Bulletin of the Chemical Society of Japan
Online ISSN : 1348-0634
Print ISSN : 0009-2673
ISSN-L : 0009-2673
Volume 41 , Issue 2
Showing 1-50 articles out of 66 articles from the selected issue
  • Taku Matsuo, Hiroshi Aiga
    1968 Volume 41 Issue 2 Pages 271-274
    Published: 1968
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    The charge-transfer (CT) absorptions of complexes of tetracyanoethylene with trans-stiibene and related compounds were measured both in solution and in solid media. The first and the second CT bands were found to be affected differently by the substituents on the donor molecule; thereupon they were assigned to the transitions of an electron from, respectively, the highest occupied and the second highest occupied orbitals of the donor to the lowest unoccupied orbital of the acceptor. Both the location and the intensity of the first CT band were found to be extremely sensitive to variation in media and temperature. The explanation was arrived at by the use of a model where an acceptor molecule was assumed to associate independently with several different sites of a donor molecule.
  • Hiroji Ohigashi, Yukio Kurita
    1968 Volume 41 Issue 2 Pages 275-284
    Published: 1968
    Released: March 27, 2006
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    Electron spin resonance spectra of X-irradiated single crystals of zinc acetate dihydrate have been studied at 9.2 Gc in the temperature range from 77°K to 380°K. The radicals trapped at 77°K are CH3 and CH2COO. The former disappears above 150°K. The latter is stable and persists up to 370°K. The principal values of hyperfine coupling constants for two indetical hydrogens of the radical CH2COO have been found to be 10.5, 20.6 and 33.4G. The CH2 group in the radical undergoes restricted rotation about the C–C bond. Analysis of the ESR spectra at different temperatures with a modified Bloch equation shows the activation energy and the frequency factor for the restricted rotation to be 5.8±0.2 kcal/mol and (4.4±2.7)×1012 sec−1, respectively.
  • Shigeru Tsunashima, Shin Sato
    1968 Volume 41 Issue 2 Pages 284-290
    Published: 1968
    Released: March 27, 2006
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    A comparative study has been made of the reactions of cis- and trans-2-butenes photosensitized by mercury(3P1) at room temperature and by cadmium(3P1) at temperatures ranging from 275 to 350°C. In both cases, the main reaction was cis-trans isomerization. The initial quantum yield of isomerization was the same for the two butenes. The rate of decomposition was about 10−2 and 10−3 times less than that of isomerization in the Hg- and Cd-photosensitizations, respectively. The ratio of trans- to cis-2-butene after prolonged irradiation was unity and did not vary with pressure in the Cd-photosensitization, while in the Hg-photosensitization it increased with decreasing initial pressure. This is probably due to the difference in the rates of decomposition of trans- and cis-2-butenes. It was found that the pressure dependence of Hg-photosensitized cis-trans isomerization could not be explained in terms of the simple mechanism proposed before. A possible mechanism is discussed.
  • Nobuo Nakamura, Hiroshi Suga, Hideaki Chihara, Syûzô Seki
    1968 Volume 41 Issue 2 Pages 291-296
    Published: 1968
    Released: March 27, 2006
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    The motions of the propionate anions in strontium-, lead-, and barium-dicalcium propionates were examined with the proton magnetic resonance method at low temperatures. It was found that the methyl groups rotate about the C3-axes even at 20°K in the Sr-, and the Ba-salts. In the Sr-salt the gradual decrease of the second moment below the ferroelectric transition point was observed and this phenomenon was related to the large angle torsional oscillations of the ethyl groups about the C3′-axes as introduced in Part I: Near the ferroelectric transition point the observed second moment shows the possibility of excitation of the C3′-rotation which would make the crystal to be paraelectric above the transition point. It was expected that the C3′-torsion is to some extent excited in the Pb-salt at liquid nitrogen temperature, a slight discrete change being observed at the lower transition point. A sharp line width transition was also observed in the Ba-salt and this fact resulted in the finding of a new λ-type phase transition with the peak at about 204°K by the differential thermal analysis. A slight decrease of the second moment was observed at the upper transition point and the C3′-rotation was assumed to be fully excited above that point.
  • Toshihide Kashiwagi, Noritake Yasuoka, Tatzuo Ueki, Nobutami Kasai, Ma ...
    1968 Volume 41 Issue 2 Pages 296-303
    Published: 1968
    Released: March 27, 2006
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    From the reaction of M{(C6H5)3P}4 (M=Pd or Pt) with CS2, M{(C6H5)3P}2(CS2) has been isolated. It has been found that M{(C6H5)3P}2 also reacts with sulfur dioxide to form a novel complex, [M{(C6H5)3P}4(SO2)n]. The structure of one of these compounds, Pd{(C6H5)3·P}2(CS2), was determined by means of X-rays. Pd{(C6H5)3P}2(CS2) crystallizes in the mono-clinic system, space group P21c, with four molecules in a unit cell of dimensions: a=11.55, b=19.52, c=18.38 Å and β=128°53′. The most remarkable feature of the whole structure is the coordination of CS2 to the Pd: only one of the S atoms, S(2), coordinates to the Pd, while the CS2 ligand is bent at an angle of 140°. The Pd, two P’s, S(2) and C(1) in CS2 lie approximately on the same plane. The Pd–C(1) distance of 2.00 Å is slightly shorter than the sum of the covalent radii, 2.06 Å. But the S(2)–Pd–C(1) angle of 44° is very small.
