Bulletin of the Chemical Society of Japan
Online ISSN : 1348-0634
Print ISSN : 0009-2673
ISSN-L : 0009-2673
Volume 42 , Issue 7
Showing 1-50 articles out of 75 articles from the selected issue
  • Masaru Nishikawa, Kazufumi Kuroda, Niro Matsuura
    1969 Volume 42 Issue 7 Pages 1783-1786
    Published: 1969
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    γ-Radiolysis of NH3+C3H8 mixtures was investigated at 22±1°C and total pressure ∼50cmHg. From the observed yield of hydrogen, H atom yield of ammonia radiolysis of GH=5.1–5.8 was obtained after subtraction of contribution from the propane fraction. The value is significantly lower than that determined from the study of NH3+D2 and NH3+N2H4 systems, and also that from the study of NH3+C3H8 system reported previously. A variety of possibilities is discussed with respect to the cause of the disagreement. The effect of addition of N2O or SF6, which acts as an electron scavenger, was also studied. The yield of hydrogen from NH3+C3H8 mixtures decreased appreciably, and ΔG(H2) in the absence and presence of electron scavengers was related to the change in the neutralization process.
  • Chandra Prakash, S. N. Srivastava
    1969 Volume 42 Issue 7 Pages 1787-1795
    Published: 1969
    Released: March 27, 2006
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    The effect of some cationic detergents viz. cetyl pyridinium bromide, lauryl pyridinium chloride and phenyl trimethyl ammonium chloride has been studied on stabilised by sodium alginate and gum arabic emulsions. Zeta potentials were measured at different concentrations of cationic detergents microelectrophoretically. The particle size was determined microphotographically. With the help of zeta potential and particle size the interaction energies were calculated by summing up attraction and repulsion energies in the light of D.V.O. theory. For attraction energy the van der Waals constant was computed theoretically from the optical data and was obtained to be 6.7×10−14 erg. The interaction energies thus obtained gave very high energy barriers which completely obviated the occurrence of flocculation in primary minima, causing flocculation to occur in secondary minima. The theoretical degrees of aggregation were calculated and plotted at different values of A. The flocculation occurring in the system was observed haemocytometrically by counting the number of singlets and doublets and the degrees of aggregation were calculated. With the help of observed degrees of aggregation the operating value of van der Waals constant has been estimated by interpolating them into the theoretical curves, which is an indirect approach to ascertain the value of van der Waals constant. The values of A obtained are 3.0×10−13 and 2.6×10−13 erg for sodium alginate and gum arabic systems respectively. The binding parameters, number of binding sites available and free energy of adsorption have also been calculated.
  • Hiroshi Yoneyama, Hideo Tamura
    1969 Volume 42 Issue 7 Pages 1795-1799
    Published: 1969
    Released: March 27, 2006
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    The anodic oxidation and cathodic reduction behavior of a sintered body of lithiated nickel oxide were studied. The electrode with the higher Li content was more active than that with the lower Li content with regard to the electrochemical oxidation and reduction in the potential range between oxygen and hydrogen evolution. The quantity of the higher-valency nickel oxide having an apparent valence state of nickel ions from +8/3 to +4 formed by the anodic oxidation was estimated by measuring the quantity of electricity required for reducing it to −0.14V vs. SCE. This quantity is proportional to the Li content for electrodes containing more than 0.04 atom% of Li.
  • Katsutoshi Ohkubo, Tokio Yamabe, Kenichi Fukui
    1969 Volume 42 Issue 7 Pages 1800-1806
    Published: 1969
    Released: March 27, 2006
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    A kinetic study of the homogeneous liquid-phase oxidation of cumene was carried out in order to clarify the characteristic behavior of triphenylsulfonium chloride as an autoxidation catalyst. The reaction proceeded with no incubation period. The experimental dependence of the rate upon catalyst and hydrocarbon concentrations and also upon the oxygen pressure was reproduced with a good analytic fit by the following equation:
    r=k′(RH)1.27(O2)0.68(Cat.)0 (eatebt) (a, b, and k′ are constants).
    A reaction mechanism was proposed to derive the rate equation. It seems likely from this scheme that sulfonium chloride activates molecular oxygen by means of a reversible molecular association with it.
  • Yuhei Uzu, Isamu Sano
    1969 Volume 42 Issue 7 Pages 1807-1812
    Published: 1969
    Released: March 27, 2006
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    By atomizing aqueous solutions both of electrolytes and non-electrolytes, fog droplets of 8μ in diameter were prepared, and their freezing temperatures were measured in a thermostat-like cold chamber fitted with an electrically heated platinum wire. The results were compared with that obtained with fog droplets of pure water of the same size. It was found that non-electrolytes hardly influence the freezing, whereas electrolytes do a great deal. The freezing temperature rises in the presence of an electrolyte and varies with its concentration, the highest temperatures being observed at the concentrations around 1×10−4M for 1-1 type electrolytes and at lower concentrations for 1-2 and 1-3 type electrolytes. K+ is the most effective of the alkali metal cations having the same species of anion in common, and I of the halide anions having the same species of cation in common. Applying the theory of nucleation, the sizes of the hydrated K+ and the critical nucleus developed from it for ice-nucleation were estimated to be about 6 and 21 Å in radius, respectively.
  • Tsutomu Kagiya, Y\={u}z\={o} Sumida, Tokuji Inoue, Fridrich S. Dyachko ...
