Bulletin of the Chemical Society of Japan
Online ISSN : 1348-0634
Print ISSN : 0009-2673
ISSN-L : 0009-2673
Volume 47 , Issue 8
Showing 1-50 articles out of 63 articles from the selected issue
  • Yoshimi Kurimura, Ikuko Sekine, Eishun Tsuchida, Yukio Karino
    1974 Volume 47 Issue 8 Pages 1823-1826
    Published: 1974
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    The effects of polymeric ligands on the electron-transfer reaction of the cobalt(III) complex have been studied for the reductions of the complex ions of cis-Co(en)2ACl2+ (A=poly-4-vinylpyridine, PVP, or pyridine, py) by the aquo ferrous ion and some Fe(II)-nitrilopolycarboxylate chelates. The specific rate of the Fe2+ reduction of the Co(en)2PVPCl2+ is smaller than that of the Co(en)2PyCl2+. The specific rate of the Fe(II)-chelate reduction increases considerable when the pyridine ligand in the Co(en)2-PyCl2+ is replaced by PVP. The effects of the chelating agents, the degree of coordination, the ionic strength, and the concentration of the reductant on the reduction rate of the Co(en)2ACl2+ by the Fe(II)-nitrilopolycarboxylate were also examined. The resulting reactivity patterns of the polymer complex ions could mainly explained by the effect of the higher electrostatic field caused by the positively-charged polymer structure.
  • Issei Nakamori, Hidetsugu Nakamura, Toshiyuki Hayano, Shuichi Kagawa
    1974 Volume 47 Issue 8 Pages 1827-1832
    Published: 1974
    Released: March 27, 2006
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    The thermal decomposition of silver(I) oxide and its reduction with reductive gases, such as ethylene, hydrogen, and carbon monoxide, have been studied by using a fixed-bed flow reactor. Under isothermal conditions, each reaction gave a sigmoidal shape to the fractional decomposition vs. time curves, and these curves were in good agreement with Avrami’s equation. The temperature at which the reaction commenced corresponded well to the chemical affinity of the reaction, and a linear free-energy relationship holds between the apparent activation energy and the standard enthalpy change of the reaction. In the thermal decomposition, an enlargement in particle size resulting from the melting and sintering of the product silver was recognized, but in the reduction the particle size scarcely varied during the reaction. On the basis of these results, the mechanism of each reaction was discussed.
  • Yoshiyuki Mido
    1974 Volume 47 Issue 8 Pages 1833-1837
    Published: 1974
    Released: March 27, 2006
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    By examining their N–H stretching absorptions in the hydrogen-bonding system, the steric effects of the substituent on the C=O or N–H group have been studied for sym-disubstituted alkylureas of the RHNCONHR′ type in carbon tetrachloride. By comparing the estimated percentage of the monomer, it is concluded that the steric effects are not large enough to convert the trans conformation into the cis conformation, though the branched alkyl groups may prevent another molecule from approaching more strongly than the normal alkyl groups. Correlations among some spectral parameters have been examined, such as the estimated percentage of the monomer, the frequency shift upon hydrogen-bond formation, the apparent integrated absorption intensity, and the halfintensity width of the associated band.
  • Yoshio Hori, Riki Kobayashi
    1974 Volume 47 Issue 8 Pages 1838-1842
    Published: 1974
    Released: March 27, 2006
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    With the use of high-precision gas-chromatography, the multilayer adsorption of methane on fused silica beads was precisely measured between 145.0 K and 213.6 K. The molar volume and the partial molar entropy of the adsorbed methane were determined as a function of the temperature. The molar volume in the monolayer region depends much less on the temperature than that of the bulk liquid. However, the molar volume of multilayer adsorbed methane shows a dependence on the temperature similar to that of bulk liquid, which is at a lower temperature. The volume of the monolayer is practically constant under the present experimental conditions. The apparent thickness of the adsorbed monolayer was interpreted in terms of a simple collision model. The partial molar entropy of the adsorbed phase is much lower than that of the saturated bulk liquid. The lower dependence of the molar volume on the temperature and the lower entropy suggest that the freedom of motion of the adsorbed molecules is restricted as compared with those in bulk liquid.
  • Zenpachi Ogumi, Isao Tari, Zenichiro Takehara, Shiro Yoshizawa
    1974 Volume 47 Issue 8 Pages 1843-1846
    Published: 1974
    Released: March 27, 2006
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    The electro-initiated polymerization of acrylamide was investigated in an aqueous solution of trifluoroacetic acid and potassium trifluoroacetate. An oligomer with a molecular weight of 4000–6000 was thus obtained. The initiating ability of Kolbe’s intermediate radicals was recognized by an analysis of the fluorine contained in the polymerized products as the end group. Kolbe’s intermediate radicals, R·, react with monomers, M, to form RM·, which takes the paths of polymerization and other reactions. The rate of reaction to form RM· is so fast that no Kolbe’s dimer, C2F6, is obtained. Gas analysis clarified the ratio of CF3COO· to CF3·, which reacted with the monomer. The comparison of the molecular weights as measured by the two different methods suggests that the coupling reaction of radical ends terminates the propagation reaction. The rate of oligomer production was independent of the current density.
  • Kazutoshi Tanabe, Shinnosuke Saëki
    1974 Volume 47 Issue 8 Pages 1847-1851
    Published: 1974
    Released: March 27, 2006
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    The force constants based on the simple or modified Urey-Bradley, and the general force fields have been determined from the observed fundamental frequencies, Coriolis coupling constants and centrifugal distortion constants of allene C3H4, C3D4 and C3H2D2 by the damped least-squares method. It is concluded that the simple or modified UBFF is not suitable for reproducing the observed data. In order to attain the best fit between the observed and calculated values, new bond-angle interaction constants q(CH, CCC) and q(CC, HCH) as well as the bond-bond and angle-angle interaction constants p and l should be added to the simple UBFF.
