YAKUGAKU ZASSHI
Online ISSN : 1347-5231
Print ISSN : 0031-6903
ISSN-L : 0031-6903
85 巻, 4 号
選択された号の論文の21件中1~21を表示しています
  • N-フェニルアセチルアミノ酸および近似体
    須山 正, 豊田 猛, 金尾 清造
    1965 年 85 巻 4 号 p. 279-283
    発行日: 1965/04/25
    公開日: 2010/02/19
    ジャーナル フリー
    Twenty kinds of N-phenylacetyl-amino acid were prepared from the acid chloride or anhydride of phenylacetic acid. Some of these amino acids were found to markedly accelerate plant growth. Lysine, ornithine, cystine, and 7, 8-diaminopelargonic acid formed a bis-phenylacetyl derivatives. All had lower melting point and specific optical rotation than the original amino acids, with the exception of the specific rotation of L-alanine and L-leucine.
  • 須山 正, 金尾 清造
    1965 年 85 巻 4 号 p. 284-289
    発行日: 1965/04/25
    公開日: 2010/02/19
    ジャーナル フリー
    Following alkylation of glycine, leucine, aspartic acid, phenylalanine, and tyrosine, catalytic reduction of other amino acids in the presence of formaldehyde was attempted with platinum, Raney nickel, and zinc (activated with cobalt). DL-and allo-DL-threonine were easily dimethylated but L-and threo-D-threonine were chiefly monomethylated. The same reductive methylation was attempted on N-methyl-L-valine and N-methyl-L-isoleucine, the hydrolyzed product of enniatine-B and -A. In the case of N-cystine, L-4-thiazolidinecarboxylic acid (VI) was formed. Application of methyl iodide to N, N-dimethyl-β-alanine gave trimethylamine methiodide (III) besides the methiodide (II).
  • ニトロフランキノリン体のin vitroおよびin vivoでの抗菌性について
    三浦 孝次, 池田 政男, 大橋 冨次, 五十嵐 良子, 岡田 いく子, 食見 忠弘, 石井 節子
    1965 年 85 巻 4 号 p. 289-298
    発行日: 1965/04/25
    公開日: 2010/02/19
    ジャーナル フリー
    23 derivatives of nitrofurylvinylquinoline, whose quinoline nucleus was introduced by various side chains, were synthesized in order to examine their antibacterial properties against Gram positive bacteria (Streptococcus, Staphylococcus, B. subtilis) and Gram negative bacteria (E. coli, Shigella) in vivo and the structure-activity-relationship has been studied. Among the compounds tested, 2-[2-(5-nitro-2-furyl) vinyl]-4, 6-diacetamidoquinoline (I) was found to show the strongest antibacterial activity against Streptococcus, Staphylococcus possessing much stronger antibacterial properties than maxipen (II), sodium salt of phenoxyethyl-penicillin, being used as a comparison. II showed weak antibacterial properties against Gram negative bacteria. However, I was found to have wide range of antibacterial spectrum at the γ/ml. level against E. coli and Shigella. The efficacy towards Streptococcus infected mice in vivo was shown to be pretty strong curable action with I and that of II was found to be about 1/8 of the action.
  • 燐化合物とThiophenolナトリウム塩ならびにThiamineナトリウム塩との反応 その1
    高見沢 映, 佐藤 義朗, 田中 幸子
    1965 年 85 巻 4 号 p. 298-304
    発行日: 1965/04/25
    公開日: 2010/02/19
    ジャーナル フリー
    Reactions were carried out between the sodium salt of thiophenol (IV) with benzoyl (IIIa), p-toluoyl (IIIb), p-nitrobenzoyl (IIIc), acetyl (IIId), dimethylcarbamoyl (IIIe), and diethyl (IIIf) cyanophosphonate. Only S-acylation and S-ethylation were-effected in IIIa to IIId, and only S-ethylation in IIIe and IIIf. At the same time, diphenyl disulfide (VII) was formed from IIIa to IIId. In the case of IIIc, formation of phenyl p-nitrothiobenzoate (Vc) and phenyl ethyl sulfide (VI) was so small as to be barely isolable and VII was the main product.
