Bulletin of the Chemical Society of Japan
Online ISSN : 1348-0634
Print ISSN : 0009-2673
ISSN-L : 0009-2673
Volume 39 , Issue 4
Showing 1-50 articles out of 54 articles from the selected issue
  • Yoshisada Ogino, Takeshi Kawakami, Kazuyuki Tsurumi
    1966 Volume 39 Issue 4 Pages 639-642
    Published: 1966
    Released: March 27, 2006
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    Experimental studies of the chemical properties of the surface of potassium bisulfate samples which had been subjected to compressions of 0–3750 kg./cm2 at room temperature were carried out. Namely, on the compressed sample, the surface acidity at room temperature was measured by the indicator method, while the catalytic activity for the conversion of acetaldehyde to metaldehyde was measured at the temperature of a dry ice-methanol mixture by the bulk polymerization technique. Experimental results showed that the compression of the bisulfate resulted in an increase in the surface acidity at H0=1.5 and in a reduction of the acidity at H0=4.0. Further, it was found that the increase in the compressing pressure resulted in an increase in the catalytic activity of the sample. Thus, the existence of a close relation between the catalytic activity and the surface acidity at H0=1.5, and the effectiveness of the pressure in the improvement of the catalytic activity through changing the acid strength distribution on the sample surface were experimentally demonstrated.
  • Masayuki Kashiki, Kazuyoshi Ishida
    1966 Volume 39 Issue 4 Pages 642-644
    Published: 1966
    Released: March 27, 2006
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    A colorimetric method for the direct estimation of thiophene in petroleum naphtha without interference from the other sulfur compounds present has been worked out. The test is based on the blue-green color produced by the reaction between thiophene and α-nitroso-β-naphthol in the presence of sulfuric acid. The procedure accounted for from 10.0 mg./ml. of thiophene sulfur down to a mere trace of thiophene, of the order of 0.01 mg./ml. thiophene sulfur.
  • Kichisuke Nishimoto
    1966 Volume 39 Issue 4 Pages 645-650
    Published: 1966
    Released: March 27, 2006
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    Correlation relations between the Hückel molecular orbital energies and the absorption wavelengths of the 1La, 1Lb, and 1Bb species of an alternant hydrocarbon are presented. After a small modification, the present relations are applied fairly well to the calculations of the electronic spectra of α-substituted hydrocarbon and N-heterobenzenes. This shows us that the nature of the electronic spectra of these compounds are very similar with those of parent hydrocarbon. On the other band, the calculation for β-substituted derivatives does not give good results, although the agreement between the calculated and observed values is semi-quantitatively satisfactory. This should be attributed to the complicated configuration interaction scheme between the lower excited configurations of the molecule.
  • Yoshio Nagai, Chin-Chuan Huang
    1966 Volume 39 Issue 4 Pages 650-654
    Published: 1966
    Released: March 27, 2006
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    Several new polyesters were synthesized by the reaction of ethylene glycol with such carbazoledi-carboxylic acids as carbazole-3, 6-dicarboxylic, 9-ethylcarbazole-3, 6-dicarboxylic, carbazole-3, 6-dibutanoic and 9-methylcarbazole-3, 6-dibutanoic acid in the presence of various catalysts.
  • Tsuguo Takaya, Tadashi Koga, Tadashi Hara
    1966 Volume 39 Issue 4 Pages 654-664
    Published: 1966
    Released: March 27, 2006
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    A new method has been found by which terephthalic acid can easily be obtained by a single-stage oxidation of p-xylene in glacial acetic acid. p-Xylene was oxidized with ozonized oxygen or air at 90°C in the presence of cobaltous acetate, ammonium bromide and an unsaturated aliphatic compound such as tetrachloroethylene. The effects of various factors on the oxidation rate were examined by measuring the absorption rates of oxygen. The reaction rates were measured for two steps, i. e., p-xylene to p-toluic acid and p-toluic acid to terephthalic acid, in the presence and absence of ozone respectively. The reaction mechanisms for each step have been discussed. It seems that the role of ozone and tetrachloroethylene in the present oxidation reaction can be attributed to the formation of ozonide which is transformed to hydroperoxide and which then participates in the chain reaction.
  • Tadashi Koga, Tadashi Hara
    1966 Volume 39 Issue 4 Pages 664-672
    Published: 1966
    Released: March 27, 2006
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    Concerning the oxidation of toluene and p-xylene with atmospheric oxygen at 90°C in glacial acetic acid in the presence of cobaltous acetate and acetylacetone (HAAH), it was found that the reaction proceeds smoothly only at the mole ratio of [HAAH]/[Co2+]=2. When the absorption rate of oxygen was then measured for acetic acid solutions containing cobaltous ions and HAAH, the following results were obtained:
    at [HAAH]⁄[Co2+]≤3, −d[O2]⁄dt=Ka[HAAH]1⁄2[Co2+]−1⁄3
    at [HAAH]⁄[Co2+]≥4, −d[O2]⁄dt=Kb[HAAH][Co2+]1⁄4
    These rates agree well with those derived by means of elementary equations in the radical chain reactions. It was further supposed, on the basis of the elementary equations, that active intermediates, such as Co3+, [Co3+(AAH)2]+, and some radicals, were produced smoothly at the mole ratio of [HAAH]/[Co2+]=2. However, ketones, such as acetonylacetone and ethyl acetoacetate, were still active even at the mole ratio of [ketone]/[Co2+]=3. This seems to stem from the differences in complex stabilities between cobalt and HAAH or other ketones.
