Bulletin of the Chemical Society of Japan
Online ISSN : 1348-0634
Print ISSN : 0009-2673
ISSN-L : 0009-2673
Volume 43 , Issue 5
Showing 1-50 articles out of 77 articles from the selected issue
  • Toshio Ikeda, Kazuo Sueoka
    1970 Volume 43 Issue 5 Pages 1273-1275
    Published: 1970
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    The viscometer method was applied to determine the magnetic susceptibilities of aqueous solutions of cupric salts. The effective magnetic moments of the cupric ions obtained were in agreement with values in literature, except for cupric nitrate and acetate. The former showed a relatively high value and the latter gave variable values, which suggest some dimerization effect occuring in aqueous solution with increasing concentration.
  • Toshiaki Kishikawa, Yasuyuki Aratono, Chiro Shinomiya
    1970 Volume 43 Issue 5 Pages 1276-1282
    Published: 1970
    Released: March 27, 2006
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    Antimony tribromide and a molecular compound between antimony tribromide and benzene (2:1) have been irradiated to provide 82mBr sources. The results obtained by the dissolution of the irradiated molecular compound, by means of which technique the chemical effects of 81Br(n,γ)82gBr and 82mBr(I.T.)82Br were determined separately, had shown very low organic yields from either (n,γ) or (I.T.) excitation. The reaction of 82mBr(I.T.)82Br in benzene showed a growth in the organic yields. Moreover, the organic yield of 82Br was lower when the system was frozen than when it was stored as a liquid. These results are explained by assuming that, in the frozen system, the antimony tribromide (82mBr) forms a molecular compound with the benzene. The higher organic yields in the frozen systems than those in the molecular compound itself must be due to the formation of free bromine (82mBr), which turns out to be an organic radiobromide. The hydrolytic behavior of the irradiated antimony tribromide and the molecular compound supports the idea of the presence of free bromine (82mBr) at the end of the irradiation.
  • R. C. Sharma, M. M. Sharma
    1970 Volume 43 Issue 5 Pages 1282-1286
    Published: 1970
    Released: March 27, 2006
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    The kinetics of the alkaline hydrolysis of some acyl acetals (liquid and solid) was studied in 90 parts (wt/wt) aqueous ethanol medium. Steric and inductive effects were found to play an important role. A straight line relationship was observed between the rate constants for the alkaline hydrolysis of benzylidene-, and m- and p-nitrobenzylidene diacetates and Hammett’s substitution constant, σ. In the case of n-butylidene and benzylidene diacetates the theory of mass transfer accompanied by fast pseudo first-order reaction was employed for the determination of rate constants in an aqueous medium.
  • Isao Kamiya, Sadao Kato
    1970 Volume 43 Issue 5 Pages 1287-1292
    Published: 1970
    Released: March 27, 2006
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    We have found that the chemiluminescence emission of several xanthene dyes with hydrogen peroxide is comprised of two emission components; one is a greenish-yellow emission whose spectral distribution is similar to that of the fluorescence of the dye, and the other is a blue emission similar to the fluorescence band which appears during the course of the reaction. Summarizing the results, we can conclude that the chemical formation of an excited species from the oxidation of a dye, and an energy-transfer process from the species to an unoxidized dye, are likely to be the mechanism for the luminescent reaction. Certain dyes, uranin, eosin Y, eosin R, erythrosin B, 2′,7′-dichlorofluorescein, mercurochrome, rhodamine B, rhodamine 6G, and rhodamine S, showed similar characteristic chemiluminescence emissions, whereas phloxine, rose bengale, 4-nitrofluorescein, 4,5,6,7-tetrachlorofluorescein, sulfonfluorescein, and pyronine G did not chemiluminesce under comparable conditions.
  • Enzo Tachikawa, Toshiki Kahara
    1970 Volume 43 Issue 5 Pages 1293-1297
    Published: 1970
    Released: March 27, 2006
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    The roles of the excess kinetic energy and the thermal ionic processes in the reaction of the 80Br from the isomeric transition of 80mBr in gaseous CH4 and CD4 were investigated using a rare gas additive. A possible isotope effect has appeared on the substitution reaction of the energetic Br atom to form CH380Br or CD380Br, but not on the thermal processes to form CH380Br and CH280BrBr or their isotopic alternatives. At a zero mole fraction of moderator, the CH380Br/CD380Br ratio for the energetic process was found to be 2.7±0.3. This is consistent with the moderator and/or probability integral isotope effects. However, in a highly moderated system the results indicated that the former effect is more important than the latter. Furthermore it can be inferred from the total pressure effects on the energetic reaction products that the excited primary products are able to decompose unimolecularly due to internal excitation.
  • Akira Kunugi, Toshiyuki Shimizu, Shigeo Nagaura
    1970 Volume 43 Issue 5 Pages 1298-1302
    Published: 1970
    Released: March 27, 2006
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    The anodic oxidation of the propionate anion in aqueous solutions of propionic acid at a platinum electrode has been studied in the presence of several organic compounds in order to demonstrate the formation of both propionoxy and ethyl radicals as the reaction intermediates. One of the following organic compounds was added to each solution: two vinyl monomers (acrylic acid and acrylamide), two alkylbenzenes (toluene and cumene), and two aliphatic alcohols (methanol and isopropanol). The electrooxidation of sodium propionate in the presence of acrylamide resulted in polymerization, which was confirmed to be initiated by the ethyl radical. Acrylic acid, unlike acrylamide, gave no polymers. In this case, both the current efficiency for the formation of carbon dioxide and the yield ratio of ethylene to carbon dioxide were always less than those observed in the absence of acrylic acid. While the addition of alcohols gave no definite results, the addition of toluene or cumene resulted in an appreciable decrease in the yield ratio of ethylene to carbon dioxide, but affecting neither the ratio of ethane to carbon dioxide nor the current efficiency for the carbon-dioxide evolution. These results indicate that the anodic oxidation of the propionate anion proceeds through the consecutive formation of propionoxy and ethyl radicals as the reaction intermediates.