    The same reaction between the sodium salt of thiamine (VIII) and IIIa unexpectedly gave some crystals (IX) of m.p. 163-164°, and not the anticipated S-ethylthiamine or O, S-dibenzoylthiamine. The composition of IX agreed with that of dibenzoylthiamine but the compound was apparently different from the result of ultraviolet (Fig. 1), infrared (Fig. 2), and NMR (Fig. 4) spectra. Alkali treatment of IX liberated one mole of benzoic acid. Its fundamental structure is very stable and the compound is different from the known thiamine derivative. It was assumed that the pyrimidine portion in this compound remains intact and the benzoyl group has been introduced into the thiazole portion, with the hydroxyethyl group forming a benzoate, thus creating a new type of thiamine compound.
  • 中垣 正幸, 西野 操
    1965 年 85 巻 4 号 p. 305-310
    発行日: 1965/04/25
    公開日: 2010/02/19
    ジャーナル フリー
    Theoretical equations based on the plate theory were applied to the discussion on the changes, observed on the gas chromatogram, when a chemical reaction of gas, A→B, occurs in the packing of the column. According to the equations, method was discussed to determine the theoretical plate number n, the rate constant of the chemical reaction K and the adsorption coefficient of A, kA, from the width of the peak, the retention volume and the area of the peak, and to determine the adsorption coefficient of B, kB, from the starting point of the peak of B. Then, the change of the position and the shape of chromatogram due to the variation of parameter values was discussed. By using these results, it was also shown for the isomerization reaction of cyclopropane that the theoretical and experimental chromatograms agree with each other.
  • 4H-フロ [3,2-c] [1] ベンゾピラン-4-オン類の合成について
    小林 五郎, 桑山 良像, 土田 拓生
    1965 年 85 巻 4 号 p. 310-313
    発行日: 1965/04/25
    公開日: 2010/02/19
    ジャーナル フリー
    Condensation of acetobutyrolactone and o-methoxybenzoyl chloride with magnesium gave o-methoxybenzoylbutyrolactone, treatment of which produced 3-(2′-hydroxyethyl)-4-hydroxycoumarine with aluminum chloride. By refluxing it in methanolic hydrochloric acid, 2, 3-dihydrofuro [3, 2-c] coumarine was prepared. When it was refluxed with N-bromosuccinimide in carbon tetrachloride, easy dehydration gave furo [3, 2-c] coumarine. These reaction products obtained were ascertained to be α-pyrone compounds by ultraviolet and infrared spectra.
  • 上尾 庄次郎, 新宮 徹朗, 原田 紘
    1965 年 85 巻 4 号 p. 314-317
    発行日: 1965/04/25
    公開日: 2010/02/19
    ジャーナル フリー
    Dehydrogenation of 2, 3, 4, 5-tetrahydro-1H-1-benzazepine over 40% palladium-carbon in ethyl cinnamate at 240-260° gave a mixture of basic products consisting of 40% of quinoline, 15% of 2-methylquinoline, 18% of 3-methylquinoline, and 27% of 4-methylquinoline as shown by gas chromatography. Likewise, dehydrogenation of 6, 8-diethyl-2, 3, 4, 5-tetrahydro-1H-1-benzazepine under the same conditions as above yielded a variety of bases including an overwhelming amount of 5, 7-diethylquinoline along with small amounts of 2-methyl-, 4-methyl-, and probably 3-methyl-5, 7-diethylquinoline. 5, 7-Diethylquinoline and its 2- and 4-methyl homologs were prepared from 3, 5-diethylaniline by the standard methods and used as reference compounds for the gas chromatography.
  • 有機分析試薬の薄層クロマトグラフィー その1
    西本 行雄, 豊島 昭二
    1965 年 85 巻 4 号 p. 317-321
    発行日: 1965/04/25
    公開日: 2010/02/19
    ジャーナル フリー
    Organic reagents were analyzed by thin-layer chromatography with Kieselgel G. and 21 reagents out of 36 showed the tailing, which was prevented by the pre-treatment with EDTA⋅2Na in adsorbents. The reagents which show the tailing have relatively larger chelating stability constants of approximately more than log KFe 17-18. However, the tailing may be caused also by the other factors as well. An identification of reagents is usually difficult in metallic ion solutions but the coloration has not been differed even by the pre-treatment of EDTA⋅2Na in the adsorbent. The coloration with various metallic ions have also been studied.
