Bulletin of the Chemical Society of Japan
Online ISSN : 1348-0634
Print ISSN : 0009-2673
ISSN-L : 0009-2673
Volume 57 , Issue 4
Showing 1-50 articles out of 59 articles from the selected issue
  • Kazuo Taniguchi
    1984 Volume 57 Issue 4 Pages 909-914
    Published: 1984
    Released: June 27, 2006
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    The phosphorus-, sulfur-, and chlorine-L2,3 emission spectra in various compounds are obtained using secondary excitation. The spectra are discussed from the point of view of chemical-state analysis. It should be noted that the spectra of a highly ionic bond reveal scarcely no influence of the cations. However, the spectra with a covalent character are complex as a result of the molecular orbital generated with the covalent bond. The spectral features are influenced by the chemical condition of the surrounding atoms and are sensitive to oxygen and hydrogen.
  • Kazuo Taniguchi
    1984 Volume 57 Issue 4 Pages 915-920
    Published: 1984
    Released: June 27, 2006
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    The phosphorus-, sulfur- and chlorine-Kβ spectra in various compounds are obtained by means of secondary excitation using a simple quasi-two-crystal X-ray spectrometer. The spectra thus obtained change depending upon the chemical state. The spectra are discussed from the point of view of chemical-state analysis. The spectral features are especially influenced by the hydrogen and oxygen of the ligand. The peak on the lower-energy side appears to be related to the oxygen, and the peak grows with an increase in the oxidation number. The spectrum gives information on the structural formula.
  • Kazuo Taniguchi
    1984 Volume 57 Issue 4 Pages 921-925
    Published: 1984
    Released: June 27, 2006
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    The oxygen Kα spectra of the oxyanions in different salts are obtained by secondary excitation. The obtained spectra are affected by the cations, the central atom, and the chemical-bond condition. Generally, there are four components in the spectra, but one small component may originate from the anomalous reflection of an analyzing crystal. The spectra are discussed from the point of view of chemical-state analysis.
  • Hatsue Tamura, Toshikazu Ibata, Kazuhide Ogawa
    1984 Volume 57 Issue 4 Pages 926-931
    Published: 1984
    Released: June 27, 2006
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    The crystal structures of endo- and exo-adducts of 1-methoxy-2-benzopyrylium-4-olate with N-methylmaleimide have been determined by means of X-ray analysis. The colorless crystals of the endo-adduct are orthorhombic, with the space group P212121 and with a=14.432(3), b=11.874(2), c=7.762(1) Å, and Z=4. The colorless crystals of the exo-adduct are monoclinic, with the space group P21/a and with a=13.381(2), b=12.825(1), c=7.4793(4) Å, β=92.13(1)°, and Z=4. The structures were deduced by a direct method and refined by a block-diagonal least-squares technique. The final R values for the endo- and exo-adducts are 0.047 for 1160 observed reflections and 0.067 for 1986 observed reflections respectively. The configurations of the endo- and exo-adducts are coincident with those assigned on the basis of the NMR data. The observed values of the ring-current effect on the N-methyl chemical shift of the endo-adduct and the coupling constants of the vicinal methine protons of both adducts are in good agreement with the ones calculated on the basis of the present X-ray crystal-structure analysis.
  • Masahiro Kohno, Hiroaki Ohya-Nishiguchi, Kiyoko Yamamoto, Tosio Sakura ...
    1984 Volume 57 Issue 4 Pages 932-937
    Published: 1984
    Released: June 27, 2006
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    The ESR spectra of three paramagnetic species trapped in single crystals of chloro(5,10,15,20-tetraphenylporphyrinato)cobalt(III) (CoIIICl(tpp)), have been observed at 4.2 K to room temperature. Based on the ESR parameters obtained, the paramagnetic species have been identified as two CoII(tpp) with different axial ligand effects and a previously reported cation radical, [CoIII(tpp)]2+·(Cl)2. A correlation diagram among g, A, and axial ligation made from published data of cobalt(II) complexes has been successfully used for identification of the two trapped CoII(tpp) species: one is four-coordinate CoII(tpp) and the other five-coordinate CoIIX(tpp) in which X is presumably Cl. Their electronic and molecular structures are discussed according to McGarvey’s theory. Finally, the formation mechanism of the three paramagnetic species in CoIIICl(tpp) is discussed, based on the results obtained from the single crystalline ESR measurements.
  • Toshio Okuhara, Tomoo Kimura, Kenji Kobayashi, Makoto Misono, Yukio Yo ...
    1984 Volume 57 Issue 4 Pages 938-943
    Published: 1984
    Released: June 27, 2006
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    Ru/Al2O3 catalysts prepared from [Ru3(CO)12] and from RuCl3 were characterized by chemisorption of H2 and CO, and by infrared measurement of adsorbed CO. By using these catalysts, the effect of the dispersion on the activity and selectivity in CO hydrogenation was studied. Ru/Al2O3 catalysts prepared from [Ru3(CO)12] showed high dispersions (>80%), and were more active and selective for the production of olefins in the CO hydrogenation than Ru/Al2O3 catalysts prepared from RuCl3. However, the distribution of product hydrocarbons was not sensitive to the Ru dispersion. Infrared study of adsorbed CO revealed that twin-type CO (Ru(CO)2) as well as linear-type CO (Ru–CO) was present on each Ru/Al2O3. The twin-type CO was more strongly held and was less reactive to hydrogenation. For each series of Ru/Al2O3, the turnover frequency increased as the dispersion decreased. This change has been explained by the poisoning effect of the twin-type CO. The higher activity of Ru/Al2O3(A) was ascribed to the lower concentration of the twin-type CO on the surface.
  • Katashi Takahashi, Fudeko Tanaka, Kinsi Motomura
    1984 Volume 57 Issue 4 Pages 944-947
    Published: 1984
    Released: June 27, 2006
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    In order to obtain some information regarding the behavior of amino acids at interfaces, the monolayers of N-acyl L-α-amino acids with alkyl side chains on water have been investigated by measuring the surface pressure vs. area curves at various temperatures. It has been found that N-octadecanoylglycine and N-octadecanoylalanine form the condensed monolayers over the whole surface pressure range measured, N-octadecanoylvaline forms the expanded monolayer at a lower surface pressure, and N-octadecanoylleucine and N-octadecanoylisoleucine collapse at high surface pressures. From the experimental results, it has been concluded that the amino acid residue with a long side chain occupies a large area at the air/water interface and interferes with the condensation of acylamino acid monolayer. It has also been found that the methyl esterification of amino acid residue makes the monolayer state unstable although it produces less significant effect than the increase in the alkyl chain length of amino acid residue.
