YAKUGAKU ZASSHI
Online ISSN : 1347-5231
Print ISSN : 0031-6903
ISSN-L : 0031-6903
76 巻, 6 号
選択された号の論文の71件中1~50を表示しています
  • アミノ酸の酵素的脱炭酸反応生成物の検出
    萩原 武美雄
    1956 年 76 巻 6 号 p. 613-615
    発行日: 1956/06/25
    公開日: 2010/02/19
    ジャーナル フリー
    It was found that the paper electrophoretic method is useful in the detection of amines formed by the decarboxylation of amino acids. Using Escherichia coli No.1, arginine and its structurally allied compound, canavanine, were decomposed and the products were submitted to electrophoresis. By coloration with the Sakaguchi and nitroprusside reaction, agmatine was detected from arginine, and a new substance, possessing o-guanidyl group, with stronger basicity than the parent compound, was obtained from canavanine. Its structure was presumed from the distance of its migration. Decomposition of arginine and canavanine was examined with Staphylococcus aureus 209 P, Lactobacillus 17-5, and Streptococcus fecalis R, and found that the decomposition was effected in all the cases without decarboxylation. The present method was also used in examining the activity of decarboxylase of amino acids with E. coli No.1, and it was found that the decarboxylation was effected with arginine, canavanine, lysine, glutamic acid, histidine, and ornithine, while this bacillus did not have any ability of decarboxylating canarine, tyrosine, tryptophan, phenylalanine, leucine, serine, threonine, aspartic acid, citrulline, diaminobutyric acid, valine, alanine, and DOPA.
  • 山田 俊一, 藤田 公司, 溝口 富茂
    1956 年 76 巻 6 号 p. 616-620
    発行日: 1956/06/25
    公開日: 2010/02/19
    ジャーナル フリー
    Several thiamine alkyl sulfides, such as CH3 (X), C2H5 (XI), C3H7 (XII) and C4H9 (XIII) were prepared by alkylating the thiamine with dimethyl sulfate, halogen alkyl or alkyl p-toluenesulfonates in good yields. It was found that all these compounds have two melting points, and it seems to be a dimorphism.
    Methyl sulfonium iodide of (X) was obtained by the reaction of thiamine methyl sulfide and methyl iodide.
  • 中島 正太郎, 奥山 源一
    1956 年 76 巻 6 号 p. 620-624
    発行日: 1956/06/25
    公開日: 2010/02/19
    ジャーナル フリー
    The Ehrlich reaction, the blue coloration formed by the reaction of tryptophan and p-dimethylaminobenzaldehyde in strong acid solution, is accelerated by heating the solution or by the addition of an oxidation agent but at the same time, the color becomes unstable and liable to be discolored. In this case, the addition of acid hydrolyzate of proteins effects stabilization of coloration and prolongation of the maintenance period of maximum coloration. In order to find substances which can stabilize this coloration, various amino acids were submitted to the test. It was found that methionine effected the greatest stabilization of the color, the color formed having been maintained over three months. This was followed by cystine, tyrosine, histidine, aspartic acid, and glutamic acid, which possessed a certain amount of stabilization effect, while the action of other amino acids was weaker. As for compounds other than amino acid, levulic acid possessed a strong action similar to that of methionine, while pyruvic acid and fructose also possessed a fairly strong action. These results indicated that compounds possessing a sulfur atom or a carbonyl group possessed strong action. Based on these results, 0.1-1.0% solution of methionine was adopted as the solvent for the coloration solution of tryptophan, in place of acid hydrolyzate of proteins.
  • 瀘紙クロマトグラフィー及び瀘紙電気泳動法によるモルフィン型アルロカイドの分離並びに検出について
    刈米 達夫, 井上 隆夫
    1956 年 76 巻 6 号 p. 625-628
    発行日: 1956/06/25
    公開日: 2010/02/19
    ジャーナル フリー
    Separation of morphine, ethylmorphine, heroine, codeine, and hydrocodeine by buffer chromatography and paper ionophoresis was examined. Buffer chromatography at various pHs between pH 1 and 12, utilizing the method of McFarren, effected a considerable difference in the Rf values of ethylmorphine and heroine, and between codeine and hydrocodeine, which are difficult to separate on the filter paper. Comparative examination of detection of several alkaloids for minimum detectable range indicated platinum chloride-potassium iodide reagent to be the most sensitive.
    Paper ionophoreses were carried out at various pHs using the Sørensen and Clark-Lubs buffer solutions and the best results were obtained at pH 9-11. Migration with the use of 0.01-1% ammonia water was found to effect marked change in the migration distance in accordance with a slight change in the concentration of ammonia water. By selecting a suitable concentration, all the alkaloids could be separated clearly from each other.
  • 濾紙クロマトグラフィーによるキサンチン塩基の分離について
    井上 隆夫
    1956 年 76 巻 6 号 p. 629-631
    発行日: 1956/06/25
    公開日: 2010/02/19
    ジャーナル フリー
    Separation of caffeine, theophylline, theobromine, 3-methylxanthine, and xanthine by paper partition, buffered paper, and circular paper chromatography was examined. Numerous developing solutions were used but the best results in separation were obtained from butanol saturated with 0.1% ammonia and a 7:1 mixture of isopropanol and 0.1% ammonia water. Better separation of theophylline and theobromine was effected by developing on a paper treated with Sørensen's buffer of pH 3-8. For circular paper chromatography, circular filter paper of 18cm. diameter, using the Giri method, was employed and by developing with the foregoing solutions, five kinds of xanthine derivatives were clearly separated in about 7 hours. The use of a short-wave ultraviolet light of 240-270mμ made it possible to detect caffeine, theophylline, and theobromine up to 0.5γ, and 3-methylxanthine and xanthine up to 0.1γ.