  • Kimiyoshi Matsumura
    1970 Volume 43 Issue 5 Pages 1303-1306
    Published: 1970
    Released: March 27, 2006
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    The solution properties of poly-o-methylstyrene in toluene were measured by the light-scattering and viscosity methods, and the results were compared with those obtained from poly-o-chlorostyrene and other polystyrene derivatives. The dependencies of the intrinsic viscosity, the second virial coefficient, and the end-to-end distance of the polymer chain on the molecular weight are as follows:
    & [η]=9.22×10^-5·M_w^0.72(dl/g), A_2=3.89×10^-2·M_w^-0.38 (mol·cc/g^2)
    & and ⟨L^2⟩^1/2=0.197×M_w^0.62 (Å).
    It was made clear that the unperturbed dimension of poly-o-methylstyrene was larger than that of poly-p-methylstyrene, and that the cause of this difference is the large steric repulsion between the side groups of the former. Moreover, the unperturbed dimension of poly-o-methylstyrene was smaller than that of poly-o-chlorostyrene. From these results, it is considered that the large extension of poly-o-chlorostyrene was affected by the electrostatic repulsion between the side groups.
  • Seiki Sakanoue, Yasushi Kai, Noritake Yasuoka, Nobutami Kasai, Masao K ...
    1970 Volume 43 Issue 5 Pages 1306-1312
    Published: 1970
    Released: March 27, 2006
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    The crystal structure of an organic charge-transfer complex, 1-ethyl-2-methylquinolinium iodide, [(C12H14N)+·I], has been determined by means of three-dimensional X-ray data (MoKα). The crystals are monoclinic, space group P21/c, and have four formula units in a unit cell with the dimensions of a=7.187±0.002, b=15.914±0.002, c=10.331±0.002 Å, and β=94.67±0.01°. The structure is built up from an iodide anion and a planar 1-ethyl-2-methylquinolinium cation, which lie roughly on a plane. The cations are stacked approximately parallel to the a-plane, forming an endless column along the a axis; the interplanar spacings of these cations are alternately 3.4 and 3.6 Å. The iodide anions are located in the spaces between these columns and the ethyl groups of the cations. The closest distance between an iodide anion and the carbon atoms of a 1-ethyl-2-methylquinolinium ring is 3.93 Å.
  • Kunio Fukushima
    1970 Volume 43 Issue 5 Pages 1313-1318
    Published: 1970
    Released: March 27, 2006
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    A normal coordinate treatment of the potassium oxalate monohydrate crystal as a whole was carried out. On the basis of the results of the calculation, the nature of the lattice vibrations and the bound state of the water of crystallization were discussed.
  • Shin Sato, Chiharu Takahashi, Shigeru Tsunashima
    1970 Volume 43 Issue 5 Pages 1319-1322
    Published: 1970
    Released: March 27, 2006
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    The cadmium-photosensitized decomposition of acetone has been studied and compared with the 3261 Å direct photolysis at 270±1°C. The data could be consistently explained by the following reaction mechanism:
    & Cd(^3P_1)+CH_3COCH_3→Cd+^3A^*\labeleq1
    & ^3A^*→2CH_3+CO\labeleq2
    & CH_3+CH_3COCH_3→CH_4+CH_3COCH_2\labeleq3
    & 2CH_3→C_2H_6\labeleq4
    & CH_3+CH_3COCH_2→C_2H_5COCH_3\labeleq5
    & 2CH_3COCH_3→(CH_3COCH_2)_2\labeleq6
    The mechanism from (2) to (6) is exactly the same as that proposed for the 3130 Å direct photolysis at temperatures higher than 100°C. By using the cis-trans isomerization of 2-butene as the actinometer, the quantum yield of the photosensitized decomposition of acetone was estimated to be 0.3. Kinetic analysis showed that the energy-rich ethane produced by the recombination reaction (4) has the lifetime of 2×10−8 sec at 270°C.
  • Makoto Nagai, Atsuo Nishioka, Juji Yoshimura
    1970 Volume 43 Issue 5 Pages 1323-1329
    Published: 1970
    Released: March 27, 2006
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    The PMR spectra of 22 amino acids and peptides were measured in a D2O solution. From the change in the NMR parameters in amino acids and their di- and tripeptides, it has been concluded that a tripeptide is a good model for polypeptides. The chemical shift of the α-proton of an aminoacid residue in tripeptide can be obtained from those of amino acid and dipeptide. The spin-spin coupling constant of an amino acid grows larger, and the population of a trans rotamer becomes larger, as its amino (or carboxyl) group forms a peptide bond. The PMR spectra of two diasteroisomers of valyl-valyl-valine were also measured, and the influences of the configuration of an aminoacid residue on the NMR parameters of its peptides were investigated.
  • Kazuie Kimura, Takuji Miwa, Masashi Imamura
    1970 Volume 43 Issue 5 Pages 1329-1336
    Published: 1970
    Released: March 27, 2006
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    The γ-radiolysis of eosin has been studied in deaerated neutral and alkaline methanolic solutions. Eosin is reduced principally with CH2OH radicals in dilute solutions. In neutral solutions, G(–eosin) is about 2 at the eosin concentration of 10−5M and increases as the concentration of eosin is increased. The final products are leuco-eosin and an unidentified substance which has an absorption peak at 455 nm. In an alkaline solution (10−5M), G(–eosin) is about 4 and the product is semireduced eosin, which is stable in the dark and which undergoes photo-debromination. The ESR spectrum of semireduced eosin has also been recorded. Comparative studies have also been made on uranin solutions.