  • Tsuyoshi Arakawa, Midori Takakuwa, Jiro Shiokawa
    1984 Volume 57 Issue 4 Pages 948-951
    Published: 1984
    Released: June 27, 2006
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    The adsorption of water, methanol, and acetic acid on an activated Eu(III) ion-exchanged mordenite(Eu–M) has been studied by the measurement of the fluorescence of the Eu2+ ion which was produced by the dehydration at 500 °C. The emission peak of the Eu2+ ion sifted to a shorter wavelength on exposure to water and other simple molecules. The magnitude of the shift was correlated to the specific dielectric constant of the adsorbate. The quantum yield for the Eu2+ emission band after gas adsorption decreased in all cases. Also, the lifetime in the Eu2+-adsorbate system was shorter than that in an activated Eu–M sample. The rate constants for the radiationless transitions were more sensitive to the nature of the adsorbates, and the order of the quenching power was H2O>D2O>CH3OH.
  • Takeo Ozawa
    1984 Volume 57 Issue 4 Pages 952-955
    Published: 1984
    Released: June 27, 2006
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    Crystallization of poly(tetrafluoroethylene) was observed by differential scanning calorimetry at constant cooling rates. A method for kinetic analysis of thermoanalytical data of nonisothermal crystallization was applied to analyze the data, and it was elucidated that poly(tetrafluoroethylene) crystallizes one-dimensionally from preexisting nuclei, which are presumably impurities. These results are in accordance with electron-microscopic observation of the crystalline morphology of poly(tetrafluoroethylene), which consists of band-like or star-like crystallites. The kinetic parameters, especially the temperature dependence of the linear growth rate, were estimated.
  • Makio Iwahashi, Kazuhide Ashizawa, Miyuki Ashizawa, Yoshihide Kaneko, ...
    1984 Volume 57 Issue 4 Pages 956-959
    Published: 1984
    Released: June 27, 2006
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    The polymorphic relationship between optically active (R)- and for racemic (RS)-forms of 1,2-distearin and 1,2-dipalmitin were studied by X-ray diffraction, infrared spectrum, and the thermal analysis. These glycerides have two crystalline forms, α and β, wherein α is metastable and β is stable under ordinary conditions. The α→β transformation for the (RS)-1,2-distearin crystal was extremely slow as compared with that for the (R)-form crystal, implying that the β-form crystal of (RS)-1,2-distearin is an eutectic mixture of small (R)- and (S)-crystals while the α-form crystal of (RS)-1,2-distearin is composed of a replacement type solid solution of (R)- and (S)-1,2-distearin molecules. Almost the same results were obtained with 1,2-dipalmitin, for which the rate of α→β transformation is higher than that for the 1,2-distarin, probably because of a higher mobility of this compound.
  • Tomohiro Ohta
    1984 Volume 57 Issue 4 Pages 960-966
    Published: 1984
    Released: June 27, 2006
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    Reactions of hydroxyl radicals with 1,3-butadiene and cis-1,3-pentadiene in the presence of oxygen were studied in the gas phase. Two OH radical sources were employed; photolysis of H2O2 at 254 nm and photolysis of methyl nitrite at 360 nm. In the reaction system for 1,3-butadiene, furan was detected besides acrylaldehyde and in the cis-1,3-pentadiene system, 2-methylfuran was detected besides acetaldehyde, acrylaldehyde, and crotonaldehyde by gas chromatographic analysis. Approximate yields of furan and 2-methylfuran were 5.3–6.7% and 6.7–8.4%, respectively, which were sensitive to the conditioning of the surface of reactor but insensitive to hydroxyl radical sources, the surface material of reaction vessel or the surface to volume ratio of reactors. The yields of aldehydes were also measured. Isotopic labeling experiment with 18O2 by use of mass spectrometry indicated that abstraction of vinyl–hydrogen from 1,3-butadiene and cis-1,3-pentadiene occurred about 3% of the time. Photooxidation of 2,5-dihydrofuran initiated with ·OH radicals was also discussed to explain the increase of furan in the dark after the irradiation.
  • Shozo Uryu, Makoto Aratono, Michio Yamanaka, Kinsi Motomura, Ryohei Ma ...
    1984 Volume 57 Issue 4 Pages 967-971
    Published: 1984
    Released: June 27, 2006
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    The surface tension of the aqueous solution of 2-(octylsulfinyl)ethanol and decylammonium chloride mixture has been measured by changing the total molality and composition of surfactants at 298.15 K under atmospheric pressure. It has been observed that the surface tension decreases with increasing the total molality at a constant composition and with decreasing the composition of decylammonium chloride at a constant total molality. Further the surface tension vs. total molality curve has been found to have a break point at a relatively low concentration. The thermodynamic equations have been developed so as to be applicable to the adsorption of nonionic–ionic mixture and used to calculate the surface density and the surface composition. It has been shown that the surface density vs. molality curve has the discontinuous change caused by the transition from a gaseous to an expanded film. By drawing the two-dimensional phase diagram and comparing it with the diagrams of the ionic–ionic surfactant mixtures, it has been proved that the shape of the phase diagram is affected greatly by the difference in the surface activity between the two surfactants.
  • Kazuhiko Nakayama, Takashi Komorita, Yoichi Shimura
    1984 Volume 57 Issue 4 Pages 972-979
    Published: 1984
    Released: June 27, 2006
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    The magnetic circular dichroism (MCD) spectra of K2PtCl4 and K2PdCl4 have been carefully remeasured over the visible-near UV region. The examination of the electronic absorption and the MCD spectra together with their Gaussian analyses strongly suggests that the band of K2PtCl4 at 30.3×103 cm−1 contains both Γ5(1Eg) and Γ3(1B1g)←Γ1(1A1g) transitions, and the band of K2PdCl4 at 21.1×103 cm−1 all three spin-allowed d-d transitions. The separation of the Γ2(1A2g) and Γ5(1Eg) excited states is considerably large with K2PtCl4 as compared with K2PdCl4. The MCD for the high-intensity absorption bands in K2PtCl4 is different from that reported previously. On the basis of new MCD result, the bands at 43.3 and 46.6×103 cm−1 have been assigned to d-p transitions, a2u(pz)←a1g(dz2) and eg(dxz,yz), respectively.
