YAKUGAKU ZASSHI
Online ISSN : 1347-5231
Print ISSN : 0031-6903
ISSN-L : 0031-6903
68 巻 , 1-2 号
選択された号の論文の25件中1~25を表示しています
  • 長簀鯨油の常壓水素添加に就て
    三宅 良一
    1948 年 68 巻 1-2 号 p. 1-4
    発行日: 1948/11/12
    公開日: 2010/02/19
    ジャーナル フリー
    Partial hydrogenation of finback whale oil with nickelsilica gel as catalyst to the extent that the products indicate the iodine value of 83 shows that highly unsaturated acids with F2 or more are selectively hydrogenated mostly to F1-acids, while F1-acids remain unsaturated. The reaction is not affeeted by the temperature (180° and 210°) and proceeds, at 210°, 1.44 times faster than at 180°.
  • 三宅 良一
    1948 年 68 巻 1-2 号 p. 5-7
    発行日: 1948/11/12
    公開日: 2010/02/19
    ジャーナル フリー
    An exceptionally good acetic acid for Wijs' solution is obtained in a gratifying yield by distilling a mixture of commercial acetic acid, which has been brought into contact with potassium permanganate crystals and carbon tetrachloride. The boiling point at 760mm. Hg of the binary system of carbon tetrachloride and acetic acid was sought.
  • H. Adkins觸媒による長簀鯨油, 大豆油の水素添加
    三宅 良一
    1948 年 68 巻 1-2 号 p. 8-11
    発行日: 1948/11/12
    公開日: 2010/02/19
    ジャーナル フリー
    Hydrogenation under atmospheric pressure at temperatures 180° and 210° of finback whale oil and soy bean oil using H. Adkins' copper-chromium oxide catalyst shows that highly unsaturated acids above the linolic acid series undergo selective partial hydrogenation to form acids of the oleic acid series, while acids of the oleic acid series remain intact. The reduction involved does not occur in the acid radical. The reaction with hydrogen at the initial pressure of 40 atmospheres produces at 140° the same results as that at atmospheric pressure but brings about the saturation of the oleic acid series as well as reduction of the acid radical at 180°.
  • 選擇的水素添加法によるをなもみ油成分檢索
    三宅 良一
    1948 年 68 巻 1-2 号 p. 12-13
    発行日: 1948/11/12
    公開日: 2010/02/19
    ジャーナル フリー
    The conclusion of the author's second communication indicates that the quantity of saturated acids in a fatty oil whose constituents are unknown might be determined by subjecting the oil to exhaustive hydrogenation under atmospheric pressure with the copper-chromium oxide catalyst and by determining the iodine value of the resulting oil. It is also derived that if none but linolic acid alone is contained as highly unsaturated acid, the quantitative determination of linolic acid might be possible on the basis of the reduction of the iodine value due to hydrogenation. This method was applied to the analysis of the seed oil of Xanthium Strumarium L.
  • H. Adkins觸媒の研究 (その一). クロム酸アンモニウム銅の分解温度と活性との關係
    三宅 良一
    1948 年 68 巻 1-2 号 p. 14-17
    発行日: 1948/11/12
    公開日: 2010/02/19
    ジャーナル フリー
    The decomposition of copper ammonium chromate in the air under atmospheric pressure is completed at 280°. The decomposition temperature is independent of the addition of barium chromate or Kieselguhr and of the acidity or the alkalinity of the mother liquor in which the chromate is precipitated. Heating up to 280° is enough to produce a catalyst with high activity. At 7mm. Hg the decomposition temperature is lowered to 260°, but no appreciable increase in the activity of the catalyst is registered thereby.
  • H. Adkins觸媒の研究 (其二) 觸媒還元と接觸能
    三宅 良一
    1948 年 68 巻 1-2 号 p. 18-21
    発行日: 1948/11/12
    公開日: 2010/02/19
    ジャーナル フリー
    The reduction of copper oxide in H. Adkins' copper-chromium oxide catalyst with hydrogen at atmospheric pressure commences at 120°. The reaction in which highly oxidized chromium is reduced to Cr2O3 begins at 140° and proceeds slowly. It takes place, however, with considerable rapidity when the copper oxide catalyst co-exists. It is reduced copper that actually has a catalytic action in the hydrogenation of fatty oils. Copper chromate is likewise reduced into reduced copper and Cr2O3.
