Bulletin of the Chemical Society of Japan
Online ISSN : 1348-0634
Print ISSN : 0009-2673
ISSN-L : 0009-2673
Volume 52 , Issue 7
Showing 1-50 articles out of 73 articles from the selected issue
  • Hisao Negita, Tsuneo Kubo, Michio Maekawa, Akinobu Ueda, Tsutomu Okuda
    1979 Volume 52 Issue 7 Pages 1881-1883
    Published: 1979
    Released: April 19, 2006
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    The 14N nuclear quadrupole resonances (NQR) in sulfuric diamide (sulfamide), H2NSO2NH2, and methanesulfonamide, CH3SO2NH2, were studied by the pulse method. The resonance frequency and the spin-lattice relaxation time (T1) were measured in the temperature range from liquid nitrogen temperature to room temperature. In the case of sulfuric diamide, T1 decreases monotonously as the temperature rises, and is dominated by the thermal torsional motion below 140 K. On the other hand, T1 is attributed to the reorientation of the amino group in the temperature range from 200 to 240 K, whereas it is due to the reorientation of the molecule above 240 K; the activation energies in these orientations are 43.5 and 61.5 kJ·mol−1 respectively. In the case of methanesulfonamide, the minimum of T1 is found near 130 K. This is caused by the rotation of the methyl group. The activation energy for this motion is calculated to be 9.6 kJ·mol−1. The dominant relaxation mechanism is attributed to the reorientation of the amino group from 200 to 240 K and to the reorientation of the molecule above 240 K. The activation energies for these motions are 19.2 and 40.6 kJ. mol−1 respectively.
  • Teruyo Yamashita, Hiroshige Yano, Tatsuya Yasunaga
    1979 Volume 52 Issue 7 Pages 1884-1886
    Published: 1979
    Released: April 19, 2006
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    The ultrasonic absorptions of Aerosol OT in dodecane solution were measured in the frequency range 5–95 MHz at various temperatures. An excess absorption caused by single relaxation was observed above the second critical micelle concentration. This is attributed to the conformational change in structure of two kinds of Aerosol OT micelles, since the maximum excess absorption per wave length depends on the concentration and temperature. The thermodynamic and kinetic parameters were determined in relation to the reaction.
  • Shigeo Yoneda, Tokuzo Kawase, Zen-ichi Yoshida
    1979 Volume 52 Issue 7 Pages 1887-1889
    Published: 1979
    Released: April 19, 2006
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    The electronic spectrum and structure of tetracyanotetrathiafulvalene have been investigated by the ASMO-SCF-CI method, in which the 3d orbitals of sulfur atoms are taken into account. The calculated results showed that the absorption band at the longest wavelength can be interpreted in terms of intramolecular charge-transfer.
  • Junichiro Mizusaki, Kazuo Fueki, Takashi Mukaibo
    1979 Volume 52 Issue 7 Pages 1890-1895
    Published: 1979
    Released: April 19, 2006
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    In order to determine the chemical diffusion coefficients for AgBr and α-AgI, a new experimental technique was developed. A Pt probe was inserted into the middle of the AgX (X=Br or I) pellet in an improved d.c. polarization cell of the Ag/AgX/carbon type, and the applied potential difference between the Ag and carbon electrodes was changed abruptly. The accompanying change in E(L⁄2), the EMF between the Ag electrode and the Pt prcbe, was followed, and the cherrical diffusion coefficient, \ ildeD, was determined by the analysis of the change in E(L⁄2) with the time. In the temperature range from 325 to 400 °C, \ ildeD for AgBr with excess silver was found to be
    \ ildeD=7.10×102exp\left(−\frac1.96×104 cal molRT\ ight)cm2s−1. (i)
    In the temperature range of 330 to 500 °C, \ ildeD for a-AgI was
    \ ildeD=4.95×10−1exp\left(−\frac7.71×103 cal mol−1RT\ ight)cm2s−1. (ii)
    Using these chemical diffusion coefficients and the electronic conductivity data, the nonstoichiomctry, and apparent mobility of electronic carriers of AgBr and α-AgI were determined.
  • Kojun Okamoto, Kiyotane Sekido, Jun Itoh, Teruo Noguchi, Sakutaro Hiro ...
    1979 Volume 52 Issue 7 Pages 1896-1898
    Published: 1979
    Released: April 19, 2006
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    The crystal structure of trans-1,4-dibenzoyl-2,5-dimethyl-piperazine has been determined by the X-ray method. The space group is P21/c, with a=7.483, b=6.577, c=19.939 Å, β=116.71° and Z=2. The structure was solved by the direct method and refined by the least-squares method to the final R factor of 0.094 for 2559 independent reflections. A nitrogen atom and three carbon atoms bonded to the nitrogen atom are approximately in a plane. The molecule is centrosymmetric, the piperazine ring having a chair-form. The methyl groups are in the axial position. The oxygen atom is approximately in a plane formed by N, C(carbonyl), and C(benzene). The dihedral angle between this plane and the benzene ring is approximetely 70°.
  • Ikuo Abe, Katsumi Hayashi, Mutsuo Kitagawa, Toshihiro Urahata
    1979 Volume 52 Issue 7 Pages 1899-1904
    Published: 1979
    Released: April 19, 2006
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    The adsorption isotherms, from aqueous solution onto activated carbon, have been determined for the 22 aliphatic monofunctional compounds; alcohols, carboxylic acids, ketones, ethers, esters, and aldehydes. The free energy change for the adsorption process has been calculated from the adsorption equilibrium constant at infinite dilution; a linear relationship exists between the free energy change and the number of carbon atoms in the solute. The free energy of adsorption has been divided into two contributions: the hydrocarbon and the functional group contribution. The free energy change for the adsorption process has been compared with the free energy change for the precipitation process from solution into the pure liquid solute. The free energy contribution per individual methylene group to the adsorption process shows an approximate agreement with that for the precipitation process indicating that the adsorption process of the hydrocarbon portion of the solute is analogous to the precipitation process. The free energy contribution of the functional group to the adsorption process is smaller than that for the precipitation process indicating that the functional group portion of the solute is not appreciably dehydrated in the adsorption phase.