  • 有機分析試薬の薄層クロマトグラフィー その2 ジチゾンについて
    西本 行雄, 豊島 昭二
    1965 年 85 巻 4 号 p. 322-326
    発行日: 1965/04/25
    公開日: 2010/02/19
    ジャーナル フリー
    When dithizone was applied in the analysis by thin-layer chromatography, it showed the tailing and multi-spots production, reacted with traces of metals of the impurities in adsorbents. Among them, zinc was found to form main chelating reaction. The tailing may be prevented by the pre-treatment with EDTA⋅2Na, however, the chelation can not be completely prevented. The impurities in the marketed dithizone have been certified to be dehydrodithizone, which could be eliminated by the usual ammonia purification.
  • エピレナミン系薬物の薄層クロマトグラフィー
    西本 行雄, 豊島 昭二
    1965 年 85 巻 4 号 p. 327-331
    発行日: 1965/04/25
    公開日: 2010/02/19
    ジャーナル フリー
    Epirenamine series of drugs can not well be seperated by thin-layer chromatography (TLC) analysis even in various conditions. It is because of the chelate formation reactions of reagents with traces of metals in the adsorbents. To prevent this inconvenience, adsorbent was pre-treated with EDTA⋅2Na, and the TLC was developed with a solvent mixture of acetone-formic acid-water (7:1:2) which gave a better result. As a developing reagent, phosphomolybdic acid-ammonia method was found to be specific with a high limit of identification. Between RM value and carbon number of alkyl groups combined to a nitrogen atom, almost a linear relation has been observed.
  • 加藤 鉄三, 山中 宏, 引地 学
    1965 年 85 巻 4 号 p. 331-334
    発行日: 1965/04/25
    公開日: 2010/02/19
    ジャーナル フリー
    The reaction between quinoline N-oxide (I) and seven kinds of fatty Grignard reagents (R=methyl, ethyl, propyl, isopropyl, cyclohexyl, benzyl and phenethyl) has been studied and the production of 2-substituted quinoline N-oxide (II), 2-substituted quinoline (III) and quinoline (IV) have been observed. II and IV had never been produced in the Grignard reaction with I and the mechanism has been discussed.
  • 蓮子芯のアルカロイド その2 一新Biscoclaurine型塩基Neferineの構造
    古川 宏
    1965 年 85 巻 4 号 p. 335-338
    発行日: 1965/04/25
    公開日: 2010/02/19
    ジャーナル フリー
    A new base, neferine (methiodide, m.p. 180-182°, C38H44O6N2⋅2CH3I⋅2H2O), as well as isoliensinine (I) has been isolated from “Lien Tze Hsin” (embryo of Nelumbo nucifera GAERTN.), in Hong Kong market. O-Methylneferine (IV) (styphnate, m.p. 139-140°, [α]D -93.3° (acetone)) was found to be completely identical with the synthesized O, O-dimethylisoliensinine (IV), reported previously. When O-ethylneferine (V) was subjected to the cleavage reaction by metallic sodium in liquid ammonia, D-1, 2, 3, 4-tetrahydro-6-methoxy-1-(p-methoxybenzyl)-2-methyl-7-isoquinolinol (VI) and D-O-ethylarmepavine (VII) were obtained. Therefore, it has been verified that the structure of neferine was represented by the formula III.
    The neferine (III), synthesized from VI and D-3′-bromoarmepavine (VIII) in the presence of cupric oxide and anhyd. potassium carbonate in pyridine was completely identical with the natural product (Table I).