  • Abdul Wasey, Raj K. Bansal, Masatada Satake, Bal K. Puri
    1984 Volume 57 Issue 4 Pages 980-983
    Published: 1984
    Released: June 27, 2006
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    A method is proposed for the extraction of lead, zinc, and cadmium as their diethyldithiocarbamates into molten naphthalene. These complexes are quantitatively extracted into molten naphthalene. After extraction, the solidified naphthalene containing the colorless complex of each of the above metals is dissolved in chloroform and the metal is replaced by copper(II) to develop a yellow color of copper(II) diethyldithiocarbamate. The absorbance is measured at 440 nm. Beer’s law is obeyed in the concentration range of 5.0–130.0 μg for lead, 3.0–60.0 μg for zinc, or 5.0–100.0 μg for cadmium in 10 ml of the final solution. The molar absorptivities (1 mol−1 cm−1) and Sandell sensitivities (μg/cm2) for lead, zinc, and cadmium are calculated to be 1.15×104, 0.0098, 1.11×104, 0.0059, and 1.15×104, 0.0098 respectively. Solutions containing 45.0μg of lead, 40.0μg of zinc, and 43.0μg of cadmium separately gave mean absorbances of 0.250, 0.620, and 0.440 with standard deviations of 0.0027, 0.0059, and 0.0038, respectively. Conditions have been decided for the determination of lead, zinc, and cadmium in some alloys and synthetic mixtures.
  • Norikazu Ueyama, Satoru Ueno, Michio Nakata, Akira Nakamura
    1984 Volume 57 Issue 4 Pages 984-988
    Published: 1984
    Released: June 27, 2006
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    The 2Fe–2S ferredoxin model complexes of two peptide ligands, Z–L-Ala–L-Cys–OMe (Z=benzyloxycarbonyl) and Z–L-Cys–L-Ala–L-Ala–L-Cys–OMe, were synthesized from [NMe4]2[Fe2S2Cl4] by addition of triethylamine. These were characterized by absorption, CD, and MCD spectra in dimethyl sulfoxide or N,N-dimethylformamide. Incorporation of inorganic sulfide to the iron(III) complex, [Fe(Z–cys–Ala–Ala–cys–OMe)2] (rubredoxin models), results in the selective formation of a 2Fe–2S cluster by a controlling ability of the peptides.
  • Kyoko Nakabayashi, Kaoru Doi, Masaaki Kojima, Junnosuke Fujita
    1984 Volume 57 Issue 4 Pages 989-996
    Published: 1984
    Released: June 27, 2006
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    Several cobalt(III) complexes of the [Co(apS or apSe)(N4)]2+ type were prepared, where apS and apSe denote chiral 1-amino-2-propanethiolate-N,S and 1-amino-2-propaneselenolate-N,Se ligands, respectively, and N4 is (en=ethylenediamine)2, (R-chxn=(R,R)-1,2-cyclohexanediamine)2, or tren=tris(2-aminoethyl)amine. Their circular dichroism (CD) spectra were compared with one another and with those of complexes containing such ligands as achiral 2-aminoethanethiolate-N,S, 2-aminoethaneselenolate-N,Se or chiral 1-amino-2-propanolate-N,O (apO). The vicinal CD curves of S-apS obtained from CD spectra of the en and R-chxn complexes are similar and very large in magnitude in the d-d absorption band region. These curves are very similar to the CD spectrum of [Co(S-apO)(NH3)4]2+. The vicinal CD curve of S-apSe shows a similar pattern, but the magnitude is smaller than those of the S-apS and S-apO ligands. The vicinal effect of the protonated S-apSH ligand is much smaller compared with that of its conjugate base (S-apS) ligand. The tren complexes of S-apS and S-apSe exhibit CD spectra fairly different from the vicinal CD curves of the respective ligands in the d-d absorption band region.
  • Koji Araki, Masato Sakuma, Shinsaku Shiraishi
    1984 Volume 57 Issue 4 Pages 997-1002
    Published: 1984
    Released: June 27, 2006
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    Monosaccharides were oxidatively degraded by FeCl3 with irradiation of a near-UV to visible light under aerobic atmosphere. D-Fructose and D-arabinose were degraded to D-erythrose in a yield of more than 80 mol%. D-Glucose and D-mannose were at first degraded to D-arabinose, which was subsequently degraded to D-erythrose. While, D-ribose was directly degraded to D-erythrose and D-glyceraldehyde. The degradation processes were selective, and these reactions were shown to proceed via formation of an Fe(III)–monosaccharide complex. The kinetic data and other features of these reactions were also discussed.
  • Masatatsu Suzuki, Hajime Kanatomi, Youichi Demura, Ichiro Murase
    1984 Volume 57 Issue 4 Pages 1003-1007
    Published: 1984
    Released: June 27, 2006
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    The dinucleating ligand, 2,6-bis[bis(2-pyridylmethyl)aminomethyl]-4-methylphenol](Hbpmp), formed two types of dinuclear copper(II) complexes, [Cu2(bpmp)X2]n+(X=Cl, N3 py(pyridine), or Him(imidazole), and n=1 or 3), and [Cu2(bpmp)X]2+(X=CH3COO or im). On the basis of the dinucleating nature of the ligand (bpmp), the elemental analyses and the conductivity measurements in acetonitrile, it is concluded that the complexes have dimeric unit of [Cu2(bpmp)X2]n+ or [Cu2(bpmp)X]2+. In [Cu2(bpmp)X2]n+ type complexes, two copper(II) ions are linked only by a single phenolate bridge. Magnetic susceptibilities of those complexes obey Curie-Weiss law in the temperature range 80–300 K with the Weiss constants ≈−4 K, indicating that weak antiferromagnetic interactions are present in these complexes. In [Cu2[bpmp)X]2+ type complexes, however, two copper(II) ions are bridged by phenolate and acetate, or phenolate and imidazolate. Cryomagnetic measurements of the acetato and the imidazolato complexes showed antiferromagnetic interactions with the −2J values of 82 and 66 cm−1, respectively. All the complexes exhibited absorption bands at 20000–22000 cm−1 except for the azido complex. The origin of those bands are discussed.
