polymer was confirmed by a study of the infrared spectra and bv turbidimetric titration. The thermal stability of the copolymer was much better than that of homopolyacetaldehyde. The copolymer was soluble in chloroform, and films were cast from chloroform solutions.
  • Takashi Ueshima, Shimpei Tomita, Takeo Saegusa
    1968 Volume 41 Issue 5 Pages 1194-1200
    Published: 1968
    Released: March 27, 2006
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    Seven haloalcoholates of aluminum and zinc were prepared by the reactions of haloalcohols with metal alky Is in ethyl ether, and their properties were examined. The following differences have been observed between these haloalcoholates and the usual alcoholates, those with no halogen in the alkyl groups. (1) The metal haloalcoholates are unstable to heat and decompose at 90–220°C. Except for Al(OCH2CF3)3, they are neither distilled nor sublimed even in vacuo. The usual aluminum alcoholates, such as ethoxide and isopropoxide, are easily distilled under reduced pressures. (2) The haloalcoholates are stronger Lewis acids than the usual alcoholates. The acid strength of some aluminum haloalcoholates is even higher than triethylaluminum. The strong acid nature of the aluminum haloalcoholate can be ascribed to the electron-withdrawing effect of halogen. (3) As expected from their strong acid strength, the haloalcoholates induce the cationic polymerizations of vinyl monomers and cyclic ethers, such as styrene, α-methylstyrene, isobutyl vinyl ether, 3,3-bis-(chloromethyl)oxacyclobutane, and tetrahydrofuran. The usual metal alcoholates are weaker acids and do not cause the polymerizations of these monomers. In the ethylene oxide polymerization, both the haloalcoholates and the usual alcoholates showed catalytic activity. However, these two types of alcoholates differ from each other in the catalysis mechanism. For the polymerization of ethylene oxide by the haloalcoholate catalyst, a cationic polymerization mechanism was assumed on the basis of the formation of dioxane as a by-product. The polymerization by the usual alcoholate catalysts is assumed to be of a coordinate anionic mechanism.
  • Yoshiyuki Kawase, Mutsumu Nanbu, Hirokazu Yanagihara
    1968 Volume 41 Issue 5 Pages 1201-1208
    Published: 1968
    Released: March 27, 2006
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    4-Hydroxyfuro[2′,3′:7,8]coumarin (16) and its 3-phenyl (10) and 3-(2-methoxyphenyl) (11) derivatives were prepared from the corresponding 4-hydroxy-5-benzofuranyl ketones (15, 8a and 8b) by the action of ethyl carbonate and sodium. The furocoumarin 11 thus obtained was converted to 5H-benzofuro[3,2-c]furo[2,3-h][1]benzopyran-5-one (18), a compound having a new pentacyclic ring system, by the demethyl-cyclization with pyridine hydrochloride, hydroiodic acid or aluminum chloride. The attempted preparation of these compounds through their dihydro compounds is also described; 2,3-dihydro-4-hydroxybenzofuran (1) was acylated with phenylacetic acid, with 2-methoxypheny lace tic acid or with 2,4,5-trimethoxyphenylacetic acid by the action of polyphosphoric acid to give a mixture of the 5- and 7-acylated compounds (3 and 2), and the formers were converted to the corresponding 4″,5″-dihydrofuro[2″,3″:7,8]isoflavones (6), 4″,5″-dihydro-2-methylfuro-[2″,3″:7,8]isoflavones (4) and 4′,5′-dihydro-4-hydroxyfuro[2′,3′:7,8]coumarins (7). The 2,3-dihydro-4-hydroxy-5-benzofuranyl benzyl ketone (3a) and the dihydrofuroisoflavones (4a and 4b) were also obtained by the catalytic reduction of the corresponding furo-compounds.
  • Mitsuru Katsuhara, Shigeru Wakahara, Kanji Tokuyama
    1968 Volume 41 Issue 5 Pages 1208-1220
    Published: 1968
    Released: March 27, 2006
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    An acid-catalyzed reaction in acetic anhydride was found to isomerize 1,3,4,5-tetra-O-acetyl-2-deoxyl-L-sorbopyranos-2,3-ene (V) to four new unsaturated compounds. When the reaction was allowed to continue for a longer period, they underwent polymerization, but did not afford 2-hydro-xyacetylfuran acetate (XXVIb). The reaction in acetic acid containing water was shown to mainly convert V into XXVIb. This reaction pathway was thought to be different from the above.