  • Makoto Kiyomiya, Naohiro Momma, Iwao Yasumori
    1974 Volume 47 Issue 8 Pages 1852-1857
    Published: 1974
    Released: March 27, 2006
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    The mechanism of H2–D2 equilibration reaction over the copper surface was studied in the 40–90 °C range of temperature and in the pressure range of 4–45 Torr. From the studies of the hydrogen adsorption and the reaction between gaseous deuterium and preadsorbed hydrogen, the reaction was confirmed to proceed via combination between hydrogen and deuterium atoms on the surface. The rate constants for the adsorption and the desorption were optimized by a computer simulation of the reaction-time course and were found to be in satisfactory agreement with the observed results. A marked isotope effect was found in these rates; its influence on the partial pressure dependence of the reaction was discussed.
  • Tsuguhiro Kaneda, Noriyoshi Sakabe, Jiro Tanaka
    1974 Volume 47 Issue 8 Pages 1858-1862
    Published: 1974
    Released: March 27, 2006
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    The crystal structure of (+)-2,5-dimethoxy-8-chlorotriptycene has been investigated by the X-ray method. The crystal system is monoclinic, and the space group is P21. The cell dimensions are a=8.231, b=13.320, c=8.156 Å, and β=96.49°. The structure was deduced from the Patterson map and from the calculation of the R-factor minimized by varying the rotational and translational parameters. The structure parameters were refined by the block-diagonal least-squares method by using 1227 independent reflections; the final R-value was 0.073. The absolute configuration was determined to be 1R6S from the CuKα anomalous scattering of the chlorine atom.
  • Shuji Saito, Fumio Makino
    1974 Volume 47 Issue 8 Pages 1863-1867
    Published: 1974
    Released: March 27, 2006
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    The microwave spectra of normal, 2–13C, and three monodeuterated isotopic species of 3,3,3-trifluoropropene have been studied. The combined structure of ro and rs was obtained from the rotational constants observed. It has been necessary to take account of a tilt angle of the symmetry axis of the trifluoromethyl group. The following structural parameters have been determined: r(C–C)=1.489±0.002Å, r(C=C)=1.312±0.010Å, r(C–H1)=1.085±0.011 Å, r(C–H2)=1.092±0.009 Å, r(C–H3)=1.109±0.003 Å, ∠F–C–F=106.8±0.3°, ∠C–C=C=124.8±0.4°, ∠C=C–H1=120.6±1.0°, ∠C=C–H2=122.8±1.0°, ∠C=C–H3=121.2±1.0°, and θt=1.0±0.8° on the assumption that r(C–F)=1.345±0.003Å, where θt denotes the tilt angle of the CF3 top axis relative to the C–C bond away from the double bond of the vinyl group. The components of the electric dipole moment have been determined to be μa=2.331±0.014 D and μb=0.698±0.025 D; these values give a total dipole moment of 2.433±0.020 D at an angle of 7±1° with the symmetry axis of the trifluoromethyl group. The relative intensity between the rotational transitions in the ground state and in the first torsionally-excited state has been measured. The torsional frequency has been determined to be 88±25cm−1.
  • Sumio Shinoda, Yasukazu Saito
    1974 Volume 47 Issue 8 Pages 1868-1871
    Published: 1974
    Released: March 27, 2006
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    The reaction of 2-hydroxy-1-propylmercuric perchlorate with sodium formate in an aqueous solution was found to be a redox-type reaction: CH3CH(OH)CH2HgClO4+HCOONa=CH3CH=CH2+Hg(0)+CO2+H2O+NaClO4. The concentration of the mercurial coordinated by the formate ion was determined in situ by analyzing the geminal 199Hg-1H spin-coupling constant. By changing the ratio of [CH3CH(OH)CH2HgClO4]/[HCOONa], the initial reaction rate was confirmed to be first-order with respect to the formato-mercurial: v=k[CH3CH(OH)-CH2HgOCOH]. From the variation in k with the temperature, the values of Ea=17.5 kcal mol−1 and A=4.0×108 s−1 were obtained. On the grounds of the kinetic isotope effect for DCOONa and the stereochemical study with threo- and erythro-CH3CH(OH)CHCH3HgClO4, a mechanism is proposed in which the reaction proceeds solely through the unimolecular redox-decomposition of the formato-mercurial, involving an anti-elimination of olefin coupled with a two-electron transfer from the formate ligand to the mercurial.
  • Ken Hirotsu, Akira Shimada
    1974 Volume 47 Issue 8 Pages 1872-1879
    Published: 1974
    Released: March 27, 2006
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    The crystal structure of β-lactose (C12H22O11) was solved by direct phasing methods with integrated photographic intensity data. The structure was refined by the anisotropic least-squares method to give a final R value of 0.068 for the observed reflections. The space group is P21 with Z=2 and with unit cell dimensions of a=10.839 (6), b=13.349 (6), c=4.954 (5) Å, and β=91.31 (9)°. All the hydrogen atoms were located on different syntheses. The crystals are nearly isostructural with those of β-cellobiose except for the axial O(4) atom. The exocyclic C(5)–C(6) and C(5′)–C(6′) bonds are significantly shorter than the other C–C bonds. The lengths of the two ring C–O bonds are unequal in the galactose unit and equal in the glucose unit. The C(1)–O(1) and C(1′)–O(1′) bond lengths are shorter by 0.015 Å and 0.030 Å than the mean exocyclic C–O length of 1.417 Å. The structure contains an intramolecular hydrogen bond and exhibits an asymmetrical twist about the bridge bond. All the oxygen atoms, except the bridge oxygen atom, are involved in the hydrogen-bonding network, which comprises two terminating chains.
