Bulletin of the Chemical Society of Japan
Online ISSN : 1348-0634
Print ISSN : 0009-2673
ISSN-L : 0009-2673
Volume 39 , Issue 3
Showing 1-50 articles out of 60 articles from the selected issue
  • Nobuo Nakabayashi, Eiichi Masuhara, Yoshio Iwakura
    1966 Volume 39 Issue 3 Pages 413-417
    Published: 1966
    Released: March 27, 2006
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    1-Chloro-2-hydroxypropyl sulfonates are obtained by the reaction of glycidyl sulfonates with hydrochloric acid at room temperature. They are converted into 1,3-dichloro-2-propanol by the action of hydrochloric acid at 100°C, or into epichlorohydrin by that of bases. The reaction of glycidyl sulfonates and sodium carboxylates affords glycidyl carboxylates. In the preparation of glycidyl carboxylates, glycidyl sulfonates act as a direct alkylation agent for sodium carboxylates. The addition of amines to the epoxide is carried out at first in the reaction of glycidyl sulfonates and amines. The adducts are converted into glycidyl amines by the action of sodium hydroxide, or into N-[β-hydroxypropylene(α,γ)]-ammonium sulfonates by the isomerization, by heating them or letting them stand for a long time. The latter is an intermediate used in preparing 1,4-dioxane derivatives in the presence of sodium hydroxide.
  • Hiroshi Hotta, Nobutake Suzuki, Toshihiko Abe
    1966 Volume 39 Issue 3 Pages 417-422
    Published: 1966
    Released: March 27, 2006
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    When benzene was oxidized to phenol in an oxygen-18 enriched aqueous solution of iron and copper sulfates, the oxygen-18 was much concentrated to phenol. The oxygen-18 content depended on the kind of metal ion and on the temperature. This suggests that the oxygen in the phenol produced is donated not only by the molecular oxygen, but also by the water. Therefore, it is assumed for the termination process that phenol is formed by the ionic reactions. Furthermore, when an equimolar mixture of benzene and benzene-d6 was oxidized, the isotope effect of hydrogen, kH/kD, as estimated from the isotopic composition of the phenol produced, was about 1.2. This value seems to be small for the hydrogen abstraction reaction of radicals. Therefore, when we compare these results with the other facts reported previously, the main reaction of the propagation process may be supposed to be the abstraction reaction of hydrogen by phenyl peroxide. In this experiment, it was also found that phenol exchanges hydrogen with water. The rate constant of the exchange reaction was estimated by Bateman’s equation. The rate constant is the highest in the ferric sulfate solution.
  • Nobutake Suzuki, Hiroshi Hotta, Hitoshi Hashimoto
    1966 Volume 39 Issue 3 Pages 422-425
    Published: 1966
    Released: March 27, 2006
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    When an oxygen-18 enriched aqueous solution of ferrous, ferric and cupric sulfates was heated between 130 and 200°C, the oxygen-18 content decreased in the order of FeII>FeIII>CuII in water; and it increased in the sulfate group and in the molecular oxygen of the gaseous phase. A transfer of oxygen from water to the sulfate group was also observed, even in a nitrogen atmosphere. The oxygen transfer was promoted in all the cases in the presence of molecular oxygen, and it increased further in the presence of benzene. Since the exchange reaction of oxygen does not occur between water and sulfate ions, the above facts may be attributed to the reactions between water and the thermal decomposition products of the sulfate group, and between water and the hydrogen peroxide produced. The peroxy species, produced by the oxidation of the decomposition products, are more reactive in such a transfer of oxygen, since the reaction is promoted in the presence of oxygen. The peroxides in the autoxidation of benzene seem also to be reactive in it.
  • Kôichi Tonosaki
    1966 Volume 39 Issue 3 Pages 425-428
    Published: 1966
    Released: March 27, 2006
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    The reaction between iron(III) and methylthymol blue has been studied spectrophotometrically in an attempt to establish the optimum conditions for determining small amounts of iron. Depending on the acidities of a solution, iron(III) reacts with methylthymol blue to form one of two complexes. The 1-to-1 complex, which has its maximum absorbance in the acidity range from 0.07 to 1.00 M with respect to perchloric acid, has an absorption maximum at about 580 mμ against a reagent blank. The 1-to-2 (metal-reagent ratio) complex, which has its maximum absorbance in the pH range from 4.5 to 5.5, has an absorption maximum at about 520 mμ against a reagent blank. With either complex, Beer’s law is obeyed over the range from 5 to 50 μg. of iron(III) in 25 ml. of complex. The apparent molar extinction coefficients of the two complexes at their absorption maxima were calculated to be 15000 and 14000 respectively (the former, at 0.08 M HClO; the latter, at pH 5). According to Sandell’s notation, the sensitivities of the reactions are 0.004 μg. of iron(III) per cm2 at 580 mμ and 0.005 μg. of iron(III) per cm2 at 520 mμ respectively. The effect of diverse ions was examined with a solution containing iron(III) and 25 cations.