  • Kazuie Kimura, Takuji Miwa, Masashi Imamura
    1970 Volume 43 Issue 5 Pages 1337-1342
    Published: 1970
    Released: March 27, 2006
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    Semireduced eosin was found to undergo photo-debromination and was identified with a precursor in the photo-debromination of eosin in alkaline methanolic solutions. Semireduced eosin was prepared by the γ-irradiation of an eosin solution. The photolysis of semireduced eosin was investigated by the use of continuous and flash light. From the absorption spectral change and a study of the decay, the mechanism of the photo-debromination was proposed. The debromination process of the photo-excited semireduced eosin was explained satisfactorily by assuming the transient formation of the debrominated-eosin σ-radical as an intermediate. In addition, we found an electron-transfer reaction from semireduced debrominated eosin to eosin, which results in the formation of semireduced eosin and debrominated eosin in the dark. A general conclusion as to the photo-dehalogenation of xanthene dyes is also given.
  • Toshihide Tsuji, Shunichi Murakoshi, Kazuo Fueki, Takashi Mukaibo
    1970 Volume 43 Issue 5 Pages 1343-1345
    Published: 1970
    Released: March 27, 2006
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    A miscibility gap in AgBr-LiBr solid solutions has been found by the high temperature X-ray diffraction method, and a new phase diagram is presented. Activity, partial molar free energy, enthalpy and entropy of AgBr in AgBr-LiBr solid solutions have been obtained at 350 and 400°C from the e.m.f. data of galvanic cells of the type Ag/AgBr-LiBr/Br2. It has been found that the solid solution forms a regular solution dinned by Hildebrand.
  • Tadayoshi Sakata, Saburo Nagakura
    1970 Volume 43 Issue 5 Pages 1346-1353
    Published: 1970
    Released: March 27, 2006
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    The charge-transfer interaction is investigated theoretically for linear chain systems in molecular crystals. The charge-transfer excitation energy is shown to diverge in crystals by the usual configuration interaction method considering only one-molecule excitation. In order to overcome this difficulty, the second quantized Hamiltonian is solved with the Bose approximation for the charge-transfer exciton. Consequently, reasonable results are obtained for the stabilization of the ground state due to the contribution of many virtual excitons, for the electric dipole moment of the ground state, and for the transition moment of a charge-transfer excitation. The results correspond well to those by Mulliken’s theory for an electron donor-acceptor pair. The second quantization model is also applied in the extended form to crystals of charge-transfer complexes and ionic radicals of complex stoichiometry. The lower excited states in these crystals are understood as the coupled ones of the one-site and two-site charge-transfer configurations.
  • Eeki Yasaki, Isao Oonishi, Hiroshi Kawaguchi, Shinichi Kawaguchi, Yosh ...
    1970 Volume 43 Issue 5 Pages 1354-1359
    Published: 1970
    Released: March 27, 2006
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    The crystal structure of trans-[Co(NO3)2(tn)2]NO3 (tn: H2N–CH2–CH2–CH2–NH2) has been determined from three-dimensional X-ray diffraction data. The dimensions of the monoclinic unit cell are: a=8.62 Å, b=10.04 Å, c=9.61 Å, β=114.0°, and Z=2. The space group is P21/c. The structure has been refined by the least-squares method to R=0.114. The complex ion has a slightly distorted octahedral coordination, with four N atoms of trimethylenediamine molecules at 1.990±0.009 Å and two O atoms of nitrate ions at 1.898±0.007 Å. The two six-membered cobalttrimethylenediamine rings are identical, as is required by the center of symmetry, and take the chair form. The complex ions and nitrate ions are tightly bound together by N–H···O hydrogen bonds in the layers parallel to the (100) plane, but there exists no evidence for hydrogen bonding between the layers.
  • Kunishige Naito, Shinsuke Takei, Taijiro Okabe
    1970 Volume 43 Issue 5 Pages 1360-1364
    Published: 1970
    Released: March 27, 2006
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    The quantitative determination of some low valence sulfur compounds, especially low polythionates, which appeared as intermediate products in the oxidation of elemental sulfur with compressed oxygen in aqueous ammonia was investigated by means of thin-layer chromatography and colorimetry with methylene blue to establish the mechanism of the oxidation of elemental sulfur. Thiosulfate and some low polythionates could be resolved clearly by thin-layer chromatography using silica gel as an absorbent. A suitable solvent for the development was a mixed solution of ethyl alcohol, n-butyl alcohol, aqueous ammonia, ammonium acetate and distilled water. The amount of sulfur in the developed spot of the thin-layer chromatogram was determined photometrically with precision of 10 to 20% using methylene blue as a color reagent. Sulfate, sulfite and thiosulfate could not be developed effectively by this method.
  • Kunishige Naito, Masahiro Yoshida, Mu-Chang Shieh, Taijiro Okabe
    1970 Volume 43 Issue 5 Pages 1365-1372
    Published: 1970
    Released: March 27, 2006
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    The oxidation of ammonium thiosulfate with compressed oxygen in aqueous ammonia solution was examined. It was found that ammonium sulfamate and ammonium sulfate are mainly produced and a small amount of nitrite and imidodisulfonate obtained in the final solution. The most suitable conditions to produce ammonium sulfamate from ammonium thiosulfate industrially are as follows: reaction temperature 100°C, oxygen pressure 50 kg/cm2, concentration of ammonia 16 mol/l, concentration of cupric ion 0.1–0.2 mol/l. The electrolytic oxidation, hydrogen peroxide oxidation and ozone oxidation of ammonium thiosulfate were also examined.
  • Kunishige Naito, Mu-Chang Shieh, Taijiro Okabe
    1970 Volume 43 Issue 5 Pages 1372-1376
    Published: 1970
    Released: March 27, 2006
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    The decomposition and oxygen oxidation of tetrathionate in aqueous ammonia solution have been investigated. In the decomposition, thiosulfate, sulfate and sulfamate were formed through penta- and trithionate as intermediate compounds. The molar ratio of the products (SO42−+SO3NH2)/S2O32− was roughly equal to 2/7, where 0.1N ammonia solution was used. The deficient use of ammonia made the solution neutral or weakly acidic and the precipitation of sulfur and the formation of higher polythionates were observed. The polythionate was detected by means of TLC (Thin Layer Chromatography). In the oxidation, tetrathionate was supposed to go through the following three sequent steps. 1) Decomposition of tetrathionate to form thiosulfate, tri- and pentathionate, and further decomposition of pentathionate to thiosulfate. 2) Oxidation of thiosulfate to tetrathionate and partly to sulfate. 3) Decomposition of trithionate to form sulfate, sulfamate and thiosulfate.