  • Hisashi Ueda
    1979 Volume 52 Issue 7 Pages 1905-1910
    Published: 1979
    Released: April 19, 2006
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    In order to study the carrier effects on the supported catalysts of vanadium, the ESR spectra of vanadium ions supported on γ-Al2O3, SiO2, ZrO2, TiO2, MgO, or CaO and reduced in H2 at 500 °C were studied. When γ-Al2O3, SiO2, ZrO2, or TiO2 were used as the carriers, the main spectral component could be assigned to the V4+ ion. The results of data analysis, assisted by spectrum calculation, showed that, on catalyst which had a high activity in the reduction of NOx by NH3, the V4+ ion had a highly populated dxy orbital, while on catalyst of low activity, V4+ had a dxy with a low spin density. If the carrier was MgO, the V ion was reduced to V2+. If the carrier was CaO, no ESR signals due to V ions were observed. It has been suggested that an inhomogeneous and axially symmetric crystal-field model may interpret the intensity ratios among the hyperfine lines of the V4+ ESR absorption rather than a non-axial symmetry model of the V4+ unpaired electron.
  • Kazuo Mukai
    1979 Volume 52 Issue 7 Pages 1911-1915
    Published: 1979
    Released: April 19, 2006
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    Mono- and dimethyl derivatives (II) and (III) of Yang’s biradical (I) were prepared, and the methyl-substitution effects on the molecular symmetry and spin-density distribution of Yang’s biradical have been studied. Resolved hyperfine structures were observed in the ESR spectra of liquid solutions of the biradicals (II) and (III), giving the hyperfine splitting values theoretically expected for their triplet states. In a fluid solution, the biradical molecules retain a three-fold symmetry, as has been reported for Yang’s biradical, and the expected methyl-substitution effect is too small to induce any asymmetric, unpaired spin distribution. The g- and D-tensor values of the (II) and (III) biradicals were determined from analyses of the asymmetric ESR spectra of frozen solutions containing the biradicals. The results suggest that these biradicals must also lack a three-fold symmetry in a frozen solution, as has been observed for Yang’s biradical. Essentially the same g- and D-tensor values as those of Yang’s biradical are observed for the monomethyl derivative (II). On the other hand, the dimethyl derivative (III) shows quite different g- and D-tensor values.
  • Shoji Noda, Yasunari Ohta, Hiroshi Yoshida
    1979 Volume 52 Issue 7 Pages 1916-1919
    Published: 1979
    Released: April 19, 2006
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    The reactions of electrons injected by field emission into solutions have been investigated. Free radicals generated by the dissociative electron attachment to chlorinated solutes in benzene solutions were detected by the spin trapping-ESR method, using pentamethylnitrosobenzene as a spin trapping agent. Nondissociative electron attachment to styrene caused by the field emission was also evidenced by detecting the α-methylbenzyl radical generated secondarily from the styrene radical anion. The electrons field-emitted into the solutions are captured almost quantitatively by the electron scavenging solutes. The field emission method has been found to be useful for generating authentically free radicals and for studying the anionic reaction induced by electrons without interference of countercations and of any reaction intermediates from solvent molecules. As an example of the chemical utilization of the field emission technique, the ESR parameters of the spin adducts of several hydrocarbon radicals have been collected by this technique.
  • Yasuyuki Takeda, Hiroshi Got\={o}
    1979 Volume 52 Issue 7 Pages 1920-1922
    Published: 1979
    Released: April 19, 2006
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    The overall extraction equilibrium constants (Kex) for 1:1:1 complexes of 15-crown-5 (15C5) and 18-crown-6 (18C6) with several univalent metal picrates between benzene and water have been determined at 25 °C. The Kex sequences of the univalent metal ion with 15C5 and 18C6 are Ag+>Na+>Tl+>>K+>Rb+>Cs+>Li+ and Tl+>K+>Rb+>Ag+>Cs+>Na+>>Li+ respectively. The Kex series for each same crown ether reflects the stability and the extractability of the univalent metal ion-crown ether complex in the aqueous phase. The Kex sequences for the 15C5 system depends entirely on the extractability of the univalent metal ion-crown ether complex. In the case of the 18C6 system this largely depends on the stability of the univalent metal ion-crown ether complex.
  • Natsuko Kanzaki, Iwao Yasumori
    1979 Volume 52 Issue 7 Pages 1923-1927
    Published: 1979
    Released: April 19, 2006
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    Molecular Oxygen anion radicals (O2) were produced on X-zeolites by γ-irradiation in the presence of O2. Their properties were systematically investigated by means of ESR spectroscopy. Two kinds of O2 species with different gz values were formed on monovalent cation-exchanged (LiX, KX, RbX, CsX) zeolites and MgX, while three and single O2 species were observed on divalent cation-exchanged (CaX, SrX, BaX) and trivalent cation-exchanged (LaX) zeolites, respectively. These O2 radicals showed different reactivities with N2O or 1-butene, and their gz values were classified into four groups. By considering the results from the gz values and the effect of introduced high pressure O2 on the O2 spectra, the adsorption sites for the radicals on zeolites were determined.
  • Visit Kasempimolporn, Hisashi Okawa, Sigeo Kida
    1979 Volume 52 Issue 7 Pages 1928-1931
    Published: 1979
    Released: April 19, 2006
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    Trinuclear cobalt(II) complexes, [Co(R1R2-L)]2CoX2 (R1 R2=H, Me; L=en, ch, ph; X=Cl, Br), have been synthesized, where H2(R1,R2-L) denotes the Schiff bases obtained by condensing a 5(R1), α(R2)-substituted salicylaldehyde with a diamine (H2N-L-NH2) in a 2:1 mole ratio. From IR spectra and cryomagnetic properties, it was concluded that these complexes are in mixed-spin state of a Co(II)(s=l/2)-Co(II)(s=3/2)–Co(II)(s=l/2) system, strong antiferromagnetic spin-exchange interaction operating between low-spin and high-spin cobalt(II) ion via dπ(low-spin Co)-pπ(O)-dπ(high-spin Co) super pathway.