  • 富田 眞雄, 奥井 清
    1956 年 76 巻 6 号 p. 632-634
    発行日: 1956/06/25
    公開日: 2010/02/19
    ジャーナル フリー
    Using mescaline (II) and 4-methoxyphenylacetic acid as the starting materials, the base corresponding to the dl-O-methyl ether of corpaverine (I), the alkaloid of Corydalis aurea WILLD., i.e. dl-1-(p-methoxybenzyl)-6, 7, 8-trimethoxy-2-methyl-1, 2, 3, 4-tetrahydroisoquinoline (VII), was synthesized.
  • 富田 眞雄, 石井 永
    1956 年 76 巻 6 号 p. 634-637
    発行日: 1956/06/25
    公開日: 2010/02/19
    ジャーナル フリー
    Repandulinic acid, the permanganate oxidation product of repanduline, was proved by the synthetic work of Todd and others to be 2, 3-methylenedioxydiphenyl ether-5, 4′-dicarboxylic acid (I). The synthesis of this substance was followed and a preparation of 3, 4-methylenedioxydiphenyl ether-6, 4′-dicarboxylic acid (II) was carried out to compare their data (Table I).
  • Tosyl EsterによるN-置換Phenothiazineの合成
    藤井 輝一
    1956 年 76 巻 6 号 p. 637-640
    発行日: 1956/06/25
    公開日: 2010/02/19
    ジャーナル フリー
    By the application of tosyl chloride to γ-dimethylaminopropanol and N-methylpiperidyl-(3)-methanol, the corresponding tosylates were obtained, whose reaction with phenothiazine and its ring substituted compounds under the presence of sodium amide afforded the artificial hybernating agent, 10-γ-dimethylaminopropyl-phenothiazines and 10-N-methylpiperidyl-(3)-methylphenothiazine.
  • 10-β-Cyanoethylphenothiazineの還元について
    藤井 輝一
    1956 年 76 巻 6 号 p. 640-644
    発行日: 1956/06/25
    公開日: 2010/02/19
    ジャーナル フリー
    2-Chloro-10-β-cyanoethylphenothiazine, obtained by the reaction 2-chlorophenothiazine and acrylonitrile, was submitted to catalytic reduction and 2-chloro-10-γ-aminopropylphenothiazine thereby obtained was methylated to 2-chloro-10-γ-dimethylaminopropylphenothiazine. Reduction in the presence of formylation agent afforded 2-chloro-10-γ-formamidopropylphenothiazine whose direct methylation afforded the 10-γ-dimethylamino derivative. Reduction with lithium aluminum hydride yielded the 10-γ-monomethylamino derivative. Methylation of bis-[2-chlorophenothiazinyl-(10)-propyl]amine, formed as a by-product, followed by the Hofmann degradation of its methiodide resulted in the recovery of 2-chloro-10-γ-dimethylaminopropylphenothiazine and 2-chloro-10-allylphenothiazine.
  • 10-β-Cyanoethylphenothiazineの二級アミン存在下の還元並びにβ-Cyanoethylamine誘導体の還元によるN,N´-Tetrasubstituted Propylenediamine誘導体の合成について
    藤井 輝一
    1956 年 76 巻 6 号 p. 644-648
    発行日: 1956/06/25
    公開日: 2010/02/19
    ジャーナル フリー
    Catalylic reduction of 2-chloro-10-β-cyanoethylphenothiazine in the presence of dimethylamine afforded 2-chloro-10-γ-dimethylaminopropylphenothiazine. The same reduction in the presence of diethylamine, piperidine, or morpholine yielded the corresponding homologs. In these cases, the 10-γ-aminopropyl derivative and bis [2-chlorophenothiazinyl-(10)-propyl] amine were invariably formed as by-products. Reaction of carbazole, indole, or benzimidazole with acrylonitrile gave the N-β-cyanoethyl derivatives whose reduction in the presence of dimethylamine afforded N-γ-dimethylaminopropyl derivatives.
  • ウドモドキ根の成分 その1
    刈米 達夫, 秦 清之
    1956 年 76 巻 6 号 p. 649-651
    発行日: 1956/06/25
    公開日: 2010/02/19
    ジャーナル フリー
    A new coumarin derivative was isolated from the root of Angelica glabra MAKINO (family Umbelliferae) and was named glabralactone (I). This plant is an allied species of A. pubescens and is different from A. dahurica (FISCH.) BENTH., which had been reported as A. glabra MAKINO and yields byak-angelicin, a furocoumarin derivative. (I) comes as crystals melting at 129-130° and agrees with the molecular formula C16H16O5; it gives negative ferric chloride reaction, decolorizes permanganate and bromine; forms an adduct with hydroxylamine, and forms a dihydro compound (III) by catalytic reduction. Potash fusion of (III) affords phloroglucinol, acetic acid, and isovaleric acid, while heating of (I) with acetic acid added with sulfuric acid gives 5, 7-dimethoxycoumarin (IV) and γ, γ-dimethylacrylic acid (V). It follows, therefore, that (I) is formed by the bonding of the acid residue (V) to the benzene ring of (IV).