  • Yoshinori Sugitani, Kozo Nagashima, Shizuo Fujiwara
    1966 Volume 39 Issue 4 Pages 672-674
    Published: 1966
    Released: March 27, 2006
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    The existence of two types of protons in beryl was proved by the proton magnetic resonance technique; one is as a molecular form of water in the channel of the crystal, while the other is as a hydroxyl-ion replacing O2− ion of the crystal lattice. The proton-proton line of the water was found to be parallel to the c-axis of the crystal.
  • Sueo Machi, Miyuki Hagiwara, Masao Gotoda, Tsutomu Kagiya
    1966 Volume 39 Issue 4 Pages 675-680
    Published: 1966
    Released: March 27, 2006
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    The gamma-radiation-induced polymerization of ethylene was carried out in the intermediate pressure region from 70 to 400 kg./cm2 with a dose-rate from 5×103 to 4.3×105 rad./hr. and at a temperature of 30°C. An overall G-value of the 104 order was usually obtained. No induction period for polymerization was observed. The polymerization rate and the molecular weight of the polymer formed were shown to increase almost proportionally with the reaction time and with the pressure of ethylene. The dose-rate exponents of the rate and the molecular weight were found to be 0.9 and 0 respectively. These results indicate that the stationary-state hypothesis, i. e., that the rate of initiation is equal to that of termination, is not realized in this polymerization. From the kinetic discussion of the initial stage of polymerization, where the concentration of monomer remains essentially constant, it was concluded that the rates of termination and transfer reaction are very small; the life of polymer radicals is, therefore, quite long and the growing of polymer radicals proceeds successively under irradiation.
  • Jiro Kashima, Takuo Yamazaki
    1966 Volume 39 Issue 4 Pages 681-684
    Published: 1966
    Released: March 27, 2006
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    The determination of minute quantities of sulfur in metals is an important problem in refinery processing. This paper will describe a combustion-gas chromatographic method which gives precise results. This method is applicable to various metals, including iron and steels. Standard samples containing 0.011% of sulfur show a standard deviation of 0.0001%. Titanium and copper containing from 0.004 to 0.008% of sulfur show a mean deviation of 0.0003%. The limit of detection is 10 μg. (0.001%) of sulfur in a 1.0 g. sample. It takes about 10 min. to determine the sulfur content by this method.
  • Kazutoshi Kenjo
    1966 Volume 39 Issue 4 Pages 685-694
    Published: 1966
    Released: March 27, 2006
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    Colloid chemical studies of the phase diagrams of binary systems of aqueous polyoxyethylene nonylphenyl ethers with different degrees of the polymerization of ethylene oxide, n, have been undertaken. The phase diagrams obtained have been divided into the heterogeneous region 1, existing in the range of temperature higher than cloud points; the homogeneous phase region II; the heterogeneous region III, existing below the II region; and the solid phase region IV. The II region contains a gel-like hardening region. The III region has been further divided into two sub-regions, on the higher and lower concentration sides; these subregions contain one hardening region each. The molecular and micellar structure models of these hardening regions have been presented. An unusual zone has been found in the phase diagram of the system for n=7.5 its state has also been discussed. Further, the mechanisms of the phase separation and phase inversion have been proposed, and three different types distinguished for the phase separation at the cloud point. A functional relationship has been found between the cloud point, the water content of an aqueous solution at the cloud point (the water affinity), and the n value. A linear relation has also been found between the solidification points of 100% surfactants and the ethylene oxide contents of the surfactants.
  • Sekio Mitsui, Yasuhisa Senda, Hideyo Saito
    1966 Volume 39 Issue 4 Pages 694-697
    Published: 1966
    Released: March 27, 2006
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    2-Cyclopentylidenecyclopentanol (I) was hydrogenated over Raney Ni to produce a mixture of 95% of trans- and 5% of cis-2-cyclopentylcyclopentanol (III). However, over a Pd catalyst I gave a mixture of 2-cyclopentylcyclopentanone (IV), cyclopentylcyclopentane (V) and trans-and cis-III. In the hydrogenation of I over PtO2, trans-III was a predominant product (93%) in ethanol, whereas in acetic acid a mixture of 2 parts of trans- and 1 part of cis-III was obtained, and in acetic acid with one drop of hydrochloric acid, the ratio of trans and cis was one to two. A large amount of V was also obtained in cases of both acetic acid. The hydrogenation of 2-benzylidene-1-tetralol (II) resulted in 2-benzyl-1-tetralols (VI), the yields of trans- and cis-VI being as follows: over Raney Ni, 78% and 19%; over Pd, 33% and 63%; and over PtO2 in ethanol, 58% and 34%, respectively. From these results, it was found that, in the cases of Raney Ni and PtO2 in ethanol, the directive effect of the hydroxyl group is very efficient, but that it is small over Pd, while in acetic acid, especially with hydrochloric acid, such an effect decreases over PtO2.