  • Yoneichiro Muto, Tadashi Tokii, Kiyohiko Chijiwa, Michinobu Kato
    1984 Volume 57 Issue 4 Pages 1008-1011
    Published: 1984
    Released: June 27, 2006
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    Three complexes with the empirical formula of Cu(RCOO)2·L, where R=CH3, CH2Cl, or CHCl2 and L=3,5-dichloropyridine, were prepared and studied. These complexes display the antiferromagnetic behavior typical of dimeric copper(II) carboxylates. The singlet-triplet splitting energy (−2J) is 349 cm−1 for the acetate, 340 cm−1 for the monochloroacetate and 312 cm−1 for the dichloroacetate. Comparison of their magnetic and electronic spectral properties with those of the corresponding pyridine adducts indicates that both the −2J and \ ildeνmax(absorption maximum of Band I) values of the respective 3,5-dichloropyridine adducts are higher than those of the pyridine adducts. The influence of the pyridines on both the magnetic and spectral properties was discussed.
  • Noriaki Ishio, Yukio Nakamura, Seichi Okeya
    1984 Volume 57 Issue 4 Pages 1012-1020
    Published: 1984
    Released: June 27, 2006
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    Reactions of trans-chloro(cyanomethyl)bis(triphenylphosphine)palladium(II), trans-[PdCl(CH2CN)(PPh3)2] (1), with an equimolecular amount of Tl(β-dik) (β-dik=etac, acac, tfac, bzac, and dbm) in dichloromethane afforded the O,O′-chelated β-dik complexes [Pd(CH2CN)(β-dik)(PPh3)] (3). Hydrogen peroxide oxidation and chloride abstraction by AgClO4 or AgBF4 of 1 gave the neutral [PdCl(CH2CN)PPh3]n and the cationic [Pd(CH2CN)(PPh3)2]mXm (X=ClO4 or BF4), respectively, from either of which complexes 3 were also obtained by the reactions with the β-dik anions. No pure product corresponding to 3 was isolated by a similar treatment of 1 with Tl(hfac). On the other hand, chloro(cyanomethyl){1,2-bis(diphenylphosphino)ethane}palladium(II), [PdCl(CH2CN)(dppe)] (2), reacted only with Tl(hfac) in refluxing acetone to give the cationic [Pd(CH2CN)(dppe)]2(hfac)2, which was also derived from 2 via [Pd(CH2CN)(dppe)]2X2 (X=ClO4 or BF4).
  • Hideo Doine, Yasuhisa Ikeda, Hiroshi Tomiyasu, Hiroshi Fukutomi
    1984 Volume 57 Issue 4 Pages 1021-1025
    Published: 1984
    Released: June 27, 2006
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    The anation reactions in [UO2(dmso)5]2+ (dmso=dimethyl sulfoxide) and [UO2(hmpa)4]2+ (hmpa=hexamethylphosphoric triamide) ions by SCN and N3have been studied by the stopped-flow method in DMSO and acetonitrile. For the anation reactions of [UO2(dmso)5]2+ in DMSO as a medium, the pseudo-first order rate constant(kobsd) is expressed by kobsd={k−1+(k1+k−1Kos[X]}/(1+Kos[X]), where X=SCN and [UO2(dmso)5]2+ for the anation reactions by SCN and N3, respectively. The values of k1, k−1, and Kos at 25 °C are 2.06×102 s−1, 62 s−1, 35 M−1 (M=mol dm−3), and 7.60×102 s−1, 0.0 s−1, and 41 M−1 for the SCN and N3 anation reactions in [UO2(dmso)5]2+, respectively. For the anation reaction in [UO2(hmpa)4]2+ by SCN, the pseudo-first order rate constant was found to be proportional to the concentrations of [UO2(hmpa)4]2+ and free HMPA: kobsd=kf[UO2(hmpa)42+]+kb[HMPA]free. The values of kf and kb at 25 °C are 9.70×103 M−1 s−1 and 9.05×102 M−1 s−1, respectively. The equilibrium constants for the titled reactions were also measured at 25 °C: K=85 M−1for the anation reaction of [UO2(dmso)5]2+ by SCN in DMSO and K’=42.7 for the SCN anation reaction in [UO2(hmpa)4]2+ in acetonitrile. The kinetic results suggest that the anation reactions in uranyl complexes proceed through an associative or an associative interchange mechanism.
  • Yuzuru Masuda, Masayuki Hoshi, Akira Arase
    1984 Volume 57 Issue 4 Pages 1026-1030
    Published: 1984
    Released: June 27, 2006
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    Trialkylboranes prepared from alkenes via hydroboration react with lead(IV) acetate azide in dichloromethane at −25 °C to form the corresponding azidoalkanes in a one-pot manner. One or two of the alkyl groups of trialkylboranes are utilized in the reaction. For example, 1-azidohexane is afforded from 1-hexene in 50% yield based on the alkene employed.
  • Hiroki Kondo, Kanzi Morita, Tatsuya Kitamikado, Junzo Sunamoto
    1984 Volume 57 Issue 4 Pages 1031-1034
    Published: 1984
    Released: June 27, 2006
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    The β-elimination reaction of methyl 3-chloroalaninate has been investigated in the absence and presence of pyridoxal methochloride (2) or pyridoxal (3). Apparently, compound 2 was about twice as effective as 3 in the catalytic reaction that proceeds via a Schiff base of substrate and 2 or 3. The pH-rate profiles for the catalytic reaction with 2 and 3 were analyzed in terms of ionization of the various Schiff base species present in solution. It was found that the reactivity of the Schiff base decreases as the ionization of the molecule progresses. The reaction mechanism and its relevance to the catalysis of pyridoxal phosphate–dependent enzymes are discussed.
  • Makoto Nitta, Tomoshige Kobayashi
    1984 Volume 57 Issue 4 Pages 1035-1039
    Published: 1984
    Released: June 27, 2006
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    The thermal reactions of [Fe2(CO)9] or the photochemical reactions of [Fe(CO)5] with organic azides and an azirine in protic media have been investigated. The thermal reaction of azidobenzene (1) with [Fe2(CO)9] in methanol under mild conditions gave aniline and methyl phenylcarbamate, along with N,N′-diphenylurea, while in the presence of water, 1 afforded aniline and N,N′-diphenylurea, in good combined yield. Similarly, the thermal reaction of α-azidostyrene (4) with [Fe2(CO)9] in methanol gave methyl 1-phenylvinylcarbamate and acetophenone which could be derived from the corresponding enamine, while in the presence of water, 4 gave only acetophenone in good yield. The photoirradiation of [Fe(CO)5] with 1 or 4 also gave results similar to the [Fe2(CO)9]-induced reaction. However, the thermal reaction of 3-phenyl-2H-azirine (5) with [Fe2(CO)9] in methanol gave 2,5-diphenylpyrazine in low yield, in addition to acetophenone and methyl 1-phenyl-vinylcarbemate, although 5 afforded only acetophenone in the presence of water. The reaction pathways for the formation of the products are discussed on the basis of the formation of a complexed nitrene intermediate, reduction of which induces amine or enamine and carbonyl insertion to yield an organic isocyanate in protic media.
