Bulletin of the Chemical Society of Japan
Online ISSN : 1348-0634
Print ISSN : 0009-2673
ISSN-L : 0009-2673
Volume 42 , Issue 12
Showing 1-50 articles out of 62 articles from the selected issue
  • Tadayoshi Tanei, Hiroyuki Hatano
    1969 Volume 42 Issue 12 Pages 3369-3372
    Published: 1969
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    The present work was undertaken in order to examine a photochemical intermediate from benzene using rigid organic matrices: EPA (a mixture of E: diethyl ether, P: isopentane, and A: ethyl alcohol, 5:5:2, v/v), diethyl ether, and isopentane. The UV irradiation of EPA, diethyl ether, and ethyl alcohol at 77°K, in wavelength regions from approximately 2200Å to 2600Å, gave ESR spectra which can be ascribed to the ethyl and/or the ethanol radical, even when a solute was not added. On the contrary, the UV irradiation of isopentane under similar conditions did not show any ESR spectrum. However, the UV irradiation of isopentane containing benzene in concentration regions from 10−1 to 10−2 M gave two kinds of ESR spectra, ascribed to phenyl and tert-pentyl radicals. This reaction may be interpreted as a sensitized photodecomposition brought about by an excitation and/or a photolytic degradation of benzene.
  • Yoshiyuki Mido, Hiromu Murata
    1969 Volume 42 Issue 12 Pages 3372-3379
    Published: 1969
    Released: March 27, 2006
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    The infrared absorption spectra of symmetric and asymmetric dimethylurea have been observed in the 4000—400 cm−1 region. In order to investigate the amide characteristic bands, the spectra of CH3NHCONHCH3 and CH3NDCONDCH3 have also been measured in the solid and liquid states, and in solutions. The in-plane normal vibrations of these molecules have been calculated. As a result of our measurements and calculations, it has been found that: (1) The contribution of the polar resonance structure of asymmetric dimethylurea is small compared with that of symmetric dimethylurea, and molecular geometry contributes to the formation of hydrogen bonding. (2) From the position of the amide bands, the molecular configuration of symmetric dimethylurea is the “trans” form as well as that of methylurea. (3) The results of normal coordinate analysis show a good agreement with that observed within an average deviation of 2.6%.
  • Miyuki Hagiwara, Takeshi Miura, Tsutomu Kagiya
    1969 Volume 42 Issue 12 Pages 3380-3384
    Published: 1969
    Released: March 27, 2006
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    The cobalt-60, γ-radiation induced copolymerization of ethylene with tetrafluoroethylene was carried out in the gas phase and in the liquid phase by using five solvents (liquefied carbon dioxide, carbon tetrachloride, ethylchloride, chloropentafluoroethane, and 1,2-dichloro-tetrafluoroethane) at a dose rate of 25000 rad/hr under a pressure of 300 kg/cm2 at 30°C. A lower rate of the copolymerization and a copolymer of a lower molecular weight were obtained in liquid carbon dioxide and carbon tetrachloride than in the gas phase without a solvent. In ethyl chloride, the rate increased slightly, but the molecular weight decreased. On the other hand, both the rate and the molecular weight increased markedly in the fluorocarbon solvents. As a result of a detailed investigation of the copolymerization in 1,2-dichloro-tetrafluoroethane, a linear increase in the copolymerization rate and the copolymer molecular weight with the amount of solvent was noted, and there was no noticiable influence of the solvent on the copolymer composition. A kinetical discussion indicated that the addition reaction of tetrafluoroethylene to radicals produced by the influence of primary radiation on the reaction mixture is an important step in initiating the copolymerization. Also, the propagation reaction seemes to be strongly promoted by the fluorocarbon solvents.
  • Takeshi Ohno, Shunji Kato
    1969 Volume 42 Issue 12 Pages 3385-3389
    Published: 1969
    Released: March 27, 2006
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    The quenching efficiencies of five tervalent chromium complexes on the phosphorescence of erythrosin and benzil have been compared at the temperatures of dry ice and liquid nitrogen. The results were well explained in terms of the collisional energy transfer. It was observed that aromatic ligands enhanced the rate of the energy transfer even if the triplet energy of the donor was lower than that of the ligands.
  • Kayoko Ozeki, Jiro Tanaka
    1969 Volume 42 Issue 12 Pages 3390-3393
    Published: 1969
    Released: March 27, 2006
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    Cyclohexane-1,4-dione is an aliphatic ketone with two carbonyl groups. The absorption due to the n–π* transition of the carbonyl group extends from the 30000 cm−1 to the 42000 cm−1region. The transition is symmetrically forbidden and is assigned to the A1-A2 transition in the C2v system. The spectra in the crystal and in a solution of EPA at 77°K show only prominent carbonyl stretching vibrations. The polarized single crystal absorption spectra at 4.2°K are composed of many sharp lines; the vibrational structures are analyzed in detail. The 0–0 transition is observed at 31408 cm−1; the distinct basic frequencies of the excited state are 1096, 790, 557, 375, 247, and 122 cm−1, while the lattice vibrations are 61, 32, and 22 cm−1. The transition is explained by the vibronic coupling mechanism, assuming the C2v symmetry for the carbonyl group. Two different types of progressions are noticed; one is induced by the out-of-plane b2-type vibration, while the other is allowed by the a2-type vibration. The dichroic properties of the crystal spectra allowed the assignment of the vibrational modes. These vibrations are compared with the infrared and Raman spectral data.