  • Kensei Kobayashi, Kitao Fujiwara, Hiroki Haraguchi, Keiichiro Fuwa
    1979 Volume 52 Issue 7 Pages 1932-1936
    Published: 1979
    Released: April 19, 2006
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    A method for the determination of trace zinc has been investigated by using enzymatic activity of carbonic anhydrase. The recovery of enzymatic activity of apo-carbonic anhydrase was proportional to the amount of zinc in solution theoretically and experimentally, when it was monitored spectroscopically using the substrate, p-nitrophenyl acetate. The amount of zinc in the sample solutions was therefore determined from the curve, zinc concentration vs. the enzymatic activity. The limit of detection is 10 ng/ml or 2 ng. The method has been applied to the analysis of zinc in fruit juices and water samples.
  • Tokuji Ikeda, Kazunobu Toriyama, Mitsugi Senda
    1979 Volume 52 Issue 7 Pages 1937-1943
    Published: 1979
    Released: April 19, 2006
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    The electrochemical behavior of Clostridium pasteurianum ferredoxin and spinach ferredoxin was studied by cyclic d.c. and cyclic phase-selective a.c. voltammetry with a hanging mercury drop electrode. An irreversible adsorption of these ferredoxins on the electrode surface is described. In successive cyclic voltage scans both d.c. and a.c. voltammograms of ferredoxins change gradually in both height and form until a steady state is attained, indicating that the ferredoxins adsorbed on the electrode surface decompose to cluster-free ferredoxins. Apoferredoxins give the same voltammograms as the steady state voltammograms of ferredoxins. The steady state voltammograms are assigned to RSH/RSHg redox reaction of the cysteine residues in apoferredoxin. At pH lower than 8 the d.c. waves are explained by an equation for reversible one-electron surface redox reaction. Kinetic parameters of the redox reaction were determined by a.c. voltammetry.
  • Yoshiaki Kusuyama
    1979 Volume 52 Issue 7 Pages 1944-1949
    Published: 1979
    Released: April 19, 2006
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    Ten cis-2-substituted 1-cyclopropanecarboxylic acids (substituents: H, CH3, C6H5, CH3O, C2H5O, Cl, Br, CH3CO, CH3OCO, and C2H5OCO) were prepared, and their pKa values were determined in water at 25 °C, along with those of the trans-2-chloro and 2-methoxy derivatives. The pKa values for cis isomers are somewhat larger than those for the corresponding trans isomers, except for the chloro and bromo derivatives. The substituent effects obtained were in the usual order in the sense of the electronic effects, except for the phenyl group, which produced a decrease in acidity relative to the unsubstituted acid. It was shown that the carbon-13 chemical shifts for the methylene carbon of the ethyl group in the ethyl cis-2-substituted 1-cyclopropanecarboxylate obtained in deuteriochloroform gave a reasonable linear relation with the pKa(cis) values.
  • Seizi Kozuka, Takuro Kitamura, Noboru Kobayashi, Kenji Ogino
    1979 Volume 52 Issue 7 Pages 1950-1952
    Published: 1979
    Released: April 19, 2006
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    The acyloxy exchange reactions of acyloxysilane with carboxylic acids have been studied kinetically. The rate of reaction has been found to proceed faster with a stronger attacking acid and more basic leaving acyloxy group. The rate was markedly accelerated by the addition of base. The steric effect due to substituents on the silicon atom and hydrogen-deuterium kinetic isotope effects have been examined. A mechanism involving the 5-coordination of the silicon atom prior to the rate-determining proton transfer has been suggested.
  • Morio Asaoka, Naoyuki Sugimura, Hisashi Takei
    1979 Volume 52 Issue 7 Pages 1953-1956
    Published: 1979
    Released: April 19, 2006
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    The reaction of 2-(trimethylsiloxy)furan (1) with orthocarboxylic esters, acetals, and acylal in the presence of Lewis acids afforded the corresponding 4-substituted 2-buten-4-olides. The reaction of 5-methyl-2-(trimethyl-siloxy)furan with orthocarboxylic esters gave unstable 2-substituted 3-penten-4-olides as major products; these gave 2,5-alkanediones upon hydrolysis. The furan (1) also reacted with 1,1-diacetoxy-2-butene to give a mixture of 5-acetoxy-2,6-octadien-4-olide and 7-acetoxy-5-methyl-2,6-heptadien-4-olide. From the former compound, nigrosporalactone was synthesized.
  • Takashi Matsumoto, Taishi Ohmura, Shuji Usui
    1979 Volume 52 Issue 7 Pages 1957-1963
    Published: 1979
    Released: April 19, 2006
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    Condensation of β-cyclocitral with 2-isopropyl-3,4-dimethoxybenzyl chloride afforded an alcohol (15) which was converted into (±)-12,13-dimethoxytotara-8,11,13-trien-6-one (18). Demethylation of (±)-18 followed by air oxidation gave (±)-maytenoquinone. Reductive cleavage of the hydroxyl group in (±)-15 produced a phenethyl derivative which was cyclized to give (±)-12,13-dimethoxytotara-8,11,13-triene (23) and its cis-isomer (24). Oxidation of (±)-23 with chromium trioxide, followed by demethylation of the resulting 7-oxo compound (25), afforded (±)-dispermone. The Wittig reaction of (R)-(−)-α-cyclocitral with 2-isopropyl-3,4-dimethoxybenzyltriphenylphosphonium chloride yielded a styrene derivative. This was partially hydrogenated and then cyclized to give (+)-23 and (−)-24. The trans-isomer (23) was converted into (−)-dispermone (3) via (−)-25 and also partially demethylated to (+)-12-methoxytotara-8,11,13-trien-13-ol (2), the proposed structure for dispermol. Since the synthetic (+)-2 was not identical with the natural compound, (−)-3 was then converted into (+)-13-methoxytotara-8,11,13-trien-12-ol, which was identical with natural dispermol. (−)-25 was also converted into (+)-maytenoquinone.