  • Shin Sato
    1968 Volume 41 Issue 2 Pages 304-306
    Published: 1968
    Released: March 27, 2006
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    A diffusion model proposed in the previous paper (Bull. Chem. Soc. Japan, 40, 1818 (1967)) has been applied to explain the ionic reactions occurring in the γ-radiolysis of cyclohexane. The effects of an electron scavenger (N2O) and a positive ion detector (CH3OD) were consistently interpreted. The ratio of the diffusion coefficient of electrons to that of parent positive ions has been estimated from the calculation to be in the range of 4 to 5. The calculating method has been compared with that recently published by Freeman (J. Chem. Phys., 46, 2822 (1967)).
  • Tsutomu Koide, Tsutomu Oda, Kiyoshi Ezumi, Koji Iwatani, Tanekazu Kubo ...
    1968 Volume 41 Issue 2 Pages 307-311
    Published: 1968
    Released: March 27, 2006
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    Infrared spectra of Cl(CH3)2C–C(CH3)2Cl were obtained over the region from 400 cm−1 to 4000 cm−1 at room temperature in the gas phase, dilute solutions, and KBr-disk. In the KBr-disk case, spectra were also obtained at lower temperatures. In the gas phase, and in the disk at lower temperatures, spectral simplifications were obtained. Raman spectra at room temperature were photographed for the crystalline sample, and also for 17–25% solutions in several solvents. The coexistence of trans-gauche isomers in the high-temperature solid phase of this compound was verified by spectral comparison between trans- and gauche-isomers. The energy difference between two isomers was estimated to be about 1.5 kcal/mol from temperature changes in the infrared intensities.
  • Michio Sorai, Hiroshi Suga, Syûzô Seki
    1968 Volume 41 Issue 2 Pages 312-321
    Published: 1968
    Released: March 27, 2006
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    An adiabatic low-temperature calorimeter, capable of measuring the heat capacities of solid or liquid between 1.4 and 21.0°K, was constructed. A mechanical thermal switch is used for cooling the sample cell, the temperature of which is measured with a doped germanium thermometer. The resistance-temperature calibration data for the resistor was fitted to a function of the form log10R=AT+B+CT+DT2. By using this formula the thermodynamic temperature scale is represented to within ±0.02°K and by combining the correction curves the final deviations of the calibration data from the thermodynamic temperature scale were within ±0.003°K in the whole temperature range investigated. The heat capacity measurements of CsBr and CsI crystals were made with two kinds of adiabatic calorimeter assemblies, one for the temperature range 1.4 to 21°K and the other for the range 12 to 300°K. Values of the heat capacity Cp°, entropy S°, enthalpy function (H°−H0°)/T, and Gibbs energy function −(G°−H0°)/T at 298.15°K are: 12.441, 26.785, 10.415, and 16.370 for CsBr and 12.571, 29.127, 10.788, and 18.339 for CsI, respectively, in cal·mol−1.°K−1.
  • Wahid U. Malik, Iqbal A. Khan
    1968 Volume 41 Issue 2 Pages 321-325
    Published: 1968
    Released: March 27, 2006
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    The influence of dyes on the gelation of aluminium hydroxide sol has been studied with the help of viscometric and pH metric methods. From these studies it is inferred that the behaviour of acid dyes towards alumina is different from that of basic dyes. The results have been interpreted in terms of various structural changes taking place in the dye molecule. Adsorption studies reveal that the data do not fit well into the Langmuir or Freundlich adsorption isotherm equation in the case of alizarin sulphoric acid, while in the cases of methyl orange, methylene blue, and malachite green, the data are found to fit well into the Langmuir adsorption equation.
  • B. Krishna, H. S. Singh
    1968 Volume 41 Issue 2 Pages 325-328
    Published: 1968
    Released: March 27, 2006
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    In the reaction between the iodide ion and hexacyanoferrate(III), the order is unity with respect to the iodide ion and two with respect to the ferricyanide ion. It has been observed that the rate of the reaction increases with the increase in the dielectric constant of the medium. It has also been observed that the reaction occurred between trivalent and univalent negative ions.
  • Yoshinaga Oka, Toyoaki Kato, Hui-Tuh Tsai, Koichi Nomura
    1968 Volume 41 Issue 2 Pages 329-333
    Published: 1968
    Released: March 27, 2006
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    An internal-monitor method has been developed to eliminate many of the errors probable with activation analysis. This method involves the measurement of the composed radioactivity of the species to be analyzed and of an appropriate internal-monitor, and the estimation of the ratio of the induced activity of both the species. The present report will describe the principles and the applicability of the method to the determination of a trace amount of silver in palladium by means of thermal neutron irradiation. After the silver activity is chemically separated from the irradiated sample, the γ-ray spectrum corresponding to the mixture of 110mAg and 111Ag formed by the β decay of 111Pd is measured. Synthetic mixtures of silver and palladium with known weight ratios have been prepared to check the accuracy of the method. A good proportionality has been obtained between the ratios of the 110mAg to 111Ag activities and the ratios of the concentrations. By using this relationship, silver analysis can easily be achieved. Contents of silver in a palladium sample down to about 1 ppm can be determined with a relative error of within ± 2%. By this method the errors which arise from neutron flux irregularities and self-shielding effects can be avoided, and no correction for chemical yield is necessary.