  • Hidetake Kakihana, Masunobu Maeda, Toshihiko Amaya
    1970 Volume 43 Issue 5 Pages 1377-1379
    Published: 1970
    Released: March 27, 2006
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    In the present work, experiments were carried out for the systems of 20, 80 and 99.8% heavy water. It has turned out that the relationship between the emf and the lyonium ion concentration in a H2O–D2O mixed solvent can be expressed at 25°C by the so-called Nernst equation within the limits of experimental accuracy of ±0.1 mV. This means that the lyonium ion concentration in a H2O–D2O mixed solvent can be measured with the same experimental accuracy (uncertainty of ±0.1 mV) as that in light water by the use of a glass electrode.
  • Akiko Sat\={o}, Shin Suzuki
    1970 Volume 43 Issue 5 Pages 1380-1382
    Published: 1970
    Released: March 27, 2006
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    The distribution of U(III) between hydrochloric acid solutions and benzene solutions of bis(n-butyl) orthophosphoric acid or cyclohexane solutions of bis(2-ethylhexyl) orthophosphoric acid has been investigated by using the uranium-237 isotope as a tracer. It has been found that the log-log plot of the distribution ratio vs. the concentration of dimeric organophosphoric acids, and that of the distribution ratio vs. the hydrogen ion concentration, always show a good linearity, with a slope of 3. This indicates that the complex-forming reaction is as follows:
    U^3++3(HA)_2\ ightleftarrowsU(HA_2)_3+3H^+
    where (HA)2 represents the dimeric solvent, (HDBP)2 or (HDEHP)2. The above results are in agreement with the conclusions reached in the cases of other trivalent actinide and lanthanide elements by other investigators.
  • Ryokichi Tsuchiya, Kiyoko Murai, Akira Uehara, Eishin Kyuno
    1970 Volume 43 Issue 5 Pages 1383-1387
    Published: 1970
    Released: March 27, 2006
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    The thermal decomposition of trans-[CoCl2pn2](H5O2)Cl2 in solid-phase was measured by derivatography and the isothermal method with a thermobalance. It was found by the latter that dehydration and dehydrochlorination took place with partial isomerization below 170°C. The rate of isomerization gradually increased with temperature until it became equal to the rate of dehydration and dehydrochlorination above 170°C. The activation energies for dehydration and dehydrochlorination and for isomerization were calculated from the isothermal measurement below 170°C to be 10 kcal/mol and 23 kcal/mol, respectively. The activation energy obtained from DTA curve analysis at about 144°C in the derivatogram was 33 kcal/mol. The reaction was explained in terms of “aquation-anation” mechanism. Since the trans-cis isomerization in anhydrous state at 180°C gave a larger activation energy in DTA analysis, the “twisting” mechanism might be preferable to “aquation-anation” for the reaction.
  • Emiko Ohyoshi
    1970 Volume 43 Issue 5 Pages 1387-1389
    Published: 1970
    Released: March 27, 2006
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    An attempt to determine the optimum concentration of ligand ion for the separation of adjacent pairs of rare earth elements by electromigration was made using the method employed for the determination of the stability constant of complex. To examine the theory, separation of lanthanum and cerium, and cerium and praseodymium was carried out using α-hydroxyisobutyric acid as a complexing agent. From the results, factors necessary for the separation of all kinds of rare earth elements were discussed.
  • Kenzo Kitayama
    1970 Volume 43 Issue 5 Pages 1390-1393
    Published: 1970
    Released: March 27, 2006
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    The activity-composition relation in the pyroxene solid solution, MgSiO3–FeSiO3, is determined by the quenching method in the atmosphere of a gas mixture of CO2 and H2 at 1154, 1204, and 1250°C. A non-ideality is found in the solution at these temperatures, and it increases with a decrease in the temperature. The standard free energy values of the formation of ferrosilite, FeSiO3, from metallic iron, silica, and oxygen are −42.5±0.3, −41.7±0.2, and −41.3±0.2 kcal per mole of FeSiO3 at 1154, 1204, and 1250°C respectively. Using the data by Darken and Gurry, the standard free energies of the formation of ferrosilite from wüstite and silica are obtained as −1.8±0.3, −1.5±0.2, and −1.8±0.2 kcal per mole of FeSiO3 at 1154, 1204, 1250°C respectively.
  • Akira Uehara, Eishin Kyuno, Ryokichi Tsuchiya
    1970 Volume 43 Issue 5 Pages 1394-1397
    Published: 1970
    Released: March 27, 2006
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    The geometrical structures and some properties of the following complexes were investigated: K[Co(ida)2]·H2O (I), K[Co(ida)2]·2H2O (II), K[Cr(ida)2]·3H2O (III), Ba[Cr(ida)2]2·6H2O (IV), K[Co(mda)2] (V), K[Cr(mda)2] (VI), K[Co(eda)2]·H2O (VII) and K[Cr(eda)2]·H2O (VIII), where ida, mda and eda are the abbreviations of iminodiacetate, methyliminodiacetate and ethyliminodiacetate ions, respectively. IV, VII and VIII are new compounds. On the basis of electronic spectra, it was found that VII and VIII have the trans form with respect to nitrogen atoms in the ligands, and IV, the cis form. Comparison of the properties and structures of the cobalt-(III) complexes with those of the corresponding chromium(III) complexes were also made.