  • Shizuo Arichi, Seiji Mitsuta, Noriyuki Sakamoto, Hiromu Murata
    1966 Volume 39 Issue 3 Pages 428-434
    Published: 1966
    Released: March 27, 2006
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    2-Vinylpyridine has been polymerized by the suspension method. A stable suspension has been obtained using a mixture of sodium butylnaphthalene sulfonate and gelatine as a stabilizer in the concentration ranges of 0.025–0.75 per cent (for the former) and 0.75–1.0 per cent (for the latter) in water. The molecular weight of polymers thus obtained from this stable suspension system could be controlled by varying the concentration of azo-bis-isobutyronitrile and the temperature. The Mw/Mn ratios of the polymers obtained by the above method are relatively large; from 3.5 to 5. Precipitation fractionation has been carried out for a polymer obtained using ethyl methyl ketone as a solvent and ligroin as a precipitant at a constant temperature. Three kinds of molecular weight distribution curves have been obtained by applying the data of fractionation to (1) Tung’s method, (2) exponential-type and (3) logarithmic normal-type molecular weight distribution functions. By comparing the average molecular weights, Mw and Mn calculated from each curve with the experimental values, it was found that the molecular weight distribution of the fraction can be well represented by the function 2 or 3.
  • Shizuo Arichi, Hiroatsu Matsuura, Yoshio Tanimoto, Hiromu Murata
    1966 Volume 39 Issue 3 Pages 434-439
    Published: 1966
    Released: March 27, 2006
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    The viscosity and osmotic pressure of a fraction of poly-2-vinylpyridine have been measured in various solvents, and the parameters concerning the solubility of this polymer, that is, the osmotic second virial coefficient, A2, the polymer-solvent interaction parameter, μ, and the solubility parameter, δ2, have been obtained. From the values of these parameters, the following conclusions have been obtained: poly-2-vinylpyridine has a solubility parameter of ca. 10.4 (cal./cc.)1⁄2 and acts as an electron donor. As a result of the specific interaction between a solvent and the pyridine nitrogen of this polymer, the solvent power is greater in an acidic solvent and smaller in a basic than would be expected from the solubility parameter alone. An especially strong interaction between poly-2-vinylpyridine and aliphatic alcohols, chloroform and nitroethane has been observed and its nature has been discussed.
  • Shizuo Arichi
    1966 Volume 39 Issue 3 Pages 439-446
    Published: 1966
    Released: March 27, 2006
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    The viscosity, osmotic pressure and light-scattering of a series of 14 fractions of poly-2-vinylpyridine in various solvents have been measured. The following results have been obtained: The constants, Kw and v, in the Mark-Houwink equation have been determined for the solutions of: (a) 92.01 weight per cent ethanol, (b) methanol, (c) dimethylformamide, (d) benzene and (e) dioxane as follows:
    (a) [η]=1.22×10−4Mw0.73 (d) [η]=1.70×104Mw0.64
    (b) [η]=1.13×104Mw0.73 (e) [η]=3.09×104Mw0.58
    (c) [η]=147×10−4Mw0.67
    The molecular weight of the polymers ranged from 3.4×104 to 93×104, while the viscosity was measured at 25±0.01°C. The constant, K′ in the Mark-Houwink equation in the case of a homogeneous molecular weight has been calculated assuming the exponential- and logarithmic normal-type molecular weight distribution functions for each fraction. The Flory constant, K, defined as [η]θ=KM1⁄2 has been found by the method of Fixman and Krigbaum to be: (8.7±1.0)×10−4 at 25°C. The K value has also been found to be (9.1±1.1)×104 by measuring the intrinsic viscosity in benzene at the θ-point, 16.2°C. The short range interactions of this polymer have also been discussed.
  • Kiyoshi Arakawa, Nobuo Takenaka
    1966 Volume 39 Issue 3 Pages 447-452
    Published: 1966
    Released: March 27, 2006
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    The ultrasonic velocity and the absorption have been measured over the 5–45 Mc./sec. frequency range for aqueous solutions of polyvinyl alcohol by means of an ultrasonic pulse technique which was similar in principle to that used by Pinkerton (Proc. Phys. Soc. B62, 286 (1949)). The temperature varied over the 3–70°C range. The velocity-versus-temperature curves have been found to be convex upwards, like that of pure water, but the peak shifts upwards and to the lower-temperature side with an increase in the concentration. The ultrasonic absorptions of aqueous solutions of partly-saponified polyvinyl alcohol have been found to be larger than those of perfectly-saponified alcohol at the same concentrations. Two relaxation mechanisms have been found for each sample. For the solutions of the perfectly-saponified sample, the first relaxation frequency, f1, is 35 Mc./sec. at 12°C, while the second relaxation frequency f2 is 40 Mc./sec. at 60°C, for example. On the other hand, these values have been found to be nearly equal for the solutions of the partly-saponified sample. The activation energy, ΔH2, obtained from the temperature dependence of f2 is about 4 kcal./mol., irrespective of the quantity of resuidal acetate groups, and the ΔH1 value forf1 is of the order of 10 kcal./mol.
  • Yasushi Kobayashi, Kozo Hirota
    1966 Volume 39 Issue 3 Pages 453-456
    Published: 1966
    Released: March 27, 2006
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    Further evidence on the adsorptive heterogeneity of the nickel surface has been presented by the use of the technique described in our previous paper. The results support the conclusion already proposed that more than 20–30% of the surface can adsorb carbon dioxide strongly over the temperature range between −78° and 300°C.