  • フラン誘導体の合成 その2 Furo[3,2-c]pyridine誘導体及びその関連化合物の合成
    亀谷 哲治, 野村 幸雄, 森田 規矩子
    1956 年 76 巻 6 号 p. 652-654
    発行日: 1956/06/25
    公開日: 2010/02/19
    ジャーナル フリー
    1-(3′-Methoxy-4′-benzyloxyphenyl)-3, 4-dihydrofuro[3, 2-c]pyridine possesses uterus contracting action about 1/50 of that of oxytocin but its debenzylated compound is devoid of such action. This seemed to suggest that the benzyloxy group bonded to the phenyl in 1-position is the effective group and a compound in which the benzyloxy and methoxy groups in the above compound had been exchanged, the dibenzyloxy compound, the reduction product of each compound, and the benzoyloxy compound, i.e. 1-(3′-benzyloxy-4′-methoxyphenyl)-, 1-(3′, 4′-dibenzyloxyphenyl)-, and 1-(3′-methoxy-4′-benzoyloxyphenyl)-3, 4-dihydrofururo [3, 2-c]-pyridine, and 1-(3′-benzyloxy-4′-methoxyphenyl)- and 1-(3′, 4′-dibenzyloxyphenyl)-1, 2, 3, 4-tetrahydrofuro[3, 2-c]pyridine, were prepared by the Bischler-Napieralski reaction of the corresponding acid amides followed by reduction with sodium borohydride. Further, in order to examine the effect of the substituent in 1-position, N-methyl-3-methoxy-4-benzyloxybenzylamine was synthesized.
  • 高木 誠司, 安田 博幸
    1956 年 76 巻 6 号 p. 655-656
    発行日: 1956/06/25
    公開日: 2010/02/19
    ジャーナル フリー
    The purplish brown coloration of formyldesoxybenzoin by trivalent iron is specific to ferric ion in common elements. The composition of this coloration is Fe (C15H11O2)3 and was determined as the Fe+++ complex salt of formyldesoxyben-zoin (β-form), melting at 204.5-205°. From its facile solubility in organic solvents, this salt is assumed to be an inner complex compound. The coloration reactions due to the formation of this complex is advantageous in that the reaction can be carried out in dilute hydrochloric acid but is interfered by phosphoric acid and is not feasible in alkaline solution.
  • フェネチルアルコール, フェニルプロピルアルコール及びN-ベンチルアセトアマイドの水銀化について
    鵜飼 貞二, 山本 譲, 四塚 勝, 市村 藤雄
    1956 年 76 巻 6 号 p. 657-660
    発行日: 1956/06/25
    公開日: 2010/02/19
    ジャーナル フリー
    Mercuration of phenethyl alcohol (I), phenylpropyl alcohol (II), and N-benzyl-acetamide (III) was carried out and the position of the substituent and formation ratio of each product were compared with those of the known phenol and benzyl alcohol. The results seem to endorse the writers' assumption that the mercuration proceeds through a transitory ring formation and it was also found that it would be necessary to consider the effect of steric hindrance in this reaction.
  • アルキルクレゾールの酸化防止作用
    河合 友彦, 清水 常一, 千葉 久枝
    1956 年 76 巻 6 号 p. 660-665
    発行日: 1956/06/25
    公開日: 2010/02/19
    ジャーナル フリー
    Thirty-one kinds of alkyl-o-, -m-, and -p-cresol were synthesized and the effect of the position of the alkyl and hydroxyl groups and the number of carbon atoms in the alkyl group on the antioxidative action on vitamin A was examined. None of the compounds synthesized in the present series of experiments was as effective as 2, 6-di(tert-butyl)-p-cresol but it was found that the antioxidative effect of the alkyl derivatives differed according to cresol isomers and the m-cresol derivatives were markedly inferior than the o- and p-cresol derivatives. Cresol itself does not show any antioxidative effect and derivatives fomed by tthe introduction of an alkyl group show such an effect, the strongest being those with 4-5 carbon atoms in the alkyl group.
  • ウドモドキ根の成分 その2
    秦 清之
    1956 年 76 巻 6 号 p. 666-669
    発行日: 1956/06/25
    公開日: 2010/02/19
    ジャーナル フリー
    Boiling of the glabra-lactone (I) with 30% potassium hydroxide affords 5, 7-dimethoxyacetylcoumarin (VI) and oxidation of the ethyl ether, formed by ethylation of the hydroxyl forming the lactone, with potassium permanganate gives 2, 4-dimethoxy-6-ethoxyacetophenone. Therefore, (VI) would be represented by the structure shown in (c) and the structure of (I) should be (Ia) or (Ib). However, (Ib) must be denied since (I) is not optically active, no isomer is formed by the transition of the oxygen forming the epoxide ring, and there is no formation of a dihydroxy compound by the addition of 1 mole of water to the cleaved epoxide ring. Therefore, the formula (Ia) is given for (I).
  • 山本 譲, 山本 丈夫, 金友 昭一, 谷道 喜義, 菊井 弘司
    1956 年 76 巻 6 号 p. 670-673
    発行日: 1956/06/25
    公開日: 2010/02/19
    ジャーナル フリー
    The structure of a toxic principle, m. p. 273° (decamp), produced by Penicillium islandicum SOPP, D strain, was examined. It was assumed to be a compound having structure similar to flavoskyrin and rugulosin, and tentative structures (I) and (II) were forwarded. The formula (I) seems to be more possible. The name luteoskyrin was given to this substance.