  • Shigeru Oae, Mikihiko Yokoyama, Masahiro Kise
    1968 Volume 41 Issue 5 Pages 1221-1224
    Published: 1968
    Released: March 27, 2006
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    Oxygen exchange reaction of sulfoxides has been performed mainly in mineral acids such as sulfuric acid, aqueous hydrochloric and hydrobromic acids. We have found that concurrent oxygen exchange and racemization reactions take place also in carboxylic acids such as acetic, mono- and poly-chloroacetic acids. The pseudo first order reaction rates of both oxygen exchange and racemization reactions of p-tolyl phenyl sulfoxide have been determined using both optically active and 18O-labeled p-tolyl phenyl sulfoxides in these acids. This reaction is found to be mainly dependent on the strengths of the acids; namely, the reaction velocity is faster in an acid of smaller pKa value. Together with the fact that k(rac.)/k(exch.) is unity and the substituent effect is small, the reaction is suggested to proceed through an unimolecular type S–O bond cleavage, probably involving radical cation intermediate (II).
  • Takehiko Ichikawa, Tetsuya Kato
    1968 Volume 41 Issue 5 Pages 1224-1228
    Published: 1968
    Released: March 27, 2006
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    Geraniol (III) was reacted with trimethylhydroquinone (II) in the presence of boron trifluoride in benzene. The product was then acetylated to give a mixture of 2,5,7,8-tetramethyl-2-(4-methyl-3-penten-1-yl)-6-acetyloxychromane (VI) and 2,5,7,8-tetramethyl-2,3-(4,4-dimethylbutano)-6-acetyloxychromane (Vb). The VI was ozonized and decomposed with zinc and acetic acid to give 2,5,7,8-tetramethyl-2-(2-formylethyl)-6-acetyloxychromane (VII). Pseudoionone (VIII) was reduced with sodium borohydride to give pseudoionol (IX), but in certain cases the dehydration of IX occurred during the distillation. VII was condensed with IX by a Wittig reaction to give 2,5,7,8-tetramethyl-2-(4,8,12-trimethyl-3,5,7,11-tridecatetraen-l-yl)-6-acetyloxychromane (X), which was then hydrogenated to give α-tocopheryl acetate (I).
  • Takehiko Ichikawa, Hiroko Owatari, Tetsuya Kato
    1968 Volume 41 Issue 5 Pages 1228-1232
    Published: 1968
    Released: March 27, 2006
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    Trimethylbenzoquinone (XII), a raw material for the synthesis of trimethylhydroquinone (XIII), was synthesized from trimethylcyclohexenones and trimethylcyclohexene by oxidation. Ethyl α-propionylpropionate (II) prepared from ethyl propionate was condensed with methyl vinyl ketone to yield 4-methyl-4-ethoxycarbonylocta-3,7-dione (IV), which was then dehydrated with beryllium chloride to give 2,3,6-trimethyl-6-ethoxycarbonyl-2-cyclohexen-1-one (V). The product (V) was heated with alkali to give 2,3,6-trimethyl-2-cyclohexen-1-one (VI). The refluxing of a solution of IV in a mixture of acetic acid and hydrochloric acid also gave rise to VI. When II was condensed with crotonaldehyde, 2,5,6-trimethyl-2-cyclohexen-1-one (VIII) was obtained in a single step. 1,4(or 1,5)-Dimethyl-5-(or 4)-formyl-1-cyclohexene (IX), obtained by the Diels-Alder reaction of crotonaldehyde with isoprene, was reduced by hydrazine hydrate to give 1,4,5-trimethyl-1-cyclohexene (X). X was oxidized with t-butyl chromate and acetic anhydride to give 3,5,6-trimethyl-2-cyclohexen-1-one (XI). VI, VIII, XI, and X were oxidized with t-butyl chromate and acetic anhydride to give XII in 53, 52, 22, and 12% yields respectively. The oxidation of VIII by selenium dioxide gave XII in a 23% yield, but only a trace of XII was formed by the similar oxidation of X.
  • Takehiko Ichikawa, Tetsuya Kato
    1968 Volume 41 Issue 5 Pages 1232-1236
    Published: 1968
    Released: March 27, 2006
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    Phytone (XI), an important intermediate in the preparation of α-tocopherol, was synthesized by a selective Wittig reaction between geranyltriphenylphosphonium halide (VII) and the aldehyde group of 2-methyl-6-oxoheptanal (VIII), followed by the hydrogenation of the product. VIII was prepared from 1,3-dimethyl-1-cyclohexene (V) by ozonolysis and reductive decomposition. V could not be obtained in a pure state by the dehydration of 2,6-dimethylcyclohexan-1-ol (II), presumably because of the isomerization of the intermediate carbonium ion. The pyrolysis of the acetate of II (III) was found to give pure V. That the hardly-pyrolizable stereoisomer of III was cis,cis-2,6-dimethylcyclohexyl-1-acetate (VI) is consistent with the cis-elimination mechanism.