  • Yoshihiko Hatano, Shoji Shida
    1966 Volume 39 Issue 3 Pages 456-459
    Published: 1966
    Released: March 27, 2006
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    The direct photolysis at 1849 Å and the mercury-photosensitized reaction at 2537 Å of cis-2-butene have been studied in the gas phase at room temperature. It may be considered that the excited singlet state of cis-2-butene is formed in the former, and that the excited triplet state of cis-2-butene is formed in the latter. trans-2-Butene is predominantly produced in the latter, while the decomposition products (e. g., hydrogen, methane, ethane, ethylene, propylene, etc.) predominate in the former. The rates of the formation of all the products are pressure-independent in the former, while in the latter those of all products except trans-2-butene decrease rapidly with an increase in the initial pressure. The rate of trans-2-hutene formation in the latter, however, increases gradually with an increase in the initial pressure until it becomes constant above 100 mmHg. By comparing the pressure-dependence and the product-distribution of these two reactions with the results of the radiolysis of liquid cis-2-butene, one may conclude that the excited triplet state of cis-2-butene contributes chiefly to the formation of trans-2-butene in the radiolysis, while the excited singlet state of cis-2-butene contributes chiefly to the decomposition products.
  • Hiroshi Tsukashima
    1966 Volume 39 Issue 3 Pages 460-465
    Published: 1966
    Released: March 27, 2006
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    The infrared spectra of artificial coal prepared from Submerged Wood were observed and compared with those of lignin and cellulose. The artificial coalification seems to proceed in three stages, characterized by the corresponding infrared spectra, i. e., a cellulose-like spectrum, a lignin-like spectrum, and a spectrum resembling that of natural coal. The infrared spectrum of artificial coal is generally similar to that of natural coal with a little higher carbon content, suggesting that the degree of coalification is more advanced in artificial coal than in natural coal. The background absorption in the infrared spectra of artificial coal of a low coalification is weak, while that in the infrared spectra of artificial coal of a high coalification is strong.
  • Ikuko Akaza
    1966 Volume 39 Issue 3 Pages 465-469
    Published: 1966
    Released: March 27, 2006
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    It has been known that alkali metal ions can be extracted into nitrobenzene as their poly-iodides, but the extraction has not been attempted for various salts of alkali metals except in the case of their iodides. In this research ammonium iodide and elemental iodine were preferentially added to the extraction system in order to convert various alkali metal salts into poly-iodides. Ammonium iodide should be larger than the equivalent amount to an alkali metal present in an aqueous solution. The ratio of free iodine to ammonium iodide is an important factor; when the ratio is more than three, a higher distribution ratio is obtained. The ratio of iodine to iodide in the organic phase after the extraction is estimated to be six; therefore, the extracted species seems to be heptaiodide. The extractability of alkali metals increases in the order: Li–Na–K–Rb–Cs, and the distribution ratio decreases with the increase in the amount of metal ions taken in. Back extraction is achieved by shaking the organic phase with 10 M nitric acid. The separation factor between the metals is too low for them to be separated from one another.
  • Michinori Oki, Hiizu Iwamura
    1966 Volume 39 Issue 3 Pages 470-476
    Published: 1966
    Released: March 27, 2006
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    Nine o-(1-alkenyl)phenols, o-HOC6H4CR1=CR2R3, have been prepared and their ultraviolet absorptions and the O–H stretching bands (vO-H) in the infrared absorption measured in an effort to explore the effect of the substituents, R1–R3, on the strength of the intramolecular interaction between the OH group and the π-electron system. The K-band of the styrene chromophore at 240–250 mμ is lost in the samples involving R1, which is bulkier than methyl. As the size of R1 increases from H, by way of Me, Et, and i-Pr, to t-Bu, the angle of the twist between the planes made by the benzene ring and the ethylenic group must increase; this trend is nearly parallel with the amount of the interacting vO-H in the infrared spectrum. The phenomenon is interpreted mainly by means of the favorable overlap between the O–H group and π-orbitals. o-Isobutenylphenol shows a νO-H triplet at 3610, 3576 and 3539 cm−1. The latter two bands are assigned to the hydroxyl group interacting with π-electrons on the vinyl group intramolecularly. A tentative explanation has been developed which attributes the two interacting bands to the presence of two interacting conformations. The solvent effect on the ultraviolet absorptions is in accord with this explanation.
  • Toshihiko Hoshi, Yoshié Tanizaki
    1966 Volume 39 Issue 3 Pages 476-480
    Published: 1966
    Released: March 27, 2006
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    The configuration of the component molecules in the complex formed between Chryophenine G (G) and the direct dyes (P),such as Chlorazol Sky Blue FF, has been discussed qualitatively with respect to the relation between the steric structure of the individual P molecules and the enthalpy or the entropy changes in the complex formations. the electrons to be transferred from the partner (P) to the G molecule are the π electrons of the functional (hydroxy) groups and are those of the inner-side groups when the respective coupling components of the dye have more than one functional group. The large the charge density of such an effective functional group becomes, the more the enthalpy change (−ΔH) is increased. It may be said with certainty that there must exist a certain configuration of the component molecules peculiar to the complex formation. Such a configuration may be seen for the configuration of G and ND (NW-acid←dianisidine→NW-acid). For other combinations of which the partner of G is more deformed in free than ND state, the shifts of equilibrium to the configuration for the complex state are almost due to an entropy change (−ΔS) which increases in proportion to the magnitude of the deformation.