  • Mitsuo Abe, Takuji Ito
    1968 Volume 41 Issue 2 Pages 333-342
    Published: 1968
    Released: March 27, 2006
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    The preparation of so-called antimonic acid under various experimental conditions has been investigated in order to establish its usefulness as a chemically-stable cation-exchange material. In this experiment, the antimonic acid was mainly obtained by the hydrolysis of antimony pentachloride, and was rarely obtained from metallic antimony or potassium pyroantimonate. The hydrolyzed precipitate was amorphous at first, but it was gradually transformed into crystalline powder by keeping it in the mother liquor for a long time. The crystallization of the amorphous precipitate was facilitated by raising the temperature within a range of 0–80°C, and by increasing the concentration of strong mineral acid on aging, regardless of the kinds of starting antimony substances. The water-content of the air-dried samples is decreased by increasing the period of aging; the composition of the sample approximates Sb2O5·4H2O. The crystal of the antimonic acid is cubic and belong to the space group Oh7(Fd3m), with a lattice constant of 10.382 Å. The measurement of solubilities for the air-dried antimonic acid showed that both the amorphous and the glassy acids are soluble forms and that the crystalline is an insoluble form. The uptakes of potassium ions on these antimonic acids were little changed on the kinds of form; the uptake of lithium ions on the crystalline acid was very small as compared those on the amorphous and the glassy acids. This behavior may be attributed to the existence of different types of so-called antimonic acid, with different selectivities of their lithium ion adsorption, rather than to any difference in the size of the particle.
  • Jumpei Ando, Seiichi Matsuno
    1968 Volume 41 Issue 2 Pages 342-347
    Published: 1968
    Released: March 27, 2006
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    As a fundamental research of a calcined defluorinated phosphate containing a small amount of sodium, the system Ca3(PO4)2(tricalcium phosphate, T) - CaNaPO4(Rhenanite, R) was studied by high temperature X-ray diffraction, differential thermal analysis, etc., and the phase diagram determined. During heating, T inverted from β to α at 1180°C, and then possibly from α to α′ at 1280°C. R inverted from β to α at 690°C. In the composition range containing R from about 10 to 98% by weight, (βT+βR), the stable phase at room temperature, inverted to (βT+αR) at 650°C. The (βT+αR) changed at 980°C to form a compound “A” Ca5Na2(PO4)4 for the sample containing 50.5% R, and (“A”+βT) for samples containing a smaller amount of R. The (“A”+βT) then changed to “A” solid solution at elevated temperatures. The crystals of “A” consisted of a superlattice of αR. “A” and the solid solution changed to αR solid solution at higher temperature. By quenching the samples containing 35 to 50.5% R from 1400°C, a single phase “A” or “A” solid solution was obtained at room temperature. The “A” solid solution was the major phase of the calcined defluorinated phosphate. During heating of samples containing more than 50.5% R, (βT+αR) changed to αR solid solution at or below 980°C; during cooling of the solid solution (“A”+βR) formed at 650°C.
  • Goro Yamaguchi, Wen-Chau Chiu
    1968 Volume 41 Issue 2 Pages 348-353
    Published: 1968
    Released: March 27, 2006
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    Alumina gel, boehmite gel, ρ-alumina, η-alumina, and γ-alumina were treated with aqueous solutions of various inorganic and organic reagents at temperatures below 100°C. Boehmite gel, η-alumina and γ-alumina were found to show no change upon this treatment, while alumina gel and ρ-alumina either remained unchanged or changed into fairly well-crystallized boehmite, boehmite gel, gibbsite, bayerite, or nordstrandite, according to the treating conditions. It has been newly established that water-containing pyridine and aniline, the aqueous solution of hydrazine hydrate, and the aqueous solution of o, m-phenylenediamine are effective in forming fairly well-crystallized boehmite, nordstrandite, and gibbsite respectively.
  • Mutsuo Kodama, Tomohiko Noda, Mitsuko Murata
    1968 Volume 41 Issue 2 Pages 354-358
    Published: 1968
    Released: March 27, 2006
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    The reduction reaction of Tl(I) ions in DTPA solutions was studied d.c- and a.c.-polarographically, and the composition and the stability constants of normal and hydrogen chelates of Tl(I) ions with DTPA, TlZ4− and TlHZ3− were determined. The reduction of Tl(I)-DTPA chelates at the DME proceeds reversibly in the polarographic sense according to this scheme:
    (Remark: Graphics omitted.)
    The stability constants of TlZ4−-and TlHZ3− were found to be 105.45 and 104.24(μ=0.40). The determination of the a.c. summit-potentials, Ep, and the introduction of Ep into the Kolthoff and Lingane equation of polarographic waves of metal complexes were also discussed.