  • Akira Uehara, Eishin Kyuno, Ryokichi Tsuchiya
    1970 Volume 43 Issue 5 Pages 1397-1402
    Published: 1970
    Released: March 27, 2006
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    β-Amino-n-butyric-N,N-diacetic acid (β-ABDA) and γ-amino-n-butyric-N,N-diacetic acid (γ-ABDA) were prepared as compounds related to nitrilotriacetic acid (NTA). Bis-type cobalt(III) and chromium(III) complexes with these ligands, viz., K3[Co(β-abda)2] (I), K[Co(H-γ-abda)2]·2H2O (II) and K[Cr(H-γ-abda)2]·2H2O (III), and the same type cobalt(III) complex with β-aminoethylsulfonic-N,N-diacetic acid (AEDA), viz., K3[Co(aeda)2]·4H2O (IV), were also synthesized. Chemical properties of the above complexes were compared with those of the chromium (III) complex corresponding to IV and of the cobalt(III) and chromium(III) complexes with NTA and NPDA. From the analysis of electronic spectra, it was found that the new complexes, I, II, III and IV have the trans form with respect to the nitrogn atoms in the ligands. A spectrochemical series of these ligands, containing iminodiacetic acid (IDA), methylimino-diacetic acid (MDA) and ethyliminodiacetic acid (EDA), was determined to be:
    IDA>MDA>NPDA>β-ABDA>EDA>AEDA>NTA>γ-ABDA.
  • Yoshiaki Furuya, Kazuo Itoho
    1970 Volume 43 Issue 5 Pages 1403-1407
    Published: 1970
    Released: March 27, 2006
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    The rates of the reactions of p- and m-substituted phenyl phenoxyacetates with benzylamine in dioxane, thus forming N-benzylphenoxyacetamide and the corresponding phenols, were followed by the non-aqueous titration of benzylamine. The reaction satisfied the following general equation:
    ν={k_2’+k_3’[Amine]}[Amine][Ester]+{k_3”+k_4[Amine]}[Amine][Ester]^2.
    The reaction was a neucleophilic substitution, and the Hammett plots gave straight lines with positive ρ values. A marked enhancement in the conductivity of the reaction mixtures in 50% dioxane was observed, it increasing with the reaction time. A probable mechanism was presented which involves an ion pair of the quaternary ammonium salt type somewhat similar to that discussed in a previous paper (Y. Furuya, S. Goto, K. Itoho, I. Urasaki and A. Morita, Tetrahedron, 24, 2367 (1968)).
  • Seizi Kozuka, Hideo Takahashi, Seizo Tamagaki, Shigeru Oae
    1970 Volume 43 Issue 5 Pages 1408-1411
    Published: 1970
    Released: March 27, 2006
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    Mass spectra of substituted phenyl p-toluenesulfonates were analyzed with the aid of metastable peaks. Three steps in fragmentation were suggested as the main processes for these compounds i.e., the initial S–O bond cleavage giving sulfonylcation, the second desulfonylation and the final loss of acetylene. Effect of substituent on the rate of the decomposition was observed in these three steps. The results are discussed in terms of various internal energies of the initial fragment ions. Apparently, the rates of the initial decomposition depend on the nature of the substituents.
  • Tyo Sone, Koji Sakai, Kimio Kuroda
    1970 Volume 43 Issue 5 Pages 1411-1415
    Published: 1970
    Released: March 27, 2006
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    In the presence of iron powder, thiophene reacted with sulfuryl chloride at room temperature to give a mixture of chlorinated 2,2′-dithienyls as the main product in yields of up to 42%, while the reaction without a catalyst gave chlorothiophenes. The yield of the coupling product and the chlorine content in the product increase with an increase in the molar ratio of sulfuryl chloride to thiophene. 5,5′-Dichloro-, 3,5,5′-trichloro-, and 3,3′,5,5′-tetrachloro-2,2′-dithienyls were isolated from the reaction products. The reaction was also catalysed by Friedel-Crafts-type catalysts, the efficiency of the catalysts decreasing in the order: AlCl3>FeCl3>SnCl4>ZnCl2.
  • Shigeru Oae, Masahiro Kise
    1970 Volume 43 Issue 5 Pages 1416-1420
    Published: 1970
    Released: March 27, 2006
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    Racemization and oxygen exchange reactions were carried out by heating both optically active and 18O-labeled diaryl sulfoxides in a large excess of acetic anhydride. The rate of racemization of p-tolyl phenyl sulfoxide was found to be twice the rate of oxygen exchange, suggesting the reaction to involve a Walden inversion at the rate-determining step. When the reaction was carried out in a mixture of acetic anhydride and chlorobenzene, the rate of racemization was found to be first order with respect to both the sulfoxide and acetic anhydride. The remarkably small substituent effect is also in keeping with the SN2 type mechanism. The marked retardation of the rate of racemization by the addition of common salt is similar to well-known cases in the SN2 reaction of alkyl halides, and the remarkably large acceleration of the rates of both racemization and oxygen exchange reactions by the addition of sodium perchlorate seems to be caused by a special salt effect.
  • Masahiro Kise, Shigeru Oae
    1970 Volume 43 Issue 5 Pages 1421-1426
    Published: 1970
    Released: March 27, 2006
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    Aryl benzyl sulfoxides undergo oxygen exchange and racemization reaction with acetic anhydride, and the rate is dependent on the concentration of both the sulfoxide and acetic anhydride. The reaction proceeds faster in a more polar solvent. Addition of sodium perchlorate or acetic acid accelerates the reaction. In this case, the rate of oxygen exchange is not exactly half of that of racemization. As an example, the ratio, kex/krac, is 0.36 when the reaction was carried out at 100°C. Under the same condition, both the Pummerer reaction and thermal racemization are negligible. Similar to diaryl sulfoxides the effects of phenyl group are small. Implication of the ratio is discussed.