  • Kazuo Saotome, Hiroshi Komoto, Toshiaki Yamazaki
    1966 Volume 39 Issue 3 Pages 480-484
    Published: 1966
    Released: March 27, 2006
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    Higher ω-chloroalkanoic acids than ω-chlorooctanoic acid were prepared in good yields (over 90%) by improved methods of the hydrolysis of α, α, α, ω-tetrachloroalkanes. The reactions were carried out in fuming nitric acid, with the addition of nitrogen dioxide during the reaction or in the presence of a small amount of phosphoric anhydride. α, ω-Dichloroalkanes were derived from the ω-chloroalkanoic acids by the Kolbe electrolytic synthesis. Various other novel α, ω-disubstituted alkanes with very long methylene chains, such as glycols, dinitriles, dicar-boxylic acids, and diamines, were also prepared starting from the tetrachloroalkanes.
  • Kazuo Saotome, Kenichiro Sato
    1966 Volume 39 Issue 3 Pages 485-489
    Published: 1966
    Released: March 27, 2006
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    α,ω-Oxaalkanedioic acids with the general formula HOOC(CH2)mO(CH2)nCOOH (m, n=3–10, but in unsymmetric structures m=3 or 4) were synthesized. The symmetric acids were prepared by the catalytic dehydration of ω-hydroxyalkanoic acids or by the condensation of ω-chloroalkanoic acids in the presence of alkali hydroxide. The unsymmetric acids (m=3 or 4) were prepared by the reaction of γ-butyrolactone or δ-valerolactone with alkali alcoholates of ω-hydroxyalkanoic acids. The reaction mechanisms were also discussed. In the plots of the melting points of the two unsymmetric series (m=3, 4 in mn) against the carbon atoms in a molecule, the minimum melting points are found at 3/5 and 4/5 respectively.
  • Shin Suzuki, Yasushi Inoue
    1966 Volume 39 Issue 3 Pages 490-497
    Published: 1966
    Released: March 27, 2006
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    Many methods, such as the co-precipitation method, the solvent extraction method and the ion exchange method, had previously been proposed for the separation and the purification of protactinium. However, these methods have some defects for the separation of Pa-233 produced by the thermal neutron irradiation of thorium dioxide and the purification of commercial Pa-231, when an attempt is made to study the chemistry of protactinium. From the above point of view, a combined method of solvent extraction and anion exchange was investigated. In the present paper, the detailed conditions for the TBP extraction of protactinium from a hydrochloric acid solution and the method for its final purification by anion exchange were described. The present method is comparatively simple and rapid, and chemically- and radiochemically-pure protactinium can thus be obtained.
  • Kenichi Fukui
    1966 Volume 39 Issue 3 Pages 498-503
    Published: 1966
    Released: March 27, 2006
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    The principle of the stereoselection in organic chemistry has been discussed from the point of view of the molecular orbital theory. The stereoselectivity in the stereospecific ring-closure of conjugated polyenes and the stereospecific ring-cleavage of unsaturated carbon cycles, trans-1,2-noncycloadditions, cis-1,2-additions and cis-1,3-dipolar additions have been accounted for with a qualitative generalization. In many cases the symmetry relationship of certain particular molecular orbitals (“frontier orbitals”) plays a conspicuously significant role in the steric control of stereochemical processes. This may be put in contrast with the role of the frontier electron density in the orientation process in organic reactions.
  • Mitsuo Mashima
    1966 Volume 39 Issue 3 Pages 504-506
    Published: 1966
    Released: March 27, 2006
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    The infrared absorption spectra of tetraformaltrisazine and formalazine have been obtained in the solid state. From a tentative assignment of the bands observed, it has been shown that a molecule of tetraformaltrisazine has the bicyclic structure proposed by Hofmann and Storm, while formalazine is a polymer with a four-membered heterocyclic ring.
  • Taichiro Oyamada, Hajime Baba
    1966 Volume 39 Issue 3 Pages 507-511
    Published: 1966
    Released: March 27, 2006
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    An alkaline hydrogen peroxide oxidation of chalcones with methoxymethoxyl groups in the 2′-position and in other positions gave the corresponding poly(methoxymethoxy)chalcone oxides; these were then, in turn, easily converted into polyhydroxydihydroflavonols, with a simultaneous splitting of all the O-methoxymethyl groups, by warming with acid. The general applicability of the new method was illustrated by the synthesis of the following hydroxydihydroflavonols: 3,7-dihydroxy- (m.p. 170–171°C),3,4′-dihydroxy- (m.p. 214–216°C),3,4′-dihydroxy-3′-methoxy- (m.p. 217–218°C),3,4′,7-trihydroxy- (m.p. 214–215°C), and 3,3′,4′,7-tetra-hydroxyflavanone (dl-fustin, m. p. 217–218°C). The first four new compounds were identified by converting them into known methyl ethers, while the last one was identified by comparing it with natural dl-fustin. Their structures were also confirmed by infrared and ultraviolet spectra.
  • Yoshihiko Mizutani
    1966 Volume 39 Issue 3 Pages 511-516
    Published: 1966
    Released: March 27, 2006
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    In an active fumarole on the dome of the Showashinzan volcano, Hokkaido, Japan, a crystalline sublimate was found. It is lead grey, with a metallic luster, and forms loose clusters of aciculer crystals. X-Ray diffraction, spectrographic and micro-chemical analyses have been made of the sublimate. The results indicate that the sublimate consists of bismuthinite Bi2S3, with traces of lead, zinc, aluminum, copper, iron and titanium. A colorimetric determination has also been made of the bismuth in the fumarolic gases from Showashinzan. The variation in the bismuth content of the gases with the gas temperature suggests that, when the temperature falls to about 500°C, bismuth compounds lose their volatility in the gases and are precipitated to form a sublimate. On the assumption that the chemical equilibrium is established in the gases, the stability of bismuth minerals and a possible reaction for the formation of bismuthinite in the gases have been discussed, and it has been suggested that the bismuthinite is formed by the 2BiCl3+3H2S=Bi2S3+6HCl reaction in the gases.