  • Sei Tsuboyama
    1966 Volume 39 Issue 4 Pages 698-702
    Published: 1966
    Released: March 27, 2006
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    Asymmetric syntheses of benzaldehyde cyanohydrin in the presence of polymers of N-methyl-,N-ethyl- and N-benzyl-(s)-2-isobutylethylenimine as catalysts have been studied. The selectivity of these polymers was poor (optical yield of (−)-isomer obtained; 0–1%) compared with that of a non-N-substituted polymer (20%). It seems that the large difference in the optical yield can be ascribed to their conformation. As to the polymer being capable of promoting the reaction asymmetrically, it is assumed that the isobutyl group and a helical form are the responsible factors. On the basis of these findings, a model for the addition step has been suggested in order to explain the observed result.
  • Tomozo Koh, Iwaji Iwasaki
    1966 Volume 39 Issue 4 Pages 703-708
    Published: 1966
    Released: March 27, 2006
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    In the previous papers of this series, the present authors have found the conditions under which all three polythionates (n=4, 5 and 6) are quantitatively converted into thiocyanate. When one mole of polythionate undergoes cyanolysis, one mole of thiosulfate and (n–3) moles of thiocyanate are formed. The thiosulfate formed from polythionate is then converted into thiocyanate by the addition of a cupric chloride solution. A photometric method for the determination of polythionate when two species of polythionates, tetra-, penta- and hexathionate, are present toghther has been devised; it depends upon the determination of the different amounts of thiocyanate formed from the cyanolysis of polythionates both in the presence of cupric ions and in their absence. The mean number of sulfur atoms, n, in the formula, SnO62−, for polythionate, was determined; the polythionate composition of the solution was also evaluated from the n value
  • Oyo Mitsunobu, Takashi Ohashi, Teruaki Mukaiyama
    1966 Volume 39 Issue 4 Pages 708-713
    Published: 1966
    Released: March 27, 2006
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    A new method for the preparation of various 2, 3-disubstituted oxazolidine, 2, 3-disubstituted thiazolidine and 1, 3-disubstituted imidazolidone derivatives from β-aminoethyl phosphites and either phenyl isocyanate or phenyl isothiocyanate has been developed. When 1 mol. of ethyl bis(β-anilinoethyl) phosphite, resulting from the reaction of ethyl bis(diethylamido) phosphite with N-phenyl ethanolamine, was treated with 2 mol. of phenyl isocyanate, 2-phenylimino-3-phenyl-1,3-oxazolidine was obtained in a 57% yield, along with an oily product. This oily product afforded a 36% yield of N, N′-diphenyl-2-imidazolidone when it was treated with sodium ethoxide. On the other hand, the pentavalent phosphorus compound, ethyl bis(β-N-phenyl-ureidoethyl) phosphate, did not afford an oxazolidine derivative but was converted to imidazolidone in the presence of sodium ethoxide. The reaction of β-anilinoethyl propylene phosphite with an equimolar amount of phenyl isocyanate gave only N, N′-diphenyl-2-imidazolidone in a 32% yield; 2-phenylimino-3-phenyl-1, 3-oxazolidine could not be obtained. These reactions were then extended to the preparation of exo-imino-thiazolidines. The reactions of β-aminoethyl phosphites with phenyl isothiocyanate resulted in the formation of 2-phenylimino-3-phenyl-1, 3-thiazolidine in fairly good yields.
  • Jiro Tsuji, Tatsuo Nogi, Masanobu Morikawa
    1966 Volume 39 Issue 4 Pages 714-716
    Published: 1966
    Released: March 27, 2006
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    Rhenium pentachloride has been found to be a Lewis acid with an efficient Friedel-Crafts catalytic property. Aromatic rings have been alkylated smoothly with olefins or alkyl halides. By the reaction of ethylene with benzene in the presence of rhenium pentachloride, s-butylbenzene has been obtained as the main product. In the Friedel-Crafts acylation, a quantitative amount of the catalyst has been consumed in the reaction at a low temperature. On the other hand, the acylation reaction at a high temperature can proceed catalytically. Rhenium pentachloride is also active in the oligomerization of olefins, and in the cyclization and oligomerization of acetylenes.
  • Akiko Sat\={o}, Yasushi Inoue, Shin Suzuki
    1966 Volume 39 Issue 4 Pages 716-720
    Published: 1966
    Released: March 27, 2006
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    With the aim of developing a method for the separation of 95Zr and 95Nb, various eluants were investigated, a sulfuric acid solution was found to be most suitable for this purpose. After the stannic phosphate exchanger column had been conditioned with 1 N nitric acid, the sample solution was passed through it to adsorb 95Zr and 95Nb. By using a 2 N sulfuric acid solution and a 3 N sulfuric acid - 0.01 N hydrofluoric acid solution as eluants, 95Zr and 95Nb could be eluted respectively. The separation was not quantitative, however, because of the unfavorable tailing of the elution curves. On the basis of the above results, the posibility of the total radiochemical separation of a long-lived fission product and the mechanism of the adsorption of these ions were discussed.