  • Masahiro Kise, Shigeru Oae
    1970 Volume 43 Issue 5 Pages 1426-1430
    Published: 1970
    Released: March 27, 2006
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    The Pummerer reaction, viz., the reaction of sulfoxides having at least one methyl or methylene group with carboxylic acid anhydride gives α-acyloxy derivatives of the corresponding sulfide. Earlier, we suggested on the basis of 18O tracer experiments with 18O-labeled acetic anhydride that the Pummerer reaction of dimethyl sulfoxide with acetic anhydride proceeds through an intermolecular nucleophilic attack of acetoxy group on the methylene carbon of the ylide-ylene intermediate. Noticeable acetoxy interchange has been found to take place during a similar Pummerer reaction of aryl methyl sulfoxide. However, the Pummerer reaction is the main path when the reaction with acetic anhydride is performed at around 120°C. In the Pummerer reaction of aryl methyl sulfoxides, the substituent effect is large (ρ=−1.6) and the kinetic isotope effect (kH/kD) is also substantial, i.e., 2.9. The reaction is assumed to involve the initial acetylation and the subsequent slow proton removal steps. Addition of sodium perchlorate or acetic acid accelerates the acetoxy exchange reaction rather than the Pummerer reaction.
  • Koko Maeda, Akiko Chinone, Taro Hayashi
    1970 Volume 43 Issue 5 Pages 1431-1434
    Published: 1970
    Released: March 27, 2006
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    By the oxidation of tetraphenylpyrrole, two types of dimers of tetraphenylpyrryl were obtained. One dimer showed piezochromism and thermochromism, while the other showed photochromism and thermochromism. These phenomena were found to correspond to those of the piezochromic and photochromic dimers of triphenylimidazolyl obtained from triphenylimidazole. The photochromism, thermochromism, and piezochromism of the dimers of tetraphenylpyrryl are determined to be due to the radical dissociation caused by irradiation, heating, and grinding, the same machanism as that in the case of the dimers of triphenylimidazolyl.
  • Hiromichi Kono, Mikio Shiga, Izumi Motoyama, Kazuo Hata
    1970 Volume 43 Issue 5 Pages 1435-1439
    Published: 1970
    Released: March 27, 2006
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    The geometrical and conformational isomerism of various β-ferrocenyl-α,β-unsaturated ketones, most of which had been reported in a previous paper, was discussed on the basis of their IR spectra in the 1700–1600 cm−1 range and their NMR spectra. An unusually strong IR absorption of the olefinic double bond was observed in comparison with that of the carbonyl group. Considering the IR and NMR data, it was concluded that 3-ferrocenyl-1-(p-substituted phenyl)-2-propen-1-ones may mostly exist in a s-cis conformation.
  • Takashi Koyano
    1970 Volume 43 Issue 5 Pages 1439-1443
    Published: 1970
    Released: March 27, 2006
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    Reactions of olefins with cupric chloride were studied in methanol at 100–140°C. The reactivity of olefins was in the order, ethylene>propylene>1-butene>2-butenes. A considerable amount of 1-chloro-2-methoxy compounds were found in the reaction products of 1-olefins. Competitive formation of dichloride and methoxychloride was suggested. Chlorination of 2-butenes leads to meso- and dl-2,3-dichlorobutanes, their ratio being invariable regardless of the starting material cis- or trans-2-butene. The mechanism is discussed in terms of ionic intermediates.
  • Kunihiro Ichimura, Masaki Ohta
    1970 Volume 43 Issue 5 Pages 1443-1450
    Published: 1970
    Released: March 27, 2006
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    The reductive cyclization of α-chloro, bromo- and sulfonyloxycarbonitriles are described. α-Chlorocarbonitriles were reduced by lithium aluminum hydride to afford aziridines in sufficient yields. The Walden inversion was found to take place in the cource of the reductive cyclization of S-α-chloroisocapronitrile. We have found the two-step conversion of aldehydes to 2-mono-substituted aziridines which consists of treating aldehydes with benzenesulfonyl chloride and alkali cyanide to form α-benzenesulfonyloxycarbonitriles which are reduced by lithium aluminum hydride to the corresponding aziridines. The reduction of α-bromocarbonitriles with the hydride yielded prim. amines together with the aziridines.
  • Ko Taki, Pil Hyon Kim, Susumu Namba
    1970 Volume 43 Issue 5 Pages 1450-1454
    Published: 1970
    Released: March 27, 2006
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    Various copper metal salts of organic acid were decomposed by laser heating and conventional heating methods. The product distributions were reasonably explained in terms of the expected reaction of the decarboxylated intermediates. Generally the yield percentage of products is higher in laser decomposition than in thermal decomposition. However, in maleate and fumarate the product distribution is quite different in thermal and laser decompositions. The main product is ethylene in the thermal decomposition, but acetylene in the laser decomposition. This difference may be the result of the heating rate. Since rapid heating and quenching are characteristic of laser heating, the formation of acetylene may be brought about by the simultaneous decarboxylation of two carboxyl groups, while the formation of ethylene may be brought about by successive decarboxylation. Selective decomposition by laser heating will also be discussed in binary systems, such as maleate and ethylene.
  • Shinji Kurokawa
    1970 Volume 43 Issue 5 Pages 1454-1459
    Published: 1970
    Released: March 27, 2006
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    The action of sulfur on two naphthalenes was investigated. Cadalene was heated with sulfur to give a new sulfur-containing naphthalene, 1,5,8-trimethylnaphtho[2,1-b] thiophene. It was formylated at the C2-position of the thiophene moiety according to the Vilsmeier procedure, while an attempted acetylation according to this procedure was unsuccessful. Similarly, the reaction of eudalene with sulfur gave 3,9-dimethylnaphtho[1,2-b]thiophene, whose structure was determined by chromium trioxide oxidation, yielding o-quinone, and by a subsequent reaction with o-phenylenediamine, forming a quinoxaline derivative.