  • 藤川 福二郎, 人長 有平, 八木 代志子, 安田 和夫
    1956 年 76 巻 6 号 p. 674-678
    発行日: 1956/06/25
    公開日: 2010/02/19
    ジャーナル フリー
    Antifungal action of various compounds had heretofore been tested with soy sauce as the test sample but this method was found to be interfered by the occlusion of various bacteria, difference of the age of soy sauce, and difference in the components. In the present series of experiments, the soy sauce was replaced with one of the Henneberg media, a liquid medium suited for the growth and proliferation of two kinds of yeast, Zygosaccharomyces salsus and Z. japonicus. The medium is a solution containing 15% glucose, 0.5% peptone, 0.5% potassium dihydrogen phosphate, 0.2% magnesium sulfate, and 3% sodium chloride, which was sterilized as well as other utensils used. The two yeast bacteria mentioned above were then inoculated and the growth-inhibiting concentration was examined with p-hydroxybenzoic and orsellic acids, their esters, olivetonide, vitamin K3, ethyl thiocyanoacetate, 3, 7-dihydroxy-1, 9-dimethyldibenzofuran, sodium lauryl-sulfate, 2-hydroxy-2′-methyldiphenyl ether, 2-hydroxy-3′-methyldiphenyl ether, 2-hydroxy-4′-methyldiphenyl ether, 2, 2′-dihydroxydiphenyl ether, 3, 2′-dihydroxy-5-methyldiphenyl ether, 2-hydroxydiphenyl ether-2′-carboxylic acid, and 2-naph-thol. The results from this experiment agreed approximately with the antif ungal concentration using soy sauce as the test sample.
  • 胎盤より性腺刺激ホルモンの抽出及び精製
    松島 早苗, 難波 脩二
    1956 年 76 巻 6 号 p. 678-681
    発行日: 1956/06/25
    公開日: 2010/02/19
    ジャーナル フリー
    Villus gonadotrophic hormone is secreted from the villus tissues of the placenta and excreted in a large amount into the urine. Its isolation is chiefly made from the the urine of a pregnant woman and no attempt has been made to isolate it directly from the placenta itself. In order to study the chemical difference between the gonadotrophic hormone isolated from the urine and that from the placenta, examination was first made for the method of isolating the said hormone from the placenta in a high purity. General method of extracting and purifying proteins was applied to human placenta and the crude product obtained by extraction with ammonia water and precipitation with ethanol was extracted at pH 4.8 with 50% ethanol. This was found to give the best yield of a highly pure product of 400-600 I. U./mg.
  • 胎盤性腺刺激ホルモンのクロマトグラフィー
    松島 早苗
    1956 年 76 巻 6 号 p. 682-686
    発行日: 1956/06/25
    公開日: 2010/02/19
    ジャーナル フリー
    Further purification of the gonadotropic hormone of 400-600 I. U./mg. purity was attempted by column chromatography through Hyflo Super-Cel under various conditions and a product of 2000 I. U./mg. was obtained. The product obtained by ethanol purification was found to be composed of at least two components by paper electrophoretic analysis and these two components were separated by chromatography. Both these substances were assumed to be almost homogeneous by electrophoretic analyses and both possessed gonadotropic effect.
  • ハスノハカヅラのアルカロイド (補遺2) 三級塩基の分離について その1
    富田 真雄, 渡辺 恭男, 奥井 清, 布施 幹義
    1956 年 76 巻 6 号 p. 686-688
    発行日: 1956/06/25
    公開日: 2010/02/19
    ジャーナル フリー
    Alkaloidal component was systematically separated from Stephania japonica MIERS. from Shikoku and Kyushu area. The tertiary non-phenolic bases were separated by alumina chromatography into hasubanonine, protostephanine, two kinds of a base of mp 135° and 165°, thought to be new bases, and an alkaloid of mp 219-223°, assumed to be metaphanine. The tertiary phenolic bases afforded hypoepistephanine, homostephanoline, and a substance of mp 207-208°, thought to be a new base. These are results from the plants collected in Shikoku. The plant from Kyushu yielded, besides eight kinds of bases, epistephanine as the non-phenolic base, The content of various bases according to the locale is shown in Table I.
  • カリウムイオンの定量に就いて
    益子 安, 甘露寺 泰雄
    1956 年 76 巻 6 号 p. 689-693
    発行日: 1956/06/25
    公開日: 2010/02/19
    ジャーナル フリー
    The flame intensity of the potassium ion in mineral water, when the mineral water is directly submitted to flame photometry, at 768 mμ is either lessened or intensified by phosphate, sulfate, or sodium ion. This potassium ion was found to be determined by treating mineral water with R-Cl type resin, Amberlite IRA-410, to exchange all the anions in the water with chlorine ion, adding sodium ion to bring its content to a definite level (Na+ content: 500 p. p. m.), and by comparison with the calibration curve of the standard solution (K+ with 500 p. p. m. Na+ as its chloride). This method of determination was not affected by other components, such as Ca2+, Mg2+, Al3+, and Fe3+. Discussion on acid mineral water will be made in subsequent reports.
