Bulletin of the Chemical Society of Japan
Online ISSN : 1348-0634
Print ISSN : 0009-2673
ISSN-L : 0009-2673
Volume 60 , Issue 3
Showing 1-50 articles out of 69 articles from the selected issue
  • Haruo Nakayama
    1987 Volume 60 Issue 3 Pages 839-843
    Published: 1987
    Released: June 27, 2006
    JOURNALS FREE ACCESS
    A thermal analytic method using a differential scanning calorimeter has been applied to binary mixtures of water with tetrabutylammonium chloride. It has been found that this method can give the same results concerning the melting point (15.2 °C) and hydration numbers (around 30) of the clathrate-like hydrate of tetrabutylammonium chloride as those determined phase-diagrammatically. The apparent enthalpy of fusion of water which forms hydrogen-bonded water lattice in the clathrate-like hydrate has been observed to be 5.47 kJ mol−1, which is comparable with 5.20 kJ mol−1 determined by the direct calorimetric measurements of enthalpy of solution of the hydrate in water. It has been concluded that the proposed method can be applicable to many similar types of systems, including systems forming a hydrate which decomposes incongruently.
  • Kunio Furusawa, Miyako Iwamoto, Hideo Matsumura
    1987 Volume 60 Issue 3 Pages 845-849
    Published: 1987
    Released: June 27, 2006
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    Critical experimental data are presented on the competitive adsorption of metal cations with different ionic valences to phospholipid vesicles, and on the binding of hydrophobic ions from mixed solutions with multivalent metal cations produced under different conditions by means of the Inductively Coupled Argon Plasma. It is apparent that the preferential effect in binding between the metal cations depends not only on their ionic valences but also on the concentrations of each ion at which the corresponding binding is carried out; i.e., the binding strength of the metal cations on the membrane surface increases in the following order: K+<Mg2+<Ca2+<La3+<Th4+, and this order comes to be more pronounced in the high-concentration region of each component. Furthermore, it is realized that, in binding from mixed solutions of hydrophobic ions and multivalent metal cations (Ca2+ or Th4+), a synergistic interaction between these ions occurs; i.e., the binding of hydrophobic anions is promoted by the presence of metal cations, while the binding of hydrophobic cations is hindered by the metal cations.
  • Eiji Honda, Masao Tokuda, Hiroshi Yoshida, Masaaki Ogasawara
    1987 Volume 60 Issue 3 Pages 851-855
    Published: 1987
    Released: June 27, 2006
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    Fast reactions of diethyl fumarate anion radical (DEF) and fluorenone anion radical (Fl) with various organic halides (RX) in hexamethylphosphoric triamide have been studied by means of ns pulse radiolysis at room temperature. Reactions of acetophenone anion radical were also studied for comparison. It was found that the reaction rate of Fl was subject to the steric and resonance effects of R groups of RX in accord with the classical concept of SN2 reactions: the rate constant was reduced by 2 orders of magnitude by the steric effect when R was changed from ethyl to bulky isopropyl or t-butyl, and it was still large by the resonance effect of R even if R was changed from ethyl to an allyl or a benzyl group. While the reaction rate of DEF was not much affected when R was changed to more bulky groups, the rate constant was correlated to the reduction potential of RX. The results were interpreted in terms of a VB correlation diagram approach or rate-equilibrium relationship within a framework of SN2 reactions.
  • Hiroshi Sakai, Shu-ichi Muraishi, Yutaka Maeda
    1987 Volume 60 Issue 3 Pages 857-861
    Published: 1987
    Released: June 27, 2006
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    Resonance Raman and 129I Mössbauer spectroscopy have been applied to the phenothiazine–iodine (PT–In) complexes, which exhibit relatively low electrical resistivities. It is shown from the resonance Raman spectra that the two iodine species in the PT–I3 and PT–I2.6 complexes are present in essentially the same chemical form, consisting of a distorted I3 unit and an I2 unit strongly coordinated to the I3 unit. The 129I Mössbauer spectrum, consistent with the results of the Raman spectra, suggests that the PT–I2.6 complex can be approximately formulated as (PT)53+[(I3)3(I2)2]3−, in which about three electrons per five PT molecules are transferred to the iodine and the transferred electrons are delocalized on the thirteen iodine atoms. The radical salt is recognized as a partially oxidized mixed-valence compound. The formation of the complex is quite similar to that of the perylene–I3 complex, which has a low electrical resistivity.
  • Hiroshi Matsui, Takeo Hisano
    1987 Volume 60 Issue 3 Pages 863-870
    Published: 1987
    Released: June 27, 2006
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    The role of the adsorbate COad in the oxidation of methanol was studied under a variety of experimental conditions on the basis of the rate-ratio of the path of CO2 formation via COad to the overall oxidation of methanol at a platinum electrode in 0.5 mol dm−3 of H2SO4. The results: (a) At potentials below 0.55 V and with a short time of oxidation, COad inhibited its own formation; (b) at 0.60–0.75 V and with a long time of oxidation, COad was a poison to parallel reactions; (c) at above 0.8 V and at θ1>0.15, the formation of CO2 via COad was predominant, and the COad never hindered parallel reactions. There was no difference between the role of the COad formed from dissolved CO and that of the COad formed from methanol, though, in the absence of dissolved CO, the oxidation of methanol was, for some reason, inhibited at small coverages close to the respective limiting values. When the coverage was larger than about 0.85, COad remarkably inhibited all the parallel reactions in the methanol oxidation.
  • Kunio Ohtsuka, Mitsuru Suda, Mikiya Ono, Minoru Takahashi, Minoru Sato ...