  • Sachio Murakami, Ryoichi Fujishiro
    1966 Volume 39 Issue 4 Pages 720-725
    Published: 1966
    Released: March 27, 2006
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    Calorimetric measurements of the heat of mixing have been made at 25.0±0.01°C for binary mixtures of n-butanol with polar liquids (acetonitrile, acetone, n-butyl ether, and n-butyl amine), and for binary mixtures of polar liquids with n-hexane. The calorimeter for measuring the heats of mixing was of twin type, and a thermomodule, HTM 0516 type (Sharp Electric Co., Ltd., Osaka) was used as the temperature-sensing device. By plotting the values of the heat of mixing, ΔHx1M, against the mole fraction of component 1, x1, and by extrapolating the curve to an infinite dilution (x1→0) for each system, the heats of mixing per mole of component 1 at an infinite dilution (\undersetx1→0limΔHx1M) were obtained graphically. By using the values of \undersetx1→0limΔHx1M obtained for these systems and by using the same treatment as that described in a previous paper [S. Murakami, K. Amaya and R. Fujishiro, This Bulltein, 37, 1776(1964)], the intermolecular hydrogen bond energies between alcohol and polar molecules were estimated; it was found that the strength of the hydrogen bond was in the following order: n-butyl amine>n-butyl ether>acetone>acetonitrile. This agrees with the results obtained from the spectroscopic study.
  • Ryokichi Tarao
    1966 Volume 39 Issue 4 Pages 725-728
    Published: 1966
    Released: March 27, 2006
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    The infrared and Raman spectra of [Al(CH3)2OCH3)]3, [Al(C2H5)2OCH3]3, [Al(C2H5)2·OC2H5]2, and Al(CH3)3·(CH3)2O have been measured in the 3000—300 cm−1 region, and the infrared absorption bands and the Raman lines in the skeletal vibration region (720—300 cm−1) have been compared. For [Al(CH3)2OCH3]3 and [Al(C2H5)2OCH3]3, the results are consistent with trimeric structures with symmetry D3h. For [Al(C2H5)2OC2H5]2, the results are consistent with a dimeric structure with symmetry Vh. Thus, the structures with the oxygen bridge proposed by Hoffmann for these polymeric compounds have been confirmed by spectroscopic measurements. The structures with alkyl bridges are very unlikely. For Al(CH3)3·(CH3)2O, the results do not contradict the postulated structure, with symmetry Cs.
  • Shuzo Aoki, Kazuo Fujisawa, Takayuki Otsu, Minoru Imoto
    1966 Volume 39 Issue 4 Pages 729-733
    Published: 1966
    Released: March 27, 2006
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    The copolymerization of styrene with substituted ethylene oxides catalyzed by boron trifluoride - diethyl ether has been investigated. In all cases, rather low-molecular-weight copolymers were obtained. The copolymerization reactivity of the substituted ethylene oxides with styrene varied with the substituents, in the order of: isobutene oxide>propylene oxide>styrene oxide>epichlorohydrin. This has been explained in terms of cross-propagation or the reaction of the growing oxide cation with styrene.
    The styrene unit content of the copolymer of styrene and epichlorohydrin increases with an increase in the solvent polarity and with an increase in the temperature. It has been concluded from the experimental results that the copolymerizability of alkylene oxide toward styrene is increased by the introduction of electron-releasing substituents into the oxide and by the use of a polar solvent at a moderate temperature.
  • Ry\={u}ichi End\={o}, Tomoyuki Manag\={o}, Masatami Takeda
    1966 Volume 39 Issue 4 Pages 733-735
    Published: 1966
    Released: March 27, 2006
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    Styrenepolysulfone was polymerized and then, for its fractionation, tetrahydrofuran and methanol were used as solvent and precipitant respectively. The viscosities and osmotic pressures of fractions of this co-polymer were examined in tetrahydrofuran. The relation between the intrinsic viscosity and the molecular weight, [η]=0.389×10−4\barMn0.78, was thus obtained. The unperturbed molecular dimension was calculated by the Fixman-Stockmayer method. The results were then compared with the calculated end-to-end distance of the hypothetical freely-rotating chain. The steric parameter, σ=1.53, was also obtained and compared with that of polystyrene.
  • Shigekazu Kusabayashi, Hiroshi Mikawa
    1966 Volume 39 Issue 4 Pages 736-741
    Published: 1966
    Released: March 27, 2006
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    The iodine framework in the crystal is constructed by repeated translations of a group of two pentaiodide ions (repeating unit). The wave function of a repeating unit is calculated by Hückel’s approximation, the resonance integrals between iodine 5 p orbitals being estimated empirically from the data for the gaseous iodine molecule. The wave functions of the crystal are set up in the form of Bloch functions from the wave functions of the repeating unit. The energy is calculated by a tight-binding approximation, the values of the resonance integrals between nearest neighboring repeating units being estimated from the wave functions of the repeating unit. The band-gap energy thus calculated is 1.26 eV., satisfactorily near the experimental value of 1.36 eV. This finding supports our conclusion (This Bulletin, 37, 811 (1964)) that the iodine framework is primarily important in the electrical conductivity. It is also supposed that the band model may satisfactorily be applied to the conduction mechanism. The interactions, of the Bloch functions of different energies being very slight, the band-gap energy is influenced at most in the order of 10−2 eV. even when level interactions are taken.