  • 10H-Pyridazino [3,2-b] quinazolin-10-oneおよびその誘導体の合成 その1
    梁井 光二, 木下 敏夫, 中島 成子, 中村 光明
    1965 年 85 巻 4 号 p. 339-343
    発行日: 1965/04/25
    公開日: 2010/02/19
    ジャーナル フリー
    Catalytic reduction of 2-chloro-10H-pyridazino [3, 2-b]-quinazolin-10-one (II) over palladium-charcoal does not give dechlorinated V but affords two dihydro compounds (VII and VIII) and a tetrahydro compound (IX). The structure of these compounds was assumed from their infrared and ultraviolet spectra as 2-(2-cyanoethyl)-4(3H)-quinazolinone for VII and 1, 2-dihydro-10H-pyridazino [3, 2-b] quinazolin-10-one for VIII.
    Fusion of anthranilic acid and 3, 6-dichloro-4-methylpyridazine (X) gave two isomers (XI and XII). In order to determine the positions of their methyl groups, the methoxyl compounds (XIIIa and XIV) were prepared and these were identified by mixed fusion and from their infrared spectra with separately synthesized 2-methoxy-3-methyl-10H-pyridazino [3, 2-b] quinazolin-10-one (XIIIa) and 2-methoxy-4-methyl-10H-pyridazino [3, 2-b]-quinazolin-10-one (XIV).
  • Alkoxypyridazine 1-Oxide類の1-Alkoxypyridazinone類への転位反応 その1
    梁井 光二, 木下 敏夫
    1965 年 85 巻 4 号 p. 344-352
    発行日: 1965/04/25
    公開日: 2010/02/19
    ジャーナル フリー
    It has been found that the rearrangement products (IIIa, IIIb and IIIc), besides the respective N-oxide (IIa and IIb) were obtained, when either 3, 6-dimethoxypyridazine (Ia) or 4-methyl-3, 6-dimethoxypyridazine (Ib) was oxidized with 30% hydrogen peroxide in acetic acid. Rearrangement reactions of IIa, IIb and IIc were attempted with p-toluenesulfonic acid and the rearrangement products were found to be afforded in a good yield, however 4-methyl-3, 6-diethoxypyridazine (V) gave only two kinds (VI and VII) of N-oxide.
    The rearrangement reaction of p-toluenesulfonic acid with 4-methoxy-, 4-ethoxypyridazine 1-oxide (Xa, Xb), 4-methoxypyridine 1-oxide (XIV) and 4-methoxyquinoline 1-oxide (XVII), were attempted and the respective products (XIa, XIb, XV, and XVIII) were prepared. 5-Methoxypyridazine 1-oxide (XXa) gave also the rearrangement products (XXIa) and the structures of XXa and XXb were determined.
  • 蓮子芯のアルカロイド その3 日本産蓮子芯
    古川 宏
    1965 年 85 巻 4 号 p. 353-354
    発行日: 1965/04/25
    公開日: 2010/02/19
    ジャーナル フリー
    Several reports on the alkaloids of Loti embryo (Lien Tze Hsin) were already found and liensinine (I) was isolated from Lien Tze Hsin of Continental China, and isoliensinine (II) from the one of Formosan lotus, and both isoliensinine (II) and neferine (III) were isolated from Lien Tze Hsin in Hong Kong market.
    The author examined the alkaloidal component of the embryo from Japanese lotus and it has been verified that liensinine (I) found to be the main alkaloid, besides a small amount of neferine (III). The quaternary base has not been obtained, different from the ones from Formosa and Hong Kong market.
  • Bisbenzylisoquinoline Alkaloidsの合成研究 (第2報) 1,1´-(3,3´-Dimethoxy-4,4´-oxydibenzyl)-2,2´-dimethyl-6,6´,7,7´-tetramethoxy-1,1´,2,2´,3,3´,4,4´-octahydrodiisoquinolineの合成
    亀谷 哲治, 呂 政府, 岩淵 陽子
    1965 年 85 巻 4 号 p. 355-358
    発行日: 1965/04/25
    公開日: 2010/02/19
    ジャーナル フリー
    Dimethyl 3, 3′-dimethoxy-4, 4′-oxydiphenyldiacetate (VI) was synthesized by the reduction of 3-methoxy-3′-nitro-4, 4′-oxydiphenyldiacetic acid (III) to the amino compound (IV), its diazotization to the hydroxyl compound (V), and its methylation with diazomethane. The acid chloride of the acid (VII) obtained by the hydrolysis of VI was condensed with homoveratrylamine by the usual Schotten-Baumann reaction to the amide (XVII), cyclized to the isoquinoline compound (XVIII), and its methiodide (XIX) was reduced with sodium borohydride to obtain the objective tetramethyl derivative (II).