  • Akio Horinaka, Keizo Naya
    1979 Volume 52 Issue 7 Pages 1964-1966
    Published: 1979
    Released: April 19, 2006
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    Fukinone, possessing a cisoid enone system, is susceptible to air oxidation. The oxidation products have been extensively examined and have been established as including diastereomeric epoxides, a hydroxy ketone (petasitolone), a lactol (8β-hydroxyeremophilenolide), and a peroxy hemiacetal. Also, the products were compared with those derived from the autoxidation of pulegone, a monoterpenic analogue of fukinone.
  • Toyoki Kunitake, Yoshio Okahata, Shoichi Tanamachi, Reiko Ando
    1979 Volume 52 Issue 7 Pages 1967-1971
    Published: 1979
    Released: April 19, 2006
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    Several surfactant-like zwitterionic hydroxamates were synthesized and their reactions with p-nitrophenyl acetate were studied in water in comparison with those of simple, anionic hydroxamates. The zwitterionic hydroxamates showed enhanced reactivities in cationic, zwitterionic and nonionic micelles: 20–100 times relative to the nomicellar rate at pH 8.9, 30 °C. The rate enhancement was attributed to lowered pKa values and to activation of the hydroxamate anion in the hydrophobic domain. The rate was suppressed in an anionic micelle because of the enhanced pKa value. Deacylation of the acetyl hydroxamate intermediate was hydroxide-catalyzed. The enhanced reactivity of the zwitterionic hydroxamate in organic media was less sensitive to the water concentration than that of the hydroxamate ion pair. These results can be explained in terms of “hydrophobic ion pair.
  • Akio Yamane, Masatoshi Nagayoshi, Kimiaki Imafuku, Hisashi Matsumura
    1979 Volume 52 Issue 7 Pages 1972-1974
    Published: 1979
    Released: April 19, 2006
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    3-Acetyltropolone (1) was synthesized from 3-isopropenyltropolone by treatment with sodium azide in concentrated sulfuric acid. Methylation of 1 by diazomethane gave two isomers, 3-acetyl-2-methoxytropone (2a) and 2-acetyl-7-methoxytropone (2b). 1, 2a, and 2b reacted with hydrazine to give some 1,8-dihydrocycloheptapyrazol-8-one derivatives.
  • Nanao Watanabe, Sakae Uemura, Masaya Okano
    1979 Volume 52 Issue 7 Pages 1975-1977
    Published: 1979
    Released: April 19, 2006
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    The reaction of ω-ethoxyalkyl bromides (Cn: n=2–5) with silver(I) cyanide or nitrite in less polar solvents to give the corresponding isocyanide or a mixture of the corresponding alkyl nitrite and nitroalkane respectively, proceeded with ease only when n=4. In the latter reaction, the ratios of O- and N-attack (O/N) were 16–18/ 82–84 and 31–46/54–69 when n\ eweq4 and n=4 respectively. The facile reaction in both cases when n=4 and the increasing O-attack in the case of silver(I) nitrite may suggest that the reaction proceeds through the initial formation of a five-membered oxonium ion, the O-ethyltetrahydrofuranium ion, and a subsequent attack by CN and NO2 or their silver(I) bromide complex.
  • Hirotada Fujii, Tohru Kawai, Hiroyasu Nishikawa
    1979 Volume 52 Issue 7 Pages 1978-1982
    Published: 1979
    Released: April 19, 2006
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    Hydrolytic reactions of several p-nitrophenyl esters were studied with and without catalysts in reversed micellar systems consisting of sodium octanoate, 1-hexanol and water. Hydrolytic rate constants become very large as compared with those in aqueous solutions, increasing with decrease in the molar ratio of water to sodium octanoate (R-value). The results of kinetic measurements were discussed in terms of the behavior of water molecules and polar groups of sodium octanoate as revealed by means of IR and 1H, 13C and 23Na-NMR spectroscopy. It was concluded that the decrease in the R-value induces the increase in the mobility of water molecules and the decrease in the polarity of the water core, which affects the partition coefficient of p-nitrophenyl esters between the 1-hexanol phase and the water phase, enhancing hydrolytic reactions.
  • Yoshiji Fujita, Shigetoshi Amiya, Takashi Onishi, Takashi Nishida
    1979 Volume 52 Issue 7 Pages 1983-1988
    Published: 1979
    Released: April 19, 2006
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    Oxy-Cope rearrangement of diastereomeric l,5-hexadien-3-ols, new key intermediates for terpenoids pio-duction in industrial scale, were investigated in neat systems and solvent assisted systems. Various solvents affecting the selectivity of [3,3]-shift were classified by means of NMR studies on hydroxyl proton exchange time.
  • Junji Inanaga, Kuniko Hirata, Hiroko Saeki, Tsutomu Katsuki, Masaru Ya ...
    1979 Volume 52 Issue 7 Pages 1989-1993
    Published: 1979
    Released: April 19, 2006
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    A rapid and mild esterification method using carboxylic 2,4,6-trichlorobenzoic anhydrides in the presence of 4-dimethylaminopyridine was developed. The method was also successfully applied to the synthesis of large-ring lactones, including DL-2,4,6-tridemethyl-3-deoxymethynolide.
  • Yasuhisa Senda, Jun-ichi Ishiyama, Shin Imaizumi
    1979 Volume 52 Issue 7 Pages 1994-1997
    Published: 1979
    Released: April 19, 2006
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    The 13C NMR spectra of stereoisomeric 4-t-butyl-2-methylcyclohexanols, 5-t-butyl-2-methylcyclohexanols, 2-methylcyclohexanols, and their acetates were measured. The observed chemical shifts were compared with the values estimated by using the substituent parameters of methyl, t-butyl, and hydroxyl groups. An appreciable deviation by vicinal substitution was found between the predicted and observed chemical shifts of C-1 and C-2. The substituent parameters of the acetoxyl group on the cyclohexane ring were estimated by means of a comparison of the chemical shifts of cis- and trans-4-t-butylcyclohexyl acetate, and those of t-butylcyclohexane.