  • Minoru Ukita
    1966 Volume 39 Issue 4 Pages 742-749
    Published: 1966
    Released: March 27, 2006
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    The polarized infrared spectra of isotactic polybutene-1 in a hexagonal form will be measured in the region from 4000 to 700 cm−1. The normal vibrations of this polymer, which takes a three-fold helical conformation, will be calculated by the use of the GF-matrix method, with the modified Urey-Bradley force field. It will be found that the parallel and perpendicular bands correspond reasonably well to the calculated frequaencies of the A and E(2π/3) symmetry species respectively. In accordance with these correspondences, the assignments of these bands will be made and their vibrational modes discussed.
  • Akira Kotera, Keizo Suzuki, Kimiyoshi Matsumura, Mikiko Shima, Etsuro ...
    1966 Volume 39 Issue 4 Pages 750-757
    Published: 1966
    Released: March 27, 2006
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    The p-methoxystyrene monomer has been synthesized from anisole through p-methoxyacetophenone and p-methoxyphenyl methyl carbinol. Then copolymers of p-methoxystyrene and styrene have been prepared. The dielectric properties of the copolymers in a benzene solution have been measured, and it has been found that the value of the dipole moment, μ, of the p-methoxystyrene monomer unit in the copolymers increases with an increase in the styrene content, e. g., from 1.21 D (for poly-p-methoxystyrene) to 1.32 D (for the copolymer in which the mole fraction of p-methoxystyrene is 0.175) at 20°C. The variation in the value of μ has been discussed in view of the detailed arrangement of polar monomer units. The theory concenring the relation between the dielectric polarization and the detailed structure of the copolymer molecule developed in the preceding paper, Part I, has been applied to the experimental results. In addition, a similar analysis has been made for the dielectric polarizations of the p-chlorostyrene-styrene copolymers which had been measured previously by one of the authors.
  • Akira Kotera, Mikiko Shima, Katsuo Akiyama, Masako Kume, Machiko Miyak ...
    1966 Volume 39 Issue 4 Pages 758-761
    Published: 1966
    Released: March 27, 2006
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    The infrared absorption spectra of polymers and copolymers of methyl acrylate and methyl methacrylate have been measured, and then used as the basis of a spectrophotometric method for the analysis of the copolymers. The 6.73 μ band, which may be due to methyl (–C–CH3) vibration, was selected as the key band for measuring the methyl methacrylate component, while the 6.89 μ band was used as the standard. The monomer reactivity ratios for copolymerization of methyl acrylate-methyl methacrylate system have been determined to be r1=0.5±0.1, and r2=2.3±0.4 (M1 methyl acrylate, M2; methyl methacrylate) at 130°C. These values are in good agreement with those previously obtained by the deuterium tracer method. It has also been shown that the procedure used in this study is appropriate for the analyses of methyl acrylate-methyl methacrylate copolymers.
  • Yojiro Tsuzuki, Koko Tanabe, Kikuhiko Okamoto
    1966 Volume 39 Issue 4 Pages 761-766
    Published: 1966
    Released: March 27, 2006
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    We have measured the rotatory dispersion (RD) and the ultraviolet absorption of twelve nitrates of glucopyranosides carrying a nitrate chromophore, –O–NO2, in the position of the carbon atoms 1, 2, 3, 4, and 6. On the basis of the experimental results and of those results already reported concerning four nitrates, studies have been made as to the correlation between the configuration and the Cotton effect. The sign of the Cotton effect has been determined by the RD curve as well as by the dispersion constant as computed from the dispersion data. A regular relation has been found, namely, irrespective of the position of the nitrate group on the carbon atom, α-glucosides with α nitrate chromophore in the α- or (D)-configuration show negative Cotton effects, while the sign of the Cotton effects of the corresponding β-glucosides is positive. On the contrary, α-glucosides with a nitrate chromophore in the β- or (L)-configuration show positive Cotton effects, while the sign of the Cotton effects of the corresponding β-glucosides is negative.
  • Masashi Tanaka, Jiro Tanaka, Saburo Nagakura
    1966 Volume 39 Issue 4 Pages 766-771
    Published: 1966
    Released: March 27, 2006
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    The electronic structures and electronic spectra of 1-chloro-1-nitrosocyclohexane, nitrosyl chloride, methyl nitrite and dimethylnitrosoamine were studied by making molecular orbital calculations and by measuring the electronic absorption spectra. Concerning 1-chloro-1-nitrosocyclohexane, the n→π* and π→π* bands were observed at 650 and 160 mμ respectively. The conjugation effect of electron donors such as Cl, OCH3 and N(CH3)2 upon the electronic spectrum of the nitroso group was studied. The intramolecular charge-transfer bands characteristic of the donor-acceptor interaction were found at 190, 210 and 230 mμ for nitrosyl chloride, methyl nitrite and N,N-dimethylnitrosoamine respectively. This shows that the intramolecular charge-transfer bands appear at longer wavelengths in the order of the increasing ability of the electron donors, Cl<OCH3<N(CH3)2. On the other hand, the n→π* bands shift to shorter wavelengths in the same order.