    1987 Volume 60 Issue 3 Pages 871-876
    Published: 1987
    Released: June 27, 2006
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    Nickel(II)–hydroxide–(sodium fluoride tetrasilicic mica) intercalation complexes were prepared by titrating nickel(II) nitrate solutions in the presence of mica with sodium hydroxide. As the degree of interlayering increased, the I(002)⁄I(001) intensity ratio increased and the specific surface areas decreased. The composition of fully developed nickel(II) hydroxide interlayer, to be exact, hydroxonickel(II) complex was [Ni3(OH)5(H2O)]+ per formula unit. Nickel(II) hydroxide within the interlayers of the silicate was reduced at about 500 °C in H2 flow and then 5–10 nm ultra fine nickel particles were distributed over the whole surface of mica. With an increase of reducing temperature, the amount of reduced nickel increased and sintering of nickel particles on the surface of mica proceeded.
  • Hideo Suganuma, Itaru Shimizu, Itsuhachiro Hataye
    1987 Volume 60 Issue 3 Pages 877-883
    Published: 1987
    Released: June 27, 2006
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    The backward solvent extraction with dithizone(H2dz)–CCl4 solutions was used to examine the chemical species of bismuth(III) in 1 mol dm−3 of a (H,Na)Cl solution. A tracer concentration of bismuth(III) (ca. 10−11 mol dm−3) was found to exist mainly in the form of [BiCl5]2−, [BiCl5(OH)]3−, [BiCl4(OH)]2−, and [BiCl3(OH)3]3− in the (H,Na)Cl solutions. The constants of the successive hydrolysis, β1, β2, and β3, were calculated by using the distribution data. The resulting logβ1, logβ2, and logβ3 values were 10.9, 17.5, and 30.2 respectively. The chemical composition of the extracted species was most probably [Bi(Hdz)3].
  • Yoshiko Arikawa
    1987 Volume 60 Issue 3 Pages 885-890
    Published: 1987
    Released: June 27, 2006
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    The total sulfur content was determined for 140 samples of Japanese volcanic rock by the mercury(II) thiocyanate photometric method of hydrogen sulfide formed by a wet reduction of the sample by tin(II)–strong phosphoric acid. Though determined values are widely scattered from 5390 down to 10 ppm (or less), the cumulative frequency distribution of the sulfur contents shows lognormality. The geometric and arithmetic means are 26 ppm (mg kg−1) and 116 ppm, respectively. The alkaline rocks have high sulfur contents, the geometric mean of which is 62 ppm. Little significant difference was observed among the rhyolitic rock, the andesite and the trachyte, and the basaltic rock. Japanese and foreign standard rock samples were analyzed for sulfur. Almost all results were in good agreement with those obtained by other authors. In this case foreign standard samples also have higher sulfur contents than those of Japanese samples. The fact that the sulfur contents of Japanese volcanic rocks are lower than the previously accepted values seems to be characteristic of the islands arc of volcanism.
  • Yasushi Inoue, Hiromichi Yamazaki
    1987 Volume 60 Issue 3 Pages 891-897
    Published: 1987
    Released: June 27, 2006
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    A satisfactory method was established for synthesizing a hydrous zirconium(IV) oxide ion exchanger; also, its ion-exchange properties and thermal stability were studied. The exchanger was synthesized reproducibly by hydrolyzing a ZrOCl2 solution at pH 9.3 with the addition of NH3 aq. This material was an amphoteric ion exchanger possessing an isoelectric point close to pH 6.5. The order of affinity for the cations was, transition metal> alkaline earth metal>alkali metal. Transition metal ions form a coordinate bond with OH groups in the exchanger. The OH groups, which were easily condensed by a heat treatment, were not restored even when the samples subjected to thermal treatment were immersed in water: Thirty percent of the initial ion-exchange capacity was lost when the exchanger was heat-treated at a temperature as low as 70 °C, and the exchange sites were completely destroyed between 400 and 550 °C.
  • Shiroo Itoh, Yasuhiko Yukawa, Yoshie Inomata, Toshio Takeuchi
    1987 Volume 60 Issue 3 Pages 899-902
    Published: 1987
    Released: June 27, 2006
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    An X-ray diffraction study of the title complex has been carried out. The crystal is monoclinic, with the space group P21; Z=2, a=8.712(1), b=6.055(1), c=8.187(1) Å, β=109.83(1)°. Block-diagonal least-squares refinements have led to the final R value of 0.052. The structure consists of a one-dimensional polymer chain bridged by only one carboxylato group of a 4-hydroxy-L-prolinato ligand. The chains are parallel to the b axis; each is connected with the neighboring one by hydrogen bonds between water oxygen atoms and chlorine atoms. Thus a sheet forms parallel to the (0 0 1) plane. One carboxylato oxygen atom of the 4-hydroxy-L-prolinato ligand is coordinated to two copper atoms, and the other is coordinated to one of these two copper atoms. The copper atom is surrounded by three carboxylato oxygen atoms, one water oxygen atom, one nitrogen atom in a pyrrolidine ring, and one chlorine atom. Therefore the copper atom has distorted octahedral coordination.
  • Kenji Kikuchi
    1987 Volume 60 Issue 3 Pages 903-909
    Published: 1987
    Released: June 27, 2006
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    A new numerical method for theoretical analysis of polarographic catalytic current is proposed and applied to well-studied systems to prove that the method is dependable. In this method, a system of partial differential equations of diffusion is transformed to finite-difference form by using Crank–Nicolson difference scheme, and the latter is solved by using both Gauss–Seidel and successive over relaxation methods. Chemical kinetics terms in the diffusion equations is substituted by ones rewritten by three alternative procedures. The method has been applied to a system of copper(II) and hydrogen peroxide. Resulted rate constant of participating chemical reaction agrees with the rate constant obtained from bulk solution experiments. This and other results show that the method is a useful tool for theoretical analysis of catalytic waves.
  • Motomi Katada, Yoshio Uchida, Kumiko Iwai, Hirotoshi Sano, Hiroshi Sak ...