  • H. Adkins觸媒の研究 (其三). 助觸媒酸化クロムに就て
    三宅 良一
    1948 年 68 巻 1-2 号 p. 22-25
    発行日: 1948/11/12
    公開日: 2010/02/19
    ジャーナル フリー
    In order to hydrogenate highly unsaturated fatty oils at atmospheric pressure, it is necessary to add a promoter to reduced copper which is employed as the catalyst. When the copper-chromium oxide catalyst is subjected to thermal treatment, it remains intact up to 550°, but above this temperature the reduction of copper oxides slows down. This means that here is no correlation between the extent of oxidation and the promoter action of chromium oxide. Copper chromate derived from potassium chromate can also be converted though reduction into a copper-chromium oxide catalyst with high activity.
  • H. Adkins觸媒の研究 (その四)
    三宅 良一
    1948 年 68 巻 1-2 号 p. 26-28
    発行日: 1948/11/12
    公開日: 2010/02/19
    ジャーナル フリー
    Chromium oxide in H. Adkins' copper-chromium oxide catalyst has also a catalytic action of its own in the hydrogenation of the carbonyl group.
  • Adkins觸媒の研究 (その五) 醋酸洗滌による活性化の意義
    三宅 良一
    1948 年 68 巻 1-2 号 p. 29-31
    発行日: 1948/11/12
    公開日: 2010/02/19
    ジャーナル フリー
    H. Adkins recommended washing the copper-chromium oxide catalyst with acetic acid in order to promote the activity of the catalyst, but the author maintains that washing with water is sufficient for the purpose. No direct effect is exerted on the copper catalyst by washing with water. This indicates that the essential object of washing with water is to eliminate water-soluble poisons.
  • 珪藻土附銅觸媒の接觸能
    三宅 良一
    1948 年 68 巻 1-2 号 p. 32
    発行日: 1948/11/12
    公開日: 2010/02/19
    ジャーナル フリー
    The copper catalyst dispersed on Kieselguhr is capable of performing selective hydrogenation of highly unsaturated acids in fatty oils to acids of the oleic acid series under atmospheric pressure, as is the case with the copper-chromium oxide catalyst.
  • 銅觸媒の分散度とその表面積並活性度の關係
    三宅 良一
    1948 年 68 巻 1-2 号 p. 33-37
    発行日: 1948/11/12
    公開日: 2010/02/19
    ジャーナル フリー
    A method of preparing a copper catalyst relatively uniformly scattered on Kieselguhr was described. Sintering was observed when the copper catalyst was repeatedly subjected to reduction and oxidation. It was inferred that the degree of dispersion and the surface area of the copper catalyst on a carrier (Kieselguhr) which went through sintering as stated above be related hyperbolically. This inference is in agreement with the experimental results. A comparative study of the degree of dispersion and the activity of the copper catalyst after sintering in the hydrogenation of finback whale oil showed that high activity is attained at a certain degree of dispersion. In this respect H. Adkins' catalyst after sintering is no exception. It should be mentioned, however, that it is outstanding in regard to uniform dispersion as compared with the copper catalyst on Kieselguhr. This explains why the high activity of H. Adkins' catalyst is confined to the short period of time before sintering. The addition of barium chromate to H. Adkins' catalyst does not hamper the reduction of copper oxide. It should be construed as an increase in the amount of carrier.
  • H. Adkins觸媒の研究 (その六) 特徴, 用法及添加クロム酸バリウムの意義に就て
    三宅 良一
    1948 年 68 巻 1-2 号 p. 38-39
    発行日: 1948/11/12
    公開日: 2010/02/19
    ジャーナル フリー
    H. Adkins' catalyst falls under the same category as the copper on kieselguhr catalyst in the light of the relationship between the activity as seen in the hydrogenation of fatty oils and the degree of dispersion and the surface area of the copper catalyst on a carrier. But with respect to uniform dispersion the copper on kieselguhr catalyst pales before H. Adkins' catalyst. This explains why the high activity of H. Adkins' catalyst is confined to the short period of time before sintering. The addition of barium chromate to Cu-Cr-O does not hamper the reduction of copper oxide. It should be construed as an increase in the amount of carrier.