    1969 Volume 42 Issue 7 Pages 1812-1819
    Published: 1969
    Released: March 27, 2006
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    An empirical evaluation of the activation energy has been carried out for the radical substitution reaction involving polyatomic molecules. The potential energy along the reaction path is assumed to be expressed for the initial and the final systems by the two Morse functions with the coefficient “a′,” which is different from the “a” in the usual Morse function of the bond. The difference between the aΔr* values in the Morse functions of the initial and the final systems in the transition state is empirically determined as a function, afΔrf*aiΔri*Q, of the reaction heat, Q. From the Morse function with “a′” and the above relation, the activation energy is calculated by using the bond dissociation energies of the initial and the final molecules. The treatment proposed is useful for the evaluation of the activation energies of many types of radical substitution reactions.
  • Wataru Murayama, Masatsune Kainosho
    1969 Volume 42 Issue 7 Pages 1819-1824
    Published: 1969
    Released: March 27, 2006
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    The crystal structure of 5,5-dimethyl-2-oxo-2-hydroxy-l,3,2-dioxaphosphorinane monohydrate (I) has been determined by the three dimensional X-ray diffraction method. The crystals belong to monoclinic system, with space group P21. The unit cell dimensions are; a=9.50, b=5.86, c=8.31 Å, β=106°8′, and two molecules per unit cell. The six-membered dioxaphosphorinane ring has a chair conformation, with P=O bond in equatorial position. The bond angles and distances of the phosphate group are similar to those found in the corresponding acyclic phosphates.
  • Jun-ichi Aihara, Motoyuki Tsuda, Hiroo Inokuchi
    1969 Volume 42 Issue 7 Pages 1824-1830
    Published: 1969
    Released: March 27, 2006
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    The solvent effects of charge-transfer complexes were examined in various solvents. During the course of investigations pertaining to aromatic-TCNE complexes, Brownstein’s and McRae’s formulae were found to be valid. The gas-phase spectra of these charge-transfer complexes may be regarded as the origin of the solvent effects. The anomalous behaviour of carbonyl solvent molecules was also discussed.
  • Haruo Shizuka, Toshifumi Morita, Yuji Mori, Ikuzo Tanaka
    1969 Volume 42 Issue 7 Pages 1831-1836
    Published: 1969
    Released: March 27, 2006
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    The photochemical rearrangements of phenyl acetate and p-substituted phenyl acetates have been studied. The quantum yields of the rearrangements of phenyl acetate in cyclohexane were independent of the irradiation time, the concentration of phenyl acetate (<2×10−2 mol/l), the temperature (20–70°C), and the presence of piperylene (a triplet quencher) or oxygen. The quantum yields for the formations of o- and p-hydroxyl acetophenones and of phenol were 0.17, 0.15, and 0.06 respectively in cyclohexane. Comparing the quantum yields for phenyl acetate rearrangements with those for p-methylphenyl acetate, the quantum yields for the predissociation of the O–CO bond and the back reaction, and the recombination ratio were estimated to be 0.61, 0.23, and 0.9 respectively in cyclohexane. The relative rate constants of the back reaction and the o- and p-rearrangements were parallel to the odd π electron densities of the phenoxy radical. These results have shown that the reaction scheme of phenyl acetate in the liquid phase at 2537 Å is similar to that of acetanilide.
  • Yoshio Yamada, Akinori Hasegawa, Masaji Miura
    1969 Volume 42 Issue 7 Pages 1836-1840
    Published: 1969
    Released: March 27, 2006
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    The ESR spectra assigned to the anion radicals of SO2, (TCNE) (tetracyanoethylene), and O2 were obtained for, respectively, sulfur dioxide, TCNE, and oxygen when these gases were adsorbed on γ-irradiated silica gel. As regards sulfur dioxide, a characteristic change in the concentration of the SO2 radical was observed during the post-irradiation with high-energy UV light. In the case of carbon dioxide, the CO2 radical was produced only when UV post-irradiation was added to γ-irradiation. The assignments were principally made in comparison with the reported g-values. Especially, the identification of the CO2 radical was ascertained by using 13C. The analyses of the g-factor for the O2 radical and of 13C hyperfine constants for the CO2 radical gave information on the interaction of the radicals on a solid surface with the cations in the adsorption center. In view of the fact that each of these molecules possesses a different degree of electron affinity, the results described above indicate that the electrons trapped in the defects of the silica gel surface transfer to the adsorbed molecules and that UV light promotes the electron transfer.
  • Jiro Tanaka, Masagi Mizuno
    1969 Volume 42 Issue 7 Pages 1841-1852
    Published: 1969
    Released: March 27, 2006
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    The electronic spectra and the intermolecular interaction of Würster’s radical have been studied for the dimer state and for the crystalline states. The polarization properties of the excited states have been investigated in detail, and the longest wavelength absorption band of the dimer has been established as having a charge-transfer character. The strength of the charge-transfer band and the shift of the monomer band in the dimer or in the crystalline states are shown to be intimately correlated with the strength of the intermolecular interactions between the stacked radicals. A theoretical analysis of the excited state of the dimer and the crystals is presented; the results are in good agreement with the experimental findings.
  • Akira Suzuki, Ritushi Tukuda
    1969 Volume 42 Issue 7 Pages 1853-1857
    Published: 1969
    Released: March 27, 2006
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    The kinetics of the phase transformation of anatase to rutile was studied by means of X-ray diffraction. Samples of anatase were prepared by sulfate and chloride processes. The kinetic data could well be expressed by the equation
    α=1−ebtn,
    where α is the fraction of anatase transformed in time t, and b and n constants. The activation energy of the phase transformation is 105 kcal/mol for the sample prepared by the sulfate process, and 107 kcal/mol for the sample prepared by the chloride process. These values of activation energy are compared with those previously obtained.