  • Shin Sato, Seishi Nishida, Kiyoshi Hosoya
    1974 Volume 47 Issue 8 Pages 1880-1882
    Published: 1974
    Released: March 27, 2006
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    The photolysis of deuterium iodide at the wavelength of 2288 Å was carried out in the presence of cis-2-butene and iodine at 40 °C. Among the products, hydrogen (D2 and HD), methane (CH3D), propylene (CH3CH=CHD), n-butane (CH3CHDCHDCH3), and 1-butene were measured as a function of the pressure of cis-2-butene. The formation of HD at higher pressures of cis-2-butene was attributed to the abstruction of H atoms from cis-2-buteneby hot D atoms. This reaction accounted for 8% of the total D atom-reaction. The formations of CH3D, C3H5D, and C4H8D2 were well explained by the successive reactions of hot butyl radicals, C4H8D*.
  • Masao Kakimoto, Tsunetake Fujiyama
    1974 Volume 47 Issue 8 Pages 1883-1885
    Published: 1974
    Released: March 27, 2006
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    A theoretical calculation is made to explain the widths of the isotropic parts of polarized Raman lines in liquids. The calculation is based on the model of the intermolecular resonance-type vibrational relaxation through the vibration-dependent term of the Lennard-Jones atom-atom interaction. The result is applied to the Raman lines of liquid nitrogen, oxygen, and carbon disulfide, and compared with the experimental data.
  • Yoshiro Sakai, Yoshihiko Sadaoka, Hirofumi Yokouchi
    1974 Volume 47 Issue 8 Pages 1886-1888
    Published: 1974
    Released: March 27, 2006
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    The electrical properties of evaporated thin films of copper phthalocyanine (CuPc) were investigated by the ac method. The frequency dependence of conductivity and capacitance, and the activation energy for dc conductivity in α- and β-CuPc were determined. No significant variation in the electrical properties was observed with the difference in the phases of CuPc films in vacuo. The frequency dependence of conductivity and capacitance can be explained in terms of the simultaneous hopping and band conduction, viz., σ=σdc+A1·ωn and C=C+A2·ω1−n. The energy gap for α- and β-CuPc in vacuo is 1.80 eV and 1.89 eV, respectively. The adsorbed O2 gas has a great effect on the dc conductivity but little on the ac conductivity of α-CuPc film. The adsorption of oxygen on α-phase GuPc might be the cause of high dc conductivity and low activation energy(0.5–0.7 eV) as compared with those in vacuo.
  • Takeshi Sawai, Toshinari Shimokawa, Yoshiharu Shinozaki
    1974 Volume 47 Issue 8 Pages 1889-1893
    Published: 1974
    Released: March 27, 2006
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    The radiolysis of solutions of polychlorinated biphenyls (PCB’s) and potassium hydroxide in simple aliphatic alcohols was studied. The major products in alkaline 2-propanol solutions were potassium chloride, acetone, lower chlorinated biphenyls, and biphenyl. Their yields increased and the concentration of the hydroxide ions decreased with the dose. Acetone and potassium chloride were formed in high yields, and their concentrations were almost equal to the diminution in the hydroxide ions. The dechlorination yield was determined as a function of the dose, the dose rate, and the concentrations of PCB’s, potassium hydroxide, and organic solutes. The chain-dechlorination reaction proceeded in the alkaline 2-propanol solution, but not in alkaline methanol, ethanol, 1-propanol, and butanols. The 2-propoxide radical anion, which is formed by the electron transfer from the hydroxide ion to the 2-propanol radical, is the chain carrier for the dechlorination reaction of PCB’s in alkaline 2-propanol solutions. The mechanism is discussed in detail.
  • Yoshiro Yonezawa, Takayuki Fueno
    1974 Volume 47 Issue 8 Pages 1894-1897
    Published: 1974
    Released: March 27, 2006
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    Vibrational excitation of X2CO-type polyatomic molecules (X=F, Cl, Br, and H) on collision with an argon atom at temperatures 1000–3000 K was treated by the SSH-Tanczos method with a more tractable formula of average vibrational factor. Bending modes are more easily excited than bond-stretching modes in carbonyl halides. Excitation of the carbonyl stretching mode, the most difficult to occur in T–V process, becomes realizable when coupled with other modes to satisfy the near-resonance conditions.
  • Hiroyuki Yamaguchi, Takeshi Nakajima
    1974 Volume 47 Issue 8 Pages 1898-1900
    Published: 1974
    Released: March 27, 2006
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    The magnetic susceptibilities for nonbenzenoid aromatic hydrocarbons have been examined by using the modified London-Hoarau method in the framework of the Wheland-Mann-type SCF MO approximation. By taking into account the double-bond fixation quite common in these molecules, we obtained a general agreement between the calculated results and the available experimental values.
  • Takeshi Ohno, Shunji Kato
    1974 Volume 47 Issue 8 Pages 1901-1907
    Published: 1974
    Released: March 27, 2006
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    The fluorescence yield (ΦF) and the phosphorescence yield (ΦP) of acetylacetone, benzoylacetone, and dibenzoylmethane were enhanced by coordination of Zn2+, Al3+, and Be2+ in an increasing order. In the bis- and the tris-bidentate complexes, not only did the ratios of ΦP to ΦF increase, but also the lifetimes of the phosphorescences became a little longer than that of the corresponding mono-bidentate complex. This change originates from some kinds of interaction between the ligands in the excited and ground states. Such an inter-ligand interaction was supported by the measurement of the polarization. However, the interaction energy is smaller than the expected values in the analyses of the absorption spectra and the circular dichroism in the region of the ligand band. A difference in the absorption spectra between the mono- and the bis- or the tris-bidentate complexes was seen only in the Franck-Condon factors; this finding supports the extension of the excited state through the two or the three ligands due to the weak inter-ligand interaction.