  • Thiazol-2-essigsäure同族體に就て
    大田 正樹, 須藤 六郎, 加藤 和雄
    1948 年 68 巻 1-2 号 p. 40-41
    発行日: 1948/11/12
    公開日: 2010/02/19
    ジャーナル フリー
    The condensation of malonic amid-thioamide (NH2COCH2-CSNH2) with monochloroacetone or α-chloroacetoacetic ester was re-examined. In this study the authors found that the melting points of 4-methylthiazole-2-acetic acid and 4-methyl-5-carboxythiazole-2-acetic acid which they reported in the first communication of their present study were wrong, and gave 93° (decomp.) and 235° (decomp.) respectively as the true melting points.
  • フルアミヂン類に就て
    高橋 酉藏, 西海枝 東雄, 木村 隆一, 吉名 多賀重
    1948 年 68 巻 1-2 号 p. 42-43
    発行日: 1948/11/12
    公開日: 2010/02/19
    ジャーナル フリー
    N-Ethyl-furamide (1) has been prepared by the action of ethylamine upon pyromucic acid eth ylester. On condensing furoyl chloride with ethylamine, we synthesized the amide (1) (oil of b. p. 130-132°/10mm). When treated the latter with PCl5 the dichloro-compound C4H3O⋅CCl2⋅NHC2H5 was formed, which produced N-ethyl-N′-pyridyl-(3)-furamidine (II) (oil of b.p. 126-128/8mm) on the condensation with 3-amino-pyridine.
    Starting from furoyl chloride and allylamine, N-allyl-furamide (III) (oil of b.p. 157-159°/14mm) was obtained. By condesing the dichloro-compound C4H3O⋅CCl2NHC3H5 prepared from the amide (III), with p-anisidine, p-phenetidine, 2-aminopydridine and 2-amino-4-methyl-thiazole, we repecitvely obtained N-allyl-N-anisyl-(4)-furamidine (IV) (colorless plates of m.p. 65-66°), N-allyl-N′-phenetyl-(4)-furamidine (V) (syrup of b.p. 210-216°/2mm), N-allyl-N′-pyridyl-(2)-furamidine (VI) (oil of b.p. 130-135°/4mm) and N-allyl-N′-[4-methyl-thiazolyl-(2)]-furamidine (VII) (oil of b.p. 110-115°/2mm).
  • シアン水銀に就て
    野事 嘉造
    1948 年 68 巻 1-2 号 p. 44-48
    発行日: 1948/11/12
    公開日: 2010/02/19
    ジャーナル フリー
    Mercuric cyanide was dissolved in three kinds of buffer solution, i.e. phosphoric acid-sodium phosphate, citric acid-sodium hydroxide, and tartaric acid-sodium hydroxide, and quantities of free hydrocyanic acid liberated were measured at temperatnres 15°, 37°, 60° and 100° at varying pH. No free hydrocyanic acid was detected at 15° in any of the buffer solutions; the highest coneentration of the liberated HCN was 0.00288 per cent at 37°, 0.0334 per cent at 60°, and 0.0772 per cent at 100°.
    The amount of hydrocyanic acid liberated from mercuric cyanide solution is thus so small in the neighborhood of human temperature that its toxicity is of no significance. However, it is pointed out that the toxicity of the liberated HCN should be taken into consideration at lower values of pH and at temperatures above 60° depending on the time of contact and the presence of catalyzer, and that besides the toxicity of HCN that of the mercuric compounds should also be taken into account.