  • Isao Suzuki, Shigeko Suzuki
    1969 Volume 42 Issue 12 Pages 3394-3398
    Published: 1969
    Released: March 27, 2006
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    The change in the oscillation frequencies of a CO2 laser was examined when foreign gases were introduced into a cell placed inside the cavity. Several gases which have absorption bands around 10 μ region were investigated: sulfur hexafluoride, ammonia, ethylene, trans-dichloroethylene, methyl bromide, trichloroethylene, acrolein, and isopropyl alcohol. The CW laser oscillations in the P-branch of the 9.6 μ band as well as those in the R-branch of the 10.6 μ band were observed when some foreign gases with appropriate pressures were introduced in the cavity. It was also found that the presence of ammonia or methyl bromide even in a very low pressure suppressed the usually strong P(20) line of the 10.6 μ band. This is interpreted as due to a near coincidence of the laser line with one of the vibration-rotation transitions in these molecules.
  • Kenichi Fukui, Hiroshi Fujimoto
    1969 Volume 42 Issue 12 Pages 3399-3409
    Published: 1969
    Released: March 27, 2006
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    The importance of the overlapping between the highest occupied (HO) molecular orbital (MO) of an electron donor and the lowest unoccupied (LU) MO of an electron acceptor in determining the favorable position and spatial direction of a chemical reaction is emphasized by setting up the following auxiliary principles: the principle of a positional parallelism between the chargetransfer and the bond-interchange, the principle of a narrowing of the inter-frontier energy-level separation, and the principle of a growing frontier density along the reaction path. These subprinciples work in a cooperative manner to enable us to arrive at this general governing principle: most of the chemical interactions are liable to occur at the position and in the direction where the overlapping of the HO and the LU of the respective reactants is at its maximum; in an electron-donating reactant, HO predominates in the overlapping interaction with the MO’s of the other reactant, whereas LU does so in an electron-accepting reactant; in the reactants which possess singly-occupied (SO) MO’s, these play the part of HO or of LU, or of both. These particular MO’s, HO, LU, and SO are “generalized frontier orbitals” in chemical reactions. This principle is applied to uni-centric reactions to give the orientation rule; if it is applied to multi-centric reactions, the stereoselection rule is obtained.
  • Akira Nakajima
    1969 Volume 42 Issue 12 Pages 3409-3414
    Published: 1969
    Released: March 27, 2006
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    Anomalous emission observed at long wavelengths in the systems of condensed aromatic hydrocarbons and aliphatic tertiary amines has been studied. The anthracene-tri-n-butylamine system has been dealt with in detail. On the basis of the absorption spectrum, the temperature dependence of the long-wavelength emission and the relation between the quenching of the hydrocarbon fluorescence and the intensity of the long-wavelength emission, it has been concluded that this emission originates from the excited complex formed between an excited hydrocarbon and an amine. The interaction involved in excited-complex formation is of a charge-transfer type. This was confirmed by the correlation of the wavelengths of the excited-complex emission with the ionization potentials of amines and the electron affinities of aromatic hydrocarbons and by the large dipole moment of the excited complex.
  • Hisae Enokido, Takako Shinoda, Yo-ichiro Mashiko
    1969 Volume 42 Issue 12 Pages 3415-3421
    Published: 1969
    Released: March 27, 2006
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    Thermodynamic properties of solid and liquid carbon tetrafluoride were measured at temperatures from 4°K to 100°K. The heat of transition was found to be 349.5±0.9 cal/mol, the transition temperature 76.221°K, the heat of fusion 168.6±0.05 cal/mol, the triple point temperature 89.515°K and the triple point pressure 0.80±0.03 Torr. The amount of impurity in the specimen of CF4 was estimated to be 0.0147 mol% from the measurement of the melting point range. The values of molal entropy of CF4 as an ideal gas at 298.2°K, were calculated from the calorimetric and spectroscopic data as 62.63 e.u. and 62.45 e.u., respectively. The Debye characteristic temperature at 0°K was derived from the low temperature heat capacity data, and the θD(T) curve was compared with that for neopentane taking into account the octupole interaction of molecules in the crystal.