  • Kikuhiko Koyama, Kunihisa Yoshida, Shigeru Tsutsumi
    1966 Volume 39 Issue 3 Pages 516-521
    Published: 1966
    Released: March 27, 2006
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    Electrolyses of an acetonitrile solution of benzoic acid containing triethylamine have been carried out in the presence of anisole by the use of a platinum anode in an undivided cylindrical glass cell under various conditions. The electrolysis with benzoic acid at 15–23°C gave o- and p-methoxyphenyl benzoates (60%) as the main products, but the m-isomer could not be detected. The ratio of the isomers was 2 (ortho) : 1 (para). The other products identified in this experiment were carbon dioxide and biphenyl. The yield of the benzoates decreased when the electrolysis temperature was raised. The peaks of carbon dioxide and biphenyl on the vapor phase chromatograms in the experiment at 84°C, on the contrary, were relatively large compared with that observed in the low temperature electrolysis. Analogous products were obtained from the electrolysis of both p-toluic and p-anisic acids. These results have been compared with those obtained from the thermal decomposition of diaroyl peroxide in anisole. The mechanism of this anodic aroyloxylation of anisole has also been discussed.
  • Tomihito Kambara, Shogo Watarai
    1966 Volume 39 Issue 3 Pages 521-524
    Published: 1966
    Released: March 27, 2006
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    When the radio-frequency polarographic current, iRF, is regarded approximately as the difference between the Fournier current and the ordinary DC polarographic current, iDC, one can elucidate the temperature dependence of iRF. It may be theoretically predicted that the relative temperature coefficient of iRF for the completely-reversible system is less by 0.66% than that of iDC. The plot of log(iRF·T2) against 1/T, where T is the absolute temperature, gives two straight lines which join each other at a knick, coresponding to the transition from a completly reversible process to a less reversible one. Experiments with thallium(I) and zinc(II) ions in various supporting electrolytes reveal the essential validity of the present theory.
  • Kazu Kurosawa, Heitaro Obara
    1966 Volume 39 Issue 3 Pages 525-530
    Published: 1966
    Released: March 27, 2006
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    The assignment of the configuration of racemic trans-trans and cis-cis-2,3-dicarboxycyclopentylacetic acid previously proposed has been confirmed by the syntheses of these compounds through other unambiguous reaction sequences. The trans-cis-isomer has been prepared by the epimerization of the 3-carboxyl group of the cis-cis-isomer, but the attempt to synthesize the fourth isomer (cis-trans) has been unsuccessful.
  • Kazu Kurosawa, Heitaro Obara, Hisashi Uda
    1966 Volume 39 Issue 3 Pages 530-535
    Published: 1966
    Released: March 27, 2006
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    The racemic tetrahydroanhydrodesoxyaucubigenin, one of the derivatives from a glycoside, aucubin, has been synthesized using cis-cis-2-(2′-hydroxyethyl)-5-methoxycarbonylcyclopentane-carboxylic acid δ-lactone as an intermediate. 6,7-Dimethoxycarbonyl-2-oxa-bicyclo[3.3.0]-octane has also been synthesized, and the mechanism of the base-catalyzed rearrangement of the naturally-derived tetrahydroanhydroaucubigenin p-toluenesulfonate has been elucidated.
  • Mitsuru Kondo, Kuniyoshi Yamada, Kiichi Takemoto, Minoru Imoto
    1966 Volume 39 Issue 3 Pages 536-537
    Published: 1966
    Released: March 27, 2006
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    The graft polymerization of methyl methacrylate on natural rubber was studied in an aqueous suspension at 90°C, in the absence of initiators. It was found that methyl methacrylate could be grafted fairly smoothly on uncured natural rubber crepe and latex, both of which had previously been extracted with acetone.
  • Yasuhiro Itagaki, Tadashi Kurokawa, Shin-ichi Sasaki, Chin-Te Chang, F ...
    1966 Volume 39 Issue 3 Pages 538-543
    Published: 1966
    Released: March 27, 2006
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    The fragmentation of flavonoid compounds by electron impact has been studied and the following results described: 1) Chalcones gave the usual fragmentation pattern; however, 2′-hydroxy chalcones showed complex spectra according to the isomerization of chalcone to flavanone. 2) The fragmentation pathways of flavones were decided by comparison with many kinds of halogen-substituted flavones. 3) Isoflavone gave the M-1 ion as the base peak, and no loss of CO was observed.
  • Akira Nakamura
    1966 Volume 39 Issue 3 Pages 543-547
    Published: 1966
    Released: March 27, 2006
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    2,2′-Bi-π-allylene(hexacarbonyl)di-iron, [(OC)3Fe]·(Remark: Graphics omitted.)·[Fe(CO)3], was found to be a product of the reaction of allene with Fe3(CO)12. A study of the NMR spectrum, however, showed that a rapid valence tautomerisation takes place, even at −10°C between the 2,2′-bi-π-allylene structure and the related butadiene-type structure. In the presence of an excess of Co2(CO)8, allene yielded the [(C3H4)Co(CO)3]2 complex. The structure of this complex in which a (Remark: Graphics omitted.) skeleton was bound to two Co(CO)2 groups via π-allyl and acyl groups, was suggested.