  • Isao Kamiya, Keizo Aoki
    1974 Volume 47 Issue 8 Pages 1908-1911
    Published: 1974
    Released: March 27, 2006
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    In the present study, we found that the absorbance at 395 nm of the chemiluminescent reaction system of eosin Y with hydrogen peroxide initially increased to a maximum, and then gradually decreased. From the finding that the absorption spectrum of a chromatographically-isolated blue-fluorescent product (ME) showed a peak at the same wavelength (395 nm), we could confirm that the increment of the absorbance at 395 nm (Δ395) was mainly due to the generation of ME; we then extended the investigation of the mechanism for the chemiluminescent reaction by a kinetic analysis of ME. The observed value of Δ395 could be approximately calculated by the expression of [ME], which was derived from a kinetic scheme proposed in the previous paper. The ratio of the generation rates of ME in different media, which was calculated from the observed values of Δ395, was in good agreement with that estimated from the curves of the chemiluminescence emission intensity versus the time measured in the media. These results gave additional evidence in support of the view that the blue-fluorescent species is the primary excited product in the reaction.
  • Tetsuko Takabe, Masashi Tanaka, Jiro Tanaka
    1974 Volume 47 Issue 8 Pages 1912-1916
    Published: 1974
    Released: March 27, 2006
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    The electronic absorption spectra of 2,4-hexadiyne-1,6-diol, diphenylacetylene, and diphenyldiacetylene were measured in a single crystalline state with a polarized light. The results of the polarization measurement and the theoretical calculations gave confirmative assignments of the electronic transitions of these molecules.
  • Tetsuko Takabe, Masashi Tanaka, Jiro Tanaka
    1974 Volume 47 Issue 8 Pages 1917-1920
    Published: 1974
    Released: March 27, 2006
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    The electronic absorption spectra of [3,3]-paracyclophadiyne and [4,4]-paracyclophadiyne have been investigated in solution and in the crystalline state. A trans-annular interaction between the diacetylene group and the benzene ring has been found, and a theoretical study has been made to confirm the assignment. The bathochromic shift and the CT band from the benzene ring to the diacetylene group are particularly noticeable for [3,3]-paracyclophadiyne, where the inter-group distance is significantly shorter than the normal van der Waals distance.
  • Reita Tamamushi
    1974 Volume 47 Issue 8 Pages 1921-1926
    Published: 1974
    Released: March 27, 2006
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    The individual ionic activity coefficients of strong electrolytes in dilute aqueous solutions are derived from the ionic conductivity data, using the Debye-Hückel-Onsager theory of strong electrolyte solutions. The mean activity coefficients computed by the present method are in good agreement with the experimental values in most of the uni-univalent and some of the uni-multivalent electrolytes studied, which demonstrates the validity of the method in deriving the individual ionic activity coefficients. Comparisons are made of the values of individual activity coefficients of various ions in dilute aqueous solutions of strong electrolytes, as determined by different methods including measurements of potential differences across membranes at varying concentrations. The influence of the ion of opposite sign on the individual ionic activity coefficient has been observed.
  • S. P. Walvekar, A. B. Halgeri
    1974 Volume 47 Issue 8 Pages 1927-1929
    Published: 1974
    Released: March 27, 2006
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    Depolymerization of paraldehyde in benzene catalyzed by SiO2–ZrO2, SiO2–TiO2, Al2O3–ZrO2, TiO2–ZrO2, Al2O3–TiO2 (calcined at various temperatures) has been studied. It is observed that in all the cases the catalytic activity (first order rate constant, k) exhibited a maximum against the temperature of heat treatment of the catalyst. The acid sites at pKa≤−3.0 correlate best with catalytic activity for depolymerization of paraldehyde.
  • Tsutomu Fujimoto, Ichiro Hirao
    1974 Volume 47 Issue 8 Pages 1930-1937
    Published: 1974
    Released: March 27, 2006
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    The telomerization of methyl acetate and cyanoacetate with ethylene initiated by di-tert-butyl peroxide was investigated. Methyl esters of linear and α-branched alkanoic acids, and linear and α-branched alkyl acetates, as well as hydrocarbons, were identified in the system of methyl acetate. The methyl esters of linear and α-branched α-cyanoalkanoic acids were identified in the system of methyl cyanoacetate, but no alkyl cyanoacetates could be found. It was suggested that intramolecular 1,5-hydrogen transfer in telomer radicals with two ethylene units and a chain-transfer reaction to the telomers gave the branched telomers. The chain-transfer constants were estimated in the system of methyl cyanoacetate. The introduction of the cyano group to methyl acetate at the α-position gave a favorable system for chain-transfer reactions and facilitated intramolecular 1,5-hydrogen transfer in the telomer radicals. The relatively higher relative reactivity of the methoxy group to the acetyl group in methyl acetate in the telomerization with ethylene was discussed.
  • Toshiki Otake
    1974 Volume 47 Issue 8 Pages 1938-1944
    Published: 1974
    Released: March 27, 2006
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    Seven tritylated derivatives have been synthesized by the tritylation of the primary hydroxyl group of sucrose. The 1H NMR spectra of their peracetyl derivatives have been determined at 100 MHz and 220 MHz in order to assign the sugar-ring-proton signals with the aid of the double-resonance technique and NMR spin simulation. The relationship between the chemical shifts of their methine protons and the substituted position of the bonded trityl groups is discussed. Crystalline 1′-mono-O-tritylsucrose derived from 6,6′-di-O-palmitolysucrose is also described.