    1987 Volume 60 Issue 3 Pages 911-917
    Published: 1987
    Released: June 27, 2006
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    The structural diagnosis and lattice dynamics of three complexes, {[R3Sn](μ-NC)[Au(μ-CN)]}x (R=Me, Bu(n-Bu), or Ph), {[R3Sn]2[(μ-NC)4Pt]}x (R=Me, Bu, or Ph), and {[R3Sn]3[(μ-NC)6Fe]}x (R=Bu or Ph) have been undertaken by means of 57Fe-, 119Sn-, and 197Au-Mössbauer spectroscopic techniques. The Mössbauer parameters for the complexes indicate that all the tin atoms are coordinated with three alkyl or aryl groups and two cyano groups having a trigonal–bipyramidal structure. The asymmetry of the quadrupole split-peak intensity observed in the 119Sn-Mössbauer spectra for the complexes was attributed to the anisotropic mean square vibrational amplitude with respect to a molecular symmetry axis. The temperature dependence of the recoil-free fraction of the 119Sn-Mössbauer atom shows that the mean-square vibrational amplitude of tin atoms in the complexes falls in the range of values found for a number of one-dimensional organotin polymers. In 57Fe-Mössbauer spectroscopy, the quadrupole splitting for {[Bu3Sn]3[(μ-NC)6Fe]}x rapidly decreases with an increase in the temperature, reflecting small separations among the three dε levels in energy. The very large 197Au-quadrupole splitting for {[R3Sn](μ-NC)[Au(μ-CN)]}x was explained by assuming strong σ-donating and π-accepting properties of the CN ligand.
  • Tatsuya Kawamoto, Hisahiko Einaga, Jinsai Hidaka
    1987 Volume 60 Issue 3 Pages 919-924
    Published: 1987
    Released: June 27, 2006
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    The Raman spectra of the tris(bidentate)cobalt(III) complexes containing the six-membered tn and/or β-ala chelate ring, where tn and β-ala denote 1,3-propanediamine and β-alaninate respectively, were measured in order to investigate the relation between the Raman spectra and the structures of the complexes. The Raman bands can be classified into four vibration modes: A totally symmetric stretching vibration mode in the 440–640 cm−1 region, a stretching vibration mode excluding the totally symmetric one in the 380–480 cm−1 region, a metal-ligand skeletal bending deformation mode in the 260–400 cm−1 region, and a chelate ring deformation mode in the 220–290 cm−1 region. The present complexes characteristically exhibited more Raman bands than the complexes with the five-membered chelate rings in the totally symmetric stretching vibration mode. For the [Co(β-ala)2(tn)]+ complex, the three geometrical isomers, trans(O), C2-cis(O), and C1-cis(O), which were prepared for the first time, each exhibited characteristic Raman spectral features.
  • Kensei Kobayashi, Kimikazu Iwase, Shinya Hashimoto, Hirotaka Ueda, Kit ...
    1987 Volume 60 Issue 3 Pages 925-931
    Published: 1987
    Released: June 27, 2006
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    Alkaline phosphatase activity (both dissolved and total) in Lake Kasumigaura was determined periodically together with concentrations of phosphorus compounds therein. Distinct negative correlation was found between the dissolved alkaline phosphatase activity and the orthophosphate concentration during the phosphorus-limited season. The decrease of the concentration of dissolved alkaline phosphatase was observed at the level of 1 ng ml−1 of orthophosphate. The present results suggest that both alkaline phosphatase in vivo and dissolved alkaline phosphatase in the lake water play important roles in phosphorus cycles in natural water.
  • Kazuhiro Toyoda, Hiroki Haraguchi
    1987 Volume 60 Issue 3 Pages 933-939
    Published: 1987
    Released: June 27, 2006
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    Rare earth elements (REEs) in twelve standard rock samples have been determined by inductively coupled plasma atomic emission spectrometry after separation of diverse metal ions with cation exchange resin. These rock samples are old six standard rocks (W-1, BCR-1, AGV-1, GSP-1, JB-1, JG-1) and new six standard rocks (JB-2, JB-3, JA-1, JR-1, JR-2, JGb-1) issued from the Geological Survey of Japan. These samples are various types of igneous rocks, which show various shapes of the REE distribution patterns. Geochemical characteristics of these standard rock samples will be discussed from the relationships between rock types and the shapes of the REE pattern.
  • Tetsuaki Nishida, Yoshimasa Takashima
    1987 Volume 60 Issue 3 Pages 941-946
    Published: 1987
    Released: June 27, 2006
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    A Mössbauer spectrum of a series of potassium vanadate glasses containing 10 mol% Fe2O3 shows a paramagnetic quadrupole doublet, of which isomer shift proves to be smaller than 0.4 mm s−1 with respect to metallic iron. This indicates that the individual Fe3+ ion is present at the substitutional site of the V5+ (and probably V4+) ion constituting a VO4 tetrahedral unit. An increase in the K2O content of the potassium vanadate glasses results in a continuous decrease in the glass transition temperature (Tg), ranging from 239 to 200 °C, when the K2O content is changed from 5 to 30 mol%. This suggests a decrease in the coordination number of the V5+ (and V4+) ion from 5 to 4 and a formation of nonbridging oxygen atoms in the VO4 and FeO4 tetrahedral units. The formation of nonbridging oxygen atoms in the VO4 and FeO4 units is also estimated from a continuous decrease in the quadrupole splitting, suggesting a decrease in the electric field gradient at the iron nucleus and an increase in the symmetry around the Fe3+ ion. These results lead to the conclusion that the introduction of the alkali oxide (K2O) into the V2O5 results in a structural change of the V5+ (and V4+) ions from VO5 tetragonal pyramid (or trigonal bipyramid) to VO4 tetrahedral units.