  • Kaoru Harada, Shozo Shiono
    1984 Volume 57 Issue 4 Pages 1040-1045
    Published: 1984
    Released: June 27, 2006
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    Two isomers(E and Z) of benzoin oxime and 2-hydroxy-1-phenyl-1-propanone oxime were catalytically hydrogenated by using palladium on charcoal and erythro amino alcohols were obtained in about 80% diastereomeric excess. The syn-anti isomerization of these oximes in the presence of palladium on charcoal was also studied in connection with the stereoselectivity of the catalytic hydrogenation of the oximes.
  • Susumu Okazaki, Akito Kurosaki, Shinzo Suzaki
    1984 Volume 57 Issue 4 Pages 1046-1051
    Published: 1984
    Released: June 27, 2006
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    Studies showed that the ternary oxide having the atomic ratio of Ti/Si/Al=47.5/47.5/5 exhibited a high catalytic activity for cumene cracking after a surface fluorination using 1 wt% hydrofluoric acid. The catalytic activity for CH3OH conversion into olefins was highly dependent on the preparation method. That is, the ternary mixed oxide promoted olefin formation slightly when the mixed oxide was prepared only by coprecipitation. Surface treatment, using gaseous CF3Cl was effective in enhancing catalytic activity. Although the binary oxide, TiO2–Al2O3, itself, was catalytically inactive for olefin formation, TiO2–Al2O3 prepared by coprecipitation became active after the treatment using CF3Cl. Such an enhancement was found also for the ternary oxide, TiO2–SiO2–Al2O3, and is ascribable to increased acid strength, as determined by NH3 adsorptions at various temperatures. The XPS measurements showed that F atoms introduced into mixed metal oxides by the fluorination using CF3Cl, selectively combined with Al atoms on the mixed oxides prepared by coprecipitation. The XPS measurements of the mixed oxides before and after fluorination using CF3Cl showed that the coprecipitation preparation is more preferable than the impregnation method in maintaining surface composition during fluorination.
  • Hideki Matsui, Akihiro Yoshino, Tadayoshi Yoshida, Kensuke Takahashi
    1984 Volume 57 Issue 4 Pages 1052-1054
    Published: 1984
    Released: June 27, 2006
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    Thermodynamical parameters for the restricted rotation of the title carbanions have been obtained by means of the DNMR techniques. The activation energies and entropies thus obtained are about 93 kJ mol−1 and 95 J K−1 mol−1 for the two carbanions studied; these values are larger than those of the similar rotations observed in arylmethanide ions. The methylene rotation is thus extremely hindered in these carbanions.
  • Yasuyuki Takeda, Tsuyoshi Namisaki, Shizuo Fujiwara
    1984 Volume 57 Issue 4 Pages 1055-1057
    Published: 1984
    Released: June 27, 2006
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    In order to obtain enthalpy (ΔH1°) and entropy changes (ΔS1°) for overall extraction reactions of 15-crown-5 (15C5) with alkali metal picrates between benzene and water, and those (ΔH2° and ΔS2°) for partition of 15C5 itself, overall extraction equilibrium constants of 1:1:1 complexes of 15C5 with the salts and distribution coefficients of 15C5 were determined at 20, 30, 35, and 40 °C. The ΔH1° and ΔS1° values of 15C5 for the alkali metals are all negative. Both the ΔH2° and ΔS2° values are positive. In general, the ΔH2° and ΔS2° values play a major role in determining the magnitude of ΔH1° and ΔS1° values, respectively, except the case of entropy change for the potassium system. Enthalpy (ΔH4°) and entropy changes (ΔS4°) for ion-pair extractions of 15C5-alkali metal ion complexes by picrate anions were calculated by using the ΔH1° and ΔS1° values, and the literature values for complex-formation reactions of 15C5 with alkali metal ions in water. Both ΔH4° and ΔS4° values vary with the alkali metal ion held in the 15C5 cavity. The ΔH4° and ΔS4° values for Na+, Rb+, and Cs+ are all negative, whereas those for K+ are all positive.
  • Atsushi Togashi, Yoshio Matsunaga
    1984 Volume 57 Issue 4 Pages 1058-1060
    Published: 1984
    Released: June 27, 2006
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    Phase diagrams were prepared for the fifteen binary systems consisting of pyrene as an electron donor and N-alkyl-2,4,6-trinitroanilines as electron acceptors. The thermal stability of the orange 1:1 complex between pyrene and the unsubstituted 2,4,6-trinitroaniline (mp 236 °C) is drastically decreased by N-alkylation; e.g., the N-pentyl-2,4,6-trinitroaniline complex melts at 97 °C. The systems with the N-hexyl and N-heptyl derivatives give two peritectics each, while most of the higher homologues produce a single peritectic or a eutectic. Unstable red solids were formed on rapid cooling of the molten pyrene–N-hexyl-2,4,6-trinitroaniline mixtures. This red complex becomes relatively more stable with increase of the alkyl chain length, possibly because of the enhanced tendency for chain alignment. In the systems with the N-pentadecyl and N-heptadecyl derivatives, the stable existence of the red 1:1 complex could be demonstrated.
  • Satoshi Tachiyashiki, Hideo Yamatera
    1984 Volume 57 Issue 4 Pages 1061-1066
    Published: 1984
    Released: June 27, 2006
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    The kinetics of the racemization and dissociation of [Fe(phen)3]2+ were investigated in the presence of a series of 1-alkanesulfonate ions (n-CnH2n+1SO3, n=2,4,6,…,14). The racemization rate increased, while the dissociation rate decreased, gradually as a function of the alkanesulfonate concentration at low concentrations of each alkanesulfonate. With alkanesulfonates of n≥8, the second phase of rate changes, i.e., steep increases in both rates, were observed at higher concentrations. The gradual initial changes in the rates were explained in terms of the formation of the 1:1 aggregate of the complex cation with the alkanesulfonate ion caused by hydrophobic interaction. The formation constant (mol−1 dm3) increased almost exponentially from 4 (n=4) to 770 (n=14) with the increase in the alkyl-chain length, the energy of the hydrophobic interaction of the complex cation and the alkanesulfonate anion being 0.9 kJ mol−1 per methylene group of the latter. The second phase of the rate changes were explained in terms of the formation of the 1:m aggregate of the complex cation with the alkanesulfonate ions. The rate behavior of the hydrophobic aggregates is discussed in connection with the reaction mechanisms of the racemization and dissociation of [Fe(phen)3]2+.
