YAKUGAKU ZASSHI
Online ISSN : 1347-5231
Print ISSN : 0031-6903
ISSN-L : 0031-6903
85 巻, 7 号
選択された号の論文の23件中1~23を表示しています
  • (5-Nitro-2-furyl) vinylpyridine誘導体および関連化合物の合成
    藤田 昭夫, 山本 格次, 松本 純一, 南 新作, 高松 秀二
    1965 年 85 巻 7 号 p. 565-570
    発行日: 1965/07/25
    公開日: 2010/02/19
    ジャーナル フリー
    In order to examine their antibacterial activity, 2- or 4-[2-(5-nitro-2-furyl) vinyl] pyridine derivatives (I), 1-[2-(5-nitro-2-furyl) vinyl] isoquinoline (II), α-(2- or 3-pyridyl)-5-nitro-2-furanacrylic acid, and their esters, amides, and nitrile derivatives (III) were synthesized. 3-[2-(5-Nitro-2-furyl) vinyl] pyridine (IV) was derived from III, and N-oxides (I′, II′, IV′) of I, II, and IV were also synthesized.
  • 漢薬辛夷抽出分画の薬理効果とその薬理活性による同類生薬との比較について
    木村 正康, 吉崎 正雄, 室 郁子, 志甫 伝逸
    1965 年 85 巻 7 号 p. 570-578
    発行日: 1965/07/25
    公開日: 2010/02/19
    ジャーナル フリー
    Pharmacological activity of various fractions of the aqueous extract of a Chinese drug, “Shin-i” was examined by the Magnus method, with that of “Shin-i” on the rectus abdominis of a frog as the index, comparing drugs prepared in Japan and in China. In general, there was no pharmacological difference between these two kinds of preparations in any of the fractions. The only crystalline component obtained from the phenolic base of both products was an alkaloid of m.p. 208°, with empirical formula of C17H19O3N, which was found to have a curare-like action by experiment with nerve muscle preparation. Aqueous extract, corresponding to the decoction in Oriental medicine, showed a marked acetylcholine-like action and it was proved by comparative examination of various methods of extraction that the predominant active component in this fraction cannot be obtained by the usual method of alkaloid extraction in order to find the cause of such action. It was also revealed that the pharmacological activity of the aqueous extract was the cumulative result of additive and cancellative action of each fraction.
  • ハスノハカズラStephania japonica MIERSのアルカロイド (補遺10) Metaphanineの分解物Phenanthrene誘導体の合成 1,5-Diethoxy-2,6-dimethoxyphenanthrene, 1,6-Dimethoxy-2,5-diethoxyphenanthreneおよび1,2
    井深 俊郎
    1965 年 85 巻 7 号 p. 579-584
    発行日: 1965/07/25
    公開日: 2010/02/19
    ジャーナル フリー
    The non-phenolic alkaloid, metaphanine (I), obtained from Stephania japonica MIERS (Menispermaceae), was acetolysed to diacetoxy-dimethoxyphenanthrene (IIa), hydrolyzed, and finally ethylated to obtain diethoxy-dimethoxyphenanthrene. In order to determine the positions of the four substituents, three kinds of phenanthrene derivative were synthesized; i.e. 1, 5-diethoxy-2, 6-dimethoxyphenanthrene (IIc), 1, 6-dimethoxy-2, 5-diethoxyphenanthrene (IId), and 1, 2-diethoxy-5, 6-dimethoxyphenanthrene (IIe). Comparison with the degradation product of I showed the substance to be identical with IIe and, consequently, 1, 2-diacetoxy-5, 6-dimethoxyphenanthrene (IIa) must have been formed by the acetolysis of I.