  • Tadashi Shiraiwa, Hirokazu Yoshida, Makoto Tsuda, Hidemoto Kurokawa
    1987 Volume 60 Issue 3 Pages 947-952
    Published: 1987
    Released: June 27, 2006
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    The racemic structures of the ammonium salts (AM salts) and seven organic ammonium salts of N-acetyl-DL-2-aminobutyric acid (DL-AcAbu) and N-acetyl-DL-norvaline (DL-AcNva) were studied on the basis of thermodynamic analyses to explore the possibility of optical resolution by preferential crystallization. An empirical equation has been derived from thermodynamic data at melting points of ammonium and organic ammonium salts of N-acyl-DL-amino acids to predict racemic structures around room temperature. The AM salts of DL-AcAbu and -AcNva exist in conglomerate around room temperature. It is possible to resolve optically these DL-AM salts by preferential crystallization in ethanol at 10 °C, and the successive preferential crystallization followed by purification gave D- and L-2-aminobutyric acids and -norvalines with optical purities close to 100%.
  • Hajime Satonaka, Kazuhisa Abe, Minoru Hirota
    1987 Volume 60 Issue 3 Pages 953-961
    Published: 1987
    Released: June 27, 2006
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    The 13C NMR spectra have been reported on substituted 2-thiophenecarboxylic acid methyl esters. The chemical shift of ring carbons in methyl (4- and 5-substituted 2-thiophenecarboxylate)s was correlated linearly with that of the corresponding carbons in substituted thiophenes. Plots of the 13C–H coupling constants of methyl (substituted 2-thiophenecarboxylate)s against those of substituted thiophenes showed a good linear relation. The 13C NMR data were interpreted by the stable conformation and percent s character of C–H bonds obtained by MNDO calculation.
  • Shinro Yasui, Masayuki Fujii, Kaoru Nakamura, Atsuyoshi Ohno
    1987 Volume 60 Issue 3 Pages 963-968
    Published: 1987
    Released: June 27, 2006
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    The reduction of diethyl acetylenedicarboxylate, diethyl fumarate, and diethyl maleate as well as several α,β-unsaturated carbonyl compounds by a model of NAD(P)H on silica gel was examined. The order of the reactivity for the reduction was reverse to that of the degree of adsorption of the substrates onto the surface of silica gel. Semiquantitative analysis of the results suggests the possibility that silanol groups on the surface of silica gel act as general acid catalysts in the course of the reduction.
  • Michihiko Noguchi, Ryoichi Tamai, Noriyuki Tanigawa, Hiroyuki Okumura, ...
    1987 Volume 60 Issue 3 Pages 969-975
    Published: 1987
    Released: June 27, 2006
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    The oxidation of the methylene moiety of 4,5,6,7-tetrahydrocyclohepta[hi]pyrrolo[2,1,5-cd]indolizines with NBS gave 5-bromo-6,7-dihydro- (4) and 5-bromo-cyclohepta[hi]pyrrolo[2,1,5-cd]indolizines. The dehydrobromination of 4 with DBU afforded cyclohepta[hi]pyrrolo[2,1,5-cd]indolizines in good yields. The characteristic electronic features of these cycloheptapyrroloindolizines are discussed on the basis of the MO calculations and the spectroscopic properties.
  • Shigeru Sugiyama, Hitoshi Takeshita
    1987 Volume 60 Issue 3 Pages 977-980
    Published: 1987
    Released: June 27, 2006
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    By a high-pressure kinetic analysis in isopropylbenzene, 1,4-dioxane and N,N-dimethylformamide, the activation parameters for the (6+4)π cycloaddition reaction of tropone with 2,3-dimethyl-1,3-butadiene were determined. The findings support the concerted nature for the Woodward–Hoffmann rule-allowed thermal addition reaction of tropone. A secondary orbital interaction, which was used to predict the correct stereochemistry of the adducts, exerted no effect on the volume profile.
  • Tadashi Masamune, Masaki Anetai, Akio Fukuzawa, Mitsuo Takasugi, Hidek ...
    1987 Volume 60 Issue 3 Pages 981-999
    Published: 1987
    Released: June 27, 2006
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    Hatching stimuli, designated as glycinoeclepins, for the soybean cyst nematode (Heterodera glycines) have been isolated by repeated chromatography of the aqueous extracts of dried roots of kidney bean (Phaseolus vulgaris), one of the host plants of the nematode. One of these compounds, glycinoeclepin A, stimulates the hatching and emergence of larvae in vitro in highly diluted aqueous solutions.
  • Tadashi Masamune, Akio Fukuzawa, Akio Furusaki, Mitsuhiko Ikura, Hidek ...
    1987 Volume 60 Issue 3 Pages 1001-1014
    Published: 1987
    Released: June 27, 2006
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    The structures of three new compounds, glycinoeclepins A, B, and C, isolated from the hatch-stimulating extracts of kidney beans for the soybean cyst nematode, have been determined. The structures were resolved by using spectroscopic methods, especially by the difference NOE techniques, and confirmed by the X-ray diffraction analysis. These structures are characterized by (1) migration of two methyl groups in the C and D rings, (2) oxidative cleavage of the B ring with loss of one carbon atom and (3) presence of the 7-oxabicyclo[2.2.1]heptane system in the A ring, compared with those of cycloartanes, and are regarded as pentanor- (GEA) or nortriterpenes (GEB and GEC).
  • Kazuhiro Maruyama, Soichi Morikawa, Atsuhiro Osuka
    1987 Volume 60 Issue 3 Pages 1015-1019
    Published: 1987
    Released: June 27, 2006
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    Concentration quenching phenomena of singly and doubly bridged porphyrins and their zinc and magnesium complexes were studied. Hypothetical nonfluorescent dimer trap was suggested to be not a coplanarly stacked face-to-face dimer but a loosely interacting pair.