  • Toshio Sugita, Yasuo Yamasaki, Osamu Itoh, Katsuhiko Ichikawa
    1974 Volume 47 Issue 8 Pages 1945-1947
    Published: 1974
    Released: March 27, 2006
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    The oxymercuration-demercuration of styrene with optically active mercuric tartrate, 2-phenylpropionate, mandelate, camphorate, menthoxyacetate, and monomethyl tartrate resulted in a partial asymmetric synthesis of 1-phenylethanol. When mercuric tartrate was used, exceptionally high optical yields (25–32%) were observed. The mechanisms for the asymmetric synthesis are discussed.
  • Ken-ichi Watanabe, Kiyoshi Murayama
    1974 Volume 47 Issue 8 Pages 1948-1950
    Published: 1974
    Released: March 27, 2006
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    Spectrophotometric studies on the catalytic hydration of 2-pyridinecarbonitrile derivatives in the presence of [Cu(en)2]Cl2·2H2O and CuCl2·2H2O under nearly neutral conditions revealed that the products are their amides. In some cases, the yields were calculated from the weight of amides obtained. The hydration of the nitrile group was influenced by electronic and steric effects. Selective hydration of the nitrile group in α-position was observed in the case of dinitrile. The selectivity was applied to hydrolysis of nitriles to carboxylic acids.
  • Kunihide Fujimori, Kameji Yamane
    1974 Volume 47 Issue 8 Pages 1951-1953
    Published: 1974
    Released: March 27, 2006
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    Benzo[5,6]cyclohept[1,2-b]indole-6,11,12-triones (benzoindolotropoquinones)(VIIIa–c) were prepared by the oxidation of 11,12-dihydrobenzo[5,6] cyclohept[1,2-b]indol-6-ones (Va–c) with sodium dichromate in acetic acid. Compound VIIIa was rearranged by means of a coned sodium hydroxide solution into a known benzocarbazole-1,4-quinone. The pyrrolotropolone derivative (VII) was also obtained through the ring closure of the 5-hydrazinotropolone derivative (VI).
  • Fumio Toda, Koji Yuwami
    1974 Volume 47 Issue 8 Pages 1954-1956
    Published: 1974
    Released: March 27, 2006
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    Neither the oxidation of 2-diphenylmethylenecyclobutane-1,3-dione (I) with SeO2 nor the hydrolysis of 4,4-dibromo- (III) and 4,4-dimethoxy-2-diphenylmethylenecyclobutane-1,3-dione (IV) afforded the title cyclobutanetrione (II). The title acetal (IV) was dissolved in coned HCl-MeOH without hydrolysis, probably in the protonated form (X) on its carbonyl oxygen. The basification of a solution of IV in coned HCl–MeOH-d4 recovered the IV undeuterated. On the other hand, IV was dissolved in KOH-MeOH in the form of the enolate anion (XII). The acidification of a solution of IV in KOH–MeOH-d4 afforded the deuterated acetal (IV-d6).
  • Yoshimori Omote, Tokuo Hirama, Toshihiko Komatsu
    1974 Volume 47 Issue 8 Pages 1957-1959
    Published: 1974
    Released: March 27, 2006
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    The oxidation of 4-substituted catechols including DOPA with o-chloranil or cerium(IV) sulfate to give the corresponding o-benzoquinones was examined. The trapping of o-benzoquinones with o-phenylenediamine immediately after oxidation was successfully used to isolate 2-substituted phenazines, the substituents being –CH3, –CH(CH3)2, –(CH2)2CO2H, –(CH2)2CO2CH3, –CH=CHCO2H, –CH=CHCO2CH3, –(CH2)2NHCOC6H5, and –CH2CH(NHCOC6H5)CO2CH3. Dopaquinone was identified in a protected form.
  • Kazuhiro Maruyama, Seiichi Arakawa
    1974 Volume 47 Issue 8 Pages 1960-1966
    Published: 1974
    Released: March 27, 2006
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    The reaction products of the photochemical reactions of 1,4-naphthoquinone and its methyl- or halogenoderivatives with xanthene were investigated. Methyl-substituted 1,4-naphthoquinones produce the corresponding 1,4-naphthohydroquinones, but naphthoquinone and its halogeno-derivatives react to give substituted or added products by the xanthyl group in addition to the hydroquinone derivatives. Stable free radicals, which remain unchanged under atmospheric pressure, are also obtained in the latter reactions. The courses of the photochemical reactions were investigated by means of the CIDNP technique, and the reaction mechanism was discussed.
  • Akira Kasahara, Taeko Izumi, Kazuyoshi Endo, Toru Takeda, Motomu Ookit ...
    1974 Volume 47 Issue 8 Pages 1967-1970
    Published: 1974
    Released: March 27, 2006
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    1,5-Cyclooctdiene reacted with phenylpalladium chloride to give di-μ-chloro-bis-(1-phenylcyclooct-4-ene-8σ,4π)-dipalladium(II). Similarly, the reaction of endo-dicyclo-pentadiene with phenylpalladium chloride led to di-μ-chloro-bis-[endo-6-phenyl-3a,4,5,6,7,7a-hexahydro-endo-4,7-methanoindene-endo-5σ,(2–3)π]-dipalladium (II). The σ-bonded structures of these complexes have been confirmed by studies of the IR and NMR spectra.
  • Toshimitsu Suzuki, Toshiaki Kobayashi, Yoshinobu Takegami, Yuzo Kawasa ...