  • Hiroaki Yamada, Yuho Tsuno, Yasuhide Yukawa
    1970 Volume 43 Issue 5 Pages 1459-1472
    Published: 1970
    Released: March 27, 2006
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    The Hammett type treatment of the chemical shift of substituted aromatic side chain protons has not always been successful. The failure might be ascribed to the neglect of magnetic longrange effects. When the corrections were made both for the ring current diminution due to the contribution of polar resonance structure of the introduced substituent and for the substituent magnetic anisotropy effect, an excellent equation was obtained to relate, the chemical shifts of meta-substituted aromatic side chain protons to the Hammett’s constants.
  • Noboru Sugiyama, Choji Kashima, Hiroshi Kataoka, Keiko Tanaka
    1970 Volume 43 Issue 5 Pages 1473-1477
    Published: 1970
    Released: March 27, 2006
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    This paper will describe the photoreaction of trans-β-(p-ethylbenzoyl)acrylic acid (II) in methanol to give 5-(p-ethylphenyl)-5-methoxy-2-oxo-2,5-dihydrofuran (III), β-(p-ethylbenzoyl)-α-methoxypropionic acid (IV), and its methyl ester (V). The kinetic study of this reaction has revealed that II gives III and IV parallel by the first-order reaction and that IV then changes into V. Furthermore, the irradiation of p-substituted β-benzoylacrylic acids has been studied. From the product ratio and the substituent effects at the para position, the mechanism of the photoreactions of γ-oxoacrylic acids in methanol is proposed. This mechanism is also supported by the HMO calculations.
  • Yoshinobu Takegami, Toshimitsu Suzuki, Takashi Shirai
    1970 Volume 43 Issue 5 Pages 1478-1484
    Published: 1970
    Released: March 27, 2006
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    The insertion reaction of isoprene into metal-ethyl bonds in various transition-metal salt (VCl4, Fe(AA)3, Co(AA)2, CoCl2, Ni(AA)2, or NiCl2-ethylaluminum compound (AlEt2Cl or AlEt3)) catalyst systems was studied. With the vanadium and the nickel catalysts, 2-methyl-2-hexene and 2-methyl- 1-hexene were mainly formed by the methanolysis of the reaction mixture, showing that metal alkenyls, (Remark: Graphics omitted.) and (Remark: Graphics omitted.) respectively, are formed in the reaction system. However, in the iron catalyst, only 2-methyl-2,5-hexadiene and 3-methyl-2,5-hexadiene were formed from (Remark: Graphics omitted.) and (Remark: Graphics omitted.) respectively by the elimination reaction. These results suggest that the stability of metal alkenyls decreases in the order: V>>Ni>Co>Fe.
  • Toshimitsu Suzuki, Yoshinobu Takegami
    1970 Volume 43 Issue 5 Pages 1484-1489
    Published: 1970
    Released: March 27, 2006
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    In order to clarify the mechanism of the syndiotactic polymerization of olefin, the insertion reaction of several olefins into metal-ethyl bonds in VCl4-AlEtnCl3−n, VOCl3-AlEtnCl3−n, and V(AA)3-AlEtnCl3−n systems were studied. Cyclohexene was easily inserted into metal-ethyl bonds in these catalysts to give a metal-ethylcyclohexyl bond at −70°C. Pentene-1 and 4-methylpentene-1 gave (Remark: Graphics omitted.) (I) and (Remark: Graphics omitted.) (II). At −70°C with VCl4-AlEt2Cl, where the syndiotactic polymerization of propylene proceeds, four times as much (II) as (I) was obtained. However, at 0°C or in the VCl4-AlEt3 catalyst system, the amount of (I) exceeded the amount of (II). With the VOCl3-AlEtnCl3−n or the V(AA)3-AlEt3Cl3−n system, the selectivity for the formation of metal-alkyl (II) was decreased. The above results lead to the conclusion that, in the course of syndiotactic polymerization, the secondary metal-alkyl bond (II) was an intermediate of the polymerization. By means of this mechanism every experimental result reported can be explained without difficulty.
  • Yoshihiro Sugi, Sekio Mitsui
    1970 Volume 43 Issue 5 Pages 1489-1496
    Published: 1970
    Released: March 27, 2006
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    In order to assess the effects of solvent and additive on the stereochemical course of the catalytic hydrogenolysis of styrene imine derivatives, the hydrogenolysis of optically active 2-methyl-2-phenylaziridine (Ia), 1,2-dimethyl-2-phenylaziridine (Ib), and l-acetyl-2-methyl-2-phenylaziridine (Ic) was carried out under various conditions. The hydrogenolysis of la and Ib over palladium hydroxide occurred preferentially with an inversion of the configuration in ethanol, but with a retention in benzene. Moreover, Ia was hydrogenolysed with a predominant inversion of the configuration in n-hexane, and the inverted product increased with a decrease in the adsorption strength of the hydrocarbon solvent. The hydrogenolysis of Ic, however, occurred with a significant inversion of the configuration in both ethanol and benzene. The addition of sodium hydroxide to the reaction mixture strongly promoted a retention of the configuration in the hydrogenolysis of Ia over palladium hydroxide, and finally Ia was hydrogenolysed with a stereospecific retention. In contrast, no such variations could be observed in the cases of Ib and Ic. The stereoselectivity was not affected significantly by the addition of sodium hydroxide in the Raney nickel-catalyzed hydrogenolysis of Ia. However, the addition of sodium hydroxide prompted a retention of the configuration in the case of Ib. These results can be explained consistently by the previously-proposed mechanism.
  • Masakatsu Matsumoto, Yoichi Matsumura, Akira Iio, Teijiro Yonezawa
    1970 Volume 43 Issue 5 Pages 1496-1500
    Published: 1970
    Released: March 27, 2006
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    2,4-dimethyl- (I-a), 2-methyl-4-phenyl- (I-b), and 2,4-diphenyl-1,5-benzodiazepine (I-c) were irradiated with a high-pressure mercury arc under an oxygen atmosphere in benzene and in acetic acid. In all cases oxidative ring-contraction products, 2-acylquinoxalines (II), were obtained. It was found that there was a solvent effect in these reactions ; e.g., in benzene the diazepine (II-d) leads to 2-benzoyl-3-methylquinoxaline (II-d), while in acetic acid it leads to 2-acetyl-3-phenyl-quinoxaline (II-b).