  • Satoshi Arimitsu, Katsumi Kimura, Hiroshi Tsubomura
    1969 Volume 42 Issue 7 Pages 1858-1861
    Published: 1969
    Released: March 27, 2006
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    Electronic absorption spectra of unstable species formed by the ultraviolet irradiation of N,N-dimethylaniline (DMA) were studied in various rigid matrices at 77°K. It was concluded that there are two unstable species which exhibit similar absorption spectra in the visible and the near ultraviolet regions. These species were identified with the cation radical ([(Remark: Graphics omitted.)])+ and the neutral radical ((Remark: Graphics omitted.)), based on various experimental results concerning solvent effect, electron attachment, stimulated emission by the infrared light, etc. The molar extinction coefficient of the cation at 470 mμ was found to be about 1200 (l/cm·mol).
  • Kenichi Fukui, Tokio Yamabe
    1969 Volume 42 Issue 7 Pages 1862-1870
    Published: 1969
    Released: March 27, 2006
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    A theory of the molecular-size distribution of the cross-linked polymers to be formed from a mixture of vinyl monomers with a distribution of functionalities by radical polymerization is presented. It is assumed that all the unconverted vinyl groups are equireactive to the propagation, which proceeds without cyclization. The distribution is obtained by applying the statistical theory of gel formation with multifunctional interunit junctions, which are, in this case, equivalent to cross-linking chains. The general theory is applied to three practical cases; the curing reaction of unsaturated polyesters, the polymerization of polyvinyl compounds, and the copolymerization of vinyl and divinyl compounds.
  • Masamichi Tsuboi, Minoru Terada, Teruo Kajiura
    1969 Volume 42 Issue 7 Pages 1871-1874
    Published: 1969
    Released: March 27, 2006
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    The Raman spectra corresponding to the (bc) component (B2 type vibrations) of the polarizability tensor in the ferroelectric sodium nitrite crystal (C2v20) have been observed with various directions of the phonon propagation. It has been found that one of the B2 Raman lines at 160 cm−1 splits into two components when the phonon propagates in a direction 45° from the c axis in the ac plane. This splitting has been ascribed to an interaction of a B2 and B1 type lattice-vibrations whose frequencies are accidentally equal to each other in the phonon propagation direction now in question.
  • Kimiyoshi Matsumura
    1969 Volume 42 Issue 7 Pages 1874-1878
    Published: 1969
    Released: March 27, 2006
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    The solution properties of poly-m-chlorostyrene in toluene and butanone were measured by the light-scattering and viscosity methods. The dependencies of the second virial coefficients, the end-to-end distances, and the intrinsic viscosities on the molecular weights were not very different from those of the other polystyrene derivatives. It was made clear that the unperturbed dimension of poly-m-chlorostyrene was larger than that of poly-p-chlorostyrene, and similar to that of poly-o-chlorostyrene. The relationships between poly-m-chlorostyrene and solvents (toluene and butanone) were similar to those between polystyrene and poly-o-chlorostyrene and the solvents, but the reverse of that between poly-p-chlorostyrene and the latter; that is, compared with butanone, toluene was a “good” solvent for poly-m-chlorostyrene.
  • Yoshio Toshiyasu, Yoshio Taniguchi, Ko Kimura, Ryoichi Fujishiro, Masa ...
    1969 Volume 42 Issue 7 Pages 1878-1881
    Published: 1969
    Released: March 27, 2006
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    The electric dipole moments of diphenyl sulfide, sulfoxide, and sulfone and their derivatives were determined in benzene solutions at 25°C. The observed moments are used to estimate the mesomeric moments on the assumption of the vector addition of group moments. The mesomeric moments of the phenylmercapto, phenylsulfinyl, and phenylsulfonyl groups are estimated to be −0.12, 0.10, and 0.44 D, respectively. The steric effect of ortho-substituents is also discussed on the basis of the dipole moment data.
  • Ryokichi Tsuchiya, Yoriko Kaji, Akira Uehara, Eishin Kyuno
    1969 Volume 42 Issue 7 Pages 1881-1885
    Published: 1969
    Released: March 27, 2006
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    By using a Derivatograph, the simultaneous analyses in TGA, DTA and DTG on the several aquopentaamminechromium(III) complexes were attempted. The enthalpy changes, ΔH, in the deaquation-anation processes of aquopentaamminechromium(III) nitrate, chloride, bromide, iodide, sulfate and sulfite were calculated as 11.9, 6.1, 9.0, 10.8, 13.8 and 12.8 kcal/mol, respectively, the activation energies, E\ eweq, in the corresponding processes of the nitrate, chloride, bromide, sulfate and sulfite were obtained by the DTG curve analysis as 18, 28, 38, 36 and 33 kcal/mol, and those in the nitrate, chloride, bromide, iodide, sulfate and sulfite were obtained by the DTA curve analysis as 14, 25, 36, 19, 39 and 32 kcal/mol, respectively.