  • Yoshitaka Yamada, Izumi Kumashiro, Tadao Takenishi
    1968 Volume 41 Issue 5 Pages 1237-1240
    Published: 1968
    Released: March 27, 2006
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    The chemical reactivities and the synthesis of various derivatives of 4,5-dicyanoimidazole formed by heating a solution of hydrogen cyanide in liquid ammonia were studied, as were the partial hydrolysis, hydrogenation, and addition reaction of cyano groups and the alkylation, cyano-ethylation, and vinylation of the imidazole ring. From these experiments, a few new compounds were synthesized, which had been expected as intermediates of polymers containing imidazole rings.
  • Katsuhiko Ichikawa, Osamu Itoh, Takahisa Kawamura
    1968 Volume 41 Issue 5 Pages 1240-1245
    Published: 1968
    Released: March 27, 2006
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    The reaction of oxymercurial of ethylene with dimedone in acetic acid containing perchloric acid, followed by treatment with sodium chloride, gave 2-(β-chloromercuriethyl)-5,5-dimethyl-cyclohexan-1,3-dione. Upon treating this mercurial with an equimolar amount of aqueous potassium hydroxide, 6,6-dimethyl-spiro[2,5]octan-4,8-dione was obtained. Oxymercurial of propylene reacted with dimedone to form a mixture of 4-oxo-2,6,6-trimethyl-2,3,4,5,6,7-hexahydrobenzofuran and 4-oxo-3,6,6-trimethyl-2,3,4,5,6,7-hexahydrobenzofuran under simultaneous demercuration; the mercurial corresponding to that in the case of ethylene could not be isolated.
  • Tokiti Noda, Michio Inagaki, Shin-ichi Hirano, Kiyoshi Amanuma
    1968 Volume 41 Issue 5 Pages 1245-1248
    Published: 1968
    Released: March 27, 2006
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    The effect of the presence of limestone on the graphitization of carbon was investigated by the heat treatments of the carbon sample under the quasi-hydrostatic pressure of 3.2 kbar. The carbon sample used was a coke (PV-7) prepared by carbonization of polyvinylchloride up to 680°C. It was placed between two disks of limestone so as to make a sandwich-type specimen. The heat treatments were performed in a simple piston-cylinder type vessel at various temperatures of 800–1300°C for 20–240 min. Above 1000°C, the carbon specimens were obtained as caked tablets. The profiles of (002) diffraction line of these carbon tablets were found to be composite, consisting of a sharp component profile at 26.5° and a broad one at lower angle than 26.2°. The component GM corresponding to the sharp component profile seemed to have the graphite structure. The content of the component GM increased very rapidly with the increase in heat treatment temperatures above 1000°C. Phenomenally, the developement of the graphite structure seemed to be closely related to the recrystallization and the melting of coexisting limestone, but some chemical effects should not be excluded.
  • Shizunobu Hashimoto, Junzo Sunamoto, Hironori Fujii, Koji Kano
    1968 Volume 41 Issue 5 Pages 1249-1251
    Published: 1968
    Released: March 27, 2006
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  • Kazuhiro Sasaki
    1968 Volume 41 Issue 5 Pages 1252-1254
    Published: 1968
    Released: March 27, 2006
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  • Keikichi Nakamura
    1968 Volume 41 Issue 5 Pages 1254-1256
    Published: 1968
    Released: March 27, 2006
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  • Hitoshi Kamada, Keiichi Furuya
    1968 Volume 41 Issue 5 Pages 1256-1258
    Published: 1968
    Released: March 27, 2006
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  • Tadashi Sasaki, Yoshiyuki Yoshioka
    1968 Volume 41 Issue 5 Pages 1258-1260
    Published: 1968
    Released: March 27, 2006
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  • Takehiro Abe
    1968 Volume 41 Issue 5 Pages 1260-1261
    Published: 1968
    Released: March 27, 2006
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  • Kanae Hayashi, Torao Takagaki, Kiyoshi Takada, Koichiro Hayashi, Seizo ...
    1968 Volume 41 Issue 5 Pages 1261-1263
    Published: 1968
    Released: March 27, 2006
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  • Ichiro Kawasaki, Isao Kusumoto, Takeo Kaneko
    1968 Volume 41 Issue 5 Pages 1264-1265
    Published: 1968
    Released: March 27, 2006
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  • Hitomi Suzuki
    1968 Volume 41 Issue 5 Pages 1265
    Published: 1968
    Released: March 27, 2006
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  • Satoe Hase, Reiko Kiyoi, Shumpei Sakakibara
    1968 Volume 41 Issue 5 Pages 1266-1267
    Published: 1968
    Released: March 27, 2006
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