  • N-Acetyl-p-toluidineとクロラールの反応 その3 中性物質の構造について
    安江 政一
    1956 年 76 巻 6 号 p. 693-696
    発行日: 1956/06/25
    公開日: 2010/02/19
    ジャーナル フリー
    Of the three neutral substances obtained by the reaction of N-acetyl-p-toluidine and chloral, two were determined as 4-methyl-3-(α, β, β, β-tetrachloroethyl)acetanilide (I), m. p. 166-168°, and 5-acetamido-2-methylbenzaldehyde (II), m. p. 129°, while the third of m. p. 268° (decomp.) was too small to be submitted to structural determination. (I) forms an N, N-diacetyl cmpound of m. p. 134-136° with acetic anhydride, its deacetylated compound of m. p. 120-122°, and loses 1 mole of hydrogen chloride by treatment with ethanolic sodium hydroxide. It is reduced with zinc dust and glacial acetic acid to 4-methyl-3-(β, β-dichloroethyl) acetanilide (VI), m. p. 135-136°, which is also obtained by its reduction with hydriodic acid and red phosphorus, followed by acetylation. (VI) forms a vinyl derivative (VII), m. p. 132-134°, with ethanolic sodium hydroxide and oxidation of (VII) gives 5-acetamido-2-methylbenzoic acid (VIII). Heating of (I) with conc. sulfuric acid for 18 hours at 60-70° yields 5-acetamido-2-methylphenylglycolic acid, m. p. 229°(decomp.), and an attempt to change the chlorine in the α-position of (I) alone to hydroxyl group did not succeed.
    5-Acetamido-2-methylbenzaldehyde (II) (oxime, m. p. 165-167°: semicarbazone, m. p. 268-270° (decomp.)) also forms on boiling 5-acetamido-2-methylphenylglycine and 5-amino-2-methylphenylglyoxylic acid with Al3+.
  • Alkyl化合物の物理化学的性質と結核菌に対する抗菌作用との関係 その1
    渡邊 煕
    1956 年 76 巻 6 号 p. 696-701
    発行日: 1956/06/25
    公開日: 2010/02/19
    ジャーナル フリー
    Investigations to date indicate that the relationship between the number of carbon atoms in the alkyl of alkylated compounds and their antibacterial power against tubercle bacilli can be indicated by a heaped curve. The antibacterial power increases with the increasing number of the carbon in alkyl group, reaches a maximum, and decreases with further increase of the alkyl chain. In order to analyse this curve, relationship between the physicochemical properties of the compounds and length of their alkyl chain, was examined, together with its correlation to antibacterial power. It was thereby concluded that the increase in antibacterial power with increasing number of carbon chain is due to gradual increase of adsorptive ability of the compounds on bacterial surface, while the decrease is due to gradual decrease of the penetrability on the bacterial surface. The height of the curve is limited by the parental structure of the homologs and abnormal phenomena can be well explained by this assumption.
  • シォール型Thiamine誘導体について その7 Thiazolium化合体のS-Acyl化
    川崎 弌
    1956 年 76 巻 6 号 p. 702-705
    発行日: 1956/06/25
    公開日: 2010/02/19
    ジャーナル フリー
    Acylation of thiazolium compounds in alkaline medium effects acylation of the thiol group formed by the cleavage of the thiazole ring and corresponding S-acyl compounds are obtained. The compounds thus tested were 3-(2′-methyl-4′-amino-pyrimidyl-5′) methyl-4-phenyl-5 β-hydroxyethylthiazolium chloride hydrochloride (VI), 3-(2′-methyl-4′-aminopyrimidyl-5′) methyl-4-methylthiazolium chloride hydrochloride (IX), 3-(2′-methyl-4′-aminopyrimidyl-5′) methyl-4-phenylthiazolium chloride hydrochloride (X), 3-benzyl-4-methyl-5-ethoxycarbonylthiazolium iodide (XV), and 3-benzyl-4-methyl-5-β-hydroxyethylthiazolium chloride (XVIII).
  • シオール型Thiamine誘導体について その8 Thiamine Alkyl Disulfide類の酸化成績体
    川崎 弌
    1956 年 76 巻 6 号 p. 706-709
    発行日: 1956/06/25
    公開日: 2010/02/19
    ジャーナル フリー
    Oxidation of thiamine alkyl disulfides with hydrogen peroxide in acetic acid solution or with perbenzoic acid in chloroform solution results in the formation of a sulfoxide of thiamine alkyl disulfides and this sulfoxide reacts with alkanethiol to form thiamine alkyl disulfides. Oxidation of thiamine benzyl sulfide with hydrogen peroxide in glacial acetic acid gave the sulfoxide of m. p. 133-134° (decomp.).
  • サリチル酸及びその誘導体の分離及び確認
    木下 彌兵衛, 森山 繁隆
    1956 年 76 巻 6 号 p. 709-712
    発行日: 1956/06/25
    公開日: 2010/02/19
    ジャーナル フリー
    In continuation of previous works, separation and determination of salicylic acid, acetylsalicylic acid, phenyl salicylate, sodium p-aminosalicylate, and salicylamide were attempted by paper electrophoresis. Migration values and conditions of each compound are indicated in Figs. 1-7. It was found that phenyl salicylate alone stayed in the original spot while the other four compounds exhibited the maximum difference in the migration distance at around pH 4.0, using any of the buffers. Detection of the migrated position was made by the Okuma's reagent, and the limit of detection was 5-10 γ. In the case of a mixture of these five compounds, as shown in Table I, the separatory detection of each is made as follows: Three kinds of sample solutions, 1% ethanolic solution, and treated with alkali and acid, are submitted to electromigration under the same conditions, and each compound is determined from its migration value, direction of migration, and coloration to the reagent. Okuma's reagent consists of 1% sodium nitroprusside, 1% hydroxylamine hydrochloride, and 1N sodium hydroxide, each of which is sprayed on an air-dried filter paper, in that order.