  • Hide Saito, Junnosuke Fujita, Kazuo Saito
    1968 Volume 41 Issue 2 Pages 359-364
    Published: 1968
    Released: March 27, 2006
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    Chromium(0), molybdenum(0) and tungsten(0) complexes of [M·(CO)4AA]0 type (AA=ethylenediamine (en), l-propylenediamine (l-pn), trimethylenediamine (tn), bipyridyl (bp), and phenanthroline (phen); l-pn and tn derivatives are new compounds) have been synthesized and their absorption spectra, rotatory dispersion (RD) and circular dichroism (CD) measured in methanol at room temperature. The nature of the absorption bands has been discussed by comparing them with one another and with those of hexacarbonyl- and piperidinepentacarbonyl complexes of these elements. The peaks in the region 23000 to 25000 cm−1 seem to be due to spinallowed d–d transition. The bands at 30000 to 33000 cm−1 appears to correspond to the metal to carbonyl charge transfer band of hexacarbonyls at ca. 36000 cm−1. Besides them, complexes of aromatic amines (bp and phen) show broad and strong bands at 21000 to 22000 cm−1 which seem to owe to metal to amine charge transfer.
  • Tasuku Ito, Nobuyuki Tanaka, Ichiro Hanazaki, Saburo Nagakura
    1968 Volume 41 Issue 2 Pages 365-373
    Published: 1968
    Released: March 27, 2006
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    The electronic structures of tris(α-diimine)iron(II) complexes have been investigated. The theoretical consideration has revealed that a considerable π-back donation takes place in the ground state and as a result unusually stable complexes of iron(II) are formed. The intense band which appears in the visible region has been proved to be due to the charge transfer transition from 3dπ AO (atomic orbital) of iron to the lowest vacant π MO (molecular orbital) of the ligand α-diimine. It was found both theoretically and experimentally that the π→π* transition with the lowest energy in α-diimine is polarized parallel to the nitrogen-nitrogen direction of the molecule, and that transition dipoles in the three ligands of tris(α-diimine)iron(II) ion interact to give resultant A1→A2 and A1→E transitions in the metal complex with D3 symmetry. Details of the electronic structures, including the splitting energy and the intensity of the local excitation in α-diimine molecule and the nature of the charge transfer band, have been discussed.
  • Akira Misono, Tetsuo Osa, Seiichiro Koda
    1968 Volume 41 Issue 2 Pages 373-377
    Published: 1968
    Released: March 27, 2006
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    We tried to prepare complexes of copper chlorides with benzophenoneimine. The complex CuCl2·2Ph2C=NH and the complex CuCl·Ph2C=NH were newly prepared, and some of their properties were investigated by physico-chemical techniques. Besides these, two other complexes were obtained, but they were not completely stoichiometric compounds.
  • R. S. Saxena, C. P. Sharma
    1968 Volume 41 Issue 2 Pages 377-380
    Published: 1968
    Released: March 27, 2006
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    The reaction between Pb2+ and VO3 was investigated by means of electrometric techniques involving potentiometric, pH-metric and conductometric titrations between Pb(NO3)2 and NaVO3 at several concentrations, with each of the reagents alternately used as titrant. The sharp breaks and inflections obtained in titration curves evidenced the formation of lead metavanadate having the molecular composition PbO·V2O5 at pH range 4.25–5.25. The precipitation of the compound has been found to be almost quantitative and the titration results are very accurate and reproducible.
  • Yoshinaga Oka, Toyoaki Kato, Koichi Nomura, Tatsuya Saito, Hui-Tuh Tsa ...
    1968 Volume 41 Issue 2 Pages 380-384
    Published: 1968
    Released: March 27, 2006
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    The yields of the (γ, p) reactions on 13 elements up to an atomic number of 80, irradiated with 20 MeV bremsstrahlung, have been given through the γ-ray spectrometric measurements of the resultant activities. The yield values, as measured in absolute disintegration rates at the end of irradiation per mole per roentgen, have been plotted against atomic number of the target nuclides. The shape of the yield curve thus obtained is similar to that of the curve for the photo-proton yield as a function of atomic number. The yield values are 105 order of magnitude in the lower-Z region, and drop rapidly with increasing atomic number up to a Z of 50. For barium and mercury targets, a yield value of 2.2×104 was obtained. Neutron excess nuclides were found to be restrictive to the (γ, p) processes. The present results permit a study of general behavior of the (γ,p) reaction yields as well as of the applicabilities of the resultant activities to photoactivation analyses for many elements distributed throughout the periodic table.
  • Kazuo Saito, Kazuyo Masuda
    1968 Volume 41 Issue 2 Pages 384-389
    Published: 1968
    Released: March 27, 2006
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    Tris-acetylacetonatoaluminum [Al(acac)3] is precipitated crystalline from tetrahydrofuran (THF) solution containing an excess of acetylacetone (acacH) by adding chilled petroleum ether. This fact enables a kinetic study of isotopic exchange of acac between [Al(acac)3] and acacH with the aid of acetylacetone-14C. The exchange rate is independent of the concentration of acacH and dependent on that of water. The rate formula at 25°C is as follows:
    R=[Al(acac)_3](6×10^-5+2.0×10^-2[H_2O]) mol l^-1min^-1
    This exchange reaction is catalysed by acids; the stronger the acid, the greater the catalytic effect. One of the acetylacetonate ligands would be present with one end free, and break of the remaining bond of unidentate acetylacetonate seems to be the rate determining step. Water can occupy the vacant coordination site of aluminum ion to retard recombination of the unidentate ligand. The donation of proton to the free end of acetylacetonate appears to impede the recombination, too, and facilitate the exchange. Hydronium ion seems to be the unique proton carrier.
