YAKUGAKU ZASSHI
Online ISSN : 1347-5231
Print ISSN : 0031-6903
ISSN-L : 0031-6903
83 巻, 11 号
選択された号の論文の18件中1~18を表示しています
  • 赤星 三彌
    1963 年 83 巻 11 号 p. 1005-1015
    発行日: 1963/11/25
    公開日: 2010/02/19
    ジャーナル フリー
  • d-Thalic-tricavine, d-Corydaline, d-Corybulbineおよびd-Isocorybulbineの絶対配位
    近藤 嘉和
    1963 年 83 巻 11 号 p. 1017-1022
    発行日: 1963/11/25
    公開日: 2010/02/19
    ジャーナル フリー
    Absolute configuration of d-thalictricavine (I), d-corydaline (II), d-corybulbine (III), and d-isocorybulbine (IV) was determined. III and IV are derived to II by methylation with diazomethane. Dehydrogenation of I with mercury (II) acetate gives 13-methyl-2, 3-methylenedioxy-9, 10-dimethoxy-5, 6-dihydrodibenzo[a, g]quinolizinium derivative (VI), whose reduction with sodium borohydride or zinc dust and acetic acid affords dl-thalictricavine (VII). Similarly, treatment of II with mercury (II) acetate gives a dehydro base (VIII) whose reduction affords dl-corydaline (IX). Infrared spectra of I and VII, and of II and IX, in chloroform solution are identical, showing absorption of trans-quinolizidine at around 2760cm-1. From the result of these oxidation and reduction reactions, the methyl group in 13-position of I and II is known to take a stable configuration was further confirmed by the comparison of NMR with that of 1-methylquinolizidine and its salt. NMR spectra of I and II in chloroform show a doublet at δMe=0.93-0.94 p. p. m., and their acetate at δMe=0.97-0.98 p. p. m. This agrees with the observation on 1(e)-methylquinolizidine. I and II also show a positive Cotton curve in ORD. Based on these experimental evidences, absolute configuration of I, II, III, and IV was determined as 14(R)-13(S, e).
  • 富田 真次, 南 新作
    1963 年 83 巻 11 号 p. 1022-1026
    発行日: 1963/11/25
    公開日: 2010/02/19
    ジャーナル フリー
    The Bischler-Napieralski reaction of N-formyl-1-(m-methoxyphenyl)cyclohexaneëthylamine (II) with phosphorus pentoxide afforded 7-methoxy-3, 4-dihydrospiro[5H-2-benzazepine-5, 1′-cyclohexane] (III) and a trace of 9-methoxy-3, 4-dihydrospiro[5H-2-benzazepine-5, 1′-cyclohexane] (VIII). On the other hand, cyclization of II with polyphosphoric acid produced III and VIII in 1:1 ratio. Reduction of III and VIII afforded 2-methyl-1, 2, 3, 4-tetrahydrospiro [5H-2-benzazepine-5, 1′-cyclohexane] derivatives.
  • 富田 真次, 有冨 治郎, 南 新作
    1963 年 83 巻 11 号 p. 1026-1030
    発行日: 1963/11/25
    公開日: 2010/02/19
    ジャーナル フリー
    2′-Methyl-1′, 2′-dihydrospiro[cyclohexane-1, 4′(3′H)-isoquinolin]-6′-ol (VI) derivatives was synthesized by cyclization of 1-(m-methoxyphenyl)cyclohexanemethylamine (II) by the Bischler-Napieralski and Pictet-Spengler reactions. The Bischler-Napieralski reaction of II derivative not possessing a methoxy group afforded 1′, 2′-dihydrospiro[cyclohexane-1, 4′(3′H)-isoquinolin] (XIV) derivative.
  • パパベリン類似化合体の合成研究 その12 1-(3,4-Dimethoxybenzyl)-6,7-dimethoxy-3,4-dihydro (および1,2,3,4-tetrahydro) isoquinolineのアルミナクロマトグラフィーによるメチレン基の酸化について
    亀谷 哲治, 福本 圭一郎
    1963 年 83 巻 11 号 p. 1031-1035
    発行日: 1963/11/25
    公開日: 2010/02/19
    ジャーナル フリー
    Chromatographic treatment of 3, 4-dihydropapaverine with commercial alumina and neutral alumina obtained by its acid treatment was found to produce 3, 4-dihydropapaveraldine, formed by oxidation of the methylene group. The same oxidation reaction was observed in the case of 1, 2, 3, 4-tetrahydropapaverine. Reduction of the oxidation product was also examined.