  • 大野 武男
    1956 年 76 巻 6 号 p. 713-717
    発行日: 1956/06/25
    公開日: 2010/02/19
    ジャーナル フリー
    Mercuration of nitrophenols and numerous compounds that might be taken as their derivatives with mercury acetate or oxide were carried out and the effect of the reaction of the solution was followed, in order to examine the relationship between the structures of the compounds during this reaction and of the mercury compounds formed.
    2-Nitrophenol (color change in the range of pH 5-7) and 4-nitrophenol (-do-, pH 5.6-7.6) are capable of being mercurated at pH 3.6-8 and respectively form 4, 6- and 2, 6-dimercuri compounds. 3-Nitrophenol (-do-, pH 6.8-8.6) can be mercurated at around pH 3-10, forming only the 4, 6-dimercuri compound at around pH 3 and a mixture of 4- and 6-mercuri compounds at around pH 10, indicating smaller tendency to form the dimercuri compound with the increasing value of pH.
    The position of the substituted mercury in these series of mercury compounds was determined by the substitution of mercury with iodine and the homogeneity of the mercury compounds was examined by paper chromatography, using a mixture of 1:2:7 volumes of 10% phenol, N sodium hydroxide, and water, as the developing solvent.
  • 大野 武男
    1956 年 76 巻 6 号 p. 718-721
    発行日: 1956/06/25
    公開日: 2010/02/19
    ジャーナル フリー
    Mercuration of 2, 4-dinitrophenol (color change in the range of pH 2.0-4.7) and 2, 6-dinitrophenol (-do-, pH 2.0-4.0) with mercury acetate or oxide yields, respectively, 6-mercuri (I) and 4-mercuri (II) compounds when the reaction is carried out at pH 3-7, but no reaction took place at above pH 7. Similar mercuration of 2, 5-dinitrophenol (-do-, pH 4.0-6.0) at around pH 3.7 afforded the 4, 6-dimercuri compound (VI), a mixture of (VI) as well as 4- (VII) and 6-mercuri compounds (VIII) at pH 4.5-6.0, and a small amount of a mixture of (VII) and (VIII) at pH 7.4, recovering majority of the starting material.
    The nitrophenol-type compounds are mercurated to some extent even on the alkaline side outside the range of color change. This is assumed to be due, in part, to the fact that the concentration of nitrophenols is far larger than that used as the indicator, so that these compounds are present as the mixture of pseudo and aci forms, and to the salt error of color change range due to the buffer used to adjust the reaction and to the mercuration agent used.
    When acetic acid is used for the reaction, a strong acidity (generally below pH 3) inhibits dissociation of mercury acetate and decreases the concentration of the mercuri ion, so that the reaction does not proceed. Therefore, mercuration with mercury acetate or oxide proceeds easily when the medium is around pH 3 to the range of color change of the compound to be mercurated.
  • 大野 武男
    1956 年 76 巻 6 号 p. 722-725
    発行日: 1956/06/25
    公開日: 2010/02/19
    ジャーナル フリー
    Mercuration of 2-nitro-1-naphthol (range of color change, pH 2-6) and 4-nitro-1-naphthol (pH 4.5-7.5) with mercury acetate or oxide at pH 3-10 respectively affords the 4-mercuri (I) and 2-mercuri (II) compounds. Both 2- and 4-vitro-1-naphthols possess such a wide range of color change and the change is so indistinct that the pseudo and aci forms are assumed to be present together over a fairly wide range of pH. They form a fair amount of mercury compounds even at above pH 9. 2, 4-Dinitro-1-naphthol (pH 2-6) afforded a compound assumed to be the 8-mercuri derivative by reaction at pH 3-6 but there was no proof of the substituted position. 1-Nitro-2-naphthol (pH 5.5-7.5) afforded by mercuration at pH 4-7 a mixture of 3, 6-dimercuri, 3-mercuri, and 6-mercuri compounds, as well as the recovery of the unreacted material.
    It is concluded from a series of these experiments that the mercuration of nitrophenols and nitronaphthols in a pH range where these compounds take the pseudo form results in the introduction of the mercury ortho or para to the hydroxyl group, while such reaction in the pH range where the compounds take the aci form with the quinoid structure, makes it difficult for the introduction of mercury into the ring. The half-masked mercury still remains as the -HgOCOCH3 group by recrystallization of the mercury compounds from conc. acetic acid or reprecipitation from sodium hydroxide solution and acetic acid but changes to -HgOH group on drying, and further canges to the anhydride.
  • 大野 武男
    1956 年 76 巻 6 号 p. 726-728
    発行日: 1956/06/25
    公開日: 2010/02/19
    ジャーナル フリー
    Both the mono- and dinitro compounds of hydroquinone and catechol possess strong reducing action and their mercuration with mercury acetate or oxide was impossible either in the cold or with heating. On the other hand, 4-nitroresorcinol (range of color change, pH 5-7) is mercurated at pH 3-7 to form the 6-mercuri compound (II), although the reaction is accompanied with some reduction reaction. Mercuration of 2, 4-dinitroresorcinol (pH 2-4) at pH 2.5-3.5 afforded the mercury compound corresponding to formula (VI) and that corresponding to formula (VII) by reaction at pH 4.6-6.0. When the reaction was carried out at around pH 7, formation of an intramolecular mercury complex, assumed to have the structure of (VIII), was observed.