  • Haruo Kuroda, Isao Ikemoto, Hideo Akamatu
    1966 Volume 39 Issue 3 Pages 547-551
    Published: 1966
    Released: March 27, 2006
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    The crystal structure of the pyrene-tetracyanoethylene (TCNE) complex has been determined by the two-dimensional Fourier method. The monoclinic unit cell dimensions are: a=14.58, b=7.34, c=8.09 Å and β=92.4°. The space group is P21/a. Two pyrene and two TCNE molecules are contained in a unit cell. Pyrene and TCNE molecules are stacked alternately along the c-axis direction, making their molecular planes parallel to each other. The center of a TCNE molecule is not directly above that of the neighboring pyrene molecule, but is displaced considerably along the long axis of pyrene. The mean separation of the molecular plane is 3.32 Å.
  • Hiroo Inoue, Yasuji Kida, Eiji Imoto
    1966 Volume 39 Issue 3 Pages 551-555
    Published: 1966
    Released: March 27, 2006
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    New semiconductive polymers have been prepared by the vulcanization of the oxidative condensation products of aniline. The polymers vulcanized are infusible black or black-violet powders insoluble in any organic solvent. The spin concentrations of the polymer vulcanized are about 1.5–2.5×1019 spins/g., about ten as much as those of the oxidative condensation products of aniline. The electrical conductivity increases with the increase in the sulfur content; the electrical resistivity at 20°C is 106–109 ohm-cm., and the activation energy is 0.68–1.18eV. The polymers vulcanized have catalytic effects on the decomposition of hydrogen peroxide at 30°C. The catalytic effects of phenothiazine and the oxidative condensation products of aniline are, however, extremely slight. The catalytic ability depends not only on the structure of the polymer vulcanized, but also to some extent on its electrical conductivity.
  • Hiroo Inoue, Kentaro Tamaki, Yoshihiro Kida, Eiji Imoto
    1966 Volume 39 Issue 3 Pages 555-558
    Published: 1966
    Released: March 27, 2006
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    The photo-reduction of phenazine was carried out in isopropyl alcohol in the presence of ferric chloride or stannic chloride. In the course of the photo-reduction, a metal chelate precipitated. The metal chelate was composed of unstable black needle crystals; it was presumed, from the results of the elementary analysis, the visible and the infrared absorption spectra and the ESR spectra, to be Fe2+- or Sn2+-chelate of N-monohydrophenazyl. On the other hand, the reduction of phenazine with stannous chloride and hydrochloric acid gave a phenazhydrin - stannic chloride-complex, which was more stable than the photo-reduction products. Their resistivities at 20°C had low values of from 105 to 108 ohm-cm.
  • Yoshié Tanizaki, Tadashi Kobayashi, Toshihiko Hoshi
    1966 Volume 39 Issue 3 Pages 558-562
    Published: 1966
    Released: March 27, 2006
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    The absorption spectra of azobenzene and its para hydroxy, amino or dimethylamino derivative, and their sodium salts have been determined above 220 mμ in mixed solutions of water and ethanol (7 : 3 in volume) at various acidities. All the samples show characteristic changes in spectra with increase in the acidity, and the respective spectral changes keep well-defined isosbestic points, indicating a binary system spectrally. The wavelengths of the color band peaks and the corresponding spectral species have been determined. Consequently, the following order of the substitution effect has been obtained;
    (Remark: Graphics omitted.)
  • Takeo Shimidzu, Tomio Hakozaki, Tsutomu Kagiya, Kenichi Fukui
    1966 Volume 39 Issue 3 Pages 562-565
    Published: 1966
    Released: March 27, 2006
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    Several Lewis acids have been found to be effective catalysts for the polymerization of ethylene-methylphosphite, giving a solid polymer with a poly(ethylene-methylphosphonate) structure. The use of Al(C2H5)3 gave a wax-like polymer with the structure of poly(ethylene-methoxy-phosphinate), while Na and Li in liquid NH3 at −78°C produced a jelly-like polymer partly composed of poly(ethylene-methylphosphite).
  • Teruaki Mukaiyama, Kazutoshi Osaka
    1966 Volume 39 Issue 3 Pages 566-568
    Published: 1966
    Released: March 27, 2006
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    The diesters of phosphorous acid were prepared in good yields by the reaction of primary or secondary alcohols, such as methanol, ethanol, and s-butanol, or of phenols, such as phenol, p-chlo-rophenol and p-cresol, with ethyl N-phenylimino phosphite and p-toluenesulfonic acid monohy-drate. Similarly, when carboxylic acids, such as acetic acid, benzoic acid, p-chlorobenzoic acid and trichloroacetic acid, were used in place of the acid monohydrate in the above experiment, the diesters of phosphorous acid were also obtained. Ethyl N-n-propylimino or ethyl N-isopropylimino phosphite could be successfully used in place of ethyl N-phenylimino phosphite in the above experiments. Further, various derivatives of methylphosphinic acid, such as ethyl dicyanomethyl-, ethyl cyanocarboethoxymethyl- and ethyl dicarboethoxymethylphosphinate, were obtained by the reaction of ethyl N-phenylimino phosphite, p-toluenesulfonic acid monohydrate and active methylene compounds, such as malononitrile, ethyl cyanoacetate and diethyl malonate.