  • Satoshi Tachiyashiki, Hideo Yamatera
    1984 Volume 57 Issue 4 Pages 1067-1069
    Published: 1984
    Released: June 27, 2006
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    The kinetics of the racemization of [Ni(phen)3]2+ were investigated in the presence of 1-alkanesulfonate ions (n-CnH2n+1SO3; n=8, 10, 12, and 14). The racemization rate decreased with the increase in the alkanesulfonate concentrations in the region of low sulfonate concentrations; then, in the region of higher concentrations, it began to increase, but it never exceeded the rate in water. The rate changes at low and high alkanesulfonate concentrations were related to the formation of the 1:1 and 1:m aggregates of the complex ion with alkanesulfonate ions respectively. A comparison of the aggregate formation constants of [Ni(phen)3]2+ with those of [Fe(phen)3]2+ confirmed that hydrophobic interaction is responsible for the aggregate formation. The energy of hydrophobic interaction between [Ni(phen)3]2+ and an alkanesulfonate ion was estimated to be 1.0±0.1 kJ mol−1 per methylene group of the latter. The kinetic behavior of the racemization of [Ni(phen)3]2+ in the aggregates was also compared with those of the racemization and dissociation of [Fe(phen)3]2+, and it was discussed in relation to the racemization mechanism of [Ni(phen)3]2+. The reaction rates of the complexes in D2O solutions were also reported.
  • Satoshi Tachiyashiki, Hideo Yamatera
    1984 Volume 57 Issue 4 Pages 1070-1075
    Published: 1984
    Released: June 27, 2006
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    The kinetics of the racemization and dissociation of [Fe(phen)3]2+ (phen=1,10-phenanthroline) and [Fe(bpy)3]2+ (bpy=2,2′-bipyridine) was investigated in aqueous sodium dodecyl sulfate (SDS) solutions. The racemization and dissociation rates of the complexes increased with the increase in the SDS concentration to reach limiting values at concentrations above the critical micelle concentration (cmc). The rate changes occurring below the cmc were explained in terms of the formation of at least three kinds of premicellar aggregates of the complex ion with dodecyl sulfate ions. In the region slightly above the cmc, where the concentration of the complex ion is larger than that of the micelle, the rates continued to increase with the increase in the micellar concentration, suggesting that the complex ions interacted with the micelles. A comparison of the kinetic behavior in aqueous micellar solutions with that in organic solvents revealed that the complexes were located inside the micelle–water interface. The mechanisms of the acceleration in the micelle were discussed.
  • Junko Akashi, Yoshio Uchida, Tomoko Kojima, Motomi Katada, Hirotoshi S ...
    1984 Volume 57 Issue 4 Pages 1076-1078
    Published: 1984
    Released: June 27, 2006
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    The chemical effects of the 6Li(n,α)T reaction in lithium tris(oxalato)ferrate(III) crystals were examined by means of Mössbauer spectroscopy. Neutron irradiations were carried out under different conditions in order to clarify the mechanism of the effects. The reduced iron(II) species observed in the spectrum of Li3[Fe(C2O4)3]·4.5H2O, subjected to neutron irradiation (8.6×1015 n cm−2) at 200 K, shows a larger Q.S. value than that in the spectrum of the sample neutron-irradiated at an ambient temperature (300–320 K) in a reactor, suggesting that the initially produced iron(II) species changes into another iron(II) species during the irradiation at the ambient temperature. A species identical with the initial iron(II) species produced in the neutron irradiation was found to be prepared by the pyrolysis of Li3[Fe(C2O4)3]·4.5H2O. A comparison of neutron-irradiated hydrous and anhydrous Li3[Fe(C2O4)3] suggests that the change in the iron(II) species is influenced by the existence of crystal water.
  • Nobuatsu Watanabe, Hidehiko Ohara, Tsuyoshi Nakajima
    1984 Volume 57 Issue 4 Pages 1079-1082
    Published: 1984
    Released: June 27, 2006
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    An aluminum fluoride film covered by graphite fluoride on metallic aluminum was prepared by reaction in the ternary system of aluminum, graphite and fluorine gas at 450–550 °C. The film consisted of a large amount of aluminum fluoride covered by thin graphite fluoride layers. The contact angle of a water drop on the film was around 120°, which decreased to 85–95° during 45 d probably due to reaction with moisture and/or water drop. Almost no oxygen was detected in the film. The film formation would be based on the reduction of oxide layer on aluminum by carbon radical produced by thermal decomposition of graphite fluoride.
  • Masamitsu Kataoka, Hirotoshi Hemmi, Tomihito Kambara
    1984 Volume 57 Issue 4 Pages 1083-1086
    Published: 1984
    Released: June 27, 2006
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    Trace amounts of molybdenum(VI) can be determined by the use of their catalytic effects on the peroxoborate–iodide redox reaction in acidic medium. The indicator reaction is transformed to a Landolt reaction by the addition of ascorbic acid into the reaction mixture, i.e., the iodine produced by the reaction is immediately reduced by ascorbic acid. The end of the induction period of the Landolt process was fluorometrically detected by the aid of disappearence of fluorescence of Rhodamine B. Trace determination of molybdenum(VI) was carried out by employing the linear relationship between the reciprocal of induction period and catalyst concentration. The most suitable concentrations of sodium peroxoborate, potassium iodide, and hydrochloric acid in the reaction mixture were found to be 9 mM, 0.1 M, and 0.1 M, respectively. By this method, molybdenum(VI) can be determined from 80 nM to 10 mM (7.675 ng ml−1 to 95.95 mg ml−1). The effect of foreign ions were studied and an equal amount of tungsten(VI), and 10-fold amounts of zirconium(IV), iron(II), iron(III), vanadium(IV), and copper(II) were found to show interference. Ascorbic acid and thiosulfate in micro mol l−1 levels were also determined by the present method employing the linear relationship between the induction period and the reductant concentration.