  • ハスノハカズラStephania japonica MIERSのアルカロイド (補遺11) Homostephanolineの構造 その2
    渡辺 恭男, 松井 又夫, 怡土 桂子
    1965 年 85 巻 7 号 p. 584-587
    発行日: 1965/07/25
    公開日: 2010/02/19
    ジャーナル フリー
    One of the alkaloids of Stephania japonica MIERS (Menispermaceae) (Japanese name “Hasunoha-kazura”), homostephanoline, m.p. 232-235° (decomp.), C20H25O5N=C16H12O⋅NCH3⋅(OCH3)3⋅OH, is known to give hasubanonine (I), m.p. 116°, C21H27O5N=C16H12O⋅NCH3(OCH3)4, on methylation with diazomethane, and the steric configuration of I has already been elucidated. In order to determine the position of the hydroxyl in homostephanoline, the following experiment was carried out.
    O-Ethylhomostephanoline (VI), C16H12O⋅NCH3⋅(OCH3)3⋅OC2H5, obtained by ethylation of homostephanoline with diazoethane, was submitted to the Hofmann degradation and acetolysis to form acetyl-O-ethylhomostephanol (VIII), which was hydrolyzed to O-ethylhomostephanol (IX), and then to the methyl ether (XI), m.p. 130-131°. This methyl ether was identified with 3-ethoxy-4, 6, 8-trimethoxyphenanthrene (XI), m.p. 131-132°, synthesized by another route.
    The present series of experiments provided evidence that homostephanoline is a new base having a hasubanan skeleton represented by formula II.
  • 数種のMachilus属植物のアルカロイド
    富田 真雄, 盧 盛徳, 藍 碧貴
    1965 年 85 巻 7 号 p. 588-593
    発行日: 1965/07/25
    公開日: 2010/02/19
    ジャーナル フリー
    Alkaloidal components were examined in the following four kinds of Formosan Machilus genus plants: (1) Machilus obovatifolia (HAYATA) KANEHIRA et SASAKI (Japanese name, “Himetabu”), (2) M. arisaensis HAYATA (Japanese name “Arisantabu”), (3) M. zuihoensis HAYATA (Japanese name “Nioitabu”), and (4) M. Thunbergii SIEB. et ZUCC. (Japanese name “Tabuno-ki”). Phenolic secondary, benzyltetrahydroisoquinoline-type bases, L-(-)-N-norarmepavine (I) and dl-N-norarmepavine (III) were isolated from all four plants, and L-(+)-laudanidine (IV) besides I and III from (1) and (2). An unknown base in short columnar crystals, m.p. 258-259° (decomp.), was obtained from (1) and (3) (cf. Table II).
  • タイワンクロモジLitsea cubeba PERSOONのアルカロイド
    富田 真雄, 盧 盛徳, 藍 碧貴, 林 富美
    1965 年 85 巻 7 号 p. 593-596
    発行日: 1965/07/25
    公開日: 2010/02/19
    ジャーナル フリー
    Examinations were made on the alkaloidal components of the tree bark of Formosan Litsea cubeba PERSOON (Japanese name “Taiwan Kuromoji”) (Lauraceae) and two kinds of bases were isolated in crystalline form. Base A, m.p. 113-114° (sinter. at 107°), [α]D26+125.4° (c=1.00, CHCl3), was determined as (+)-laurotetanine (I) from the direction of its optical rotation and by comparison of its infrared spectrum (CHCl3) with that of dl-laurotetanine. N-Methyllaurotetanine was obtained in crystalline form for the first time as colorless columnar crystals (from acetone), m.p. 158-159°. Base B, m.p. 185°, [α]D33+206.2° (c=1.83, MeOH), was determined as isocorydine (III) from its various constants, mixed fusion with the known compounds, and comparison of its infrared spectrum (in Nujol).
  • 銅ヒスチジンキレートの研究
    湊 顕, 小木曾 健人, 星野 英雄
    1965 年 85 巻 7 号 p. 596-601
    発行日: 1965/07/25
    公開日: 2010/02/19
    ジャーナル フリー
    Spectrophotometric studies on the copper-histidine chelate in solution was carried out and the composition was determined by the method of continuous variation. These results showed that the single copper-histidine chelate of 1:2 ratio was formed in the solution of pH 8.5, while a mixture of 1:1 and 1:2 chelate was formed at pH 4.5 (Figs. 3 and 5).