  • Taro Tachibana, Hideko Kambara
    1969 Volume 42 Issue 12 Pages 3422-3424
    Published: 1969
    Released: March 27, 2006
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    It was found, by electron-microscope observation, that D(or L)-12-hydroxystearic acid and its Li soap crystallize from a solution in various solvents in the form of a twisted fiber. The twist was left-handed for the D-acid and right-handed for the L-acid, while the Li soap gave results just opposite to those of the corresponding acid. The DL-acid separated out not fibers, but platelike crystals, and its Li soap produced non-twisted fibers. Thus, an enantiomorphic relationship for the sense of twist between the D-enantiomer and the L-enantiomer was found both for the acid and for the Li soap.
  • Yuko Hasegawa
    1969 Volume 42 Issue 12 Pages 3425-3433
    Published: 1969
    Released: March 27, 2006
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    The complex-formation equilibria of copper(II) in chloroform, benzene, or methyl isobutyl ketone (MIBK) containing both acetylacetone (AA) and thenoyltrifluoroacetone (TTA) have been determined by means of a liquid-liquid distribution method and a spectrophotometric method. The extraction constants or the extinction coefficients of the pure complexes were first determined in solutions containing only one of the liquids, and then these constants for the mixed complex and the equilibrium constants among the three complexes in these solvents were determined by the analysis of the results obtained from the experiments in mixed-ligand solutions. From these data, the following conclusions were reached. The constants experimentally obtained are almost identical with those statistically expected. The absorption spectrum of the mixed complex isolated from the absorption of the mixed-ligand system by the statistical analysis is more similar to that of the TTA complex than to that of the AA complex. The results obtained by these two methods are somewhat different from each other.
  • Seizo Misumi, Sigeo Kida, Toshiyuki Isobe, Yuzo Nishida, Haruko Furuta
    1969 Volume 42 Issue 12 Pages 3433-3437
    Published: 1969
    Released: March 27, 2006
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    The circular dichroism and absorption spectra of Pr(III), Nd(III), Sm(III), Dy(III), Ho(III), Er(III) and Tm(III) complexes with some natural amino acids and L-EDDS have been measured at room temperature. The “circular dichroism-sensitive bands” have been observed on the J-bands where magnetic dipole transitions are allowed to some extent. The experimental results are in accordance with the theory proposed previously. The theory can be applied at least for lanthanide(III) complexes.
  • Teizo Kitagawa, Tatsuo Miyazawa
    1969 Volume 42 Issue 12 Pages 3437-3447
    Published: 1969
    Released: March 27, 2006
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    Irreducible representations of k groups of the space group Pnam were derived with Slater’s method. Degeneracies of crystal vibrations due to space symmetry and time reversal symmetry were treated on the basis of Maradudin’s theory. With irreducible representations of k groups, symmetry coordinates of the carbon atoms of orthorhombic polyethylene were constructed from translational-symmetry coordinates with nonintegral index vectors. A general matrix method was worked out for treating crystal vibrations of any phase-difference vector. Useful methods were derived for treating molecular crystals and chain polymer crystals and for approximate treatment of low frequency lattice vibrations.
  • Yoshisato Tezuka, Toyosaburo Takeuchi
    1969 Volume 42 Issue 12 Pages 3447-3450
    Published: 1969
    Released: March 27, 2006
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    The change in NiO catalytic activity upon the variation in the irradiation of γ-rays in the presence of O2 gas was studied. Activities were determined for the reaction of CO with NiO and for the oxidation reaction of CO on NiO. The results showed a decrease in the CO-NiO reaction rate with an increase in the irradiation of NiO, particularly in the absence of oxygen; if the irradiation was more than 7×107R, the reaction rate increased as both the irradiation in the presence of oxygen and the oxygen partial pressure increased. The activity change in NiO was explained by assuming the migration of the specially-active oxygen into the oxide bulk by means of the irradiation of γ-rays.
  • Yuki Fujii, Katsumi Yamamoto
    1969 Volume 42 Issue 12 Pages 3451-3454
    Published: 1969
    Released: March 27, 2006
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    Three new mixed chromium (III) complexes containing ethylenediamine-N,N′-diacetic acid (EDDA) and amino acid, [Cr(edda)(L)] (L= anion of glycine, α-alanine and β-alanine), were prepared from [Cr2(OH)2(edda)2]·6H2O. On the basis of their chemical analyses and the visible and infrared absorption spectra, the geometrical structure of the three mixed ligand complexes was estimated to be the facial form with respect to the coordinated three nitrogen atoms, where the configuration of the coordinated edda was inferred to take the β-form (cis with respect to the coordinated oxygen atoms of edda). The new mixed ligand complex containing the glycine anion, [Cr(ox)(gly)(en)]·H2O, was also prepared from cis-[Cr(ox)(H2O)2(en)]Br, and its geometry was discussed in the connection with its visible absorption spectrum.