  • Yoshio Inagaki, Renji Okazaki, Naoki Inamoto
    1979 Volume 52 Issue 7 Pages 1998-2001
    Published: 1979
    Released: April 19, 2006
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    Reaction of 2,4-di-t-butyl-6-methylaniline (3) with disulfur dichloride afforded 2,4-di-t-butyl-6-methyl-N-thiosulfinylaniline (4) as a stable compound in 80% yield. Reaction of 2,4,6-tri-t-butylaniline (1) with disulfur dichloride gave in 70% yield 2,4,6-tri-t-butyl-7,8-dithia-9-azabicyclo[4.3.0]nona-2,4,9-triene, which in solution, exists as a tautomeric mixture with 2,4,6-tri-t-butyl-N-thiosulnnylaniline (2b) as a minor component. In the reactions with 2,4-di-t-butyl-6-isopropyl- or 2,4,6-trimethylaniline, N-thiosulfinylanilines obtained were unstable at ambient temperature. Aniline 1 reacted with sulfur dichloride to give 2 and the corresponding sulfur diimide and N-sulfinylaniline. The reaction of 4 with the dichloride afforded 4 and the corresponding sulfur diimide.
  • Yoshio Inagaki, Renji Okazaki, Naoki Inamoto
    1979 Volume 52 Issue 7 Pages 2002-2007
    Published: 1979
    Released: April 19, 2006
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    Thermolysis of 2,4-di-t-butyl-6-methyl-N-thiosulfinylaniline (1) in refluxing benzene afforded 2,4-di-t-butyl-8-thia-9-azabicyclo[4.3.0]nona-2,4,6,9-tetraene (6) and 2,4-di-t-butyl-6-methylaniline (7), while its photolysis resulted in the formation of N,N′-bis(2,4-di-t-butyl-6-methylphenyl)sulfur diimide (17) and 7. The mechanism of the thermolysis involving 1,5-hydrogen migration and o-quinonoid intermediate has been proposed. The electronic spectrum of the initial intermediate in the photolysis was obtained in EPA matrix and tentatively assigned to a dithionitro compound (42) or a dithiaziridine (41). Thermolysis of 2,4,6-tri-t-butyl-7,8-dithia-9-azabicyclo[4.3.0]nona-2,4,9-triene (4b) equilibrated with 2,4,6-tri-t-butyl-N-thiosulfinylaniline (4a) gave 4,6-di-t-butyl-3H-1,2,3-benzodithiazole 2-oxide (26) and 2,4,6-tri-t-butylaniline (27). The reaction in the presence of a catalytic amount of p-toluenesulfonic acid improved the yield of both 26 and 27, suggesting the ionic decomposition pathway. However, an ESR signal was observed during the thermal decomposition of 4 in the absence of oxygen, implying a concurrent homolytic pathway if not a major one. The mechanism of these reactions are briefly discussed. The photolysis of 4 led to 27 and N,N′-bis(2,4-di-t-butyl-6-methylphenyl)sulfur diimide (43).
  • Yoshio Inagaki, Renji Okazaki, Naoki Inamoto, Koh-ichi Yamada, Hiroshi ...
    1979 Volume 52 Issue 7 Pages 2008-2009
    Published: 1979
    Released: April 19, 2006
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    Thermodynamic parameters (ΔH=−4.9 kcal mol−1, ΔS=−11.3 cal mol−1 deg−1) were determined for cyclization of 2,4,6-tri-t-butyl-N-thiosulfinylaniline (1b) (the minor component) into 2,4,6-tri-t-butyl-7,8-dithia-9-azabicyclo[4.3.0]nona-2,4,9-triene (1a) (the major component) by means of NMR spectroscopy. Using these values, π-bond of thiosulfinylamino group (–N=S=S) was estimated to be weaker than that of sulfinylamino group (–N=S=O) by, at least, 25 kcal mol−1. The equilibrium ratio [1a]/[1b] is subject to considerable solvent effect, polar solvents favoring the cyclic form (1a). Similarity of the thiosulfinylamine-dithiazole equilibrium to that of azidoimine-tetrazole has been pointed out.
  • Yang Bae Kim, Sachiko Bando, Toshiyasu Hombo, Takaji Fujiwara, Ken-ich ...
    1979 Volume 52 Issue 7 Pages 2010-2012
    Published: 1979
    Released: April 19, 2006
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    The crystal structure of 3-amino-2-hydroxy-1-propanesulfonic acid was determined by MULTAN system with X-ray intensity data on a diffractometer and refined by the least-squares method to an R-value 0.087 for 1620 reflections. The crystals were orthorhombic, space group Pbca, Z=8, with a=9.909, b=12.032 and c=10.251 Å. The molecule takes the zwitterionic form, H3+NCH2CH(OH)CH2SO3. The skeletal conformation of the molecule is planar trans zigzag. The molecules are held together by three-dimensional network of hydrogen bonds.
  • Katsuyuki Ogura, Yoko Ito, Gen-ichi Tsughihashi
    1979 Volume 52 Issue 7 Pages 2013-2022
    Published: 1979
    Released: April 19, 2006
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    Methyl (methylthio) methyl sulfoxide was found to react with benzaldehyde in the presence of benzyl tri-methylammonium hydroxide (Triton B), sodium hydroxide, or potassium hydroxide, affording 1-(methylsulfinyl)1-(methylthio)-2-phenylethylene. Treatment of this product with hydrogen chloride in an alcohol gave the corresponding alkyl phenylacetate in high yield. The whole reaction sequence provides a new method for synthesizing phenylacetic esters starting from benzaldehyde. In a similar manner, (alkoxy-, halogen-, or alkyl-substituted phenyl)acetic esters could be synthesized from the corresponding aromatic aldehydes. The present method was shown to be also applicable to the production of (2-thienyl)acetic esters.