  • Takayuki Fueno, Tadashi Okuyama, Junji Furukawa
    1966 Volume 39 Issue 3 Pages 569-576
    Published: 1966
    Released: March 27, 2006
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    The nonlinearity of free energy correlations of the substituent effects in aromatic side-chain reactions has been treated by the simple LCAO MO method. The ionization equilibria of substituted phenylacetic acids, leading to the definition of “normal” substituent constants, σ0, were taken as the basis for theoretical tests of the correlations. Thus, the integral parameters for various substituents were determined in such a way that the calculated π-electron charge densities for meta and para carbons in benzenes were proportional to the corresponding σ0-constants. Several other typical side-chain reactions of substituted benzenes were simulated by the corresponding standard processes, and the effects of substituents on these reactions were examined by the perturbation calculations of the π-electron energy changes accompanying the reactions. It has been found that the substituent constants, σ, σ+ and σ, are linearly related to the calculated energy changes. It is suggested that the treatment may be extended to other reactions to account for the sliding-scale variation in substituent constants from reaction to reaction.
  • Iwaji Iwasaki, Shigeru Suzuki
    1966 Volume 39 Issue 3 Pages 576-580
    Published: 1966
    Released: March 27, 2006
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    A new photometric method for the determination of tetrathionate by means of its decomposition with sulfite has been developed. It is based on the formation of thiosulfate equivalent to the tetrathionate, and on the photometric determination of thiosulfate by measuring its decoloration of an iodine solution. 5×10−6–1×10−3 M (1 mg./l.–0.2 g./l.) of tetrathionate can be determined easily and rapidly within a range of error of ±2×10−6–2×10−5 M (0.4 mg./l.–4 mg./l.) by using 20 ml. of a sample. The tetrathionate solution is decomposed with sodium sulfite in a slightly alkaline medium. After the completion of the decomposition reaction, a formaldehyde solution is added to mask the interference of the excess sulfite remaining and this solution is acidified with acetic acid. Then the standard iodine solution is added. The absorbancy of the solution is measured at the wavelength of 372 or 440 mμ 20 min. after the addition of an iodine solution. By this method tetrathionate can be determined, even when it is coexistent with thiosulfate and sulfite in up to similar amounts. Many substances, such as aluminum, calcium, cadmium, magnesium, zinc, silicate, nitrate, sulfate, phosphate, chloride and fluoride, do not interfere, but iron(II, III), manganese(II), copper(II) and sulfide do interfere.
  • Masakazu Matsui
    1966 Volume 39 Issue 3 Pages 581-585
    Published: 1966
    Released: March 27, 2006
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    The coprecipitation of strontium with calcium oxalate was studied using dimethyloxalate to precipitate calcium from a homogeneous solution. The several effects of the coprecipitation conditions on the distribution coefficients were investigated in the fractional precipitation process of calcium-strontium oxalate mixtures. Regardless of the pH value, the concentration of acetic acid and other factors, the coprecipitation curves of strontium showed similar shapes in almost all cases, although the curves well shifted up and dawn to some extent. It appears to be an anomalous system, because an increase in the fraction of the calcium precipitated tends to decrease the distribution coefficients. It is considered that two coprecipitation mechanisms are involved in the coprecipitation system; one is the surface adsorption on fine crystals, while the other is a normal systematic type. When the adsorption part was removed, it was found that the modified system obeyed the Doerner and Hoskins logarithmic distribution law and that the coefficient gave nearly a constant, 0.1.
  • Ikuko Akaza
    1966 Volume 39 Issue 3 Pages 585-596
    Published: 1966
    Released: March 27, 2006
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    The liquid-liquid extraction of alkali metal ions as their poly-iodides had previously been investigated by the present author. In order to attain a good separation of each metal, this extraction system has now been extended to a reversed-phase partition chromatography in which Kel-F powder was used to support the organic phase of nitrobenzene-iodine-iodide. Column chromatographic separation was carried out in the presence of relatively large amounts of the metals by elution with water and 1 N or 6 N hydrochloric acid - eluting solutions. Chromatographic behavior of each metal ion was investigated and the elution from the column was found to be in the order of Li-Na-K-Rb-Cs. The distribution ratio of the metal ions varied with the quantity of the ions loaded on the column; the smaller the quantity of the ions used, the larger was the distribution ratio obtained. The actual separation of individual metal ions from the mixture was successfully achieved; a minute amount of cesium could be particularly isolated from large amounts of other alkali metals, even in a large volume of the sample solution. Elution curves of various amounts of metal were obtained as an aid to a discussion of the partition on the column. A comparison of the distribution ratio in the liquid-liquid extraction with that in the column chromatography showed that the extraction of the same mechanism proceeded in both cases.
  • Iwao Satake, Masujiro Arita, Hideo Kimizuka, Ryohei Matuura
    1966 Volume 39 Issue 3 Pages 597-602
    Published: 1966
    Released: March 27, 2006
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    The theoretical NMR dilution curves for the ethanol-carbon tetrachloride, water-acetone and water-dioxane systems have been derived without the assumption of any particular type of H-bonded complexes in the solution. The expressions so derived contain the interchange energies as variable parameters. The use of the appropriate values of interchange energies (a few kilocalories) gives reasonable quantitative fits of the experimental dilution curves over the entire concentration range of the solutions. These values suggest that the strength of hydrogen bonding in the present systems is in the order of: water-water>water-acetone>water-dioxane>ethanol-ethanol.
  • Susumu Tatsumi, Yoshiharu Izumi, Masami Imaida, Yoshio Fukuda, Shiro A ...