  • Kazuhiro Maruyama, Atsuhiro Osuka, Katsuhiko Nakagawa
    1987 Volume 60 Issue 3 Pages 1021-1026
    Published: 1987
    Released: June 27, 2006
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    Irradiation of a benzene solution of 2,3-epoxy-2,3-dihydro-2,3-dimethyl-1,4-naphthoquinone with olefins containing amide group, i.e., N-substituted acrylamides and N-allylcarboxamides predominantly gave the endo-cycloadducts. Upon further irradiation, the cycloadducts underwent photorearrangement to give spirophthalides and alkylidenephthalides.
  • Yutaka Honda, Aiichiro Ori, Gen-ichi Tsuchihashi
    1987 Volume 60 Issue 3 Pages 1027-1036
    Published: 1987
    Released: June 27, 2006
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    (S)-1-Aryl-2-sulfonyloxy-1-alkanone acetals, prepared from natural ethyl (S)-lactate or (S)-valine (chiral sources) by the use of a Grignard reaction, were rearranged under hydrolytic conditions in the presence of a base to give (S)-2-arylalkanoic esters which, in general, showed much higher pharmacological activities than their antipodes.
  • Akihiko Ishii, Renji Okazaki, Naoki Inamoto
    1987 Volume 60 Issue 3 Pages 1037-1040
    Published: 1987
    Released: June 27, 2006
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    O-Cholesteryl chalcogenoformates-d, DC(=X)(OR) (2: X=O; 3: X=S; 4: X=Se; R=3β-cholesteryl), were synthesized and allowed to react with 2,4,6-tri-t-butylphenyllithium. 1,3,5-Tri-t-butylbenzene was a main product in each reaction. The other products were 2,4,6-tri-t-butylbenzaldehyde-d (9) for 2, 2,4,6-tri-t-butylthiobenzaldehyde-d for 3, and 9, 6,8-di-t-butyl-1-deuterio-3,4-dihydro-4,4-dimethyl-1H-2-benzoselenin, bis(2,4,6-tri-t-butyl-α-deuteriobenzyl) diselenide, and bis(2,4,6-tri-t-butyl-α-deuteriobenzyl) triselenide for 4. The mechanisms for these reactions have been discussed.
  • Koji Kano, Bin Zhou, Shizunobu Hashimoto
    1987 Volume 60 Issue 3 Pages 1041-1047
    Published: 1987
    Released: June 27, 2006
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    The photolysis of 9,10-dihydro-9-methoxy-10-methylacridine (MeOA), which is a product of the nucleophilic addition of methanol to 10-methylacridinium chloride, yielded 9,10-dihydro-10-methylacridine (AH2) and 10,10′-dimethyl-9,9′,10,10′-tetrahydro-9,9′-biacridinyl ((AH)2) in various solvents. The quenching experiment using 1,3-pentadiene indicates that AH2 and (AH)2 are produced from the photoexcited singlet and triplet states of MeOA respectively. The results on the solvent effects and the photolyses in solvent matrices at 77 K suggest that the photochemical reaction of MeOA yielding AH2 occurs via hydride transfer from the methoxide anion to the 10-methylacridinium cation, these ions being generated from the heterolysis of MeOA in the photoexcited singlet state.
  • Taichi Nakano, Mikio Kayama, Yoichiro Nagai
    1987 Volume 60 Issue 3 Pages 1049-1052
    Published: 1987
    Released: June 27, 2006
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    The benzoyl peroxide-catalyzed reaction of 2-bromoalkanoic acids such as bromoacetic, 2-bromopropionic, and 2-bromobutyric acid with 1-alkenes was found to proceed through the addition of the C–Br bond across the double bond followed by cyclization affording 4-alkanolides in good yields.
  • Noritaka Abe
    1987 Volume 60 Issue 3 Pages 1053-1056
    Published: 1987
    Released: June 27, 2006
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    The reaction of 2-aminocyclohepta[b]pyrroles with ethyl acetoacetate in phoshoryl chloride–polyphosphoric acid gives 2-methyl-4H-cyclohepta[4,5]pyrrolo[1,2-a]pyrimidin-4-ones. A ring closure of diethyl N-(cyclohepta[b]pyrrol-2-yl)aminomethylenemalonates gives 4-oxo-4H-cyclohepta[4,5]pyrrolo[1,2-a]pyrimidine-3-carboxylates (2) in phosphoryl chloride–polyphosphoric acid or in hot t-butylbenzene, which are deesterified by the treatment with hot hydrobromic acid. Compounds 2 undergo replacement reactions towards some electrophiles at positions C-3, C-11, and C-7 (in that order).
  • Osamu Sakanaka, Takashi Ohmori, Shuji Kozaki, Tetsuo Suami
    1987 Volume 60 Issue 3 Pages 1057-1062
    Published: 1987
    Released: June 27, 2006
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    A protected derivative of the octose moiety of antibiotic ezomycins A1 and A2, 4-N-benzoyl-1-[methyl 3,7-anhydro-2-O-benzoyl-5-(3-N-benzoylureido)-6-O-benzyl-5-deoxy-β-D-threo-D-allooctofuranos-(1,4)-yluronate]cytosine, has been synthesized from 5-acetamido-6-O-benzyl-5-deoxy-1,2-O-isopropylidene-3-O-methylthiomethyll-β-L-erythro-D-allooctofuranose-(1,4) by a series of reactions involving 23 steps.
  • Takashi Sakai, Kazuyoshi Miyata, Masanori Utaka, Akira Takeda
    1987 Volume 60 Issue 3 Pages 1063-1066
    Published: 1987
    Released: June 27, 2006
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    Treatment of β-phenyl α,β-unsaturated ketones, cinnamic acid and its ester with Me3SiCl–NaI–ROH reagent in hexane at room temperature gave the corresponding saturated carbonyl compounds in good yields. A similar reaction of 2,4-hexadienoic acid afforded 4-hexanolide.