    The measurement of absorbance at various pH, in the presence of excess histidine and constant cupric ion concentration, indicated the formation of 1:1 chelate in the pH range of 2.8 to 4.0, and 1:1 chelate in the pH range of 7.2 to 9.2 (Fig. 6).
    In addition, negative catalytic effect of histidine on the oxidation of ascorbic acid by cupric ion was examined and the composition of copper-histidine was determined to be 1:1 at pH 3.7 and 1:2 at pH 7.8 by the Waruburg method (Fig. 7).
  • Digitoxinおよびその代謝産物の血清蛋白との結合能について
    内田 精一, 木下 良裕, 草刈 一郎, 布施 昌孝
    1965 年 85 巻 7 号 p. 602-605
    発行日: 1965/07/25
    公開日: 2010/02/19
    ジャーナル フリー
    The extent of binding of digitoxin and its metabolites to bovine albumin or rat serum was determined by the method of equilibrium dialysis or ultrafiltration. The results were as follows:
    1) It was found that the binding effect of bovine albumin or rat serum was most marked with digitoxigenin monodigitoxoside, less with digitoxin and digitoxigenin didigitoxoside, and least with digoxin.
    2) With increasing concentration of digitoxin, digitoxigenin didigitoxoside or didigitoxigenin monodigitoxoside the binding proportion decreased.
    3) In a phosphate buffer of pH 6.4-9.2, there was no obvious effect of pH on the drug-protein binding.
  • L-イドン酸塩とD-グルコン酸塩の差別定量法
    滝浦 潔, 山本 稔
    1965 年 85 巻 7 号 p. 606-610
    発行日: 1965/07/25
    公開日: 2010/02/19
    ジャーナル フリー
    Aldonates form complex compounds with markedly large specific optical rotation by reaction with molibdic or tungstic acid in acidity. This reaction was applied to the differential determination of D-gluconate and L-idonate, the intermediates in the synthesis of ascorbic acid.
    To 0.1 mmole of a synthesized mixture of sodium D-gluconate and L-idonate, molybdate (Mo 2mg. atom) and 5mmole of acetic acid were added, the total volume was brought to 10.0ml. with water, and optical rotation of the solution was measured with the D line. A linear calibration line was obtained for the ratio of the two aldonates in the mixture and specific rotation.
    It follows, therefore, that a sample containing a mixture of unknown composition can be determined in the following manner. The total amount of aldonates is measured from the consumption of periodic acid (polarography) or by other means. The sample containing about 0.1 mmole of total aldonates is accurately measured, derived to the molybdate complex as above, and optical rotation of the solution is measured, to find the specific rotation. The content of L-idonate is then calculated from the calibration curve.
  • メチルピリジンとグリニヤ試薬との反応
    加藤 鉄三, 山中 宏, 足立 毅
    1965 年 85 巻 7 号 p. 611-614
    発行日: 1965/07/25
    公開日: 2010/02/19
    ジャーナル フリー
    Determination of active methyl group by the Zerewitinoff method was carried out on seven kinds of methylpyridine homologs including 2-, 3-, and 4-picoline, 2, 4- and 2, 6-lutidine, 2, 4, 6-collidine, and aldehyde-collidine. It was thereby found that the activity decreased in the order of 2, 4, 6-collidine, 2, 4-lutidine, 2, 6-lutidine, 2-picoline, aldehydecollidine, 4-picoline, and 3-picoline. This fact was utilized for synthetic consideration, and α, α-diphenylpyridineëthanol, phenacylpyridine, and (pyridylmethyl) cyclohexanol were obtained by reacting corresponding methylpyridine with benzophenone, benzonitrile, ethyl benzoate, or cyclohexanone.
  • 上尾 庄次郎, 大和 譲
    1965 年 85 巻 7 号 p. 615-618
    発行日: 1965/07/25
    公開日: 2010/02/19
    ジャーナル フリー
    A new amorphous alkaloid, radiatine (IV), has been isolated from the bulbs of Lycoris radiates as its crystalline ethyl ether, ethylradiatine hydrochloride. Ethylradiatine gave an oxime and was converted into hippeastrine by oxidation with chromic acid in dil. sulfuric acid, proving its structure as IV. Finally radiatine was synthesized from hippeastrine by its treatment with lithium aluminum hydride in tetrahydrofuran at -50°.