  • Sango Kunichika, Yasumasa Sakakibara, Tadao Nakamura
    1968 Volume 41 Issue 2 Pages 390-396
    Published: 1968
    Released: March 27, 2006
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    The catalytic synthesis of methyl methacrylate by the carboxylation reaction of methylacetylene using nickel carbonyl as a catalyst was studied under various conditions. The experimental results concerning the effects of the reaction conditions on the reaction rate, the stability (regeneration) of nickel carbonyl, and the product yields suggested the most desirable conditions for the synthesis. It was ascertained that, in the catalytic process, the pressure of carbon monoxide played a very important roles; a high pressure gave a good regeneration of nickel carbonyl, i. e., a high value of 95% in the so-called catalytic level, but the initial reaction rate decreased remarkably with an increase in the pressure, probably in reverse proportion to its second power, or more. A semicontinuous process was much better for the synthesis than a batch process. A good yield of 85% (based on the methylacetylene used) of the total of methyl methacrylate and methacrylic acid and a high catalytic level of 95% were obtained when the reaction was carried out semicontinuously in the presence of methacrylic acid and water at a total pressure of 13 atm (initial charge of carbon monoxide at room temp.: 4 atm) at 130°C. A mechanism for the catalytic reaction was proposed to account for the experimental results.
  • Akira Misono, Yasuzo Uchida, Masanobu Hidai, Hiroyuki Shinohara, Yoshi ...
    1968 Volume 41 Issue 2 Pages 396-401
    Published: 1968
    Released: March 27, 2006
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    The end-to-end dimerization of acrylonitrile was effected with a ruthenium trichloride trihydrate catalyst under a hydrogen atmosphere, thus obtaining a mixture of cis- and trans-1, 4-dicyano-1-butene as the main products. Under nitrogen, however, only very small amounts of these products were formed. The reaction occurred at temperatures of 120–200°C under moderate hydrogen pressures in alcoholic media such as ethanol. The effects of various salts or electron-donating compounds on the catalysis were examined.
  • Kosaku Noda, Hideo Okai, Tetsuo Kato, Nobuo Izumiya
    1968 Volume 41 Issue 2 Pages 401-407
    Published: 1968
    Released: March 27, 2006
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    A series of experiments on a column chromatography of Dowex 50 with ammonium acetate solvent systems as eluent was carried out in order to find optimal conditions for the separation of the diastereomers of leucylalanine, leucylvaline, leucylleucine and leucyltyrosine. The effects of pH concentration of the salt and alcohols in the solvent systems for the separation of the diastereomers were studied. Among many conditions tested, the change of pH in the solvent system afforded most remarkable influence for the separation; the order of elution of the diastereomers of the dipeptide was found to be inverted at near pH 5.0. On a preparative scale L-leucyl-DL-valine was successfully separated into the two diastereomers by using a fairly large column. Attempt to separate benzyloxycarbonyl-L-leucyl-DL-valine benzyl ester with a column of Sephadex LH-20 was described, also.
  • Susumu Tatsumi
    1968 Volume 41 Issue 2 Pages 408-418
    Published: 1968
    Released: March 27, 2006
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    In the asymmetric hydrogenation of methyl acetoacetate to methyl 3-hydroxybutyrate using Raney nickel catalysts modified with optically active hydroxy dicarboxylic acids and related compounds (for example, Y. Izumi, S. Tatsumi and M. Imaida, Bull. Chem. Soc. Japan, 39, 2223 (1966)), the relationship between the asymmetric activities of the catalysts and the chemical or stereochemical structures of modifying reagents was discussed on the basis of data obtained previously. The effects of the conditions used for modification upon the asymmetric activity were also discussed inclusively. Moreover, the stability of asymmetric activity in the modified catalysts has been found to be very excellent.
  • Takehiko Ito, Ken-ichi Watanabe
    1968 Volume 41 Issue 2 Pages 419-423
    Published: 1968
    Released: March 27, 2006
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    The Rosenmund-von Braun reaction with aryl halide, with its Ar-X+CuCN-Base→Ar-CN+CuX-Base, has been studied in nitrobenzene in place of an organic base at 160–180°C. The free nitriles formed during the reaction were determined exactly by gas chromatography. In the use of bases with suitable coordination forces to CuCN, the reactivity of the base for the substitution was found to be in the order: prim.>sec.>tert. A steric hindrance of the base was observed, and the reactivity of the pyridine homologue followed the order: pyridine>quinoline>α-picoline>2, 6-lutidine. Ortho-substituted groups in the halobenzene seem to manifest no steric hindrance on the reaction. From the results of the kinetic study, it can be said that CuCN participates in the reaction essentially in the form of a Base(1 mol)-CuCN complex. The overall reaction is second-order, dc⁄dt=k[Complex][Ar-X]. The rate-determining step may be in the halogen exchange stage in the intervening complex, Base-CuCN-Ar-X, where the plane including CN-Cu-X and that of the benzene ring may be nearly perpendicular to each other. When an excess of CuCN over the base is used, the base is liberated from the Base-CuX complex, after the displacement, and then coordinates to the unreacted CuCN again.