  • Takashi Sakai, Akitoshi Yamawaki, Tsuyoshi Katayama, Hiroshi Okada, Ma ...
    1987 Volume 60 Issue 3 Pages 1067-1069
    Published: 1987
    Released: June 27, 2006
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    Reaction of Aromatic aldehydes or hetero-aromatic aldehydes with 3-chloro-3-methyl-2-butanone in ethanolic KOH at room temperature gave 3,3-dimethyl-5-aryltetrahydro-2-furanone as a major product. The reaction can be tentatively explained by the combination of Favorskii rearrangement and aldol reaction.
  • Hiroshi Suginome, Haruka Washiyama, Shinji Yamada
    1987 Volume 60 Issue 3 Pages 1071-1083
    Published: 1987
    Released: June 27, 2006
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    Photolysis of the hypoiodites of steroidal cyclic homoallyl alcohols such as cholesterol and of cyclic alcohols such as 5α-androstan-17β-ol generated in situ in benzene with three molar equivalents each of lead tetraacetate and iodine was found generally to result in the unprecedented formation of corresponding lactol acetates in yields up to 66%. The lactol acetates are readily hydrolysed to lactols in most cases during their isolation and lactols are isolated products. Thus, cholesterol gave 4-oxa-A-homocholest-5-en-3-ol and its acetate in a 53% yield. The products differ considerably from those reported by us after the photolysis of the hypoiodites by using mercury(II) oxide and iodine as the reagents for generating the hypoiodites; they also differ from those in the oxidation of the steroidal alcohols with lead tetraacetate alone. The photolysis of the hypoiodite of 2,2-dimethyl-5β-cholestan-3-ol was found to lead to the formation of an anomalous lactol, 2α-iodomethyl-2β-methyl-4-oxa-A-homo-5α-cholestan-4ξ-ol together with normal lactol. We discuss the paths of the formation of the lactol acetates involving β-scission of the alkoxyl radicals. A new process was found in the photolysis of 2-indanol hypoiodite in the presence of lead tetraacetate and iodine. Our previously suggested pathways to the formation of 3α,5-epoxy-6-iodo-4-oxa-A-homo-5α-cholestanes and 3-formyloxy-2-iodo-2,3-seco-A-norcholest-5-ene in the photolysis of cholesterol hypoiodite in the presence of mercury(II) oxide and iodine were supported by the results of the photolysis of 4-oxa-A-homocholest-5-en-3-ol hypoiodite in the presence of mercury(II) oxide and iodine.
  • Kazuaki Sukata
    1987 Volume 60 Issue 3 Pages 1085-1089
    Published: 1987
    Released: June 27, 2006
    JOURNALS FREE ACCESS
    The effects of alkali metal cyanide impregnated on Amberlite XAD resins (KCN/XAD, NaCN/XAD) have been examined using the cyanation of benzoyl chloride. In benzene, benzoyl cyanide was obtained in a very high yield with high selectivity under mild conditions. It is proposed that the reaction occurs on the surface of the resin. On the basis of the result obtained in the absence of any solvent, the reactivity of KCN/XAD toward dimerization of benzoyl cyanide has been found to be much poorer than that of KCN in solution. Although the reaction of acyl chlorides with KCN/XAD or NaCN/XAD in benzene gave various acyl cyanides in good to excellent yields, no aliphatic acyl cyanide could be obtained.
  • Mizue Fujio, Kimito Funatsu, Mutsuo Goto, Yoji Seki, Masaaki Mishima, ...
    1987 Volume 60 Issue 3 Pages 1091-1095
    Published: 1987
    Released: June 27, 2006
    JOURNALS FREE ACCESS
    The acetolysis rates of 2-arylethyl tosylates were determined for a series of aryl substituents. The non-linear substituent effect was reasonably accounted for on the basis of two linear LArSR relationships; one for the aryl-assisted (FkΔ) and one for the unassisted (ks) processes, respectively. A precise dissection of the apparent substituent effect into individual effects for both processes was achieved in this manner. The substituent effect on the ks process can be described as a linear function of σ° with a small ρs of −0.19, and that on the FkΔ process in terms of the LArSR Eq., with ρΔ=−3.87 and an rΔ=0.631. The use of σ+ for the FkΔ process failed to give any reasonable dissection. The r value for this FkΔ process is essentially identical to that for the neophyl solvolysis. The unique r value of 0.6 is concluded to be characteristic of β-arylassisted ionization processes in general.
  • Mizue Fujio, Mutsuo Goto, Yoji Seki, Masaaki Mishima, Yuho Tsuno, Masa ...
    1987 Volume 60 Issue 3 Pages 1097-1101
    Published: 1987
    Released: June 27, 2006
    JOURNALS FREE ACCESS
    The label scrambling within the ethylene chain of the final acetolysis products was determined for a series of α-D2 labeled 2-arylethyl tosylates by using proton NMR spectroscopy and the kΔks values were derived from the scrambling ratios. For both buffered and unbuffered acetolysis runs log (kΔks) were not correlated linearly with σ° or σ+. Application of the LArSR Eq. results in linear correlations with excellent precision, log (kΔks)=−3.70 (σ°+0.63Δ\barσR+)+0.152 for the unbuffered run and log (kΔks)=−3.97 (σ°+0.60Δ\barσR+)−0.207 for the buffered run. The ρΔ and rΔ values for the aryl-assisted pathway are estimated from the above apparent values based on the reasonable assumption of small ρs values for the ks pathway.
  • Sadao Tsuboi, Xue Han Wu, Seiji Maeda, Shinichiro Ono, Akihisa Kuroda, ...