  • ニトロプルシツトソーダに就て
    野事 嘉造
    1948 年 68 巻 1-2 号 p. 49-53
    発行日: 1948/11/12
    公開日: 2010/02/19
    ジャーナル フリー
    Sodium nitroprusside was added to three kinds of buffer solution, i.e. phosphoric acid-sodium phosphate, citric acid-sodium hydroxide, and tartaric acid-sodium hydroxide, and quantities of free hydrocyanic acid liberated were measured at 15°, 37°, 60° and 100° at varying pH. No free hydrocyanic acid was detected at 15° in any of the buffer solutions: the highest concentration of the liberated HCN was 0.0008 per cent at 37°, 0.0368 per cent at 60° and 1.3576 per cent at 100°.
    The amount of HCN liberated from sodium nitroprusside varies considerably with the compositin of the buffer; with the tartaric acid-sodium hydroxide buffer solution, the peak amount of HCN librated at 60° is witnessed at pH 3.5 and that at 100° is attained at pH 5.5-6.8. This is considered to be due to the specific effect of the tartrate ion, suggesting that the selectivity exhibited by each buffer solution with regard to HCN liberation should be taken into due consideration.
    The amount of HCN liberated from sodium nitroprusside solution is thus so small in the neighborhood of human temperature (37°) that the toxicity of the solution is of no significance. It is pointed out, howeuer, that the toxicity of the liberated HCN should be taken into account at temeratures above 60° depending on the time of contact and the presence of catalyzer.
  • Neocyaninの合成とその副生成物に就いて
    水野 義久, 西村 正子
    1948 年 68 巻 1-2 号 p. 54-57
    発行日: 1948/11/12
    公開日: 2010/02/19
    ジャーナル フリー
    (1) Compound, O. A. formed under various conditions were quantitatively investigated with a view to finding conditions under which the greatest yields of neocyanine be obtained.
    (2) O. A. 4 was identified as a derivative of Kryptocyanine, whose properties were in part described.
  • 芳香族第一級アミンと正蟻酸エチルエステルの反應
    水野 義久, 西村 正子
    1948 年 68 巻 1-2 号 p. 58-62
    発行日: 1948/11/12
    公開日: 2010/02/19
    ジャーナル フリー
    Thirteen aromatic primary amines were caused to react with ethyl orthoformate, and on the basis of the curve of the rate of formation was the order of O. A. of amines determined.
    By comparing this order of O. A. with that of Hammett's substituent constants and of ionization constants it was made plain that the more electropositive the amino group is, the more readily are amidines formed in this condensation reaction involving dealcoholizing.
  • 入谷 信彦
    1948 年 68 巻 1-2 号 p. 63-64
    発行日: 1948/11/12
    公開日: 2010/02/19
    ジャーナル フリー
    The author developed a new method of quantitative analysis for potassium, which brought better results than those obtained by the conventional method using potassium permanganate as the oxidizing agent. The procedures are: Sodium cobaltinitrite is added to a solution containing 5 to 20mg. of potassium to precipitate sodium potassium cobaltinitrite. The precipitate is oxidized with potassium bichromate and then a known quantity of ferrous solution is added. The excess ferrous ion is backtitrated with a normal solution of potassium bichromate.
  • 齋藤 徳男
    1948 年 68 巻 1-2 号 p. 65-67
    発行日: 1948/11/12
    公開日: 2010/02/19
    ジャーナル フリー
    In the first communication of the present study Sugasawa and the author reported that expected results were attained by preparing benzyl carbamate instead of the ethyl ester which is usually employed in Curtius reaction and subjecting it to saponification through catalytic reduction, which might be said to be very mild conditions as compared with the ordinary process of the reaction. They have also developed a modifed method for material containing a radical susceptible to reduction in the molecule.
    Since it is a well known fact that such linkages as O-CH or N-CH are not tight, the author investigated the saponification of the benzyl ester mentioned above, with the result that the decomposition of the ester was exceptionally readily accomplished only by boiling it under reflux for one half to one hour in 10 to 20 per cent hydrochloric acid or, in particular, in acetic acid of proper concentrations, producing the primary amine in satisfactory yields. This process is credited with the following advantages: (1) No expensive catalyst and reagents nor special apparatus are required, and (2) considerably large quantities of material can be treated at a time.