  • Katsuo Kikuchi, Masaki Yagi, Kunio Takada
    1968 Volume 41 Issue 2 Pages 424-429
    Published: 1968
    Released: March 27, 2006
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    The reaction of tropolone and phosphorus oxychloride gave 2-chlorotropone. Similarly, 5-cyano-, 5-nitro, and 5-chlorotropolones afforded the corresponding 2-chlorotropone derivatives in moderate yields. 3-Cyanotropolone gave 2-chloro-7-cyanotropone, while 3-phenyltropolone afforded only 2-chloro-3-phenylbenzaldehyde. When 3-bromotropolone and 5-bromotropolone were treated similarly, 2, 7-dichloro- and 2, 5-dichlorotropones were obtained respectively, with a facile halogen exchange. The further treatment of 2, 5-dichlorotropone with phosphorus oxychloride afforded 2, 5-dichloro- and 3,4-dichlorobenzaldehydes. The reaction of 5-p-tolylazo-, 5-phenylazo-, and 5-p-nitrophenylazotropolones with phosphorus oxychloride gave the corresponding 5-arylazo-2-chlorotropones, which, on further treatment with an excess of the reagent, gave 2-aryl-4, 5-dichloroindazoles.
  • Akio Sakurai, Hiroshi Midorikawa
    1968 Volume 41 Issue 2 Pages 430-432
    Published: 1968
    Released: March 27, 2006
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    Hitherto various heterocyclic compounds have been synthesized by the reaction of ketones with ethyl cyanoacetate or ethyl acetoacetate in the presence of excessive ammonium acetate. On the basis of these facts, the reaction of malononitrile with ketones by ammonium acetate was carried out; aminopyridine derivatives, such as 2, 4-diamino-3, 5-dicyano-6-alkylpyridines (I) and 2-amino-3-cyano-4, 6-dialkylpyridines (II), were thus obtained.
  • Haruhiko Aoyagi, Kikuo Arakawa, Nobuo Izumiya
    1968 Volume 41 Issue 2 Pages 433-437
    Published: 1968
    Released: March 27, 2006
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    The synthesis of a decapeptide, H-L-Asp-L-Arg-L-Val-L-Tyr-L-Ile-L-His-L-Pro-L-Phe-L-His-L-Leu-OH, which has an amino acid sequence assumed by Arakawa et al. for natural human angiotensin I, has been performed. The chemical and biological properties of the synthetic product have shown to be in agreement with those of the natural material, thus the structure of human angiotensin I has been confirmed by the present synthesis.
  • Shumpei Sakakibara, Yasuo Kishida, Rinzo Nishizawa, Yasutsugu Shimonis ...
    1968 Volume 41 Issue 2 Pages 438-441
    Published: 1968
    Released: March 27, 2006
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    Detailed conditions for handling simple peptide-derivatives with anhydrous hydrogen fluoride (HF) were presented. Since HF has a strong affinity for peptides, the removal of excess HF from the reaction products is rather difficult, but is essential to obtain the product as good crystals. Syntheses of the following peptides were carried out successfully as examples of the HF procedure: tosyl-L-phenylalanyl-L-phenylalanine, L-leucylglycine, L-arginylglycine, carbobenzoxy-L-prolyl-L-leucylglycine ethyl ester, L-aspartyl-L-phenylalanine amide, and BOC-β-alanyl-L-tryptophyl-L-methionyl-L-aspartyl-L-phenylalanine amide.
  • Kikumasa Sato, Yoshito Fujima, Arihiro Yamada
    1968 Volume 41 Issue 2 Pages 442-444
    Published: 1968
    Released: March 27, 2006
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    The synthesis of trimethylhydroquinone from p-xylene was carried out via two routes; one includes the formylation of p-xylene, followed by nitration, and the other, the chloromethylation of nitro-p-xylene. The oxidation of the trimethylanilines, VI and IX, prepared from 2,5-dimethyl-6-nitrobenzaldehyde and 2,5-dimethyl-3-chloromethylnitrobenzene and their subsequent reduction gave trimethylhydroquinone (TMH) in appreciable yields.
  • Kazuhiro Maruyama, Tetsuo Otsuki
    1968 Volume 41 Issue 2 Pages 444-450
    Published: 1968
    Released: March 27, 2006
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    Anion radicals of mono-, di-nitrobenzophenones, dinitrobenzil, and nitrophenanthraquinone generated by reduction with alkali metal were studied by means of electron-spin resonance. The hyperfine coupling constant and the effect of the metal species on it were investigated. The correlation between the localization of the unpaired electron and the chemically reducible position was also discussed.