  • Tadao Uyehara, Shoichi Miyakoshi, Yoshio Kitahara
    1979 Volume 52 Issue 7 Pages 2023-2027
    Published: 1979
    Released: April 19, 2006
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    The Diels-Alder reaction of five derivatives of 2-methoxytropone with dimethyl acetylenedicarboxylate proceeds regiospecifically giving dimethyl 1-methoxy-2-oxobicyclo[3.2.2]nona-3,6,8-triene-6,7-dicarboxylates, except in the case of 5-isopropyl-2-methoxytropone. The adducts undergo rearrangement selectively to dimethyl 7-methoxy-1-oxo-cis-3a,7a-dihydroindene-3a,7a-dicarboxylates, upon heating under reflux in xylene. Regiochemical aspects of the cycloaddition and mechanistic aspects of the rearrangement are discussed.
  • Kenji Yoshino, Yasukazu Ohkatsu, Teiji Tsuruta
    1979 Volume 52 Issue 7 Pages 2028-2032
    Published: 1979
    Released: April 19, 2006
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    The interaction between free radicals and cobalt complexes (Co(II)TPP and Co(II)(sal)2(R-CHXDA)) has been studied using (S,S)-(−)-, (R,R)-(+)-, and meso-1,1′-diphenylazoethane as a radical source. The decomposition of meso-1,1′-diphenylazoethane by heat or UV-light in the presence of Co(II)(sal)2(R-CHXDA) having an asymmetric ligand produced an optically active (+)-2,3-diphenylbutane. The suggestion is that the α-methylbenzyl radical formed from the azo compound is stereoselectively stabilized by the Co(II)(sal)2(R-CHXDA).
  • R. P. Soni, J. P. Saxena
    1979 Volume 52 Issue 7 Pages 2033-2035
    Published: 1979
    Released: April 19, 2006
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    Some 2-alkyl-6-hydroxy[1,3,4]thiadiazolo[2,3-b]benzimidazoles have been synthesised. Their absorption spectra at different pH show bathochromic shift of the absorption band in the longer wavelengths, which is more pronounced in basic medium. This is ascribed to the dipolar nature of the compounds. Quaternary derivatives of the compounds show a further red shift in the absorption band in the visible region, which further corroborates their dipolar nature.
  • Hajime Yasuda, Yasuo Ohnuma, Michihide Yamauchi, Hisaya Tani, Akira Na ...
    1979 Volume 52 Issue 7 Pages 2036-2045
    Published: 1979
    Released: April 19, 2006
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    Series of acyclic and cyclic dienyl anions were prepared from both conjugated and non-conjugated dienes by direct metalation with alkali metals (Li, Na, K, Rb, and Cs) in tetrahydrofuran in the presence of triethylamine or N,N,N′,N′-tetramethylethylenediamine. Eight different dienyl anions of open chain or cyclic structures were isolated as crystals. All the acyclic potassium dienides of pentadienes, 2-methylpentadienes, 3-methylpentadienes, hexadienes and 2,4-dimethylpentadienes gave the corresponding 1,3-dienes upon hydrolysis, while the potassium cyclic dienide of cycloheptadienes and cyclooctadienes gave 1,4-dienes exclusively. The result of methylation of dienyl anions with methyl iodide agreed with that of hydrolysis. The reaction path for formation of these dienyl anions was studied based on the carbon skeleton and the molar ratio of the reduced diene dimers produced together with the dienyl anions. Selective oxidative coupling of the dienyl anions occurred with CuX or CuX2 to give linear tetraenes in good yield.
  • Seiichi Kondo, Kazuo Tomoi, Chynryon Pak
    1979 Volume 52 Issue 7 Pages 2046-2050
    Published: 1979
    Released: April 19, 2006
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    The properties of silica gel were studied as a function of the hydrothermal treatment of hydrogel by means of the nitrogen-adsorption isotherm, the mechanical strength, thermodilatometry, and infrared spectroscopy. As a result, the number of contact points between primary particles of silica was found to decrease, and closed pores were found to be produced, by this treatment. The analysis of the infrared absorption spectra of the OH groups of this material showed that there are three kinds of OH groups in silica gel; (1) free OH groups on the outer surface of primary particles, which can adsorb molecules easily, (2) weakly perturbed OH groups inside closed pores, and (3) strongly hydrogen-bonded OH groups on the surface around the contact points. The relative concentration of these OH groups changes drastically upon the hydrothermal treatment; this is in accord with the change in the macroscopic properties mentioned above.
  • Hirotada Fujii, Tohru Kawai, Hiroyasu Nishikawa
    1979 Volume 52 Issue 7 Pages 2051-2055
    Published: 1979
    Released: April 19, 2006
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    A new method for the determination of pH in reversed micellar systems was proposed. The degree of dissociation (α) of Phenol Red in the systems was observed spectrophotometrically. The value of pH can be obtained by use of the Henderson-Hasselbach equation with the aid of pKa of Phenol Red measured by means of 31P-NMR in the systems containing phosphate buffer solutions. The method was applied to systems consisting of sodium octanoate, 1-hexanol, and water and some buffer solutions other than phosphate buffer solutions, and found to be effective within a wide pH range. Analysis of the fluorescence spectra of 8-anilino-1-naphthalene-sulfonic acid indicates that Phenol Red molecules are present at the interface between the water core and the 1-hexanol phase in reversed micelles. The hydrolytic reaction of p-nitrophenyl acetate was also studied kinetically and found to change slightly with pH.