    1966 Volume 39 Issue 3 Pages 602-604
    Published: 1966
    Released: March 27, 2006
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    Two racemic forms of 2-methyltartaric acid were prepared, and their optical resolutions were performed. Four optically active isomers were obtained. 2, 3-Dimethyltartaric acid was also prepared and separated into two isomeric optically inactive forms. The isomer with the higher melting point could be resolved into two optically active isomers, but the other, with the lower melting point, could not. The former was, therefore, assigned to the racemic configuration, and the latter, to the meso configuration.
  • Takaji Yasui, Yoichi Shimura
    1966 Volume 39 Issue 3 Pages 604-608
    Published: 1966
    Released: March 27, 2006
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    The geometrical structures of bis(α-amino-acidato)copper(II) complexes have been determined from the data of diffuse reflectance spectra (α-amino-acid = glycine, L- and DL-α-alanine, L- and DL-valine, L- and DL-threonine, L- and DL-isoleucine and α-aminoisobutyric acid). It has been shown that pairs of cis(N) and trans(N) isomers exist in glycinato and valinato complexes. It has been clarified that the other amino-acidato complexes studied exist either only in the cis(N) form or only in the trans(N) form; that is, the needle and the scaly complexes of DL-alanine, the complexes of DL- and L-threonine, and the complex of α-aminoisobutyric acid exist only in the trans(N) form, while the complexes of L- and DL-isoleucine exist only in the cis(N) form.
  • Ko Kimura, Ryoichi Fujishiro
    1966 Volume 39 Issue 3 Pages 608-610
    Published: 1966
    Released: March 27, 2006
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    The dipole moments of ethylene glycol dimethyl ether (N=1), diethylene glycol dimethyl ether (N=2), triethylene glycol dimethyl ether (N=3), and tetraethylene glycol dimethyl ether (N=4), were measured in n-hexane or benzene at 25°C and 45°C. The observed dipole moments of N=1, N=2, N=3, and N=4 are 1.59 D, 1.92 D, 2.16 D, and 2.44 D, respectively, in n-hexane at 25°C, 1.71 D, 1.97 D, 2.22 D, and 2.45 D, respectively, in benzene at 25°C, and 1.72 D, 1.98 D, 2.27 D, and 2.50 D, respectively, in benzene at 45°C. The dipole moments were theoretically calculated on the assumptions that: (i) the dipole moments of these chain molecules are given by the vector sum of the polar groups of ether whose group moment is 1.20 D, and (ii) all the internal rotations of a chain molecule are free. The calculated values of N=1, N=2, N=3, and N=4 are 1.67 D, 2.03 D, 2.33 D, and 2.60 D, respectively. The agreement between the observed and the calculated values is satisfactory. The solvent effect and the temperature dependence of the observed dipole moments have also been discussed in terms of chain flexibility.
  • Shigeru Oae, Reiko Kiritani
    1966 Volume 39 Issue 3 Pages 611-614
    Published: 1966
    Released: March 27, 2006
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    The reaction of phenol with ethyl alcohol in strong acidic media at a somewhat high temperature gave phenyl ethyl ether in a 61% yield. The product isolated from a similar reaction between phenol and n-propyl alcohol was practically pure phenyl n-propyl ether, and no isopropyl isomer was detected. When 18O-labeled phenol was treated with unlabeled ethyl alcohol, the phenetole isolated was found not to contain any excess 18O. The reaction of phenol with ethyl alcohol in the presence of hydrogen chloride gave no isolable amount of phenetole. The mechanism for these reactions was then discussed.
  • Waichiro Tagaki, Kunihiko Kikukawa, Norio Kunieda, Shigeru Oae
    1966 Volume 39 Issue 3 Pages 614-617
    Published: 1966
    Released: March 27, 2006
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    When diphenyl sulfoxide was allowed to react with bromine in a mixture of acetic acid and 18O-enriched water, the sulfoxide was recovered, together with a small amount of diphenyl sulfone. The sulfoxide recovered incorporated a very small amount of 18O from the water. Meanwhile, diphenyl sulfoxide was found to undergo a facile oxygen exchange reaction with water in the presence of hydrobromic acid. Possible mechanisms for these reactions have been discussed.
  • Jun Katsuhara, Hajime Watanabe, Komei Hashimoto, Masahisa Kobayashi
    1966 Volume 39 Issue 3 Pages 617-618
    Published: 1966
    Released: March 27, 2006
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  • Toshio Takiguchi, Minoru Abe, Katsutoshi Takahashi, K\={o}ji Urano
    1966 Volume 39 Issue 3 Pages 619-620
    Published: 1966
    Released: March 27, 2006
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  • Hiroshi Midorikawa, Heinosuke Yasuda, Hiroe Asaba, Tatsuo Takeshima
    1966 Volume 39 Issue 3 Pages 620-622
    Published: 1966
    Released: March 27, 2006
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  • Shozo Yamaguchi, Shoei Ito, Asao Nakamura, Naoto Inoue
    1966 Volume 39 Issue 3 Pages 622-623
    Published: 1966
    Released: March 27, 2006
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  • Shoichi Kawamura, Masami Izawa
    1966 Volume 39 Issue 3 Pages 624-625
    Published: 1966
    Released: March 27, 2006
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  • Yoshiko Takeoka
    1966 Volume 39 Issue 3 Pages 625-627
    Published: 1966
    Released: March 27, 2006
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