  • Zenzi Hagiwara, Hideo Oki
    1969 Volume 42 Issue 12 Pages 3454-3458
    Published: 1969
    Released: March 27, 2006
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    The adsorption of HEDTA (H3Ch) on the hydrogen form of Dowex 50W, X-8, 100–200 mesh, has been studied as a function of the concentration of H3Ch in the aqueous phase. The experiments were performed by means of either the column or a combination of the column and batch methods, with the latter being employed for the adsorption of HEDTA on the resin in equilibrium with dilute solutions. In solutions up to approximately 0.07 mol/l, such as H3Ch, the experimental data are consistent with the Langmuir equation expressed by: [H3Ch]/(‾ChTE)=1⁄Bk+[H3Ch]⁄B. The adsorbed amount is represented in the term ‾ChTE, where ‾ChT is the total amount of cationic species of HEDTA on the resin, and E, the exchange capacity of resin. A good straight line is obtained with B=0.571 and K=0.420. The results show that, because of a high concentration of hydrogen ion inside the resin, the adsorbed HEDTA is present mainly in the H5Ch2+ species and partly in the H4Ch+ species.
  • S. P. Anand, R. K. Multani, B. D. Jain
    1969 Volume 42 Issue 12 Pages 3459-3461
    Published: 1969
    Released: March 27, 2006
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    The formation of π-cyclopentadienyl tungsten oxychlorodialkoxides as a result of the interaction between cyclopentadiene or its sodium derivative with tungsten oxy-dichlorodialkoxides, having the general formula C5H5WOCl(OR)2, where R is CH3, C2H5, (Remark: Graphics omitted.), CH3CH2CH2 and CH3CH2CH2CH2 along with the thermal stabilities and infrared spectra of the above products, has been studied and reported.
  • Kazuo Saito, Michihiko Takahashi
    1969 Volume 42 Issue 12 Pages 3462-3466
    Published: 1969
    Released: March 27, 2006
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    Bisacetylacetonatopalladium(II) [Pd acac2] was precipitated crystalline free from excessive acetylacetone (Hacac) by adding the reaction mixture in anisole, benzene or 1,2-dichloroethane to chilled petroleum ether. Its specific counting rate was measured by liquid scintillation technique. The isotopic exchange rate is measurable at 40 to 80°C and the kinetics is expressed by the ordinary two term formula, Rate=[Pd acac2](k1+k2[Hacac]). The second term corresponds to the reagent path, in which acetylacetone molecule rather than acetylacetonate anion acts as nucleophilic reagent. The first term seems to express a dissociation mechanism rather than the solvent path; the break of Pd–O bond without the aid of nucleophilic attack by the solvent molecule is responsible for determining the exchange rate. The exchange reaction is accelerated by acids, and the acid-catalyzed reaction path operates independent of the reagent path to give the following kinetic formula:
    Rate=[complex](k1+k2[Hacac]+k3[acid])
  • Itsuro Kawai, Tadashi Hara
    1969 Volume 42 Issue 12 Pages 3466-3470
    Published: 1969
    Released: March 27, 2006
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    A new method for the indirect determination of mercury in an aqueous solution has been established on the basis of the fact that the absorption and evolution of propylene in the reaction between mercuric ion and propylene take place reversibly and quantitatively under proper conditions. In the method proposed, the propylene in the 1 : 1 π-complex is displaced with such complexing agents as chloride, bromide, iodide and EDTA, and the quantity of the propylene evolved is measured manometrically. By the present method, up to 70 mg Hg can be estimated within ±0.08 mg in about 15 min. Common cations and anions do not interfere. Though silver(I) and palladium ions interfere, their interferences are removed by suitable procedures. By improving the apparatus, it should be possible to estimate much smaller amounts of mercury than the above value.
  • Akira Misono, Seiichiro Koda, Yasuzo Uchida
    1969 Volume 42 Issue 12 Pages 3470-3477
    Published: 1969
    Released: March 27, 2006
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    Three cobalt(II) complexes, bis-(salicylaldehyde)-ethylenediimine-cobalt(II), bis-(salicylaldimino) cobalt(II), and di-(salicylal)-3,3′-diimino-di-n-propylamine-cobalt(II), were mixed with poly-4-vinylpyridine. These mixtures showed ESR signals which reversively appeared under oxygen. We tried to identify these signals on the basis of the electonic structure, cobalt(III)-O2−1. The oxygenation-deoxygenation rates were also observed and found to obey the Elovich rate equation.