  • Takeshi Amakasu
    1968 Volume 41 Issue 2 Pages 451-454
    Published: 1968
    Released: March 27, 2006
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    A new route to the syntheses of 4-methyldihydrocoumarins has been developed by means of the aluminum chloride-catalyzed reaction of phenols with allyl cyanide. The reaction of excess phenol with allyl cyanide in the presence of 2 equivalents of anhydrous aluminum chloride and an excess of hydrogen chloride yielded β-(p-hydroxyphenyl)-butyronitrile in a 16% yield. In contrast, the corresponding 4-methyldihydrocoumarins were obtained, together with β-arylbutyronitriles, from o- and m-cresols. p-Cresol gave rise to 4,6-dimethyldihydrocoumarin as the sole product in a 8% yield. In diisopropyl ether, resorcinol underwent a similar reaction with allyl cyanide and afforded 4-methyldihydroumbelliferone in a 50% yield.
  • Shigetoshi Takahashi, Toshiki Shibano, Nobue Hagihara
    1968 Volume 41 Issue 2 Pages 454-460
    Published: 1968
    Released: March 27, 2006
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    It has been found that palladium-phosphine complexes coordinated by dienophile and tetrakis-(triphenylphosphine) palladium catalyzed the linear dimerization of butadiene. The dimerization of butadiene with bis(triphenylphosphine)(maleic anhydride)palladium in aprotic solvents, such as benzene, tetrahydrofuran, and acetone, gave octatriene-1,3,7 selectively in good yields. In such alcohols as methanol, ethanol, and isopropanol, butadiene was converted to 1-alkoxyoctadiene-2,7 and/or octatriene-1,3,7, depending on the nature of the alcohols employed. The dimerization in secondary amines, such as morpholine, piperidine, and diisopropylamine, gave butadiene dimer-amine adducts of the R2N(C8H13) type, while that in primary amines, such as aniline and n-butylamine, gave a mixture of RNH(C8H13) and RN(C8H13)2. Phenoxy- and acetoxyoctadiene were also obtained from the reactions in phenol and acetic acid respectively.
  • Oyo Mitsunobu, Kyoko Kodera, Teruaki Mukaiyama
    1968 Volume 41 Issue 2 Pages 461-464
    Published: 1968
    Released: March 27, 2006
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    Triethyl phosphite and tri-n-butyl phosphite were oxidized to the corresponding trialkyl phosphates by means of p-quinones and benzyl alcohol. On the other hand, when diethyl (N-diethyl)phosphoroamidite was treated with p-benzoquinone and benzyl alcohol, 4-ethoxyphenyl ethyl (N-diethyl)phosphoroamidate was obtained in a 69% yield and no diethyl (N-diethyl)-phosphoroamidate was isolated. The reaction of 2,3,5,6-tetrachloroquinone with diethyl benzyl phosphite in the presence of ethanol resulted in the formation of triethyl phosphate and 4-benzyloxy-2,3,5,6-tetrachlorophenyl diethyl phosphate in 16% and 68% yields respectively.
  • Sumio Umezawa, Kuniaki Tatsuta
    1968 Volume 41 Issue 2 Pages 464-468
    Published: 1968
    Released: March 27, 2006
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    In continuing our study of the relationship between structural and biochemical characteristics of aminoglycosides, amino-deoxy derivatives of polysaccharides have been synthesized. The six primary hydroxyl groups of Schardinger α-dextrin and the three primary hydroxyl groups of raffinose have successfully been replaced by amino groups respectively, to give hexa-(6-amino-6-deoxy)-cyclohexaglucan (α-1,4) (IV) and 1″,6,6″-triamino-1″,6,6″-trideoxyraffinose (X). Their structures were confirmed by their NMR and IR spectra and by the studies of their chemical reactions. It has been found that hexa-(6-amino-6-deoxy)-cyclohexaglucan (α-1,4) showed significant antitumor activity.
  • Hiroshi Suginome, Masakazu Murakami, Tadashi Masamune
    1968 Volume 41 Issue 2 Pages 468-475
    Published: 1968
    Released: March 27, 2006
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    The results of photolysis of a number of nitrite esters derived from jervine, in which the respective β-carbon of nitrite group bears nitrogen, are described. It has been found that in these nitrites when a nitrogen on β-carbon was in the amide group, the irradiation caused the cleavage of α, β-single bond to the nitrite group. The reaction is exemplified by photolysis of 3O, N-diacetyl-22,27-imino-11-oxojerva-5,13(17)-diene-3β, 23β-diol 23-nitrite ester (Ic) to afford an aldehyde II. When a nitrogen on β-carbon of nitrite was tertiary (e.g., XIb), however, no photoinduced fission of carbon-carbon bond in these nitrites was observed and the starting alcohol recovered unchanged. These results coupled with others, e.g., the result of photolysis of 3O-acetyl-N-benzoyl-22,27-imino-11-oxojerva-5,12-diene-3β, 23β-diol 23-nitrite ester (IIIf) indicate the selective cleavage of acyl-nitrogen bond followed by acidic hydrolysis to an aldehyde during chromatography, as shown in the scheme V to VIII. It is noted that this reaction is contrasted with the reported results with regard to photolysis of nitrites bearing oxygen in place of nitrogen.