    1974 Volume 47 Issue 8 Pages 1971-1976
    Published: 1974
    Released: March 27, 2006
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    The addition to the methyl-substituted 4-t-butylcyclohexanone was studied, providing that the β-axial methyl and α-axial methyl groups hindered the axial and equatorial attacks respectively. The results obtained with fused-ring system ketones (four decalones) were explained by considering the similar stereochemical influence of 2-and 3-methylene substituents as corresponding methyl substituents. A rapid conformation equilibrium was also considered for cis-decalones. In addition, the axial attack, especially at a molar ratio of two or more, was found to be hindered by the α-equatorial methyl group. This hindrance was explained by assuming the half-chair form of the cyclohexanone ring in the transition state.
  • Mitsuru Furukawa, Motoo Goto, Seigoro Hayashi
    1974 Volume 47 Issue 8 Pages 1977-1980
    Published: 1974
    Released: March 27, 2006
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    The reactions of arylbiguanides with benzoyl and ethoxycarbonyl isothiocyanates gave 4(or 2)-arylguanidino-2(or 4)-phenyl-6-thioxo-1,6-dihydro-s-triazines and 4-arylguanidino-2-oxo-6-thioxo-1,4,5,6(or 1,2,3,6)-tetrahydro-s-triazines respectively, both of which were then converted into the corresponding oxo compounds, in which the thioxo group was converted into the oxo group, by oxidation with hydrogen peroxide. The condensation of 3-amidino-1-aryl-2-thioureas with aryl isothiocyanates afforded 1-aryl-2-arylimino-4-imino-6-thioxo-1,4,5,6-tetrahydro-s-triazines, which were also formed by the pyrolysis of 3-amidino-1-aryl-2-thioureas.
  • Renji Okazaki, Osamu Simamura
    1974 Volume 47 Issue 8 Pages 1981-1987
    Published: 1974
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    Thirteen acyl carbamoyl peroxides, a new class of peroxides, were prepared by addition of peroxy-acids to organic isocyanates and their properties were examined. The thermal decompositions, especially of benzoyl N-(p-nitrophenyl) carbamoyl peroxide and benzoyl N-benzoylcarbamoyl peroxide, were studied in crystalline state and in solution, and it was shown that they decompose via three different mechanisms, involving either an amino-radical, a nitrene or a protonated nitrene, depending on reaction conditions.
  • Ken-ichi Tomita, Keiko Urabe, Yang Bae Kim, Takaji Fujiwara
    1974 Volume 47 Issue 8 Pages 1988-1993
    Published: 1974
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    The crystal structure of DL-carnitine hydrochloride, C7H15NO3·HCl, was determined by the heavy atom method using X-ray diffraction data on a Weissenberg photograph, and refined by the least-squares method to an R-factor of 0.13 for 1969 independent reflections. The crystals are monoclinic space group P21c, Z=4, with a=6.77(1), b=11.41(2), c=15.10(3) Å and β=120.1(1)°. By protonation at carboxyl oxygen atom, carnitine molecule has the cationic form, N+(CH3)3CH2CH(OH)CH2COOH, with trans-zigzag skeletal configuration as similar as γ-amino-β-hydroxybutyric acid. The Cl ion mediates between adjacent carnitine cations by two O–H···Cl hydrogen bonds to form infinite chain elongated along the c-axis. The correlation between molecular structure and biological activity was also discussed.
  • Hajime Nagano, Yoshihiko Moriyama, Yoshiaki Tanahashi, Takeyoshi Takah ...
    1974 Volume 47 Issue 8 Pages 1994-1998
    Published: 1974
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    Two new benzofuranosesquiterpenes, farfugin A and farfugin B, have been isolated from Farfugium japonicum (L.) Kitamura, and their structures have been determined as 1 and 2, respectively.
  • Masahiro Tada, Yoshihiko Moriyama, Yoshiaki Tanahashi, Takeyoshi Takah ...
    1974 Volume 47 Issue 8 Pages 1999-2002
    Published: 1974
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    Three new furanosesquiterpenes have been isolated from Ligularia japonica LESS., and their structures including absolute configurations have been determined as furanoeremophilane-6β-diol (1), 10β-hydroxyfu-ranoeremophilan-6β-yl 2′ξ-methylbutanoate (2), and 10β-hydroxy-6β-methoxyfuranoeremophilane (3).
  • Noboru Kawata, Ken-ichi Maruya, Tsutomu Mizoroki, Atsumu Ozaki
    1974 Volume 47 Issue 8 Pages 2003-2006
    Published: 1974
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    The codimerization of butadiene with ethylene was studied with use of the catalyst system consisting of bis(triphenylphosphine)σ-arylnickel(II) halide and boron trifluoride etherate in methylene dichloride. The codimerization took place readily at 15 °C under 20 kg/cm2 to give trans- and cis-1,4-hexadiene and 3-methyl-1,4-pentadiene. A catalytic amount of water significantly enhanced the catalytic activity. The reaction path to form the codimers is discussed in terms of the variation in product distribution with time and the reaction kinetics.
  • Teruzo Asahara, Manabu Sen\={o}, Noritaka Ohtani
    1974 Volume 47 Issue 8 Pages 2007-2010
    Published: 1974
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    N-Chloroalkylamines initiate the telomerization of ethylene with chloroform to give α,α,α-trichloroalkanes CCl3(C2H4)nH(I), which are the same products as those obtained by peroxide-initiated reactions. The N-chloro-alkylamine–iron and N-chloroalkylamine–ferrous chloride systems also initiate the reaction of ethylene with chloroform to afford α,α,ω-trichloroalkanes CHCl2(C2H4)nCl (II) as the main product, and a small amount of I along with other teJomers. The rate of the reaction and the composition of the products vary widely with the kind of N-chloroalkylamine. The reaction mechanism was discussed, a “caged radical” mechanism being proposed for the N-chloroalkylamine-ferrous chloride system.