    1987 Volume 60 Issue 3 Pages 1103-1107
    Published: 1987
    Released: June 27, 2006
    JOURNALS FREE ACCESS
    Octadecapolyenoic acid derivatives such as (±)-t-butyl coriolate, α-eleostearic acid, t-butyl punicate, and t-butyl (9Z,11E)-13-hydroxy-9,11-octadecadien-15-ynoate were synthesized starting from oleic acid with high stereoselectivity and their insecticidal activity was examined.
  • Shin-ichi Hirano, K\={o}-ichi Kikuta
    1987 Volume 60 Issue 3 Pages 1109-1112
    Published: 1987
    Released: June 27, 2006
    JOURNALS FREE ACCESS
    The hydrothermal synthesis of calcite single crystal was studied by using a NaCl solution as a mineralizer. The solubility of calcite in a 3 mol kg−1 NaCl solution was measured by a weight-loss technique to be around 2 g l−1 at 500 °C and 100 MPa. An optically clear rhombohedral crystal of up to 1.0 mm could be grown in a hydrothermal NaCl solution. The growth of a homogeneous layer of calcite could be observed on the calcite seed at 400 °C.
  • Pichai Maruthamuthu, Lakshmanan Venkatasubramanian, Periasamy Dharmali ...
    1987 Volume 60 Issue 3 Pages 1113-1117
    Published: 1987
    Released: June 27, 2006
    JOURNALS FREE ACCESS
    The kinetics of oxidation of 2,2′-azinobis(3-ethylbenzothiazole-6-sulfonate) (ABTS) to the radical cation, ABTS·+ by S2O82−, HSO5, MnO4, Cr2O72−, Ce(IV), and molecular Cl2, Br2, and I2 and further oxidation to the dication, ABTS2+ by the above oxidants except HSO5, Br2, and I2 have been carried out by the stoppedflow spectrophotometric technique. The first-stage oxidation was followed by monitoring the absorption of ABTS·+ at 417 nm and the second-stage oxidation, by following the disappearance of ABTS·+ or the appearance of ABTS2+ at 513 nm. Both the reactions, formation and decay of ABTS·+ were found to obey a total second-order kinetics, first-order each with respect to [ABTS] or [ABTS·+] and [oxidant]. With I2, ABTS underwent reversible reaction, the stoichiometry of which being,
    I2+2ABTS\ ightleftarrows2ABTS·++2I with K=142.8,
    whereasBr_2generatedonlytheradicalcationandCl_2gaveadecomposedproductviaradicalcationanddicationintermediates.ABTS^2+formedinpresenceofexcessMnO_4^-,Cr_2O_7^2-,andCe(IV)decayedasinthecaseofCl_2reactionbutinpresenceofS_2O_8^2-thedicationwasstableformorethanthreedays.IntheabsenceofexcessS_2O_8^2-,ABTS^2+wentbacktoABTS^·+,possiblyviaoxidationofwater.TheradicalcationwasconvertedbacktotheparentcompoundABTSbyreducingagentssuchasdithioniteandsulfiteions.
  • Samaresh Mukherjee
    1987 Volume 60 Issue 3 Pages 1119-1123
    Published: 1987
    Released: June 27, 2006
    JOURNALS FREE ACCESS
    The fluorescence quenching of o-aminobenzoic acid, 1-naphthylamine, aniline, p-toluidine, m-toluidine, and N,N-dimethylaniline by 2-hydroxy-5-methyl-1,3-benzenedicarbaldehyde (VII) was studied. The equilibrium constant of hydrogen bonding in the ground state was evaluated from the absorption spectral change for various donor–acceptor (D–A) pairs. The rate constants of hydrogen-bond formation as well as decomposition in the excited state were evaluated in the case of several donor–acceptor pairs from fluorescence intensity measurements. In addition, the mechanism of fluorescence quenching and absorption spectral shift when VII acted as a quencher/proton donor (D) was discussed on the basis of charge-transfer and hydrogen-bond interaction.
  • Paul George Abdul-Ahad, Graham Alan Webb
    1987 Volume 60 Issue 3 Pages 1125-1128
    Published: 1987
    Released: June 27, 2006
    JOURNALS FREE ACCESS
    Semiempirical molecular orbital calculations are performed on a series of 28 6-[2-(substituted phenyl)hydrazino]uracils. Approximate ground state electronic properties are obtained for each molecule studied as well as the electrostatic potentials. First and second order interaction energies are calculated for some selected point charges in the vicinity of the parent molecule. The best correlations obtained between the biological activity and the electronic and steric indicies are considered in a mechanistic context.
  • Pritam Singh Thind, Jatinder Singh Gandhi
    1987 Volume 60 Issue 3 Pages 1129-1133
    Published: 1987
    Released: June 27, 2006
    JOURNALS FREE ACCESS
    A new inorganic ion exchanger, iron(III) selenite has been synthesized having an Fe:Se ratio of 2:3 and cation exchange capacity of 0.40 meq g−1. It is fairly stable in water and dilute solutions of acids, bases, and salts. Ion distribution studies on twenty one metal ions have been done in water. Iron(III) selenite granules in H+-form have also been used as indicators in the determination of thorium in presence of some rare earth cations using hexacyanoferrate(II) as titrant. On the basis of chemical analysis, pH titrations, thermal and infrared analyses the following scheme for the decomposition of iron(III) selenite has been proposed:
    2Fe2O3·3H2SeO3·2H2O\overset140°C→2Fe2O3·3H2SeO3\overset500°C→2Fe2O3.