  • 3-Methoxy-4-hydroxy-および3-Methoxy-4-tosyloxyphenethylamineの簡易合成
    亀谷 哲治, 高野 誠一, 苅部 悦郎
    1963 年 83 巻 11 号 p. 1035-1039
    発行日: 1963/11/25
    公開日: 2010/02/19
    ジャーナル フリー
    A new simplified method for the synthesis of 3-methoxy-4-hydroxyphenethylamine (I) and 3-methoxy-4-tosyloxyphenethylamine (IX) is described. In this method, the corresponding ω-nitrostyrene compound is submitted to the Clemmensen reduction and concentration of the reaction mixture affords the product as a crystalline zinc complexes (I′ and IX′), sparingly soluble in hydrochloric acid, in a good yield. The N-acetylated compound of IX was derived to 1-methyl-3-methoxy-4-tosyloxy-3, 4-dihydroisoquinoline (XIV) by heating it with phosphoryl chloride in toluene and it was found that the tosyl group can be used as a protecting group for the hydroxyl in the aryl group during the Bischler-Napieralski cyclization.
  • N置換イミドの閉環反応
    亀谷 哲治, 柳瀬 良文
    1963 年 83 巻 11 号 p. 1039-1042
    発行日: 1963/11/25
    公開日: 2010/02/19
    ジャーナル フリー
    There are comparatively few examples of cyclization of cyclic N-phenethylimides by phosphoryl chloride. Haworth and others carried out this reaction but failed to obtain the cyclized product, the reaction affording a chlorinated product. An attempt was made in the present series of work to obtain benzoquinolizine derivatives by cyclization of cyclic N-phenethylimide. Cyclization reaction of N-(β-3, 4-dimethoxyphenethyl)-glutarimide (I) with phosphoryl chloride produced the tautomer (II) and some structurally unknown substance. By a different synthetic route, 4H-benzo[a]quinolizinone derivative (VI) was prepared and its dehydrogenation was attempted but without avail. Catalytic reduction of the tautomer (II) afforded a product identical with VI. This lactam (VI) was derived to the known 9, 10-dirnethoxy-1, 2, 3, 4, 6, 7-hexahydro-11bH-benzo[a]quinolizine (VIII), which gave a picrate melting at the same temperature as that reported in the literature. The cyclized product of the imide (I) was derived to its picrate without alkali treatment and the picrate of the intermediate chlorinated compound (IX) was obtained. IX proved that the imide formed its tautomer (II) by alkali treatment.
  • 2H-Pyrimido[4,3-a]isoquinoline誘導体の生成機構
    亀谷 哲治, 加納 慎蔵
    1963 年 83 巻 11 号 p. 1043-1047
    発行日: 1963/11/25
    公開日: 2010/02/19
    ジャーナル フリー
    Cyclization of N-[2-(3, 4-dimethoxyphenethylcarbamoyl)ethyl]benzamide (I) with phosphorus pentoxide in chloroform was found to produce 1-(2-benzamidoethyl)-6, 7-dimethoxy-3, 4-dihydroisoquinoline (III). This was proved by the identification of 1-(2-aminoethyl)-6, 7-dimethoxy-3, 4-dihydroisoquinoline dihydrochioride (VIII), obtained by hydrolysis of III with 15% hydrochloric acid, with the product obtained by 15% hydrochloric acid hydrolysis of 1-(2-phthalinidoethyl)-6, 7-dimethoxy-3, 4-dihydroisoquinoline (VII), formed by cyclization of N-[2-(3, 4-dimethoxyphenethylcarbamoyl)ethyl]phthalimide (VI) with phosphoryl chloride, VI being obtained by the condensation of 3-phthalimidopropionyl chloride and 3, 4-dimethoxyphenethylamine. The product obtained by the cyclization of III with phosphoryl chloride was proved to be identical with 4-phenyl-9, 10-dimethoxy-6, 7-dihydro-2H- pyrimido[4, 3-a]isoquinoline (II), formed by direct cyclization of its cyclization product (I) with phosphoryl chloride.
    Cyclization of the amide (I) with phosphoryl chloride was examined under various conditions and III was found to be formed when heating was made at a comparatively low temperature and for a short period of time. These facts proved that III is an intermediate product during the process of formation of II from I.
    2-Phenyl-3-(3, 4-dimethoxyphenethyl)-5, 6-dihydro-4(3H)-pyrimidinone was synthesized and, in order to examine its cyclization reaction, its 3, 4-dimethoxyphenethylation and condensation of N-(3, 4-dimethoxyphenethyl)benzamidine and acrylonitrile were attempted but no anticipated result was obtained.