  • Hiroko Yamaguchi, Hiroshi Kimura, Kazuo Yasukouchi
    1979 Volume 52 Issue 7 Pages 2056-2059
    Published: 1979
    Released: April 19, 2006
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    A new complex [(NH4)Cu3Cl4(C6H4O2)3⁄2·H2O] was synthesized from CuCl2, hydroquinone, and NH4Cl in an aqueous solution, and its structure was characterized on the bases of its UV, IR, and ESR spectra and TGA. On heating, this complex was stable up to 100 °C, but above 120 °C p-benzoquinone was released quantitatively. The complex was found to be a polynuclear copper(I) complex containing p-benzoquinone molecules and chlorides as ligands, and to be a charge-transfer complex in which π-electrons of the ring carbons of p-benzoquinone form coordinate bonds with Cu(I). The formation process of the complex was:
    3CuCl2+3/2(C6H6O2)+H2O+NH4Cl=(NH4)Cu3Cl4(C6H4O2)3⁄2·H2O+3HCl
  • Kazuo Tajima, Akio Nakamura, Takao Tsutsui
    1979 Volume 52 Issue 7 Pages 2060-2063
    Published: 1979
    Released: April 19, 2006
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    The dissociation constant of the complex formed in the mixed and very dilute surfactant solution of 3-(dodecylammonio)-propionate (NDA) and sodium alkylsulfates (C10, C12, C14) (SAS) was determined by measuring surface tension and adsorbed amounts of the solution. The composition in the surface and bulk phases did not coincide at the equimolar mixture. The adsorbed monolayer on the solution consists of the coadsorption of NDA–SAS complex (1:1) and free NDA, while the adsorption of free SAS was almost zero in various concentrations studied. Under these conditions the surface activity of the complex alone was obtained. The relationship between the surface activity and bulk concentration for each mixed solution was discussed in terms of relative adsorbability. The surface activity of the complex was one order of magnitude higher than that of NDA and two orders higher than that of SAS.
  • Hiroaki Ohya-Nishiguchi
    1979 Volume 52 Issue 7 Pages 2064-2068
    Published: 1979
    Released: April 19, 2006
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    A simple two-electrode cell for low-temperature electron spin resonance (ESR) measurements has been designed. A helical gold wire, the working electrode with large surface area (12 cm2), generated intra muros enough positive or negative ions to measure the ESR spectra of unstable radical ions at low temperatures. To test the electrolysis conditions of the cell, the ESR spectra of about 20 aromatic compounds have been observed at temperatures as low as −90 °C. It has been shown that the cell can be applicable to the compounds with half-wave potential of 1.5 to −3.7 V SCE, provided that the ions produced are not reactive. The experimental conditions of the dimer cation generation have also been checked in polar or nonpolar solvents.
  • Kiyoshi Otsuka, Kimiaki Tanaka, Akira Morikawa
    1979 Volume 52 Issue 7 Pages 2069-2073
    Published: 1979
    Released: April 19, 2006
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    The reaction between SO2 and MnO2 has been studied by measuring the consumption of SO2-gas and the infrared spectra of the wafer of MnO2. In the low-temperature range (<200 °C) the reaction is completed within one or two surface layers of MnO2, and the reaction products are the bidentate sulfato complex (C2V) and the sulfato complex in Td symmetry. In the high-temperature range, on the other hand, the reaction progresses deep into the bulk and can be described by this stoichiometric equation; MnO2+SO2→MnSO4. The catalysis of MnO2 for the SO2-induced isomerization of cis-2-butene is closely related to the formation of the sulfate ion. The initiation step proposed for the isomerization is a polarization of the charge-transfer complex of SO2 and butene under the influence of the strong electrostatic field caused by the generation of the surface sulfato complex.
  • Haruo Shizuka, Ichiro Seki, Toshifumi Morita, Takeshi Iizuka
    1979 Volume 52 Issue 7 Pages 2074-2078
    Published: 1979
    Released: April 19, 2006
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    Photolyses of 1,2,3,4-tetraphenylcyclobutanes (TPCB) at 254 nm in hydrocarbon solvents have been studied by means of fluorometry, nanosecond time-resolved spectroscopy, and measurements of the reaction quantum yields. The photolysis of TPCB originates from the S1(π,π*) state to give trans-stilbene nearly concertedly at higher temperatures (>200 K). Significant temperature and cis-effects were observed. The radiationless rate constants for the dissociation (kr) and the other radiationless (kn) processes decreased with lowering temperature. The value of kr for γ-1,t-2,t-3,c-4-TPCB at 300 K, for example, was 4.7 times greater than that for γ-1,t-2,c-3,t-4-TPCB. The Arrhenius parameters of the relaxation processes were also determined. No intramolecular excimer emission was observed.
  • Toshiji Kanaya, Yoshihiko Hatano, Masahide Yamamoto, Yasunori Nishijim ...
    1979 Volume 52 Issue 7 Pages 2079-2083
    Published: 1979
    Released: April 19, 2006
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    Equilibrium distribution of conformations of the series of compounds, α-(9-carbazolyl)-ω-[p-(methoxycarbonyl)benzoyloxy]alkanes in the ground state was calculated to explain the intramolecular fluorescence quenching of these compounds in a rigid medium. It was found that when the radius of active sphere R0 for the intramolecular fluorescence quenching is taken to be 8.8–9.0 Å, the experimentally observed chain length dependence of the fluorescence quenching can be well simulated by this calculation. The active sphere for the dynamic intermolecular fluorescence quenching in solution was also discussed to compare with that of the intramolecular fluorescence quenching.
  • K. Dwarakanath, D. N. Sathyanarayana
    1979 Volume 52 Issue 7 Pages 2084-2087
    Published: 1979
    Released: April 19, 2006
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    The infrared spectra of N-methylthiourea (NMTU) and its N-deuterated and S-methylated species were measured. Assignment of the infrared and Raman spectra of NMTU has been accomplished by correlation with thiourea and by use of infrared band shifts on N-deuteration as well as S-methylation. Normal coordinate analysis was performed for all the fundamentals of NMTU and NMTU-d3, the assignments obtained from the force field calculations being discussed in relation to those in other related thioureas and thioamides. The potential barriers to the internal rotations for the –NH2, –CH3, and –CN groups were estimated from the force constants.