  • 大野 武男
    1956 年 76 巻 6 号 p. 729-732
    発行日: 1956/06/25
    公開日: 2010/02/19
    ジャーナル フリー
    Mercuration of 5-nitrosalicylic acid (range of color change, pH 3-4.4) and 3, 5-dinitrosalicylic acid with mercury acetate, with heating, results in decarboxylation and the former gives the 2, 6-dimercuri compound of 4-nitrophenol at pH 2.8-7, while the latter forms the 6-mercuri compound of 2, 4-dinitrophenol at pH 3.2-7, both resisting ring mercurization in the alkaline side. The mercuration of 5-nitrosalicylic acid at room temperature results in the formation of a mercury salt (formula I) in the acid range, and an intramolecular mercury comlex, assumed to take the structure shown (formula II), in the alkaline range.
    From the results of experiments carried out to date, the nitrophenols and allied compounds with the hydroxyl and nitro or carboxyl group in the ortho-positions are liable to form a mercury complex in a pH range where such compounds take the aci form and this is assumed to be due to the fact that such intramolecular complexes take a stable six-membered ring structure.
    Mercuration of 5-nitro-8-hydroxyquinoline (range of color change, pH 3-5.2) at pH 3 and 5.2 afforded a compound assumed to be an intramolecular mercury complex, whose analytical values suggested it to be of structure shown by formula (IV) or (V). The same reaction at pH 7 resulted in the recovery of a majority of the starting materials, with a small amount of the 7-mercuri compound (VI), while mercury compound was not obtained at all at pH 9.
  • 大野 武男
    1956 年 76 巻 6 号 p. 733-736
    発行日: 1956/06/25
    公開日: 2010/02/19
    ジャーナル フリー
    Color change of 4, 5-dinitrofluorescein, i.e. the change of its configuration, is assumed to take the forms indicated by (A), (B), (C), and (D). Mercuration of this compound with mercury acetate, at various pHs between 3.6 and 7.2 with heating, invariably affords a mixture of 2, 7-dimercuri (I) and 2-mercuri (II) compounds, with a residue of unreacted material. The yield of the mercury compounds decreases with the increasing pH value and the mercuration is not effected at pH 7.6 with the appearance of a reduction reaction.
    Mercuration of 3′, 3″-dinitrophenolphthalein (range of color change, pH 5.9-7.4) at pH 4-8.5 was not accompanied with any reduction reaction but afforded 5′-mercuri and 5′, 5″-dimercuri compounds and recovery of a small amount of the unreacted material.
    The appearance of a reductive action in dinitrofluorescein, in contrast to its absence in dinitrophenolphthalein, is assumed to be due to the fact that the fluorescein derivative forms the so-called hydrate in an alkaline range by the effect of the nitro groups in the 4 and 5 positions, thereby constituting a resorcinol ring.
  • 4-Carboxy-3-methylindanone-2-acetic Acid (Desoxyterracinoic Acid) の合成
    堀井 善一, 田村 恭光, 二宮 一彌, 釘田 博至
    1956 年 76 巻 6 号 p. 736-738
    発行日: 1956/06/25
    公開日: 2010/02/19
    ジャーナル フリー
    As a preliminary experiment for the synthesis of terracinoic acid, the alkaline degradation product of oxytetracycline, 4-carboxy-3-methylindanone-2-acetic acid was prepared by the route shown in the chart.
  • Terracinoic Acidの合成
    田村 恭光
    1956 年 76 巻 6 号 p. 739-742
    発行日: 1956/06/25
    公開日: 2010/02/19
    ジャーナル フリー
    Terracinoic acid is an alkaline decomposition product of oxytetracycline and plays an important role in the structural determination of this antibiotic. The structure of terracinoic acid was proved to be 4-carboxy-5-hydroxy-3-methyl-indanone-2-acetic acid (XII) by its synthesis by the route shown and identification with terracinoic acid obtained by the direct degradation of oxytetracycline.
  • 小村 忠之, 木村 豊, 村山 普
    1956 年 76 巻 6 号 p. 743-744
    発行日: 1956/06/25
    公開日: 2010/02/19
    ジャーナル フリー
    Determination of santonin in preparations by measuring the optical density of its 2, 4-dinitrophenylhydrazone was followed. It was found that by the use of a mixture (1:1) of ammonia water (Special Reagent Grade, ca. 28%) and acetone to bring the final concentration of ammonia to approximately 5.6 w/v% effected stabilization of the coloration for a comparatively long period of time (over 1 hour). By this modified method, several samples can be lined up for concurrent determination and would be convenient for application in plants. The determination error is within ±0.4% when using a sample corresponding to 40mg. of santonin.
  • 上田 英之助, 佐々木 豊作
    1956 年 76 巻 6 号 p. 745-746
    発行日: 1956/06/25
    公開日: 2010/02/19
    ジャーナル フリー
    Dioscorea Batatas DECNE forma Tsukune MAKINO contains a higher amout of useful components (Table I) and its mucuous liquid, separated from starch and fibers, precipitates a mucous substance on the addition of ethanol to 60% or of hydrochloric acid to 0.15% concentration (Table II). The former dissolves in water to form a viscous liquid but the latter is insoluble in water and forms a viscous liquid only when alkali solution is added, suggesting the role of potassium in the viscosity of such plant roots. The presence of uronic acid in the viscous substance was assumed but the amount detected by the carbonate method and phloroglucinol method were vastly different. The ethanolic solution left after removal of the viscous substance yielded allantoin (0.12%) and γ-aminobutyric acid, as well as 15 kinds of free amino acids, fructose, and galactose. Sixteen kinds of amino acids were detected from the hydrolyzate of the viscous substance but not γ-amino-butyric acid. The sugar detected was mannose alone and presence of amino sugars was not detected.