  • Nobuyuki Tanaka, Eiki Itabashi, Reita Tamamushi
    1966 Volume 39 Issue 4 Pages 772-776
    Published: 1966
    Released: March 27, 2006
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    The cation effect on the polarographic reduction of cis-dioxalatodiaquochrormate(III) and trioxalatochromate(III) ions has been reported. cis-Dioxalatodiaquochromate(III) ions give an irreversible wave corresponding to a three-electron reduction in the solutions of univalent electrolytes, while they give a double wave in the solutions of bivalent electrolytes, the first wave being of a one-electron reduction and the second wave, of a two-electron reduction. Trioxalatochromate(III) ions are reduced to chromium(0) in the univalent and the bivalent electrolyte solutions at more negative potentials than cis-dioxalatodiaquochromate(III) ions. The reduction potentials of these complex anions depend on the nature and the concentration of cations of electrolytes present in the solution, and shift to less negative potentials with increasing ionic charges of the cation and, at the constant ionic charge, with decreasing radii of the hydrated ion and increasing concentrations of the cation present. The cation effect was explained by taking into consideration of both the structure of the electrical double layer and the formation of ion-pairs.
  • Manabu Sen\={o}, Takeo Yamabe
    1966 Volume 39 Issue 4 Pages 776-778
    Published: 1966
    Released: March 27, 2006
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    The flow properties of the suspensions of ion-exchange resin particles, the highly-crosslinked polyelectrolyte gel particles, were examined, especially in relation to their charged state. The steady viscosities and the dynamic viscoelasticities of these suspensions were measured, and the results were interpreted in terms of the dispersion state of the suspended particles. The flow system of the highly-charged particles, such as Na-form resin particles, exhibits a high viscoelasticity and is in a well-dispersed state. On the contrary, the flow system of the lower-charged particles, such as Ba-form particles, is not viscoelastic, but viscous and dilatant. This behavior may be attributed to the variation in the electrical double layers around the suspended particles.
  • Shigeo Shibata
    1966 Volume 39 Issue 4 Pages 779-784
    Published: 1966
    Released: March 27, 2006
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    A new technique with an electronic circuit is described in which the ohmic and the capacitive components of the impedance of the electrode-solution interface may be registered simultaneously and continuously as a function of the time at a given frequency during polarization with a constant anodic or cathodic current. Impedance measurements were made on a smooth platinum in 2 N perchloric acid, 2 N sodium perchlorate and 2 N sodium hydroxide solutions in the region of oxygen deposition. According to the observed behavior of the impedance of the electrode, the oxide film on the electrode surface may be completed anodically through three stages; first, the adsorption of the hydroxyl radical; second, the formation of oxide (II), and finally, the conversion of this oxide to one of a higher grade. The dependence of the value of the electrode capacity at the first stage on the pH of the solution is discussed on the basis of the ion-exchange adsorption of cations and anions on the electrode surface covered by the hydroxyl radicals.
  • Hamao Watanabe, Izumi Motoyama, Kazuo Hata
    1966 Volume 39 Issue 4 Pages 784-790
    Published: 1966
    Released: March 27, 2006
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    Ferrocene derivatives with one or two glycidyl substituents, desired for the formation of polymeric ferrocene compounds, were synthesized by the epoxidation of chlorohydrin compounds obtained from the products of the addition of ferrocenyllithium to epichlorohydrin at −40–−78°C. In the course of this synthesis, mono- and di-chlorohydrin compound and a disubstituted ferrocene with a 3-chloro-2-hydroxypropyl and a glycidyl substituent were isolated. All of them are stable liquid compounds. The investigation of the relationship between the reaction conditions and the yield of glycidylferrocenes revealed that the larger molar ratio of each reactant to ferrocene at each reaction step causes a higher conversion into glycidylferrocenes. In the epoxidation reaction of chlorohydrins with caustic alkali, a small amount of ethers, formed by the reaction of epoxides and the solvent ethanol, was obtained under some reaction conditions. In all cases, a small amount of biferrocenyl was isolated; the formation of this compound was considered to be attributable to the Wurtz-type coupling reaction of ferrocenyl radicals. The structures of all these products were confirmed by their infrared absorption spectra and, in part, by the NMR spectra.