  • 金尾 清造, 篠塚 きよし
    1948 年 68 巻 1-2 号 p. 68-69
    発行日: 1948/11/12
    公開日: 2010/02/19
    ジャーナル フリー
    It was experimentally demonstrated that when methylamine or ammonia is caused to react with styrenechlorohydrin or α, α-diphenylethylene oxide, substitution by the methylamino or the amino group occurs on the C atom in the β-position against the benzene nucleus. Therefore, the reaction product of methylamine and styrenechlorohydrin is a lower homolog of ephedrine.
  • 金尾 清造, 篠塚 きよし
    1948 年 68 巻 1-2 号 p. 70-72
    発行日: 1948/11/12
    公開日: 2010/02/19
    ジャーナル フリー
    (1) Reduction of the condensation product of phenyl-nitromethane and acetaldehyde produced β-amino-β-phenyl-isopropyl alcohol (normal form) which is a structural isomer of nor-dl-ephedrine.
    (2) A normal and an iso isomer of a base were obtained by alkali-hydrolysis of phenylpropylene-Ψ-urea.
    (3) The condensation product of α-bromobenzylmethyl ketone with methylamine was reduced to a structural isomer (iso-form) of dl-ephedrine, which proved to be identical with the reaction product of phenylpropyleneisohydrin with methylamine. This indicates that α-methylamino base was formed from phenylpropyleneiodohydrin. This stands in striking contrast with the case of styrenechlorohydrin which gives β-methylamino base.
  • 藤川 福二郎, 中島 邦夫, 藤井 博
    1948 年 68 巻 1-2 号 p. 73
    発行日: 1948/11/12
    公開日: 2010/02/19
    ジャーナル フリー
    Growth of molds in soy sauce could be held up for 60 days with phenylmustard oil and ethyl o-phenylthiocarbamate in concentrations of from 0.003 to 0.005 per cent and the isopropyl ester in concentrations ranging from 0.005 to 0.007 per cent.
  • 荒田 義雄, 大橋 力
    1948 年 68 巻 1-2 号 p. 74-76
    発行日: 1948/11/12
    公開日: 2010/02/19
    ジャーナル フリー
    Kotake et al. have previously applied exhaustive methylation to desoxynupharidine (Proc. Imp. Acad. (Tokyo) 19, 490) in a different way from the authors. The authors attempted to trace the process as described by Kotake, which runs as follows:
    By oxidizing (A) with ozone were formed formic acid, acetic acid, isovaleric acid, succinic acid and an acid substance whose semicarbazone melted at 99-102°.
    Kotake et al. reported to have obtained by the oxida-tion of Kawahomin (A) n-Valeric acid, β hydroxypropionic acid and a Substance corresponding to Kawahonic acid. They were not obtained, however, by the authors. the discrepancy may be ascribable to the difference in the conditions under which C15H24O was Oxydized with Ozone.
  • 荒田 義雄
    1948 年 68 巻 1-2 号 p. 77-80
    発行日: 1948/11/12
    公開日: 2010/02/19
    ジャーナル フリー
    Estimation of C-CH3 by Karrer's method with hydrochloride of deoxynupharidine and hydiodride of dihydro-deoxynupharidine gave results of 1.786mol. and 1.783mol. CH3COOH, respectively, which proves that there are 2 C-CH3 radicals in these compds. Similar measurment of C-CH3 with hydriodide of N-methyl-tetrahydrodeoxynupharidine, obtained by the cleavage of B-ring at C-N bond, gave 1.770mol. CH3COOH, showing the presence of 2 C-CH3 radicals. In the previous report, it was reported that isovaleric acid was obtained by ozonic oxidation of C15H26O, obtained by denitrogenation of deoxynupharidine. At the same time, a monobasic acid, C9H15O⋅COOH (methyl ester, b.p.0·5 100° (bath temp.); p-phenylphenacyl ester, m.p. 55.5-56.5°) had been obtained. Oxidation of this monobasic acid gave succinic acid. The structure of deoxnu-pharidine proposed by Kotake, et al. (Proc. Imp. Acad., Tokyo. 19, 490) cannot explain the results of various experiments carried out by the author and, therefor, the author herewith proposes following formulae for nupharidine and deoxpnupharidine.
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