  • Ryokichi Tsuchiya, Akira Uehara, Eishin Kyuno
    1969 Volume 42 Issue 7 Pages 1886-1891
    Published: 1969
    Released: March 27, 2006
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    The thermal reaction processes in the solid state of the following chromium(III) and cobalt(III) aquo complexes with EDTA or the related aminopolycarboxylic acids were investigated by means of derivatography: [CrHedta(H2O)] (I), [CrHpdta(H2O)]·H2O (II), [CrHtmta(H2O)]·H2O (III), [Cr(OH)Hapda(H2O)2] (IV) and [Co(OH)Hapda(H2O)2] (V) (edta, pdta, tmta and apda are the abbreviated forms of ethylenediaminetetraacetate, propylenediaminetetraacetate, trimethylenediaminetetraacetate and ammoniapropionicdiacetate anions, respectively.). With complex I, the carboxylate anion free from coordination to metal coordinated when the dehydration took place at ca. 280°C. It resulted in the change of the coordination number of EDTA from quinquedentate to sexadentate. In the case of complexes II and III, the transition appeared below ca. 100°C where the coordinated water molecule in the coordination sphere is thermally expelled to the outer sphere as the protonated form due to the coordination of a carboxylate anion. PDTA and TMTA (conjugated acids of pdta and tmta respectively) also changed from quinquedentate to sexadentate ligands in this step. Of complexes IV and V, the coordinated hydroxo group was excluded as a water molecule together with the hydrogen in a free carboxylate anion at ca. 140°C to make the coordination number of APDA(conjugated acid of apda) change from terdentate to quadridentate. The activation energies and the enthalpy changes in each thermal reaction process were determined by the analysis of their derivatograms.
  • Kazushi Hirota
    1969 Volume 42 Issue 7 Pages 1892-1897
    Published: 1969
    Released: March 27, 2006
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    The electromotive force of the oxygen concentration cell, O2 gas/stabilized zirconia/Fe(+C)-melt+COgas, was measured at 1900°K as a function of the carbon concentration in iron melt, and the transference number of the stabilized zirconia was calculated. The transference number of the ions in the stabilized zirconia partition is less than unity over the whole range of carbon concentration. When the results are compared with the equations derived from plausible models, a reasonable coincidence is obtained.
  • Yasushi Kubo, Goro Yamaguchi
    1969 Volume 42 Issue 7 Pages 1897-1900
    Published: 1969
    Released: March 27, 2006
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    Hydrogen was analyzed on synthetic sulfur-containing sodalite-type sodium aluminosilicates. Specimens synthesized from the NaAlSiO4-Na2S system in a H2 or N2 atomsphere or in a N2-S2 atmosphere contained hydrogens which were introduced by ion-exchange during water-washing. Specimens synthesized from the same system in H2S-containing atmospheres also contained hydrogens introduced from the synthetic atmosphere. The latter specimens had the formula: Na8Al6-Si6O24xH2yS, which was characterized by a constant number of sodium ions (eight per unit cell), whereas the former contained variable numbers of sodium ions according to the duration of water-washing. A difference in correlation between the sulfur content and the lattice constant was observed between these two series of specimens, indicating different manners of existence of the hydrogen.
  • Eiki Itabashi, Shigero Ikeda
    1969 Volume 42 Issue 7 Pages 1901-1908
    Published: 1969
    Released: March 27, 2006
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    The effect of the nature and the concentration of the supporting electrolyte on the polarographic reduction of cobalt(II) acetate in acetonitrile has been investigated. An acetonitrile solution of cobalt(II) acetate yields a two-step and a three-step reduction wave in 0.05M LiClO4 and in 0.05M NaClO4 solution, respectively. The same solution gives ill-defined reduction waves in the presence of quaternary ammonium perchlorates, such as (CH3)4NClO4, (C2H5)4NClO4, or (n-C4H9)4NClO4. The Co(CH3CN)n2+, Co(OAc)+, and Co(OAc)3species are present in a solution containing alkali metal perchlorate electrolyte. Co(OAc)+ and Co(OAc)3 are the predominant species in a quaternary ammonium perchlorate solution. The reduction potential becomes more negative with increase in the number of acetate ions coordinated to cobalt(II). The reduction potential of cobalt(II) acetate becomes less negative upon the addition of alkali metal perchlorate to the quaternary ammonium perchlorate supporting electrolyte. This effect is caused by the dissociation reaction of cobalt(II) acetate, in which an acetate ligand is transferred to the alkali metal ion.
  • Nobufumi Maki, Shukichi Sakuraba
    1969 Volume 42 Issue 7 Pages 1908-1915
    Published: 1969
    Released: March 27, 2006
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    The following new cyano cobalt(III) complexes have been prepared by treating the corresponding chloro complexes with silver cyanide: cis-[Co(CN)2dip2]NO3·7H2O, cis-[Co(CN)2dip2]2-SO4·12H2O, cis-[Co(CN)2en(NH3)2]NO3, [Co(CN)3en(NH3)]·H2O, and trans-[Co(CN)dg2(NH3)]·1/2H2O. This method has also been used in the preparation of the following compounds: cis-[Co(CN)(NO2)en2]NO3·H2O, cis-[Co(CN)(SO3)en2], trans-[Co(CN)(SO3)en2], cis-[Co(CN)-(OH2)en2]SO4·2H2O, cis-[Co(CN)2en2]NO3, cis-[Co(CN)2pn2]NO3, cis-[Co(CN)2phen2]NO3· 6H2O, and cis-[Co(CN)2phen2]Cl·4H2O. Another new method has been attempted in dimethyl sulfoxide or an acetonitrile-water solution by the step-by-step substitution of a chloro ligand with a CN ion via the monocyanomonochloro complex of the [Co(CN)Cl N4]-type; we thus succeeded in obtaining these dicyano-ammine complexes, trans-[Co(CN)2(NH3)4]NO3·H2O, trans-[Co(CN)2-en(NH3)2]Cl·H2O, and cis-[Co(CN)2(NH3)4]NO3·H2O. The methods of preparing the following new complexes are also described: trans-Na[Co(CN)2dg2]·2H2O, trans-K[Co(CN)2dg2]·3/2H2O, trans-(NH4)2[Co(CN)dg2(SO3)]·4H2O, and trans-H[Co(CN)dg2Cl]·4H2O. The absorption spectra in the visible, ultraviolet, and infrared regions have been measured.