  • Mutsuo Kodama, Kyoko Namekawa, Takashi Horiuchi
    1974 Volume 47 Issue 8 Pages 2011-2016
    Published: 1974
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    The rates and the mechanisms of the dissociation reactions of aminopolycarboxylato zinc(II), lead(II), and cadmium(II) complexes were studied by analyzing their kinetic waves by conventional DC polarography. The dissociations of the zinc(II)–HIDA and–NTA complexes and the cadmium(II)– and lead(II)–HIDA complexes in an acetate buffer solution, and those of protonated lead(II)–EDTA and –EDTA–OH complexes were found to proceed through the following direct dissociation mechanisms:
    i) HIDA and NTA systems
    2&MX_2^2-2m\ ightleftharpoonsMX^2-m+X^m-& &in a rapid equil.
    &MX^2-m\ ightleftharpoonsM^2++X^m-& &r.d.s.
    \intertextii) EDTA and EDTA-OH systems
    &MHY^3-n\ ightleftharpoonsM^2++HY^1-n& &r.d.s.
    On the other hand, the dissociation of the zinc(II)-EDTA-OH and its protonated DTPA complexes gave this rate law: -d[MHiY2+im]/dt (i=0 or 1)=kdH·[H+]·[MHiY2+im]. From a comparison of the observed rate constants, the zinc(II)–HIDA and –NTA, lead(II)- and cadmium(II)–HIDA and protonated lead(II)–EDTA and –EDTA–OH complexes are concluded to dissociate through a simple glycinate reaction intermediate, and the zinc(II)–EDTA–OH and its protonated DTPA complexes, through a glycinate reaction intermediate which includes polyfurcated hydrogen bonds.
  • Yoshio Narusawa, Masao Kimura, Kunio Nakano
    1974 Volume 47 Issue 8 Pages 2017-2025
    Published: 1974
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    Kinetic studies have been carried out on the oxidation of [Cr(bipy)3]2+ and [Cr(phen)3]2+ with [Co(NH3)6]3+(bipy and phen denote 2,2′-bipyridine and 1,10-phenanthroline, respectively). The rate law is found to be −d[Cr(II)]/dt=k1[Co(III)][Cr(II)]+k2[Cr(II)]. Simulation procedures with an analogue computer were applied for the analysis of these reactions. The rate constant k1 (direct oxidation) and k2 (dissociation) for [Cr(bipy)3]2+ were 180 M−1 s−1 and 0.120 s−1 (μ=0.11 with NaCl, at 25 °C) and those for [Cr(phen)3]2+ were 310 M−1 s−1 and 0.630 s−1 (μ=0.20 with NaCl, at 25 °C), respectively. The larger value of k1 for [Cr(phen)3]2+ as compared with that of k1 for [Cr(bipy)3]2+ was interpreted as being due to the good electron conductivity of the phenanthroline as a ligand in the activated state. The activation parameters were obtained as follows: in the case of [Cr(bipy)3]2+, ΔH\ eweq=7.5 kcal/mol and ΔS\ eweq=−23 e.u. for the k1 path, and ΔH\ eweq=17.2 kcal/mol and ΔS\ eweq=−5 e.u. for the k2, path; and in the case of [Cr(phen)3]2+, ΔH\ eweq=8.2 kcal/mol and ΔS\ eweq=−20 e.u. for the k1 path, and ΔH\ eweq=21.2 kcal/mol and ΔS\ eweq=+12 e.u. for the k2 path.
  • Shiro Shimada, Ryusaburo Furuichi, Tadao Ishii
    1974 Volume 47 Issue 8 Pages 2026-2030
    Published: 1974
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    The mechanism for the promoting effects of additives on the formation of MgAl2O4 has been systematically discussed from the results of kinetic measurements. A mixture of MgO and α-Al2O3 powder containing 10 mol% additives (LiF, NaF, MgF2, GaF2, BaF2, NaCl or CaCl2) and that without additives were isothermally heated in N2 atmosphere in the temperature ranges 670–1142°C and 1190–1360 °C. The diffusion-controlled Jander’s equation was applied to all kinetic data obtained. In the case of fluoride additives, it has been found that the promoting actions are in the order LiF≥NaF>BaF2>MgF2>CaF2 and that the cations of fluorides play an important role in accelerating diffusion. The same promoting mechanism seems to be applicable in the case of chloride additives.
  • Shiro Shimada, Ryusaburo Furuichi, Tadao Ishii
    1974 Volume 47 Issue 8 Pages 2031-2035
    Published: 1974
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    The promoting actions of fluoride on the formation of MgAl2O4 in the initial stage have been studied by means of DTA and high-temperature X-ray diffraction techniques. LiF, NaF, MgF2, GaF2 and BaF2 were used as additives. The three MgO–Al2O3–fluoride (LiF, NaF or BaF2) systems showed similar DTA curves; an endothermic peak (peak-1) in the temperature range 660–800 °C, followed by an exothermic peak (peak-2) at 700–900 °C. The DTA curves for MgO–Al2O3–fluoride (MgF2 or CaF2) systems showed no thermal change. It was found that peak 1 corresponds to Reaction (2), 3MF+2Al2O3=3MAlO2+AlF3, and peak 2 to Reaction (1), 3MgO+2AlF3=3MgF2+Al2O3, and the formation of MgAl2O4. It was concluded that Reaction (2) takes place before the formation of MgAl2O4 and that AlF3 resulting from Reaction (2) initiates the formation of MgAl2O4.