  • Hamao Watanabe, Izumi Motoyama, Kazuo Hata
    1966 Volume 39 Issue 4 Pages 790-801
    Published: 1966
    Released: March 27, 2006
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    In the presence or absence of n-butyl bromide, ferrocenyllithium and cobaltous chloride reacted to give various polyferrocenyls and butylated polyferrocenyls. They were isolated, mainly by alumina chromatography, and their structures were established, principally from the NMR spectra, to be heteroannularly-bonded ones. The formation of these compounds is considered to be due to the coupling reactions of the ferrocenyl radical, the ferrocenylene biradical and the butyl radical, which were formed by homolytic fissions of some reactive intermediate and butyl halide. The presence of the alkyl halide greatly affected the sorts and yields of the products. No cyclic polyferrocenylene was obtained. The “9—10 rule” concerning the infrared spectra of ferrocene derivatives was found not to apply to di-substituted biferrocenyls. It was found, by a study of the X-ray diffraction patterns and the infrared spectra, that terferrocenyl crystallizes in polymorphic forms according to the method and the solvent of crystallization. The polymorphism may be attributable to the rotational isomerism around the central ferrocene nucleus.
  • Michio Kobayashi, Miki Terao, Asami Yamamoto
    1966 Volume 39 Issue 4 Pages 802-803
    Published: 1966
    Released: March 27, 2006
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    The salts of arylsulfinic acids were found to react with alkyl chlorosulfite to form alkyl sulfinates. p-Toluenesulfinic acids-18O was synthesized and treated with ethyl chlorosulfite to give ethyl p-toluenesulfinate-18O, which retained half of the oxygen atoms existing in the original sulfinic acid. A mechanism for this novel reaction was proposed.
  • Takeshi Nakajima, Susumu Kohda
    1966 Volume 39 Issue 4 Pages 804-809
    Published: 1966
    Released: March 27, 2006
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    The effect of bond length alternation on the magnetic properties of several Pseudo-Jahn-Teller nonbenzenoid aromatic hydrocarbons with 4ν carbon atoms will be investigated. The magnetic moment and the susceptibility of a cyclic polyene will first be formulated in terms of the bond alternation parameter. Appropriate cross-links for forming nonbenzenoid aromatic hydrocarbons, such as pentalene and heptalene, will then be treated as perturbations. It will be shown that the anomalously large paramagnetic susceptibilities of these molecules predicted by Pullman et al. (“Les Théories Electroniques de la Chimie Organique,” Masson, Paris (1952), p. 527) arise mainly from the neglect of the bond alternation inherent in them. It will then be concluded that the magnetic susceptibility is a very sensitive indicator of the bond alternation, and that the diamag-netically-induced ring currents in these molecules are very much impeded.
  • Michinori Oki, Kiyoshi Mutai
    1966 Volume 39 Issue 4 Pages 809-813
    Published: 1966
    Released: March 27, 2006
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    The thermodynamic parameters for the intramolecular interaction between the N–H group and the π-electrons in N-benzylanilines were determined from the temperature dependence of the N-H stretching absorptions. A comparison of the −ΔH’s with those for the O–H···π interaction indicates that there is no appreciable difference between the interactions involving the N–H and the O–H groups. The −ΔH’s are less than 2 kcal./mol., this figure being considered to be a borderline differentiating the X–H···π interaction from the ordinary hydrogen bond. The wave number shift accompanying the interaction cannot be a measure of the −ΔH in the N–H group, nor be indicative of the difference between two groups. The −ΔH was found to be closely related with the equilibrium constant in these derivatives.
  • Michinori Oki, Hiizu Iwamura, Takeru Onoda, Michiko Nishida
    1966 Volume 39 Issue 4 Pages 813-817
    Published: 1966
    Released: March 27, 2006
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    1, 2-Dihydro-5-hydroxy-8-methoxy-3-methylnaphthalene (III) was prepared, starting from 5,8-dimethoxy-α-tetralone, via 8-hydroxy-5-methoxy-2-methyl-1-keto-1,2,3,4-tetrahydronaphthalene. The O–H stretching absorptions (νOH) and the ultraviolet absorptions of III, 1, 17 β-dihydroxy-4-methylestra-1,3,5(10), 9(11)-tetraene (IV), and the related naphthols were measured and compared with those of o-isobutenylphenol. IV showed a νOH at 3532cm−1 which is assigned to the hydroxyl group taking part in the strong interaction with the π-electrons on the ethylenic group; it corresponds well in its location to the lowest frequency band of o-isobutenylphenol. The previous assignment of this band to the conformer II with the double bond syn to the hydroxyl was thus confirmed. III showed only a symmetric band at 3618cm−1, which was assigned to the free νOH and could not be a model for the conformer with a νOH at 3576cm−1, presumably because of the more planar structure for the overlap between the orbitals of the hydroxyl group and the ethylenic group.
  • Yoriko Nishi, Yoshio Sasada, Tamaichi Ashida, Masao Kakudo
    1966 Volume 39 Issue 4 Pages 818-826
    Published: 1966
    Released: March 27, 2006
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    The molecular structure of 1,2,3,4-tetrachlorobenzo[g]sesquifulvalene has been ascertained by X-ray crystal analysis. The crystal of this substance is monoclinic, with four molecules in a unit cell of dimensions: a=21.31, b=16.88, c=3.83 Å, and β=93.3°, the space group being P21/a. The crystal structure was determined by the Harker-Kasper inequality and the Sayer’s method. The atomic coordinates and the anisotropic temperature factors of each atom were refined by the block-diagonal-matrix least-squares method. The average length of the C–Cl bonds is 1.705 Å, a value which is in good agreement with those of several chlorobenzenes. In the sesquifulvalene skeleton, longer and shorter bonds are disposed as may be expected from the conventional chemical formula. The average length of the longer bonds is 1.461 Å, while that of the shorter ones is 1.354 Å. The mean C–C bond length in the benzene ring is 1.413 Å. The whole molecule is not on a plane, although the component ring systems are nearly planar. The five-membered ring and the seven-membered ring twist to each other by an angle of about 31° around the bond connecting these two rings. This might be due to the repulsion forces between chlorine and hydrogen atoms which approach each other closely. The plane of the seven-membered ring makes an angle of about 5° with that of the six-membered ring.