  • Shin Suzuki, Yasushi Inoue
    1969 Volume 42 Issue 7 Pages 1916-1921
    Published: 1969
    Released: March 27, 2006
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    With a view to understand the reasons for the confusion in published works as to the chemical behavior of protactinium (V) in a perchloric acid solution, the effect of the contact time and the stability of the perchloric acid solution of the pentavalent protactinium in the TTA-benzene extraction have been investigated in relation to the methods of preparing the solution. Four sample solutions, prepared by various methods, were used, and definite differences among them were observed. Two of them have been confirmed to be very stable and not to suffer a change in their distribution ratios with the time of standing, while the others are unstable-that is, their distribution ratios decrease with standing, thereby reaching a constant value which agrees with that of the former two. However, the value consistent with that obtained from backward extraction is not this constant value but the value obtained from fresh solutions of the latter type. Protactinium species in the TTA-benzene solution are also not stable, and their distribution ratios increase with standing. This increase in the distribution ratio is mainly due to the formation of unstrippable species. The mechanism of this irreversible change is assumed, from the indirect evidence of extraction experiments and absorption spectroscopy, to be the irreversible dehydration of Pa(OH)2T3·HT to form PaOT3·HT in the organic phase. These unfavorable features of the extraction equilibrium should be taken into account in interpreting the results obtained by TTA extraction experiments.
  • Yoshiaki Furuya, Iwao Urasaki, Kazuo Itoho, Akiyoshi Takashima
    1969 Volume 42 Issue 7 Pages 1922-1926
    Published: 1969
    Released: March 27, 2006
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    The rates of the acid-catalyzed reversible etherification of the allelotrope of p-nitrosophenol and p-benzoquinoneoxime with ethanol in dioxane-forming p-nitrosophenetole have been measured by ultraviolet spectrophotometry. The rate of the forward reaction was expressed as the sum of the second- and the third-orders over a fairly large concentration region of the allelotrope and of ethanol. The plots of the logarithm of the apparent forward second-order rate constant against −log(CBH+CB) gave a straight line with a slope of −0.95. A probable mechanism involving the rate-determining formation of a σ-complex by the nucleophilic attack of the hydroxyl O-atom of ethanol on the α-carbon of the hydroxyl group of protonated p-nitrosophenol, and also the rate-determining deprotonation from the oxime group of the σ-complex by the allelotrope of p-nitrosophenol, was postulated.
  • Jun Niwa
    1969 Volume 42 Issue 7 Pages 1926-1934
    Published: 1969
    Released: March 27, 2006
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    The spectral analyses of 23 meta- and para-substituted formanilides in dimethyl sulfoxide have proved that they exist in an equilibrium of cis- and trans-forms of restricted rotational isomers in the solvent. The chemical shifts of the protons on the formanilides are strongly dependent on the polar nature of the substituent. In the cis-form, the chemical shifts of both the imino and the formyl protons correlate with the Hammett σ0. In the tarns-form, a plot of the chemical shifts of the formyl protons against the σ0-constants reveals a good correlation in the case of meta-derivatives, but serious deivations for the para-substituents, both for the electron-releasing conjugative substituents and for the electron-withdrawing conjugative substituents. The deviations for both types of substituents are in the direction to be anticipated for any important extra conjugative interaction between the para-substituent and the side-chain. The Yukawa-Tsuno equation is precisely applicable to these shifts when we assume that this system has the same γ-value for both types of substituents; the relation is expressed as:
    Δδ=−12.0(σ0+1.12Δ\barσR)+0.5.
    where Δ\barσR+−σ0 for the electron-releasing conjugative substituents and where Δ\barσR+−σ0 for the electron-withdrawing conjugative substituents (r=0.993, s=0.8). From the solvent effect on the substituents, such as NH2, OH, and COOH, their σ0-values in dimethyl sulfoxide are proposed. It is also deduced that this solvent effect affects principally the part of the inductive contribution in the overall substituent effect.
  • Hisashi Okawa, Tamotsu Yoshino
    1969 Volume 42 Issue 7 Pages 1934-1937
    Published: 1969
    Released: March 27, 2006
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    2,7-Dimethyl-4,5-bis(salicylideneaminomethyl)acridone, which may form a quadridentate metal complex involving a ten-membered chelate ring, was synthesized by a sequence of steps and characterized. A monomeric cobalt(II) complex of the ligand was isolated and examined.
  • Tadao Hayakawa, Yoshiyuki Kondo, Hiroyuki Yamamoto
    1969 Volume 42 Issue 7 Pages 1937-1941
    Published: 1969
    Released: March 27, 2006
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    The conformations of poly-Nω,ω′-dicarbobenzyloxy-L-arginine, poly-Nω-carbobenzyloxy-L-arginine, and poly-L-arginine hydrobromide were studied by means of their infrared spectra (IR), X-ray photographs, optical rotatory dispersions (ORD), and circular dichroisms (CD). The presence of the α-helical conformation in poly-Nω,ω′-dicarbobenzyloxy-L-arginine and poly-Nω-carbobenzyloxy-L-arginine was confirmed by X-ray photographs and by their IR spectra. The ORD and the CD curves of these polymers were found to be characteristic of the α-helical conformation. It was also found that these polypeptides have a random coil conformation in trifluoroacetic acid. In the (2-chloroethanol : trifluoroacetic acid) solvent system, the typical helix-coil transition of poly-Nω-carbobenzyloxy-L-arginine was observed at 20–30% trifluoroacetic acid. The ORD and the CD curves of poly-L-arginine showed that the polymer took a random coil structure in the pH range from 2.7 to 11.0. However, when the pH is increased from 11.0 to 11.5, the spectra gradually change into the α-helix structure. Moreover, the polypeptide predominantly took the α-helix structure at pH 12.5. From the ORD and CD data, the polypeptide can be considered to have a right-handed α-helix conformation.