  • Yukito Murakami, Makoto Takagi
    1969 Volume 42 Issue 12 Pages 3478-3483
    Published: 1969
    Released: March 27, 2006
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    Influence of polyvalent metal ions on the hydrolysis of 2-, 3- and 4-pyridylmethyl phosphate was investigated at μ=0.01 in a lower pH range. The thorium ion accelerated the hydrolysis rate of all the phosphates to a remarkable extent as investigated at 40, 70 and 90°C. The primary participation of the phosphate moiety of each pyridylmethyl phosphate in the interaction with thorium(IV) was considered to be the main cause of this catalysis. Thus, the thorium catalysis was mechanistically distinguished from the copper catalysis which has been clarified previously. In addition, the vanadyl ion also demonstrated positive catalytic effect. On the other hand, iron(III) and aluminum(III) retarded the hydrolysis rate. This was ascribed to the reduced fraction of the active monoionic species as a result of metal-complex formation with the phosphates in the course of hydrolysis.
  • Yasuo Nakao, Akitsugu Nakahara
    1969 Volume 42 Issue 12 Pages 3484-3487
    Published: 1969
    Released: March 27, 2006
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    The reactions of bis(salicylaldehydato)copper(II) with diethylenetriamine and triethylenetetramine were investigated under several different conditions. In water, in the absence of other reagents, the reactions gave uncharged bis (salicylaldehyde)-diethylenetriamine- and -triethylenetetramine-copper(II), respectively. In the presence of an acid the resulting complexes were the respective cation complexes, in which only one of the two terminal nitrogen atoms was in the form of Schiff base with salicylaldehyde. In the presence of a salt, the resulting complex from diethylenetriamine was a cation complex, and that from triethylenetetramine an uncharged complex. Three new copper(II) chelates were obtained.
  • Junsuke Suzuki
    1969 Volume 42 Issue 12 Pages 3487-3490
    Published: 1969
    Released: March 27, 2006
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    We have proposed the determination of the kinetic parameters of the electrode reaction by means of convective voltammetry. At the pushed-out mercury-drop convection electrode (PM-DCE), the ratio of the current on a totally-irreversible wave to the limiting current was derived as follows:
    (Remark: Graphics omitted.)
    This equation was applied to the determination of the kinetic parameters for the electro-reduction of cupric ions in a 0.1 M perchloric acid solution containing 0.05% Triton X-100. It was found that the values of αn and k° the kinetic parameters are 0.59 and 4.2×10−9 cm/sec respectively.
  • Akiko Kobayashi, Satoe Hase, Reiko Kiyoi, Shumpei Sakakibara
    1969 Volume 42 Issue 12 Pages 3491-3495
    Published: 1969
    Released: March 27, 2006
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    The synthesis of an analogue of deamino-oxytocin, which has an ethylene linkage in place of the disulfide bond, was studied in order to establish a general route for the synthesis of such cyclic peptides. L-α-Aminosuberic acid (Asu) was converted to the N-benzyloxycarbonyl-ω-t-butyl ester and was used as the starting substance for the synthesis. A protected octapeptide was prepared by the step-by-step elongation method with the respective benzyloxycarbonylamino acid active esters, and finally the cyclization of the ω-carboxyl group of the Asu-residue to the amino group of the tyrosyl-residue was achieved by the trifluoroacetate method. The final product showed obviously higher oxytocin-like activities than those reported previously. The conditions for the syntheses of p-nitrophenyl and 2,4,5-trichlorophenyl trifluoroacetates were improved during the investigation.
  • Kiyo Mita
    1969 Volume 42 Issue 12 Pages 3496-3498
    Published: 1969
    Released: March 27, 2006
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    Partial methanolysis of the mucilage from Ulva conglobata gave methyl α-L-rhamnoside (29.07%), methyl α-D-xyloside (7.04%) and methyl α-D-glucoside (5.13%). Separation of a new disaccharide (methyl α-L-rhamnobioside, 3.4%) from methanolysate was achieved chromatographically. The biose was attacked by maltase but not by emulsin. The results and infrared spectrum show that the rhamnobiose derivative consists of rhamnose units linked by α-link.
  • Kenichi Somekawa, Taku Matsuo, Sanetada Kumamoto
    1969 Volume 42 Issue 12 Pages 3499-3504
    Published: 1969
    Released: March 27, 2006
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    2,3,4,5,6,6-Hexachloro-, 2,3,4,6,6-pentachloro-, and 2,4,6,6-tetrachloro-2,4-cyclohexadienones were found to undergo Diels-Alder reactions when the compounds were heated with such dienophiles as acrylic acid, methyl acrylate, methyl vinyl ketone, acrylonitrile, and ethyl vinyl ether. It was concluded, chiefly through analysis of these NMR spectra, that the reactions proceed stereospecifically to give a series of 7-substituted and polychlorinated bicyclo-[2.2.2] oct-5-en-2-ones, which is in agreement with the endo rule. The stereospecificity of these adducts does not, however, agree with the results of calculations by means of the perturbation method.