  • パパベリン類似化合体の合成研究 その13 1位にチオフェン核を有する6,7-Dimethoxy-3,4-dihydro-, 1,2,3,4-Tetrahydro-および3-Methyl-6,7-dimethoxy-3,4-dihydro-, 3-Methyl-6,7-methylenedioxy
    亀谷 哲治, 菅原 宏
    1963 年 83 巻 11 号 p. 1048-1052
    発行日: 1963/11/25
    公開日: 2010/02/19
    ジャーナル フリー
    Several kinds of 6, 7-dimethoxy-3, 4-dihydro-, 1, 2, 3, 4-tetrahydro-, 3-methyl-6, 7-dimethoxy-3, 4-dihydro-, and 3-methyl-6, 7-methylenedioxy-3, 4-dihydroisoquinolines, possessing a thiophene ring in the 1-position, were synthesized. Ia with n=2 and 3 were prepared by the cyclization of their corresponding acid amides with phosphoryl chloride, and Ib and IIb with n=2 and 3 by the simplified method of Kametani. Effect of thiophene on the cyclization of acid amides and the simplified Kametani's method were also examined.
    The 1-(2-thienyl)-6, 7-methylenedioxy-3, 4-dihydroisoquinoline compound previously prepared is now corrected to 1-(2-thienoyl)-6, 7-dimethoxy-3, 4-dihydroisoquinoline compound (V) from its infrared and ultraviolet absorptions, and from its elemental analytical data.
  • クラリンおよび関連化合物の合成研究 (第7報) インドール誘導体の生成反応
    亀谷 哲治, 福本 圭一郎, 増子 和子
    1963 年 83 巻 11 号 p. 1052-1055
    発行日: 1963/11/25
    公開日: 2010/02/19
    ジャーナル フリー
    In order to synthesize 10-amino-2, 3, 6-trimethoxy-10, 11-dihydrodibenzo[b, f]oxepine, the phenylhydrazone (V) of the ketone compound (II) was submitted to catalytic reduction in the presence of palladium-carbon catalyst and an indole derivative (VI) was obtained unexpectedly. To clarify this mechanism, desoxybenzoin phenylhydrazone (VIII) was submitted to the same reduction and an indole derivative (IX) was also obtained. IX is also obtained from VIII by Fischer's indole synthesis, as there was no depression of the melting point on their admixture. The reason why the indole derivative (VI) is not obtained from V by the usual method of Fischer's indole synthesis seems to be due to the lability of the phenylhydrazone (V), which is easily oxidized and resinifies, and the derivative is formed only in a reductive medium.
  • 藤田 公司, 虫鹿 好孝, 萩尾 克明
    1963 年 83 巻 11 号 p. 1056-1061
    発行日: 1963/11/25
    公開日: 2010/02/19
    ジャーナル フリー
    Acylation of thiamine disulfide (II) with acyl thiosulfates (IV) in aqueous alkaline solution yielded O-acylthiamine disulfides (III) such as O-benzoyl- (IIIa-β), O-(2-thenoyl)-(IIIb-β), and O-(furoyl)-thiamine disulfides (IIIc-β). (method C). These compounds, named “β-form, ” were obtained as colorless and odorless prisms having one mole of crystal water and benzene, by recrystallization from ethanol-benzene mixture or by chromatographic purification on an alumina column.
    When the above compounds were recrystallized from anhydrous ethanol, conversion to “α-form” occurred, and IIIa-β and IIIb-β lost both crystal water and benzene, while IIIc-β lost only the latter. From IR and UV spectra, and other physical constants, these compounds were proved to be identical with the corresponding acylthiamine disulfides in “α-form” synthesized by acylation of II with respective acyl chlorides in pyridine (method B).
  • 高松 秀二, 西村 温樹, 山内 脩
    1963 年 83 巻 11 号 p. 1061-1067
    発行日: 1963/11/25
    公開日: 2010/02/19
    ジャーナル フリー
    N-(o-Nitrophenylsulfonyl)glutamic acid (I) was derived to N-(o-nitrophenylsulfonyl)-5-oxo-2-pyrrolidinecarboxylic acid (II) by its dehydrative cyclization and N-(o-aminophenylsulfonyl)glutamic acids were prepared from II by the route shown in Chart 1. Reduction of II, its ethyl ester (XIV), and acid amide (IV), followed by dehydrative cyclization, as shown in Chart 2, afforded 2, 3-dihydro-1H-pyrrolo[1, 2-b] [1, 2, 4]benzothiadiazine-3-carboxylic acid 5, 5-dioxide (XIII) and its derivatives (XVI and XVIII). These products were reduced to their respective dihydro derivatives. (XIX, XX XXI).
  • 6,7-Dihydfobenzo [a] quinolizinium塩の合成と脱水素反応
    赤星 三彌, 加藤 俊雄
    1963 年 83 巻 11 号 p. 1067-1072
    発行日: 1963/11/25
    公開日: 2010/02/19
    ジャーナル フリー
    A novel Pschorr reation was carried out. When diazonium salt of 1-(2-aminophenethyl)pyridinium salt (VI) was degradated by gradual heating, only the substituted product, 1-(2-chlorophenethyl)pyridinium salt (VII) was isolated. On the other hand, when the diazonium salt was treated in the presence of Gattermann's copper powder, ring-closed product, 6, 7-dihydrobenzo [a] quinolizinium salt (IX) was obtained in a fair yield, and the structure of IX was determined unambiguously.