  • Keisuke Murayama, Takao Yoshioka
    1969 Volume 42 Issue 7 Pages 1942-1947
    Published: 1969
    Released: March 27, 2006
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    The reaction of the extremely stable free radical, 2,2,6,6-tetramethyl-4-oxopiperidine-1-oxyl (I), was carried out with benzenethiols (IV). The formation of diphenyl disulfides (VI), benzenesulfinic acids (VII), and 1-(p-substituted benzenesulfinyl)-2,2,6,6-tetramethyl-4-oxopiperidines (X) from the above reaction shows that the radical (I) can act as a hydrogen-abstracting agent, an oxidizing agent, and a radical scavenger. Possible mechanisms for the coupling reaction of the radical (I) with the S-radicals (V) to give the sulfinamides (X) were discussed. A substituent effect was observed in the formation of the disulfides (VI). The N-oxyl radical (I) and another stable free radical, such as 2,6-di-t-butyl-4-methylphenoxyl radical (XXV), were shown to react with the S-radical (XVII) derived from thiamine (XIV) to give new types of thiamine derivatives, S-(2,2,6,6-tetramethyl-4-oxopiperidino) thiamine (XX) and S-(2,6-di-t-butyl-4-methylphenoxy)thiamine (XXVI) respectively.
  • Hiroshi Yoshida
    1969 Volume 42 Issue 7 Pages 1948-1954
    Published: 1969
    Released: March 27, 2006
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    It was previously reported that xanthate reacted with t-amine to give quaternary ammonium salt at room temperature, and dithiolcarbonates at elevated temperatures. Precise study showed that these reaction products are formed by the following three reactions: the alkylation of t-amine with xanthate affords quaternary ammonium salt and the reaction of xanthate with quaternary ammonium salt yields dithiolcarbonate, while there is transesterification between thiolesters and quaternary ammonium salt. The rate constants and equilibrium constants of these reactions were calculated.
  • Tadashi Sato, Hirohisa Wakatsuka
    1969 Volume 42 Issue 7 Pages 1955-1958
    Published: 1969
    Released: March 27, 2006
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    The reactions of cyclohexanone and cyclopentanone oxime p-toluenesulfonates were studied. It was found that cyclohexanone oxime p-toluenesulfonate (IIIa) afforded a tetrahydroazepine derivative (Va), while cyclopentanone oxime p-toluenesulfonate (X) afforded δ-valerolactam p-toluenesulfonate (XIII), when both compounds were heated in benzene.
  • Akira Matsumoto, Katsutoshi Takashima, Masayoshi Oiwa
    1969 Volume 42 Issue 7 Pages 1959-1963
    Published: 1969
    Released: March 27, 2006
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    The polymerization of diallyl carbonate was carried out at 60°C, benzoyl peroxide being used as the initiator; here it has been discussed kinetically from the point of view of cyclopolymerization. The rate of polymerization, Rp, was not proportional to the square root or the first power of the initiator concentration, (I), but Rp/(I)1⁄2 and (I)1⁄2 bore a linear relationship. The rate of polymerization, the residual unsaturation, and the degree of polymerization decreased with a decrease in the monomer concentration. The relation between the rate of polymerization over the degree of polymerization, Rp/\barPn,o and the monomer concentration, (M), was also linear, as in Rp/(I)1⁄2 and (I)1⁄2. The ratio of the rate constant of the unimolecular cyclization reaction to that of the bimolecular propagation reaction of the uncyclized radical, Kc, was estimated to be 4.0 mol/l from the dependence of the residual unsaturation on the monomer concentration.
  • Shigeru Oae, Kazuo Sakai, Norio Kunieda
    1969 Volume 42 Issue 7 Pages 1964-1967
    Published: 1969
    Released: March 27, 2006
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    The basicities of nine meta- and para-substituted diphenyl sulfoxides have been determined spectrophotometrically in sulfuric acid media. The pKBH+ values thus obtained indicate that these sulfoxides possess rather weak basicities (pKBH+; −3.67–−5.74). and these pKBH+ values gave a good correlation with Brown-Okamoto’s σ+ values, (ρ=−2.00), instead of σ-values. These observations seem to suggest a considerable conjugative interaction between phenyl groups and sulfoxide group of these diphenyl sulfoxides.
  • Yong He Khim, Shigeru Oae
    1969 Volume 42 Issue 7 Pages 1968-1971
    Published: 1969
    Released: March 27, 2006
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    Tritolylsulfonium bromide was subjected to alkaline decomposition in order to clarify the mechanism of the reaction of triarylsulfonium bromide with phenyllithium in ether. Diaryl sulfides, diaryls, and other aryl derivatives were obtained and the combined yield was nearly quantitative. On the basis of the ratio of the products formed in the reaction, the alkaline decomposition is considered to proceed through two mechanistic routes, i. e., one involving the nucleophilic attack of phenyl anion on the sulfur atom (about 70%) and the other the “benzyne” route (about 20%).