  • Kamini Shravah, Sharwan Kumar Sindhwani
    1987 Volume 60 Issue 3 Pages 1135-1139
    Published: 1987
    Released: June 27, 2006
    JOURNALS FREE ACCESS
    2-Methyl-1,4-naphthoquinone monoxime (MNQM) forms yellow-colored 1:1 (M:L) complex with palladium(II) and brown-colored 1:2 complex with osmium(VIII) and iridium(III). The complexes are insoluble in water but soluble in 1-butanol. The reagent has been used for the spectrophotometric determination of Pd(II), Os(VIII), and Ir(III). The palladium, osmium, and iridium complexes have maximum absorption at 460, 460, and 450 nm respectively with the sensitivity of 0.012 μg Pd/cm2, 0.025 μg Os/cm2, and 0.014 μg Ir/cm2 for logIoI=0.001. The optimum concentration ranges for the determination of Pd(II), Os(VIII), and Ir(III) are 1.58–10.47, 3.02–23.99, and 1.6–11.5 ppm over the pH range 6.5–7.8, 6.5–7.7, and 5.9–7.3 respectively. The determinations have also been carried out in the presence of foreign ions. MNQM reacts with palladium(II) or osmium(VIII) or iridium(III) to form yellow- or brown-colored precipitates which are extractable in 1-butanol. These systems have been studied spectrophotometrically to determine the composition and other physical constants of the complexes. The possibility of determining Pd(II) or Os(VIII) or Ir(III) in presence of diverse ions has also been investigated. Palladium(II) and osmium(VIII) have been successfully determined in synthetic solutions corresponding to the alloys.
  • Mathai Mathew, Walter Eric Brown
    1987 Volume 60 Issue 3 Pages 1141-1143
    Published: 1987
    Released: June 27, 2006
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    A new structural model for octacalcium hydrogenpentakis(phosphate) succinate pentahydrate, Ca8H(PO4)5(C2H4·(COO)2)·5H2O, a reaction product of octacalcium dihydrogenhexakis(phosphate) pentahydrate, Ca8H2(PO4)6·5H2O, OCP, and succinate ions, is proposed on the basis of similarities in the unit cell dimensions and structures of OCP and calcium succinate trihydrate. This model can be used to develop information on the mode of incorporation of dicarboxylate ions into OCP and hydroxyapatite and its possible effects on biological mineralization processes.
  • Yusuf Ahmed, M. Ikram Qureshi, M. Saleem Habib, M. Amir Farooqi
    1987 Volume 60 Issue 3 Pages 1145-1148
    Published: 1987
    Released: June 27, 2006
    JOURNALS FREE ACCESS
    Quinoxaline 1,4-dioxide (XIIIa) with acetic anhydride gave 1-acetoxy-2(1H)-quinoxalinone (XIVa) which was prone to facile hydrolysis to yield 1-hydroxy-2(1H)-quinoxalinone (XVa). Both XIVa and XVa were isolated from the reaction mixture. On prolonged heating with acetic anhydride, XIIIa, XIVa, and XVa were converted slowly to the same end product, 2,3(1H,4H)-quinoxalinedione (XXa). 6-Ethoxy- (XIIIb), 6-methoxy- (XIIIc), and 6-methylquinoxaline 1,4-dioxide (XIIId) behaved similarly, except that the attack of the reagent took place exclusively on N-oxide para to the electron-donating substituents, and none of the other expected isomeric compounds XVIIb–d were isolated. Whereas 6-chloroquinoxaline 1,4-dioxide (XIIIe) bearing an electron-attracting chloro substituent on the benzene ring gave exclusively the other isomers XVIIe, XVIIIe, and XXe. A mechanism for this novel rearrangement is proposed and discussed.
  • Soo-Dong Yoh, Jong-Hwan Park, Kyung-A Lee, In-Sook Han
    1987 Volume 60 Issue 3 Pages 1149-1152
    Published: 1987
    Released: June 27, 2006
    JOURNALS FREE ACCESS
    Kinetic investigation of β-phenylethyl arenesulfonates with pyridine in acetonitrile revealed that the rates of these reactions which were lower than those of the reaction of benzyl benzenesulfonate with pyridine in acetone were increased with raising temperatures and pressures. The activation volumes were comparable to those of benzyl system, but activation entropies were negatively larger than those of benzyl system. From these phenomena it can be deduced that phenethyl system has more SN2 character in the transition state, comparing with the reaction of benzyl system. With raising pressures the Hammett reaction parameters (ρ) were decreased, indicating that the reaction is probably closer to tight SN2 character at higher pressures.
  • Sakumitsu Sakagami
    1987 Volume 60 Issue 3 Pages 1153-1154
    Published: 1987
    Released: June 27, 2006
    JOURNALS FREE ACCESS
    A liguid crystalline homologous series of N-[4-(4-alkoxybenzoyloxy)benzylidene]-4-butylanilines and their hydroxyl derivatives at the 2-position were synthesized, and then the liquid-crystalline-phase transitions were determined using a differential scanning calorimeter and a polarizing microscope. All of the members exhibit a nematic phase, and a smectic C phase can be observed for the homologues with a relatively long alkoxyl chain.
  • Shinsaku Yamazaki
    1987 Volume 60 Issue 3 Pages 1155-1156
    Published: 1987
    Released: June 27, 2006
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    Variable-Temperature 1H NMR suggests that the fluxional motion of a potentially five-coordinate complex [Pd(PPh3)(4,7-R2-phen)2][BF4]2 (R=Me, Ph) is frozen at lower temperatures, where the complex is in a rigid configuration (an unusual trigonal bipyramid). The fluxional motion is explained by two synchronous rearrangement systems, and an activation parameter, ΔG*, for the site exchange is given.
  • Hitomi Suzuki, Hiroshi Satake, Hidemitsu Uno, Hiroaki Shimizu
    1987 Volume 60 Issue 3 Pages 1157-1158
    Published: 1987
    Released: June 27, 2006
    JOURNALS FREE ACCESS
    Perfluoro(1,1-dimethylbutanide) anion generated from hexafluoropropene dimers and cesium fluoride in N,N-dimethylformamide, reacts with disulfur dichloride to give the title trisulfide as the predominant product.
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