  • 攪拌の意義とガス, 液界面の役割
    三宅 良一, 矢島 尚
    1965 年 85 巻 7 号 p. 618-623
    発行日: 1965/07/25
    公開日: 2010/02/19
    ジャーナル フリー
    It was confirmed that even when not applying forced agitation, the rate determining step is the catalytic hydrogenation of ester on a nickel-kieselguhr catalyst and not a spontaneous transportation of the reactants, since the reaction is faster, being zero order with respect to the consumption of substrates, and there is preferential hydrogenation of ethyl linoleate to ethyl oleate. A far faster consumption of hydrogen was observed by the use of a platinum catalyst.
    State of the catalyst in liquid, suspension, or sedimentation, did not give any effect on the rate. No difference was found in the above phenomena under agitation, except for higher hydrogenation rate.
    Under this transferral equilibrium, the agitation effect is illustrated in terms of the role of liquid surface, where extra high concentration of hydrogen exists as the surface excess.
    The rotational agitation used in the present experiment may cause closer approach of more catalysts to the enlarged liquid surface region.
    Hydrogenation of p-nitrophenol over nickel-catalyst was also controlled by catalysis even under non-agitation.
  • 解熱鎮痛剤の分析 その1 アスピリン, フェナセチン, カフェインなどのFragmentationおよび混合試料のMass Spectra
    立松 晃, 後藤 俊夫
    1965 年 85 巻 7 号 p. 624-630
    発行日: 1965/07/25
    公開日: 2010/03/25
    ジャーナル フリー
    The mass spectra of heterocyclic and aromatic compounds exhibit strong parent peak and molecular weight of the compounds can be calculated from its mass number. By comparison of the parent peak and fragment peak with those of the standard chart, components of drugs containing several principles can be identified from their mass spectrum. Based on these facts, mass spectrum was measured in several antifebrile-analgesics like acetylsalicylic acid, phenyl salicylate, acetanilide, acetophenetidine, and caffeine, and their fragmentation was analyzed. Several samples were prepared by mixing these compounds and evidence is presented for the identification of each component in their mixture from mass spectrum.
  • 解熱鎮痛剤の分析 その2 各種製剤中の解熱薬のMass Spectra
    立松 晃, 後藤 俊夫
    1965 年 85 巻 7 号 p. 631-637
    発行日: 1965/07/25
    公開日: 2010/02/19
    ジャーナル フリー
    In continuation of the previous work, five kinds of mixed samples of antifebrile-analgesics were prepared, including aminopyrine and antipyrine, and detection of their componental principles from the mass spectrum of mixtures was confirmed.
    Mass spectra were also measured with commercial products of powders, granules, tablets, sugar-coated tablets, and ampules of mixed drugs and it was found that identification of each component was possible in a short time with a small amount of the sample by measuring their mass spectrum. Examinations were also made on the fragment peak and pattern coefficient of various preparations of commercial cold cures and facile identification of components was found possible, not only with aspyrine, acetophenetidine, caffeine, antipyrine, and aminopyrine but also with chlorophenilamine, cyclobarbital, barbital, and dihydrocodeine. Further studies are now being made for the quantitative estimation of these components and accumulation of mass spectral data of other kinds of pharmaceuticals.
  • 内田 哲雄
    1965 年 85 巻 7 号 p. 638-641
    発行日: 1965/07/25
    公開日: 2010/02/19
    ジャーナル フリー
    O, O-Dimethyl S-(methylcarbamoylmethyl) phosphorodithioate (Dimethoate or sometimes under the name of Rogor in Europe) (I) labeled with 32P has been used for its biological study. I was synthesized labeling the CH3O position with tritium for its metabolic study. All the reactions were carried out in one flask, without transfer of the radioactive solution to other vessels, in order to avoid loss of radioactive compounds and to keep operator free from danger. Syntheses of compounds related to I are also described. Paper chromatography was carried out to separate seven of compounds related to I.