  • Kenji Fukui, Mitsuru Nakayama, Sachihiko Tanaka
    1969 Volume 42 Issue 7 Pages 1971-1975
    Published: 1969
    Released: March 27, 2006
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    5,6-Methylenedioxy-2-isopropenylbenzo[b]furan, an analogue of the naturally-occurring 5,6-dimethoxy compound, has been synthesized by the dehydration of the corresponding 2-(1’-hydroxy)isopropyl derivative, which was obtained from 2-hydroxy-4,5-methylenedioxybenz-aldehyde. By the catalytic hydrogenation of the benzofuran, its 2-isopropyl derivative and its 2-isopropyl-2,3-dihydrofurano-compound were prepared. The NMR spectra of these compounds have been compared.
  • Masaru Sato, Takehiko Ito, Izumi Motoyama, Ken-ichi Watanabe, Kazuo Ha ...
    1969 Volume 42 Issue 7 Pages 1976-1981
    Published: 1969
    Released: March 27, 2006
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    The halogen exchange reaction of haloferrocene series with copper(I) salts (halide, cyanide) in an organic base was studied in comparison with that of the halobenzene series, which is regarded as a kind of nucleophilic substitution. Chloro-, bromo-, and cyanoferrocene were all obtained from iodoferrocene by this reaction in good yields. The reactivity of the ferrocene series was much higher than that of the benzene series. The order of the reactivity of halogen, I>Br>Cl, was similar to that of the benzene series. On the other hand, the substituent effects in the comparative reactivity of 1’-substituted-1-chloroferrocene with copper(I) cyanide was observed to be as follows: Et>H>Cl>Ac. This order in the ferrocene series was opposite to that in the p-substituted bromobenzene series: CN>Ac>Br>H>Me. In view of the electrophilic tendency in the ferrocene series and its high reactivity, the reaction mechanism is discussed.
  • Teruo Hiraki
    1969 Volume 42 Issue 7 Pages 1981-1986
    Published: 1969
    Released: March 27, 2006
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    In order to ascertain the possibility of telomerization by a silent discharge, a mixture of acetic acid and ethylene was discharged in an ozonizer under various conditions. The α-C-alkylation of acetic acid which was expected to result from its discharge-induced reaction with ethylene was not observed; neither propionic acid nor higher carboxylic acids were identified by gas chromatography. However, n-butyl acetate was obtained in a good yield. The formation of the acetate can be explained as resulting from the combination of an acetoxy radical with two molecules of ethylene. The yield of the acetate, as well as those of the liquid and gaseous products, increased with a rise in the temperature and in the voltage, with the time, and with a rise in the ratio of ethylene to the acid concentration. Besides this acetate, the liquid products were confirmed to consist of ethyl methyl ketone, acetone, acetaldehyde, hydrocarbons, and ethyl and n-propyl acetates. The gaseous products were carbon dioxide, carbon monoxide, C1–C4-hydrocarbons, and hydrogen. Judging from the relative concentration of each compound in the reaction products, it may be said that the acetoxy radical (CH3COO·) and the acetyl radical (CH3CO·) are the main intermediates in this reaction system.
  • Michinori Oki, Hiizu Iwamura, Tetsuo Murayama, Isao Oka
    1969 Volume 42 Issue 7 Pages 1986-1991
    Published: 1969
    Released: March 27, 2006
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    Cyclopropylcarbinol shows two absorption maxima due to the O–H stretching, the lowerfrequency band being stronger than the higher. The results are interpreted on the basis of intramolecular interaction between the hydroxyl group and the cyclopropane ring. This kind of interaction is not clearly detected with 2-cyclopropylethanol, but 2,2-dicyclopropylethanol and 2-(1-methylcyclopropyl)ethanol give results which are best interpreted by assuming the presence of the interaction. It is concluded, from the findings on rigid molecules, that O–H···cyclopropane interaction is possible when the hydroxyl group approaches the edge within the plane of the ring. The steric effect of the methyl group is also discussed.
  • Yoshinobu Takegami, Yoshihisa Watanabe, Takeaki Mitsudo, Toshiharu Oka ...
    1969 Volume 42 Issue 7 Pages 1992-1995
    Published: 1969
    Released: March 27, 2006
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    The reactions of potassium iron carbonylates (K2Fe(CO)4, KHFe(CO)4 and K2Fe2(CO)8) with allyl halide and its derivatives have been studied. Allyl halide and its derivatives react readily with these carbonylates in ethyl alcohol at 30°C to give the corresponding and isomerized olefins. The reaction of allyl chloride in hydrous ethyl alcohol gives propylene in a good yield and 1,5-hexadiene as a by-product. In dry ethyl alcohol, the yield of propylene decreases. The reaction of trans-1-chloro-2-butene gives trans-2-butene (the major product), cis-2-butene, and 1-butene. The reaction of 1-chloro-3-methyl-2-butene and 3-chloro-3-methyl-1-butene gives 2-methyl-2-butene (the major product), 3-methyl-1-butene, and 2-methyl-1-butene. These reactions are considered to proceed via σ- and π-allyl iron carbonyl complexes.
  • Teruzo Asahara, Manabu Sen\={o}, Sadayoshi Tanaka, Norio Den
    1969 Volume 42 Issue 7 Pages 1996-2005
    Published: 1969
    Released: March 27, 2006
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    The anionic telomerizations of styrene with n-butylamine, s-butylamine, t-butylamine and isobutylamine catalyzed by sodium metal were investigated. The structures of the products were discussed by the NMR spectra obtained in carbon tetrachloride and identified to be N-butyl-2-phenylethylamines and N-butyldi(2-phenylethyl)amines. The general reaction scheme was proposed and interpreted with the concept of the anionic telomerization, where amine acts as a telogen and styrene as a taxogen.