  • Bejoy K. Seal, Ashok K. Mukherjee, Dulal C. Mukherjee
    1979 Volume 52 Issue 7 Pages 2088-2090
    Published: 1979
    Released: April 19, 2006
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    An alternative method for solving the Rose-Drago equation for the determination of equilibrium constants of molecular complexes has been developed. It yields well-defined K values even for certain systems in which the Rose-Drago procedure for solving the R-D equation is not satisfactory. Our method is based on the transformation of the Rose-Drago equation into one involving three variables and using two linear plots. In applying the method to a wide variety of experimental data, the calculated values of the equilibrium constant have been found to be in excellent agreement with those computed by the well-known iterative procedure. With good data, the calculated values are in good agreement with those from the Benesi-Hildebrand or some other modified plots.
  • Biswanath Mallik, Alpana Ghosh, T. N. Misra
    1979 Volume 52 Issue 7 Pages 2091-2096
    Published: 1979
    Released: April 19, 2006
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    The semiconductive properties of vitamin A (alcohol and acetate) on adsorption of various vapors have been studied. The adsorbed vapors increase the semiconduction currents by several orders of magnitude and decrease the semiconduction activation energies. Such change depends on the chemical nature and also on the amount of vapor adsorbed. Semiconducting vitamin A follows the three-constant equation
    σ(T)=σ0′exp(E⁄2kT0)exp(−E⁄2kT)
    where the conventional pre-exponential factor σ0 has been replaced by σ0′exp(E⁄2kTo) (the so called compensation effect). Here T0 and σo′ are constants for the substance and T0 is called the characteristic temperature. Various methods used for evaluating these constants have yielded consistent results with T0≈402 K and σ0′≈2.8×10−9 Ω−1 cm−1 for vitamin A alcohol and T0≈335 K and σ0′1.5×10−10 Ω−1 cm−1 for vitamin A acetate. Excellent correlation obtained between the relevant parameters in semiconducting vitamin A indicates that σ0 and E are physically related. Various models for conduction mechanism leading to compensation effect have been discussed. The measured activation energies on adsorption of same amount of various vapors show a linear relationship with the ionization potential of the adsorbed molecules suggesting that charge-transfer interaction is responsible for the semiconductivity enhancement.
  • Ali Boushehri, A. Abbaspour
    1979 Volume 52 Issue 7 Pages 2097-2098
    Published: 1979
    Released: April 19, 2006
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    A study of the Dufour effect was made for four different gas mixtures: SF6–N2O, SF6–N2, SF6–CO2, and He–CO2. Measurements were made at 300 K under 700 Torr. The values of the thermal diffusion factor were calculated for the above mixtures from experimental data on the basis of the thermodynamics of irreversible processes. A theoretical study was made also to calculate the thermal diffusion factor from kinetic theory.
  • Masao Hino, Yasuko Mikami
    1979 Volume 52 Issue 7 Pages 2099-2104
    Published: 1979
    Released: April 19, 2006
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    Infrared spectra of the systems of Na-Y zeolite–H2O, D2O, and HDO were measured. It was shown that there are three types of adsorbed water in the zeolite-water system. Type I: adsorbed in a state in which two hydroxyl bonds are highly non-equivalent; it gives absorptions at 3695, 3400, and 1645 cm−1, and is the same type as that on the Molecular sieve 13X. Type II: adsorbed in another state in which the bonds are nearly equivalent; it gives bands at 3610, 3540, and 1645 cm−1. Type II was more resistant to dehydration than Type I, and was irreversible for the back-adsorption of a small amount of water at room temperature, whereas Type I was almost completely reversible. Type III was observed for back-adsorption under this condition; it gives bands at 3635, 3500, and 1655 cm−1. Type III can be transformed into Type II by heat treatment at a temperature which varies depending on the amount of adsorbed water. The other bands were assigned as follows: Bands at 3750 and 3645 cm−1 correspond to stretching of surface structural OH, and that at 3240 cm−1 to overtone deformation of adsorbed water. The sites of adsorbed water molecules of Types I and II were discussed.
  • Takashi Ibusuki, Fumitoshi Toyokawa, Kazunari Imagami
    1979 Volume 52 Issue 7 Pages 2105-2109
    Published: 1979
    Released: April 19, 2006
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    The performance chracteristics of the permeation membrane device for the preparation of dilute standard gas mixtures developed by us was investigated in detail from the practical standpoint. By selecting a siliconerubber and a TFE Teflon for CO or CH4, and NO or SO2, respectively, the steady permeation state was rapidly attained. The small quantities of the gases permeating through the membranes were precisely determined within a relative standard deviation of 1% based on a pressure-differential method. It was confirmed that the permeation rates were reproducible after repeated membrane-temperature, gas-pressure, and gas-cycle changes during an experimental period of more than five months. By changing the gas pressure and the membrane temperature, and by introducing 1–2 1 min−1 of a diluent gas, N2 or air, standard gas mixtures containing 0.5–10 ppm of CO or CH4 and 0.05–0.7 ppm of NO or SO2 were easily obtained. The standard gases concerning CO, CH4, and NO were compared with those in cylinders prepared by the weighing method, and for SO2 the concentration of the gas was checked by the West-Gaeke method. A good agreement in concentration was observed for CO, CH4, and SO2; the discrepancy found for NO was explained in terms of the decrease in the NO concentration in the cylinder.
  • Takashi Nogami, Yoshio Nakano, Yoshiki Hasegawa, Yasuhiko Shirota, Hir ...
    1979 Volume 52 Issue 7 Pages 2110-2113
    Published: 1979
    Released: April 19, 2006
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    The decay of the charge-transfer (CT) absorption band in the tricyanovinylation reaction of N,N-dimethylaniline (DMA) with tetracyanoethylene (TCNE) in 1,2-dichloroethane was followed by the electronic absorption measurement. Primary hydrogen isotope effect was observed for the decay of the CT-band in line with the mechanism:
    [D+A\ ightleftharpoonsDA]→I
    I+D→NA
    NA+D\undersetslow→P
    D: DMA; A: TCNE; DA: CT-complex; I: zwitterionic intermediate; NA: p-(1,1,2,2-tetracyanoethyl)-N,N-dimethylaniline; P: p-tricyanovinyl-N,N-dimethylaniline.
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