  • Sumio Ichiba, Mitsuru Takeshita
    1984 Volume 57 Issue 4 Pages 1087-1091
    Published: 1984
    Released: June 27, 2006
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    The precipitates obtained by addition of a solution of NaHCO3 to a solution of SnCl2 at various pH were studied by thermal analysis, Mössbauer spectroscopy, and X-ray powder diffraction. The formula of the tin(II) chloride hydroxide precipitate obtained in the range of pH 1.9–2.5 was determined as 2SnO·SnCl2·H2O, or Sn3O(OH)2Cl2, and the formula of the hydroxide oxide obtained in the range of pH 7.0–7.7 was 3SnO·2H2O, or Sn3(OH)4O. In the intermediate pH range, the chloride ions were gradually replaced by hydroxide ions. The dehydration of hydroxide oxide to produce SnO occurred in two stages and the disproportionation reaction of SnO to SnO2 and β-tin proceeded via Sn2O3.
  • Katsuyuki Ogura, Nobuhiro Shibuya, Kazumasa Takahashi, Hirotada Iida
    1984 Volume 57 Issue 4 Pages 1092-1096
    Published: 1984
    Released: June 27, 2006
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    2-Alkenyl p-tolyl sulfones were converted into the corresponding 3-acetoxy(or chloro)-1-alkenyl p-tolyl sulfones via π-allylpalladium complexes which reacted regiospecifically with a nucleophile such as acetate anion or chloride anion in the presence of Cu(II).
  • Katsuhiro Kawashiro, Shiro Morimoto, Hideyuki Yoshida
    1984 Volume 57 Issue 4 Pages 1097-1103
    Published: 1984
    Released: June 27, 2006
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    Mass spectra (electron impact at 20 eV) of butyl esters and N-trifluoroacetyl (TFA) butyl esters of some iminodicarboxylic acids (IDCAs) were determined by gas chromatography-mass spectrometry. The IDCAs included iminodiacetic acid (1), 2-(carboxymethylamino)propionic acid (2), 3-(carboxymethylamino)propionic acid (3), 2,2′-iminodipropionic acid (4), 2,3′-iminodipropionic acid (5), 3,3′-iminodipropionic acid (6), N-methyliminodiacetic acid (7), and nitrilotriacetic acid (8). The mass spectra of the butyl ester derivatives are simple, exhibiting the corresponding molecular (M+) ions with the exception of 5. The α,α′-IDCAs (1, 2, 4, 7, and 8) are characterized by M+, M −101 (COOC4H9) (base peak), and M −157 (COOC4H9+C4H8) ions. The β,β′-IDCA (6) is characterized by a more complex spectrum with M+, M −73 (OC4H9), M −115 (CH2COOC4H9) (base peak), M −129 (OC4H9+C4H9), and M −171 (CH2COOC4H9+C4H9) ions. The α,β′-IDCAs (3 and 5) in general show spectra in which both ions characteristic of α,α′- and β,β′-IDCAs are observed. The addition of TFA to the imino nitrogens of 1–6 increases complexity of the resulting spectra. In these instances, although M+ ions are usually present, neither M −101 nor M −115 ions are base peaks. The fragmentation pathways of these two volatile derivatives of the IDCAs upon electron impact are discussed.
  • Kunihiko Akutagawa, Naomichi Furukawa, Shigeru Oae
    1984 Volume 57 Issue 4 Pages 1104-1107
    Published: 1984
    Released: June 27, 2006
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    The reaction of S,S-diaryl-N-(p-tolylsulfonyl)sulfilimines and N-unsubstituted diaryl-sulfilimines with hyperoxide anion radical (O2\ ewdot) in the presence of 18-crown-6 as a catalyst together with 1-bromopropane/benzene, benzoyl chloride/benzene, p-tolylsulfonyl chloride/benzene, carbon tetrachloride, chloroform, or dichloromethane, gave the corresponding sulfoximines, through nucleophilic oxidation with an intermediary dioxy species formed upon treatment of organic halides with potassium hyperoxide (KO2).
  • Tomomichi Ishikawa, Atsushi Yoneyama
    1984 Volume 57 Issue 4 Pages 1108-1111
    Published: 1984
    Released: June 27, 2006
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    The synthesis of polymeric quaternary ammonium salts linked 1,8-diazabicyclo[5.4.0]undec-7-ene(DBU) to chloromethylated polystyrenes is described. The polymers so obtained become anion exchangers with both quaternary ammonium and tertiary amino groups. The values of the total ion-exchange capacities indicated that the quaternization of the tertiary amino groups on the polymers with hydrochloric acid is difficult. The chloride forms of the resins, in spite of their bulky and steric quaternary ammonium groups containing DBU, were effective as ion exchangers for a variety of bulky anions such as sulfate, oxalate, hexacyanoferrate(II), hexacyanoferrate(III), and tris(oxalato) ferrate(III) ions. The free base forms of the resins gave low reactivity for chloride and sulfate ions. Some examples of the application of the resins is also reported.
  • Tamio Ikeshoji, Vernon D. Parker
    1984 Volume 57 Issue 4 Pages 1112-1115
    Published: 1984
    Released: June 27, 2006
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    Reversible oxidation potentials, rate constants, and activation parameters are reported for the formation and decomposition reactions of all isomers of (methyl-substituted benzene)tricarbonylchromium cation radicals. The reversible potentials were observed to depend both on the number and the positions of the methyl substituents. It was found that the effects on the reversible potentials of adding single methyl substituents to similar structures were additive. The activation energies and entropies for the decomposition reactions were found to be grouped into four different categories depending upon the numbers of adjacent unsubstituted positions on the methylarene ligands. Within each group the deviations from the averages were less than experimental error. The differences in activation parameters are explained in terms of how effective bonding is between the chromium atom and the arene ligands in the cation radicals.
  • Yukito Murakami, Jun-ichi Kikuchi, Akio Nakano, Kazunari Akiyoshi, Tor ...