  • Kenzo Nagase, Hiroko Yokobayashi
    1974 Volume 47 Issue 8 Pages 2036-2039
    Published: 1974
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    The thermal deaquation-anation reactions of aquopentamminechromium(III) nitrate, chloride, bromide, and iodide in the solid state were investigated by the techniques of TG, DSC, X-ray powder diffraction analysis, and manometry. The first-order rate constants were obtained by isothermal kinetics. The activation enthalpies calculated from the first-order rate constants increased in the order: the nitrate(24.3)<the chloride(26.4)<the bromide (29.7)<the iodide(30.7 kcal/mol). The enthalpy changes by DSC were 12.3, 6.5, 6.3, and 7.0 kcal/mol for the nitrate, chloride, bromide, and iodide respectively. The slight deviation from the first-order kinetics was observed in cases of the nitrate and the chloride.
  • Yoshinori Kidani, Kazuo Ohira, Hisashi Koike
    1974 Volume 47 Issue 8 Pages 2040-2044
    Published: 1974
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    Spectrophotometric measurements were carried out for the stability constants of the divalent metal chelates of 2-quinoxalinecarboxylic acid and copper, nickel, cobalt and zinc in a 5% aqueous ethanol solution. Successive stability constants, logK1, of the copper, nickel, cobalt and zinc chelates were 3.30, 2.87, 2.83 and 2.80, respectively. The metal complexes were difficult to dissolve in water. Copper and cadmium afforded both 1 : 1 and 2 : 1 complexes, while other divalent metals such as nickel, cobalt, manganese, zinc and lead resulted in the 2 : 1 complex formation. From the results of IR and Far-IR spectral analyses it was found that the carboxyl group and the ring nitrogen group appear simultaneously in the chelate formation. Copper complexes of 2-quinoxa-linecarboxylic acid 1- and 4-oxides, as well as its 1,4-dioxide were also studied.
  • Masayasu Kurahashi
    1974 Volume 47 Issue 8 Pages 2045-2047
    Published: 1974
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    The crystals of chloro-1-(2-thiazolylazo)-2-naphtholatopalladium(II) dioxane solvate, [PdCl(TAN)]·C4H8O2, are orthorhombic and of space group Pbcm, with unit cell dimensions: a=8.44(2), b=30.97(4) and c=6.82(2) Å and Z=4. The structure was determined by the heavy-atom method and refined by the least-squares procedure to give an R value of 0.097 for 1392 observed reflections. The crystallographic mirror plane normal to the c-axis coincides with the molecular plane of [PdCl(TAN)]. The 1-(2-thiazolylazo)-2-naphtholato group, i.e., TAN, is a terdentate ligand; the phenolic oxygen atom, azo nitrogen atom and thiazole nitrogen atom are coordinated to the palladium atom to form two five-membered chelate rinsgs. The fourth coordination position is occupied by a chlorine atom.
  • Makoto Watanabe
    1974 Volume 47 Issue 8 Pages 2048-2050
    Published: 1974
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    The hydrolysis of pyro- and tripolyphosphates was run in formic acid–water, acetic acid–water, dioxane–water, and water solvents with an initial concentration of 0.025 mol/l. The hydrolysis of both the phosphates followed first-order kinetics with respect to the concentration of the phosphate under all the conditions studied. The rate of the hydrolysis of both the phosphates in the formic acid–water and acetic acid–water solvents is slower, and that in dioxane–water solvent is faster, than in water. From the results, it has been concluded that, in the formic acid–water and acetic acid–water solvents, the nucleophilicity of the water molecule may decrease on account of the hydrogen bond of the water molecule with these acids, while, in the dioxane–water solvent, since the scission of the hydrogen bond between water molecules may occur by the interaction of the dioxane and the water molecules, the nucleophilicity of the water molecule may increase. The activation energy of the hydrolysis of the phosphates was 19–28 kcal/mol and increased with an increase in the pH value of a solution. The hydrolysis of pyro- and tripolyphosphates has been concluded to be a SN2 reaction; the rate-determining step may be the nucleophilic attack of a water molecule on the phosphorus atom of the phosphates.
  • Shingo Miyajima, Takashi Inukai, Hiroshi Harada, Ryo Yoshizawa, Tadahi ...
    1974 Volume 47 Issue 8 Pages 2051-2055
    Published: 1974
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    The liquid phase autoxidation of isobutyraldehyde to peroxyisobutyric acid was investigated with ozone as an initiator. The selectivity of the peroxyacid increases with decrease in the amount of aldehyde converted per unit volume of reacting fluid, increase in the ozone feed rate, and decrease in temperature. A few percent of water in solvents increases the selectivity, although too much water brings about a reverse effect. Isopropyl alcohol, acetone, isopropyl formate, propane, propylene, carbon dioxide, and carbon monoxide are observed as by-products besides isobutyric acid. Purified peroxyisobutyric acid (97.2 wt%) was obtained by fractionally distilling the autoxidation product and some of its physical properties were determined. The utility of the peroxyacid as an epoxidizing agent is described.
  • A. M. Osman, M. El-Garby Younes, F. M. Ata
    1974 Volume 47 Issue 8 Pages 2056-2058
    Published: 1974
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    Some specific reactions of triterpenoids had been performed on thin-layer chromatoplates. The reactions conducted were: oxidation with oxygen in K-t-butoxide, benzilic acid rearrangement, decarboxylation with lead tetraacetate, Wolff-Kischner reduction, reduction with sodium borohydride, reduction with lithium aluminium hydride, oxidation with chromium trioxide in pyridine and in acetic acid, oxidation with manganese dioxide in chloroform, methylene chloride and isopropyl alcohol, insertion of an oxygen atom in ring A of triterpenoids by the formation of acid anhydride and reduction by a modified Clemmensen method.
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