  • 溝口 富茂, 飯島 郁夫
    1965 年 85 巻 7 号 p. 641-644
    発行日: 1965/07/25
    公開日: 2010/02/19
    ジャーナル フリー
    In order to study the steric configuration of DL-5-methyl-2-pyrrolidinecarboxylic acids (Ia and Ib), these acids were derived to DL-1, 5-dimethyl-2-pyrrolidinemethanols (IVa and IVb) and DL-1, 5-dimethyl-2-pyrrolidinemethanol benzoate hydrochlorides (Va and Vb). From their respective pKa′ values and from the behavior of 1-ethyl 2-methyl 5-methyl-1, 2-pyrroledicarboxylate (XII) to reduction, steric configuration of these compounds was presumed.
  • 林 英作, 五島 廉輔
    1965 年 85 巻 7 号 p. 645-649
    発行日: 1965/07/25
    公開日: 2010/02/19
    ジャーナル フリー
    Nitration of quinoline (I) with acid mixture gives 5-and 8-nitro compounds. In the case of 1, 2, 3, 4-tetrahydroacridine (II), 2, 3-dihydro-1H-cyclopenta [b] quinoline (III), 7, 8, 9, 10-tetrahydrophenanthridine (IV), and 2, 3-dihydro-1H-cyclopenta [c] quinoline (V), the nitration occurs in the position corresponding to 5-and 8-positions in I, i.e. 8- and 5-positions in II and III, 1-and 4-positions in IV, and 9-and 6-positions in V. In all of these compounds, it is difficult to make complete separation of the two kinds of nitrated compounds formed and therefore, their formation ratio is not clear. The 8-nitro compound (VI) of II, 8-nitro compound (XIII) of III, 1-nitro compound (XVI) of IV, and 9-nitro compound (XIX) of V can be derived to their corresponding N-oxides (XII, XV, XVIII, and (XXI) by treatment with monoperphthalic acid, but not the 5-nitro compound (VII) of II, 5-nitro compound (XIV) of III, 4-nitro compound (XVII) of IV, and 6-nitro compound (XX) of V, possibly because of the steric hindrance of the nitro group in the position peri to the ring nitrogen. The substance of m.p. 138-139° obtained by Borsche by nitration of II is probably VI, but the substance of m.p. 110° obtained by Perkin and others from II is doubtful about its being a unit substance, and may be a mixture of VI and VII. The substance of m.p. 119-120°, obtained by Hollingsworth and others and presumed by them to be XIV, may also be a mixture of XVI and XVII, and not a unit substance.
  • アトロピンのエオジンによる螢光定量
    小川 俊太郎, 守田 実, 西浦 加恵子, 藤沢 和子
    1965 年 85 巻 7 号 p. 650-653
    発行日: 1965/07/25
    公開日: 2010/02/19
    ジャーナル フリー
    The fluorescence reaction reported by Laugel on the formation of a complex between nitrogen-containing base and eosin was utilized, and a simple and rapid method for microdetermination of atropine by fluorometry was devised. A chloroform solution (9ml.) containing 40γ of atropine is placed in a light-resistant vessel, 1ml. of 0.1% eosin-Y reagent is added, the mixture is shaken well, and the fluorescence intensity of this solution is measured 10 minutes later. Concentration of atropine is calculated from the calibration curve. Toshiba Super-high voltage mercury lamp was used for the excitation light source, Matsuda UV-V2 for excitation filter, AKA-UV-O1 for excitation light cutting filter, and AKA-FL-B2 for fluorescence selection filter. The control values were obtained with 9ml. of chloroform treated in the same manner with the same reagent as the sample solution. The fluorometer is adjusted to fluorescence intensity of 100 using 50γ of standard atropine. The fluorescence is stable for at least 5-20 minutes after the addition of the reagent and the relationship between the amount of atropine and fluorescence intensity was linear in the concentration range of 1-5γ/ml. of atropine, and variation coefficient was 2.6%. The fluorescence spectrum has a maximum at 556mμ and the complex formed is considered to be a combination of atropine and eosin in a ratio of 2:1 or 1:1.