  • Teruo Tsunoda
    1968 Volume 41 Issue 2 Pages 475-478
    Published: 1968
    Released: March 27, 2006
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    The analyses of organic soils extracted from naturally-soiled chloths were carried out by IR spectroscopy, gas chromatography, thin-layer chromatography (TLC), and gel filtration. The fatty-acid constituents involved in organic soil were determined by gas chromatography. The presence of triglycerides, cholesterol and its ester, and such hydrocarbons as paraffin and squalene in organic soil was also found by means of TLC. In gel filtration, two peaks were found in elution diagrams of the detergent solution after washing naturally-soiled cloths. The ultraviolet spectra, which were measured for the effluent corresponding to each peak, indicated that the nitrogen compound involved in each effluent is probably a protein-lipid complex such as lipoprotein. The nitrogen content in each effluent was also determined by the micro-Kjeldahl method. A smaller nitrogen content was given for the effluent corresponding to the first peak than for that of the second peak. The nitrogen compound involved in the effluent for the first peak was harder to remove from cloths than that for the second peak.
  • Hiroshi Uchida, Masaaki Oba, Norio Isogai, Toji Hasegawa
    1968 Volume 41 Issue 2 Pages 479-485
    Published: 1968
    Released: March 27, 2006
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    Structures of the zinc oxide-copper catalysts, whose catalytic activity in carbon monoxideshift conversion had been determined, were investigated by X-ray diffraction technique, mercury and helium-volume measurement, and electron microscopy. The electron microscopic observations were conducted in two ways; one on a catalyst sample after the activity test and the other on a raw sample while undergoing specified treatments in a reaction chamber attached to the electron microscope. On the basis of models of particle geometry obtained from the electron microscopic images, the results on pore volume, average diameters of pores and particles, all dependent on the method of preparation and the chemical composition, are explained. The models and the observed dependency of the specific activity of copper surface on the copper content indicate that the finer copper particles, whether patch-like or massive, show the higher specific activity. The fine copper particle is apt to be oxidized more readily than the well-grown particle.
  • Tokiti Noda, Kanichi Kamiya, Michio Inagaki
    1968 Volume 41 Issue 2 Pages 485-492
    Published: 1968
    Released: March 27, 2006
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    Polyvinylchloride coke was heat-treated under the quasi-hydrostatic pressure of 1,3, and 5 kbar by using a simple piston cylinder type high pressure apparatus. The process of graphitization under pressure was studied kinetically by analyzing the profile of the (002) diffraction line. It was found that the accelerating effect of pressure on the graphitization of carbon became more pronounced at higher pressure. The process of graphitization under 3, and 5 kbar seemed to take place in at least two stages. In the first stage, the profile of the (002) line shifted simply from the position of the original line to 26.0° in 2θ, which corresponded to a c0-spacing of 6.85 Å. In the next stage, a new component, having a c0-spacing of about 6.72 Å, appeared in addition to the first component, having a c0-spacing of 6.85 Å. Therefore, the profiles of the (002) line became composite. Under 1 kbar, however, no composite profiles were observed and the c0 Spacing decreased gradually with heat treatment. Approximate values for the activation energy and activation volume for graphitization under 3–5 kbar were estimated to be 80–120 kcal/mol, and −7–−9 cc/mol, respectively.
  • Sarju Prasad, Virendra Nath Garg
    1968 Volume 41 Issue 2 Pages 493-494
    Published: 1968
    Released: March 27, 2006
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  • Kenichi Murata, Akira Terada
    1968 Volume 41 Issue 2 Pages 495-498
    Published: 1968
    Released: March 27, 2006
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  • Shizunobu Hashimoto, Junzo Sunamoto
    1968 Volume 41 Issue 2 Pages 499-501
    Published: 1968
    Released: March 27, 2006
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  • Koichi Irako, Shiro Anzai, Akira Onishi
    1968 Volume 41 Issue 2 Pages 501-503
    Published: 1968
    Released: March 27, 2006
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  • Yoshinori Musha, Akio Okagawa, Tamotsu Kondo, Masuzo Nagayama
    1968 Volume 41 Issue 2 Pages 503-506
    Published: 1968
    Released: March 27, 2006
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  • Tatsuo Takeshima, Motomu Muraoka, Hiroe Asaba, Masataka Yokoyama
    1968 Volume 41 Issue 2 Pages 506-508
    Published: 1968
    Released: March 27, 2006
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  • Masao Okubo
    1968 Volume 41 Issue 2 Pages 508-510
    Published: 1968
    Released: March 27, 2006
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  • Takahiko Tsuyuki, Shûzô Yamada, Takeyoshi Takahashi
    1968 Volume 41 Issue 2 Pages 511-512
    Published: 1968
    Released: March 27, 2006
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  • Sun’ichi Nozakura, Manabu Tagaya, Heimei Yuki, Shunsuke Murahash ...
    1968 Volume 41 Issue 2 Pages 512-513
    Published: 1968
    Released: March 27, 2006
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  • Katsumi Tabei, Chihiro Ito
    1968 Volume 41 Issue 2 Pages 514-515
    Published: 1968
    Released: March 27, 2006
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