    Catalytic dehydrogenation and stability of IX were also investigated.
  • ポリウロン酸中のウロン酸残基の新定量法とその硝酸酸化デンプンペの応用
    平坂 義信, 助川 満男
    1963 年 83 巻 11 号 p. 1073-1077
    発行日: 1963/11/25
    公開日: 2010/02/19
    ジャーナル フリー
    A new method for the determination of uronic acid residues in polyuronic acids and apparatus for this determination are proposed. It has been found that acid hydrolysis of uronic acids with 14% hydrochloric acid produced a definite quantity of furfural and the fact was utilized for the present determination. In this method, polyuronic acid is decomposed with acid and furfural formed is continually extracted with xylene. The amount of uronic acid residues is calculated from the total amount of furfural formed. Satisfactory results were obtained by the application of this method to alginic acid, pectic acid, 4-O-(α-D-glucopyranosiduronyl)-D-glucose, and 4-O-(α-D-glucopyranosiduronyl)-D-glucuronic acid.
    The hitherto used method of this determination requires complicated apparatus for carbon dioxide generation and 500mg. of the sample. This method could not be applied to nitric acid-oxidized starch because it contained an oxo structure which tended to undergo decarboxylation. The present proposed method requires only a simple apparatus and only 5-10mg. of the sample, and can also determine glucuronic acid residues in the nitric acid-oxidized starch. This has enabled calculation of the amount of glucuronic acid residues in the oxidized starch which could not be determined in the past.
  • グルクロン酸とグルコースとのα (1,4) 重合体の酸加水分解について
    平坂 義信, 助川 満男, 松永 功
    1963 年 83 巻 11 号 p. 1078-1083
    発行日: 1963/11/25
    公開日: 2010/02/19
    ジャーナル フリー
    4-O-(α-D-Glucopyranosiduronyl)-D-glucose (I) and 4-O-(α-D-glucopyranosiduronyl)-D-glucuronic acid (II) were hydrolyzed with 5% sulfuric acid at 100° and their hydrolysis rate was determined. Decomposition rate of glucuronic acid under the same conditions was also determined. These reactions were all pseudo-first order reaction and the rate constant of I was about 10 times greater than that of II, while the rate constant of II was about the same as the decomposition rate constant of glucuronic acid. The amount of glucuronic acid formed by acid hydrolyses of I and II was determined and, in spite of the fact that II contains twice as much glucuronic acid residues as equimolar amount of II, the maximum amount of glucuronic acid in II was about 3/4 of that of I because of the difficulty of its hydrolysis by acid. Consequently, the starting material for glucuronic acid was unexpectedly found to be the oxidized starch in which glucuronic acid and glucose are bound alternately rather than that containing a larger amount of glucuronic acid residues.
  • 酢酸フェニル水銀の定量
    入谷 信彦, 有薗 謙蔵
    1963 年 83 巻 11 号 p. 1083-1086
    発行日: 1963/11/25
    公開日: 2010/02/19
    ジャーナル フリー
    A new method for the determination of phenylmercuric acetate by chelate titration is described.
    Addition of an excess of ethylenediaminetetraacetate (EDTA) to the aqueous solution of phenylmercuric acetate produces a precipitate of tetrakis (phenylmercuric) (ethylene-dinitrilo) tetraacetate and boiling this mixture at pH 3.5-5.0 produces Hg (II)-EDTA quantitatively. Excess of EDTA is back-titrated with the standard solution of Mg2+ or Zn2+. The reaction proceeds easily in the case of 1-300mg. of phenylmercuric acetate, and the determination is both accurate and precise.
    Application of this method to contraceptive tablets was discussed.
  • Thiocyanatopyrimidine誘導体および関連化合物の合成ならびに抗菌作用
    衣川 二郎, 落合 道彦, 山本 弘一
    1963 年 83 巻 11 号 p. 1086-1091
    発行日: 1963/11/25
    公開日: 2010/02/19
    ジャーナル フリー
    Thiocyanatopyrimidines were prepared by the application of thiocyanate to halopyrimidines (method A) or by the application of cyanogen bromide to mercaptopyrimidines (method B). 3-Thiocyanato-2, 5-dimethylpyrazine and 3-ethoxycarbonylthio-2, 5-dimethyl-pyrazine were synthesized. Antifungal activity of these novel compounds was examined and relationship between their structure and antifungal activity was discussed.
  • 今井 俊司, 村田 忠一, 藤岡 章二, 後藤 実
    1963 年 83 巻 11 号 p. 1092
    発行日: 1963/11/25
    公開日: 2010/02/19
    ジャーナル フリー
feedback
Top