  • ベンゾサイアダイアジン系化合物の安定性 その5 クロロサイアザイドのアルカリ分解反応について (補遺)
    山名 月中, 水上 勇三, 市村 藤雄
    1965 年 85 巻 7 号 p. 654-655
    発行日: 1965/07/25
    公開日: 2010/02/19
    ジャーナル フリー
    Activation energies, frequency factors of the Arrhenius equation, and equilibrium constants between chlorothiazide and the intermediate were calculated from the rate constants on the hydrolysis reaction of chlorothiazide. The equilibrium constants were found to be independent of temperature.
  • 秦 清之, 小沢 貢, 池城 安正, 顔 焜〓
    1965 年 85 巻 7 号 p. 656-658
    発行日: 1965/07/25
    公開日: 2010/02/19
    ジャーナル フリー
    Dried roots of Angelica hirsutiflora LIU, CHAO et CHUANG afforded eight kinds of coumarin derivatives; byak-angelicin (I), osthol (II), psoralen (III), bergapten (IV), xanthotoxin (V), isopimpinellin (VI), 5-methoxy-8-hydroxypsoralen (VII), and a compound (VIII) which seemed to be identical with marmesin. A chromone derivative (IX) which was already reported as a constituent of A. japonica A. GRAY and its monoacetate (X) were also isolated from the same root.
  • 高美 章, 今沢 正興, 入江 昌親, 浮田 忠之進
    1965 年 85 巻 7 号 p. 658-661
    発行日: 1965/07/25
    公開日: 2010/02/19
    ジャーナル フリー
    Hydrolysis of four 5′-ribonucleotides, 5′-adenylic acid, 5′-guanylic acid, 5′-uridylic acid and 5′-cytidylic acid in formate buffer was studied to find suitable conditions for the preparation of corresponding nucleosides. The best conditions so far examined were as follows: refluxing of 5′-adenylic acid for 40 hours at pH 5.0 or 5.5, refluxing of 5′-guanylic acid for 60 hours at pH 4.0, refluxing of 5′-uridylic acid for 120 hours at pH 4.0, and refluxing of 5′-cytidylic acid for 70 hours at pH 5.0 or 5.5.
    Using these conditions, four ribonucleosides were obtained in respective yield of 80, 83, 88, and 54% for adenosine, guanosine, uridine, and cytidine.
  • コバノシロダモNeolitsea acuminatissima (HAYATA) KANEHIRA et SASAKIのアルカロイド
    富田 真雄, 盧 盛徳, 傅 紳箕, 林 玉美
    1965 年 85 巻 7 号 p. 662-664
    発行日: 1965/07/25
    公開日: 2010/02/19
    ジャーナル フリー
    Alkaloidal components were examined in the tree bark of Formosan Neolitsea acuminatissima (HAYATA) KANEHIRA et SASAKI (Lauraceae) (Japanese name “Kobano-shirodamo”). One base was isolated as crystals of m.p. 113-114° (sint. 107°), [α]D31.5+105.9° (ethanol). By mixed fusion and comparison of its infrared spectrum (in Nujol), the base was determined as d-laurotetanine (I).
  • 朝鮮産延胡索の成分 その2
    近藤 一恵, 近藤 嘉和, 竹本 常松
    1965 年 85 巻 7 号 p. 664-665
    発行日: 1965/07/25
    公開日: 2010/02/19
    ジャーナル フリー
    A glycoside (I) of m.p. over 300°, [α]D23.5-47.5°, was obtained in 0.00008% yield from a Korean Corydalis, Corydalis bulbosa DC. var. typica REGEL (=C. remota MAXIM.). From the properties of its acetate (II), m.p. 158-160°, [α]D23.5-30.2°±2°, its hydrolysis, and by the application of Klyne's rule, I was identified as stigmasteryl β-D-glucoside.
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