  • Tsutomu Asano
    1969 Volume 42 Issue 7 Pages 2005-2013
    Published: 1969
    Released: March 27, 2006
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    Partial rate factors for the nitration of six monosubstituted benzenes with nitric-sulfuric acid in acetic acid at 45°C have been determined over the 1–2000 kg/cm2 pressure range. The ρ value for this reaction changed from −7.22 (1 kg/cm2) to −6.92 (2000 kg/cm2). This pressure dependency of the ρ value was not expected for this type of reaction. This phenomenon is interpreted in terms of the dependence of the degree of solvation of the transition states on the substituents. An abnormal deactivation due to pressure has been observed in the case of biphenyl. This deactivation has been attributed to an increase in the deviation from the coplanarity of the two phenyl groups. The dependence of the ortho: para ratios on the pressure is also discussed.
  • Teiichi Ando, Hirokazu Hosaka, Hiroki Yamanaka, Wataru Funasaka
    1969 Volume 42 Issue 7 Pages 2013-2021
    Published: 1969
    Released: March 27, 2006
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    Some bicyclic gem-dichlorocyclopropanes (Ia through Id) and gem-chlorofluorocyclopropanes (IIa through IId) were prepared by the addition of dichloro- and chlorofluorocarbene, respectively, to the appropriate cyclic olefins. The reduction of these dihalocyclopropanes with tri-n-butyltin hydride gave the corresponding monochloro- (IIIa through IIId) or monofluorocyclopropanes (IVa through IVd) in fairly good yields. When treated with an excess of hot quinoline, the endo-chloro isomers of IIa, IIb, IId, IIIa, IIIb, and IIId were converted to their ring expansion products, whereas their exo-chloro isomers were recovered unchanged. In contrast, the exo-chloro isomers of IIe and IIIc decomposed more readily than their endo-chloro isomers under similar conditions. These results were discussed on the concept of a concerted disrotatory process.
  • Takashi Maeda, Mitsuru Kimoto, Shigeru Wakahara, Kanji Tokuyama
    1969 Volume 42 Issue 7 Pages 2021-2028
    Published: 1969
    Released: March 27, 2006
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    It has been proposed that 1,3-O-benzylidene-L-sorbose (III) exists as an equilibrium mixture of a pyranose form (IIIp), a keto-form (IIIk) and a furanose form (IIIf) in solutions. The acetylation of III in pyridine afforded the acetates of IIIf; one of them (IV) is in a keto-form (IVk) in a crystalline state, and at a low temperature, while the acetates of IIIf and IIIp at higher temperatures. When a pyridine solution of III was allowed to stand for some time before acetylation, the yield of the acetate of IIIp increased. The recrystallization of III usually gave crystals of IIIf, however, while the addition of petroleum ether to the concentrated pyridine solution of III afforded a powder which was consisted mainly of IIIp. These results suggest that III exists as IIIf in a crystalline state and as an equilibrium mixture of IIIf, IIIk, and IIIp in solution; the existence of this equilibrium was also confirmed by proton magnetic resonance spectroscopy.
  • Takashi Toda, Shôji Ryu, Tetsuo Nozoe
    1969 Volume 42 Issue 7 Pages 2028-2032
    Published: 1969
    Released: March 27, 2006
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    The nucleophilic substitution reactions of 2-aminotropone (I), 2-methylaminotropone (II), 2-dimethylaminotropone (III), and 2-troponyl trimethylammonium iodide (IV), and their alkyl derivatives were investigated. It was found that the properties of I and II are similar to those of tropolones. On the other hand, those of III are analogous to those of tropolone methyl ethers, while those of IV are, rather, comparable to those of 2-halotropones or tropolone tosylates.
  • Teruji Tsuji, Shuji Teratake, Hiroshi Tanida
    1969 Volume 42 Issue 7 Pages 2033-2037
    Published: 1969
    Released: March 27, 2006
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    Rates of the Diels-Alder reaction of cycloheptatriene, tricyclo[4.3.1.0]deca-2,4-diene, 1,3-cyclohexadiene, and cis-bicyclo[4.3.0]nona-2,4-diene with excess of fumaryl chloride were measured using a dilatometer. Comparison of the rate of cycloheptatriene with that of other olefins raises the question of the free energy difference so far estimated between cycloheptatriene and norcaradiene, which has been proposed to exist in equilibrium. It is suggested that the most preferable mechanism of the Diels-Alder reaction of cycloheptatriene is not through the norcaradiene isomer, but through the transition state of the norcaradiene structure.
  • K. K. Banerji, P. Nath
    1969 Volume 42 Issue 7 Pages 2038-2040
    Published: 1969
    Released: March 27, 2006
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  • Chiro Shinomiya, Akira Oyoshi, Toshiaki Kishikawa
    1969 Volume 42 Issue 7 Pages 2040-2041
    Published: 1969
    Released: March 27, 2006
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  • Hiroshi Hotta, Nobutake Suzuki, Takuji Komori
    1969 Volume 42 Issue 7 Pages 2041-2042
    Published: 1969
    Released: March 27, 2006
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  • Kazuyuki Sugita, Ju Kumanotani
    1969 Volume 42 Issue 7 Pages 2043-2044
    Published: 1969
    Released: March 27, 2006
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  • Yukinao Noda
    1969 Volume 42 Issue 7 Pages 2044-2046
    Published: 1969
    Released: March 27, 2006
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