  • Masaharu Yoshikawa, Tetsuya Kato, Tadao Takenishi
    1969 Volume 42 Issue 12 Pages 3505-3508
    Published: 1969
    Released: March 27, 2006
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    During an investigation of the factors affecting the reaction of 2′,3′-O-isopropylidene nucleosides with phosphoryl chloride, trialkyl phosphates were found to be powerful accelerators and useful solvents for the phosphorylation. The addition of a trialkyl phosphate to a large excess of phosphoryl chloride was markedly effective in promoting the phosphorylation; further, the lower alkyl phosphates, such as trimethyl and triethyl phosphates, were able to replace the excessive amount of phosphoryl chloride as solvents. When unprotected nucleosides were treated with phosphoryl chloride in trimethyl phosphate, the corresponding 5′-phosphates were mainly produced, together with a small amount of highly-phosphorylated products, in good yields. On the contrary, the treatment of 5′-O-acetyl nucleosides in a similar manner gave the corresponding 2′(or 3′)-nucleotides in low yields. The formation of the 2′(or 3′)-phosphate was strongly inhibited by the addition of a small amount of water to the reaction mixture. Thus, the selective phosphorylation of unprotected nucleosides to the 5′-nucleotides in a one-step procedure was accomplished.
  • Koko Maeda, Taro Hayashi
    1969 Volume 42 Issue 12 Pages 3509-3514
    Published: 1969
    Released: March 27, 2006
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    The photochromic dimer of triphenylimidazolyl which is one of two dimers obtained by oxidation of triphenylimidazole shows photochromism at temperatures between room temperature and −196°C in solutions and in a solid state. At temperatures higher than about −20°C the photochromic color in solutions is reddish-purple, at temperatures lower than about −150°C the color is bluish-purple and at intermediate low temperatures the photochromic color does not appear. Absorption spectrum and ESR measured with the change of temperature showed variations corresponding to the change of color. The photochromic color in a solid state was light reddish-purple above about −70°C and bluish-purple at −196°C. The mechanism of the color change was discussed in connection with that of the photochromism at room temperature and the results obtained from spectroscopic and ESR studies.
  • Tsutomu Kagiya, Tomizo Kondo
    1969 Volume 42 Issue 12 Pages 3514-3518
    Published: 1969
    Released: March 27, 2006
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    The effect of the binary solvent systems on the polymerization of N-phenylethylenimine with a formic acid catalyst was studied quantitatively. In an acetonitrile-acetone system composed of components with similar nucleophilicities but with very different dielectric constants, the polymerization rate increases with an increase in the dielectric constant of the binary solvent system. In an acetonitrile - N,N-dimethylacetamide system composed of components with very different nucleophilicities but with similar dielectric constants, on the other hand, the rate was markedly depressed by the addition of a small amount of N,N-dimethylacetamide with a large nucleophilicity. On the basis of these results, a mechanism of the solvent effect in a binary solvent system was proposed; the rate equation of the polymerization was expressed empirically as a function of both the dielectric constant of the binary solvent mixture and the nucleophilic equilibrium constant, and the concentration of the component.
  • Tsutomu Kagiya, Tomizo Kondo, Keigo Obata
    1969 Volume 42 Issue 12 Pages 3519-3524
    Published: 1969
    Released: March 27, 2006
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    The catalytic activity of various alkyl chlorides in the polymerization of N-phenylethylenimine was studied from the structural point of view. Both the polymerization rate and the molecular weight of the polymer obtained varied with the kind of alkyl chloride. The rate of monomer consumption is expressed by a first-order rate equation with respect to the monomer concentration in the early stage of the polymerization. The efficiency factors of the catalysts differ with the kind of alkyl chloride and increase with an increase in the reaction time. When the chloride of a conjugated alkyl group is used, the polymerization rate decreases with an increase in the ionization potential of the alkyl radical, while it increases when chlorides of a non-conjugated alkyl are used. The structural study of the catalytic activity of the alkyl chloride was made quantitatively from the energetic point of view.
  • Hisayuki Sakurai, Toshiyasu Ishimaru
    1969 Volume 42 Issue 12 Pages 3524-3528
    Published: 1969
    Released: March 27, 2006
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    In order to obtain information about the stereochemistry of a fused-ring system, cis and trans isomers of 5-methyl- and 5-phenyl-2-pyrrolidinemethanols were synthesized and rate constants for their N→O acetyl migrations were measured. Each product was a mixture of cis and trans isomers. For both 5-methyl and 5-phenyl derivatives, it was observed that trans isomers migrated faster than cis isomers. The results were discussed in relation to stereochemistry.