  • Matsuji Takebayashi, Toshikazu Ibata, Kozaburo Ueda
    1970 Volume 43 Issue 5 Pages 1500-1505
    Published: 1970
    Released: March 27, 2006
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    The reaction of α-diazoacetophenone with carbonyl compounds such as benzaldehyde, acetophenone and p-phenylacetophenone, has been studied in the presence of bis(acetylacetonato) copper (II). The reaction gave the corresponding tetrahydrofurans and dioxolanes accompanied by some by-products derived from benzoylcarbene. The mechanism of the reaction has been discussed in terms of an intermediate with a structure of betaine type, produced by the reaction of a ketocarbene-metal chelate complex with carbonyl compounds.
  • Takashi Yamada
    1970 Volume 43 Issue 5 Pages 1506-1511
    Published: 1970
    Released: March 27, 2006
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    The reaction of trans- and cis-N-aryl-S-triphenylmethyldiazosulfides (I) with β-naphthol in alkaline ethanol was investigated. It was found that the dissociation of I occurs not only with the cis isomers, but also with the trans isomers, even in the dark. The kinetic study suggested that the trans-diazosulfides can dissociate not only through the cis form, but also directly, contrary to Zwet and Kooyman’s suggestion. The dissociation of the trans isomer of diaryldiazosulfides (II) was also discussed analogously. Further, by a preparation at −78°C several cis-diaryldiazosulfldes were isolated which had never before been isolated. The rate constant of the isomerization of cis-N-(p-cyanophenyl)-S-(p-toly)diazosulfide (IIf) was 2.55×10−3 sec−1 (at 0°C, in ethanol) ; this value is much larger than that for cis-I.
  • Kyoji Kaeriyama
    1970 Volume 43 Issue 5 Pages 1511-1516
    Published: 1970
    Released: March 27, 2006
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    Some ketones and aldehydes have an accelerative effect on the polymerization of various monomers by various metal chelates of acetylacetone. The conversion increases with an increase in the concentration of these additives in a correspondingly increasing polymerization time. A radical is formed by the equimolar reaction of cyclohexanone and manganese (III) acetylacetonate and by the reaction of two aldehyde molecules and a molecule of the chelate. The , order with a monomer is lowered from 1.64 to 1.13 and to 1.07 by the addition of cyclohexanone and caproic aldehyde respectively. The relation between the polymerization rate and the square root of the chelate concentration is linear without any additive ; concave and convex curves are obtained for the systems containing cyclohexanone and caproic aldehyde respectively. The apparent activation energy is lowered from 19.9 kcal/mol to 13.9 and to 14.3 in the presence of cyclohexanone and caproic aldehyde respectively. The effectiveness of ketones is dependent on the nucleophilicity. A mechanism of the initiation reaction which interprets the molar ratio of reactants, the kinetical parameters, and the spectral data is proposed.
  • Yuji Iwashita, Fumihide Tamura
    1970 Volume 43 Issue 5 Pages 1517-1520
    Published: 1970
    Released: March 27, 2006
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    Cyclotrimerization of tolane and phenylacetylene has been studied from the viewpoint of the reaction intermediates and the composition of reaction products. Rh4(CO)12 and Co4(CO)12 have been found to catalyze the trimerization of tolane and phenylacetylene to yield some substituted benzenes. By the reaction of Rh4(CO)12 with tolane, an unknown complex was obtained. The triphenyl phosphine derivative of this complex has been determined to be Rh2(CO)3(C6H5C≡CC6H5)2P(C6H5)3. From infrared spectroscopic study, it was concluded that the two tolane molecules in the complex are connected to rhodium atoms separately without completion of dimerization. On the basis of the ratio of 1,2,4-triphenylbenzene to 1,3,5-triphenylbenzene, the reaction course of trimerization is discussed.
  • Yuji Iwashita, Fumihide Tamura, Hachiro Wakamatsu
    1970 Volume 43 Issue 5 Pages 1520-1523
    Published: 1970
    Released: March 27, 2006
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    The reaction of cobalt hydrotetracarbonyl with acetylene was carried out in methanol as a model of the carboxylation of acetylene. The complexes formed in this reaction were identified by means of IR, NMR, EA and molecular weight measurement. The main product was acetylene dicobalt hexacarbonyl. From the decomposition reaction of this complex in ethanol, ethyl acrylate, ethyl propionate and diethyl succinate were obtained. The yield of ethyl acrylate increased in the presence of carbon monoxide. The reaction course from acetylene to acrylate was examined.
  • Kenji Fukui, Mitsuru Nakayama, Tokunaru Horie
    1970 Volume 43 Issue 5 Pages 1524-1529
    Published: 1970
    Released: March 27, 2006
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    2,4-Dibenzyloxy-6-hydroxy-3-methoxyacetophenone was esterified with 3,4-disubstituted benzoyl chlorides, and the resulting esters were converted into 7-benzyloxy-5-hydroxy-6-methoxyflavone derivatives via the corresponding diketones. The catalytic hydrogenolysis of the benzyloxyflavones gave the desired 5,7-dihydroxy-6-methoxyflavones. Ethyl ethers of these flavones were also prepared from 2,4-diethoxy-3-methoxy-6-hydroxyacetophenone by an unambiguous method. 6,3′-Dimethoxy-5,7,4′-trihydroxyflavone, desmethoxycentaureidin (6,4′-dimethoxy-5,7,3′-trihydroxyflavone), and 6-methoxyluteolin (6-methoxy-5,7,3′,4′-tetrahydroxyflavone) were thus prepared.
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