  • Yasuhide Yukawa, Mitsuru Sakai
    1966 Volume 39 Issue 4 Pages 827-828
    Published: 1966
    Released: March 27, 2006
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    In studying the reaction of styrene, olefins, vinyl ethers and vicinally-substituted compounds with lead tetraacetate, it was shown that the methyl group of 9-chloro-9-methylfluorene was easily acetoxylated with lead tetraacetate. This novel reaction was then applied to 1, 1-diphenylethyl chloride, 1-phenylethyl chloride and t-butyl chloride. In every case the methyl group of chlorides with an α-methyl group was acetoxylated preferentially.
  • Tokiti Noda, Hajime Kato, Toshihiko Takasu, Akihide Okura, Michio Inag ...
    1966 Volume 39 Issue 4 Pages 829-833
    Published: 1966
    Released: March 27, 2006
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    The electrical resistivity of carbon blacks was measured under compression (up to 9 kilobars) at room temperature using a pressure vessel of the piston-cylinder type. The slope of the logρ vs. logP relation was about −0.5 for all the carbon black specimens except the original channel black. For the thermal blacks heat-treated above 2100°C, i. e., the graphitized thermal blacks, the linear relation between logarithms of resistivity, ρ, and of pressure, P, broke at about 2.5—4.5 kilobars. After the break the slope of the logρ vs. logP relation for the graphitized thermal blacks had the same value as that for natural graphite. The original channel black had a value of the slope as high as −0.9, but the 1300°C-treated channel black had a value similar to that of the other samples. This was probably due to the removal of the high-resistance film on the particle surface by the heat treatment. The first stage of the decrease in electrical resistivity with an increase in the pressure seems to be due to the yielding deformation of carbon black particles caused by the increased packing of the particles, while the second stage may be due mainly to the increase in the contact of crystallites in the particles by the elastic deformation, accompanied by a change in the preferred orientation of crystallites with the pressure.
  • Rajendra Kumar Srivastava, Narendra Nath, M. P. Singh
    1966 Volume 39 Issue 4 Pages 833-837
    Published: 1966
    Released: March 27, 2006
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    The kinetic studies of the oxidation of L-arabinose and D-xylose have been carried out using potassium ferricyanide in the presence of sodium hydroxide and sodium carbonate. The order of the reaction has been found to be zero with respect to ferricyanide and first with respect to the reducing sugar. The reaction rate is also directly proportional to the hydroxide ion concentration. The reaction also has a very small induction period.
  • C. M. Gupta
    1966 Volume 39 Issue 4 Pages 837-838
    Published: 1966
    Released: March 27, 2006
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  • Niichiro Tokura, Fuminori Akiyama
    1966 Volume 39 Issue 4 Pages 838-841
    Published: 1966
    Released: March 27, 2006
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  • Setsuo Takamuku, Hiroshi Sakurai
    1966 Volume 39 Issue 4 Pages 841-843
    Published: 1966
    Released: March 27, 2006
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  • Takao Iijima
    1966 Volume 39 Issue 4 Pages 843-844
    Published: 1966
    Released: March 27, 2006
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  • Takehiro Abe, Yoshito Amako, Tadashi Nishioka, Hiroshi Azumi
    1966 Volume 39 Issue 4 Pages 845-846
    Published: 1966
    Released: March 27, 2006
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  • Yasuto Nakai, Katsuyuki Kawamura, Kazuhiko Ishizu, Yasuo Deguchi, Hide ...
    1966 Volume 39 Issue 4 Pages 847-848
    Published: 1966
    Released: March 27, 2006
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  • Yoshiaki Tanahashi, Takeyoshi Takahashi
    1966 Volume 39 Issue 4 Pages 848-849
    Published: 1966
    Released: March 27, 2006
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  • Hamao Watanabe, Izumi Motoyama, Kazuo Hata
    1966 Volume 39 Issue 4 Pages 850-851
    Published: 1966
    Released: March 27, 2006
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  • Eiichi Haruki, Toshikazu Fujii, Eiji Imoto
    1966 Volume 39 Issue 4 Pages 852
    Published: 1966
    Released: March 27, 2006
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  • Hiroshi Kotake, Tomoo Saito
    1966 Volume 39 Issue 4 Pages 853
    Published: 1966
    Released: March 27, 2006
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  • Akira Misono, Tetsuo Osa, Seiichiro Koda
    1966 Volume 39 Issue 4 Pages 854
    Published: 1966
    Released: March 27, 2006
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