  • Shigeru Oae, Yong He Khim
    1969 Volume 42 Issue 12 Pages 3528-3535
    Published: 1969
    Released: March 27, 2006
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    Alkaline decomposition of triarylsulfonium bromides with various bases was found to give different products depending on the nature of the bases. The reaction of triarylsulfonium bromide with either piperidide anion or thiophenoxide ion seems to proceed with the initial attack of piperidide anion or thiophenoxide ion of the carbon atom of C-S bond (SN reaction on carbon atom), while the reaction of diarylethoxysulfonium tetrafluoroborate with thiophenoxide ion is presumed to involve the initial attack of thiophenoxide ion on the sulfur atom at low temperature (SN reaction on sulfur atom). When triarylsulfonium bromide was subjected to the reaction with potassium hydroxide in aqueous ethanol, the main path was the alkaline decomposition which proceeds via the nucleophilic attack of the ethoxide ion on the sulfur atom. In the treatment with hydroxide ion in water, the decomposition appears to proceed mainly via two mechanistic routes, i.e., the processes involving the nucleophilic attack of hydroxide ion on both aromatic carbon and the sulfur atoms. A free radical process cannot be excluded, but appears unlikely.
  • Takeo Saegusa, Yoshihiko Ito, Toyoji Shimizu, Shiro Kobayashi
    1969 Volume 42 Issue 12 Pages 3535-3538
    Published: 1969
    Released: March 27, 2006
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    The reaction of ethyl diazoacetate (1) with CuCl2 was investigated. Ethyl chloroacetate (2), ethyl dichloroacetate (3) and a mixture of ethyl dichloromaleate (4) and ethyl dichlorofumarate (5) were produced. These products were explained by assuming 1-chloro-1-ehtoxycarbonylmethylcopper complexes, (10) and (11). The reactions of 1 with HgCl2 and CoCl2 were examined in detail as reference reactions from the mechanistic view point.
  • Masajiro Kawana, Sakae Emoto
    1969 Volume 42 Issue 12 Pages 3539-3546
    Published: 1969
    Released: March 27, 2006
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    1-(β-D-Glucopyranosyl)pyrrole (VI) was prepared by the photo-dehydrogenation of 1-(2′,3′,4′,6′-tetra-O-acetyl-β-D-glucopyranosyl)-Δ3-pyrroline (IV) in the presence of oxygen and benzophenone, followed by deacetylation. The nucleoside (VI) was also derived directly from 1-(D-glucosyl)-Δ3-pyrroline (III) by photochemical means. The synthesis of 1-(α-D-ribofuranosyl)-pyrrole (XI), its β-anomer (XII), and 1-(β-D-ribopyranosyl)pyrrole (XIII) was accomplished by photodehydrogenation of 1-(2′,3′-O-isopropylidene-D-ribosyl)-Δ3-pyrroline, followed by the removal of the protecting group. The treatment of 1-(2′,3′-O-isopropylidene-α-D-ribofuranosyl)pyrrole (VIII) with 80% aqueous acetic acid afforded a novel α-cyclonucleoside, 1-(2-C,2′-O-isopropylidene-α-D-ribofuranosyl)pyrrole (XIV), besides XI–XIII. The formation of pyrrole by the photodehydrogenation of Δ3-pyrroline (II) itself was confirmed by gas chromatography.
  • Heimei Yuki, Koichi Hatada, Kazuhiko Nagata, Ken-ichi Kajiyama
    1969 Volume 42 Issue 12 Pages 3546-3550
    Published: 1969
    Released: March 27, 2006
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    The interchange reaction: CH3OCH=CH2+ROH \ ightleftarrows ROCH=CH2+CH3OH, which is catalyzed by Hg(OAc)2, has been studied. It was found that the equilibrium could be smoothly shifted toward the product by the selective absorption of the produced methanol on molecular sieves of the type 4A (MS-4A) and that the yield of the desired vinyl ether could be increased. According to this method, we prepared various vinyl ethers, including ethyl, isopropyl, isobutyl, t-butyl vinyl ether, and benzyl vinyl ethers. The yields of the alkyl vinyl ethers decrease as their alkyl groups become more electron-donating. The effects of the reaction conditions and the pretreatment of the molecular sieves have been investigated.
  • Hideo Okai, Nobuo Izumiya
    1969 Volume 42 Issue 12 Pages 3550-3555
    Published: 1969
    Released: March 27, 2006
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    Crystalline threo-and erythro-β-hydroxy-L-asparagine were prepared via asymmetric hydrolysis of the corresponding hydroxy-L-aspartic acid diamide by leucine aminopeptidase. The isomers of hydroxy-L-asparagine obtained were compared with the natural hydroxyasparagine isolated from human urine with respect to optical rotation and chromatography. From the results it is concluded that the spacial configuration of the natural product is that of erythro-β-hydroxy-L-asparagine. Additional studies were also carried out to prepare threo- and erythro-β-hydroxy-DL-asparagine from the corresponding hydroxy-DL-aspartic acid diamide without the enzyme.
  • Atsuyoshi Ohno, Tamotsu Koizumi, Yutaka Ohnishi, Gen-ichi Tsuchihashi
    1969 Volume 42 Issue 12 Pages 3556-3558
    Published: 1969
    Released: March 27, 2006
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    The absorption spectra of O-methyl and -ethyl thiobenzoates and their p- and m-methoxy, methyl and chloro derivatives have been studied. The substituent effect on the n→π* transition of thiocarbonyl group has been discussed with the use of the Hammett relationship.