    1984 Volume 57 Issue 4 Pages 1116-1122
    Published: 1984
    Released: June 27, 2006
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    The copper(II)-catalyzed transamination of 2-methyl-3-hydroxy-4-aminomethyl-5-(dodecylthiomethyl)pyridine (C12SPM) with sodium pyruvate was investigated in an aqueous medium at pH 6.8, μ 0.10 (KCl), and 30.0±0.1 °C in the presence of molecular aggregates of N,N-ditetradecyl-Nα-[6-(trimethylammonio)hexanoyl]-L-alaninamide bromide (N+C5Ala2C14), N,N-ditetradecyl-Nα-[6-(trimethylammonio)hexanoyl]-L-histidinamide bromide (N+C5His2C14), or hexadecyltrimethylammonium bromide (CTAB). The reaction afforded the corresponding pyridoxal analogue (C12SPL) and alanine as the final products upon addition of edta which liberates the copper(II) ion from the coordination sites of the aldimine Schiff-base. The coordination interaction between the copper(II) ion and C12SPM, which takes place prior to the transamination, was clarified by electronic spectroscopy. The reactivity of the 2:1 (ketimine:CuII) complex was found to be much larger than that of the 1:1 complex in the molecular assemblies of N+C5Ala2C14 and CTAB, and the formation of the former species was more pronounced in the N+C5Ala2C14 vesicle. The bilayer vesicle formed with N+C5His2C14 allowed the formation of the 1:1 complex in preference to that of the 2:1 complex, and the coordination-free imidazolyl group of the amphiphile effectively catalyzed the isomerization as a general base.
  • Yoshitomi Morizawa, Tamejiro Hiyama, Koichiro Oshima, Hitosi Nozaki
    1984 Volume 57 Issue 4 Pages 1123-1127
    Published: 1984
    Released: June 27, 2006
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    The title reaction of 1-carbonyl substituted cyclopropanecarboxylates proceeds under C(1)–C(2) bond cleavage to produce γ-lactones. Stereochemically, the reaction takes two pathways: (1) substrates with a cationstabilizing group like vinyl on C(2) give thermodynamically favored γ-lactones having the thermodynamically more stable arrangement of substituents irrespective of the configuration of the cyclopropane substrates, (2) substrates without such a cation-stabilizing group afford γ-lactones under ca. 70% inversion at C(2) reaction center.
  • Tadashi Okuyama, Takayuki Fueno
    1984 Volume 57 Issue 4 Pages 1128-1130
    Published: 1984
    Released: June 27, 2006
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    Rates and the equilibrium constant of hydration of 1,3-benzodithiolylium ion were spectrophotometrically measured at 30 °C in aqueous acidic solutions. The hydrate was stable below pH 5 and pKR+=−0.40. The cation does not seem to be very stable as compared with the corresponding dithiolanylium ion.
  • Haruo Ohmura, Shinichi Motoki
    1984 Volume 57 Issue 4 Pages 1131-1137
    Published: 1984
    Released: June 27, 2006
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    Heteroaromatic thioketones react with maleic anhydride, norbornene, acrylonitrile, and styrene to form the Diels-Alder adducts, respectively. The thioketones also undergo cycloaddition with 2-chloroacrylonitrile followed by elimination of hydrogen chloride to give heteroaromatic analogues of o-quinodimethan derivatives. In these reactions, the thioketones act as a heterodiene on the dienophiles to give [4+2]cycloadducts regioselectively.
  • Hassan Ahmed El-Sherief, Abdalla Mohamed Mahmoud, Ahmed Ahmed Esmaiel
    1984 Volume 57 Issue 4 Pages 1138-1142
    Published: 1984
    Released: June 27, 2006
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    Formic acid and acetyl and benzoyl chloride were treated with 2-phenyl-4-quinazolinylhydrazine (1) under mild conditions to afford the corresponding hydrazides which were converted into 5-phenyl[1,2,4]triazolo[1,5-c]quinazoline, 2-methyl-5-phenyl[1,2,4]triazolo[1,5-c]quinazoline, and 2,5-diphenyl[1,2,4]triazolo[1,5-c]quinazoline (3a) respectively by heating over their melting points. Reaction of 1 with aldehydes produced the corresponding hydrazones which give the corresponding [1,2,4]triazolo[1,5-c]quinazolines (3a–i) on pyrolysis. Carbon disulfide underwent ring closure with 1 to 5-phenyl-1,2,4-triazolo[4,3-c]quinazoline-3-thiol which was readily converted into the corresponding alkylthio compounds by treatment with alkyl halides. Further, 4-(4-arylmethylene-5-oxo-2-phenyl-2-imidazolinylamino)-2-phenylquinazolines were obtained via the condensation of 4-arylmethylene-2-phenyl-2-oxazolin-5-ones with 1.
  • Akira Nakajima
    1984 Volume 57 Issue 4 Pages 1143-1144
    Published: 1984
    Released: June 27, 2006
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    The effect of the addition of ethanol on the formation of the inclusion compound between β-cyclodextrin and pyrene in aqueous solution has been studied. Based on the time dependences of the fluorescence spectra of pyrene as a probe, the rate constants estimated for the inclusion and further association in the presence of ethanol have been discussed.
  • Midori Goto, Eiichi Asada
    1984 Volume 57 Issue 4 Pages 1145-1146
    Published: 1984
    Released: June 27, 2006
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    X-Ray structural determination of the B′-form of heptadecanoic acid showed that the unit cell contains two crystallographically independent molecules. All-trans zigzag chains are found in both molecules.
  • Yasufumi Jinnouchi, Motohisa Kohno, Akira Kuboyama
    1984 Volume 57 Issue 4 Pages 1147-1148
    Published: 1984
    Released: June 27, 2006
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    The nπ* absorption intensities of 1-phenylethylene trithiocarbonate (1), p-benzoquinone (2), and 2,5-di-t-butyl-p-benzoquinone (3) in nonpolar solvents are compared with the theoretical ones calculated by the use of Abe’s formula, in which the Onsager-cavity field is used. For 3, the theoretical intensities are well correlated with the observed ones, whereas for the others there are discrepancies, especially for 1. These discrepancies are attributed to strong dispersion-force interactions with the solvents.
  • Junzo Sunamoto, Tomiko Hamada, Hiroki Kondo
    1984 Volume 57 Issue 4 Pages 1149-1150
    Published: 1984
    Released: June 27, 2006
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    Freezing of water solubilized with the cationic CTAX(hexadecyltrimethylammonium halides) and QDX (dihexadecyldimethylammonium halides) in deuterochloroform was observed by 1H-NMR method. The freezing of water was largely affected by the characteristics of the water-surfactant aggregates by the R-value(=[H2O]/[surfactant]) and the structure of surfactant. In the 0.20 M (1 M=1 mol dm−3) CTABr/0.16 M H2O/CDCl3 system, for example, the apparent freezing was observed at about −20 °C.
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