  • 濾紙電気泳動法によるキサンチン塩基の分離について
    刈米 達夫, 井上 隆夫
    1956 年 76 巻 6 号 p. 747-748
    発行日: 1956/06/25
    公開日: 2010/02/19
    ジャーナル フリー
    Separation of caffeine, theobromine, theophylline, 3-methylxanthine, and xanthine by paper ionophoresis was examined. By migration with the Sørensen buffer of pH 2.3-11.1, caffeine and theobromine migrate towards the cathodic side at any pH, while the charge of theophylline, 3-methylxanthine, and xanthine changes at around pH 8, the compounds migrating towards the cathode at below pH 8, and towards the anodic side at above that pH. The best separation was effected at pH 8-9 and migration in 0.5% borax solution was found to completely separate the foregoing xanthine derivatives. Paper ionophoresis of the aqueous extract of tea leaves and of cacao beans with 0.5% borax solution was found to collect the spot of caffeine and theobromine, respectively, on the cathodic side, while other components in the aqueous extract migrated towards the anodic side.
  • 十字花科植物成分の濾紙分配クロマトグラフィーによる検索
    刈米 達夫, 高橋 三雄, 藤多 哲朗
    1956 年 76 巻 6 号 p. 749-750
    発行日: 1956/06/25
    公開日: 2010/02/19
    ジャーナル フリー
    The mustard oil, obtained by the steam distillation of the seeds or root of 10 kinds of domestic Cruciferae plants and nasturtium, was converted to the thiourea derivatives by the application of ammonia water and submitted to paper partition chromatography. As a result following kinds of mustard oil were detected. Allyl-mustard oil from Brassica juncea, B. oleaceae, B. juncea var. intergrifolia, Chochlearia Armoracia, and B. Rapa. Benzyl-mustard oil from Tropaeolurn majus. 3-Butenyl-mustard oil from B. Rapa., B. japonica, and B. pekinensis.
  • 南天のアルカロイド その2
    富田 真雄, 久郷 威彦
    1956 年 76 巻 6 号 p. 751-752
    発行日: 1956/06/25
    公開日: 2010/02/19
    ジャーナル フリー
    By examination of quaternary bases in Nandina domestica THUNB., new aporphine-type bases, magnoflorine (I) and menisperine (II), were isolated besides the known berberine-type alkaloids found to date.
  • フラン誘導体の合成 その3 N-置換-β-2-Furyl ethylamine誘導体の合成
    亀谷 哲治, 野村 幸雄
    1956 年 76 巻 6 号 p. 753-754
    発行日: 1956/06/25
    公開日: 2010/02/19
    ジャーナル フリー
    Since 1-(3′-methoxy-4′-benzyloxyphenyl)-3, 4-dihydrofuro [3, 2-c] pyridine was found to have about 1/50 the uterus contracting action of oxytocin, the compounds in which the pyridine ring of the above compound was severed at six different places were prepared by the reduction of the corresponding Schiff bases with sodium borohydride. The compounds obtained were N-(3′-benzyloxy-4′-ethoxybenzyl)-, N-(3′-methoxy-4′-benzyloxybenzyl)-, N-(3′, 4′-dibenzyloxybenzyl)-, N-(3′, 4′-dimethoxybenzyl)-, N-(3′-methoxy-4′-hydroxybenzyl)-, N-(3′, 4′-methylenedioxybenzyl)-, and N-furfuryl-β-2-furylethylamine. Comparison of their pharmacological action with uterus contracting action of 2-methoxy-6-allylphenol diethylaminoethyl ether showed N-(3′methoxy-4′-hydroxybenzyl) compound to possess 1/10 the effect, and N-furfuryl-β-2-furylethylamine to have 1/50 the effect.
  • 岩尾 順一, 富野 耕一
    1956 年 76 巻 6 号 p. 755-756
    発行日: 1956/06/25
    公開日: 2010/02/19
    ジャーナル フリー
    In the course of a synthesis of 5-substituted hydantoin and rhodanine by the condensation of aromatic aldehydes with hydantoin or rhodanine, the usual practice is to use acetic anhydride and glacial acetic acid as a solvent, adding anhydrous sodium acetate, and heating for 0.5 to several hours. However, fusion of a mixture of aromatic aldehyde and hydantoin or rhodanine, with the addition of a small amount of diethanolamine, results in completion of the reaction in a few minutes and the 5-substituted hydantoin or rhodanine is obtained in a good yield.
  • 1956 年 76 巻 6 号 p. e1a
    発行日: 1956年
    公開日: 2010/02/19
    ジャーナル フリー
  • 1956 年 76 巻 6 号 p. e1b
    発行日: 1956年
    公開日: 2010/02/19
    ジャーナル フリー
  • 1956 年 76 巻 6 号 p. e1c
    発行日: 1956年
    公開日: 2010/02/19
    ジャーナル フリー
  • 1956 年 76 巻 6 号 p. e1d
    発行日: 1956年
    公開日: 2010/02/19
    ジャーナル フリー
  • 1956 年 76 巻 6 号 p. e1e
    発行日: 1956年
    公開日: 2010/02/19
    ジャーナル フリー
  • 1956 年 76 巻 6 号 p. e1f
    発行日: 1956年
    公開日: 2010/02/19
    ジャーナル フリー
  • 1956 年 76 巻 6 号 p. e1g
    発行日: 1956年
    公開日: 2010/02/19
    ジャーナル フリー
  • 1956 年 76 巻 6 号 p. e1h
    発行日: 1956年
    公開日: 2010/02/19
    ジャーナル フリー
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