  • Renji Okazaki, Takeo Hosogai, Masayoshi Hashimoto, Naoki Inamoto
    1969 Volume 42 Issue 12 Pages 3559-3564
    Published: 1969
    Released: March 27, 2006
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    Oxidation reactions of 2,4,6-tri-t-butylaniline with lead tetraacetate (LTA), lead tetrabenzoate (LTB), peroxybenzoic acid (PBA) and benzoyl peroxide (BPO) were studied and mechanisms of these reactions were briefly discussed. In the reaction with LTA, 4-acetoxy-1-imino-2,4,6-tri-t-butyl-2,5-cyclohexadiene (I), 2-acetamido-3,5-di-t-butylphenol (II) and 2-acetylimino-3,5-di-t-butyl-3,5-cyclohexadienone(III) were produced. Oxidation with LTB gave 4-benzoyloxy-1-imino-2,4,6-tri-t-butyl-2,5-cyclohexadiene (VI, major product) and 2-benzamido-3,5-di-t-butylphenol (VII). The reaction products with PBA were 2,4,6-tri-t-butylnitrosobenzene (VIII) and VII. In addition to the last two compounds, VI and 2,2′,4,4′,6,6′-hexa-t-butylazobenzene (XI) were obtained in the case of BPO.
  • Takashi Yamada
    1969 Volume 42 Issue 12 Pages 3565-3571
    Published: 1969
    Released: March 27, 2006
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    The rate constants of the hydrochloric acid-catalyzed rearrangement of N-methyldiaryltriazenes were determined in 95% aqueous ethanol in the presence of N-methylaniline. Electrondonating substituents on the diazo-part in triazene promoted the rearrangement. A Hammett plot of the rate constants gave a good straight line. The negative ρ-value (−3.63 at 30.0°C) and the large positive values of the entropy of activation suggested that the rate-determining step in this rearrangement is the dissociation of protonated triazene; this is in contrast with the case of the Friswell-Green mechanism. This theory was suppoted by such a solvent effect as that the rate decreased a little as the polarity of the solvent increased. The kinetic behavior of triazenes in the absence of N-methylaniline, and the incorporation of N-methyl-o-toluidine into the product in the rearrangement of 1-p-chlorophenyl-3-methyl-3-phenyltriazene (Id), were also discussed in connection with the above mechanism.
  • G. D. Baruah, S. Nath Singh, R. S. Singh
    1969 Volume 42 Issue 12 Pages 3572-3575
    Published: 1969
    Released: March 27, 2006
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    The visible emission glow of 2-methyl 1,4-naphthoquinone has been excited by an uncondensed transformer discharge in the presence of flowing vapour of benzene. The vapour absorption spectrum of the molecule has also been investigated in the region 4900–3800 Å at different temperature.
  • Naokata Takeyama
    1969 Volume 42 Issue 12 Pages 3576-3577
    Published: 1969
    Released: March 27, 2006
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  • Etsuo Niki, Yoshio Kamiya, Nobuto Ohta
    1969 Volume 42 Issue 12 Pages 3578-3580
    Published: 1969
    Released: March 27, 2006
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  • Toshihiko Asai, Tadashi Hara
    1969 Volume 42 Issue 12 Pages 3580-3582
    Published: 1969
    Released: March 27, 2006
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  • Tadashi Sasaki, Shoji Eguchi, Masatomi Ohno, Takeshi Oyobe
    1969 Volume 42 Issue 12 Pages 3582-3585
    Published: 1969
    Released: March 27, 2006
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  • Hiroshi Eguchi, Toshio Takeuchi, Akira Ouchi, Akiko Furuhashi
    1969 Volume 42 Issue 12 Pages 3585-3588
    Published: 1969
    Released: March 27, 2006
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  • Masaru Kimura
    1969 Volume 42 Issue 12 Pages 3588-3590
    Published: 1969
    Released: March 27, 2006
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  • Shûichi Hayashi, Katsumi Yano, Tamon Matsuura
    1969 Volume 42 Issue 12 Pages 3591
    Published: 1969
    Released: March 27, 2006
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  • Yoshiro Miura, Shuichi Seto
    1969 Volume 42 Issue 12 Pages 3592-3593
    Published: 1969
    Released: March 27, 2006
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  • Kimitaka Sato, Fumio Kurosawa, Ohiko Kammori
    1969 Volume 42 Issue 12 Pages 3593-3596
    Published: 1969
    Released: March 27, 2006
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  • Choji Kashima, Makoto Yamamoto, Yoshiaki Sato, Noboru Sugiyama
    1969 Volume 42 Issue 12 Pages 3596-3597
    Published: 1969
    Released: March 27, 2006
    JOURNALS FREE ACCESS
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