    On the other hand, 5-nitro-3, 3′-dimethoxy-4, 4′-oxydibenzaldehyde, prepared by the Ullmann reaction of vanillin and 3-methoxy-4-chloro-5-nitrobenzaldehyde, was derived to its amino compound by reduction of its tetraacetate, diazotized, and deaminated with hypophosphorous acid to obtain 3, 3′-dimethoxy-4, 4′-oxydibenzaldehyde. This aldehyde was oxidized to its carboxylic acid (XIV) and submitted to the Arndt-Eistert reaction with the foregoing homoveratrylamine via the diazo-ketone. The product was found to be the same as the foregoing amide (VII). The compound (II) was confirmed as its styphnate of m.p. 150-152°.
  • いわゆる “Oxythebaon” の構造について
    関 功
    1965 年 85 巻 4 号 p. 359-363
    発行日: 1965/04/25
    公開日: 2010/02/19
    ジャーナル フリー
    A chemical evidence is presented for the structure of the so-called “Oxythebaon, ” X, a Hofmann degradation product of 14-hydroxydihydrothebainone dihydromethine methiodide (VIII). X is produced by the internal alkylation of C(14)-hydroxyl group.
  • マロン酸エステルからアデニンの合成 その1
    藤本 康夫, 大野 典子
    1965 年 85 巻 4 号 p. 364-367
    発行日: 1965/04/25
    公開日: 2010/02/19
    ジャーナル フリー
    The new process for synthesis of adenine from malonic ester has been investigated. Adenine has been prepared in 25% over-all yield from diethyl malonate by a six-step synthesis which involves: (1) reaction of diethyl malonate with conc. ammonium hydroxide solution to give malonamide (76%), (2) condensation of the amide with formamide in ethanolic sodium ethoxide to give 4, 6-pyrimidinediol (76%), (3) nitration of 4, 6-pyrimidinediol in glacial acetic acid with fuming nitric acid to give 5-nitro-4, 6-pyrimidinediol (95%), (4) chlorination of 5-nitro-4, 6-pyrimidinediol with phosphorus oxychloride and N, N-dimethylaniline as a basic catalyst to give 4, 6-dichloro-5-nitropyrimidine (71%), (5) amination of 4, 6-dichloro-5-nitropyrimidine with alcoholic ammonia to give 4, 6-diamino-5-nitropyrimidine (98%) and (6) heating 4, 6-diamino-5-nitropyrimidine with formamide, formic acid and sodium dithionite to give adenine (67%).
  • マロン酸エステルからアデニンの合成 その2
    藤本 康夫, 大野 典子
    1965 年 85 巻 4 号 p. 367-370
    発行日: 1965/04/25
    公開日: 2010/02/19
    ジャーナル フリー
    Several efforts were made on the simplification of the steps, the attainment of higher yields, and the reduction of material costs in the synthesis of adenine from malonic ester reported in a previous paper.
    (1) 4, 6-pyrimidinediol has been prepared in 80% yield from diethyl malonate and formamide by a one-step synthesis using ethanolic sodium ethoxide.
    (2) Nitration of 4, 6-pyrimidinediol could be carried out in 95% yield with a mixture of nitric acid and sulfuric acid.
    (3) Methanol could be used instead of ethanol as a solvent for amination of 4, 6-dichloro-5-nitropyrimidine to 4, 6-diamino-5-nitropyrimidine.
    With these improvements, adenine has been prepared in 35% over-all yield from diethyl malonate by a five-step synthesis.
  • cis-2-Methyldecahydro-5-isoquinolinolの合成
    木本 正七郎, 岡本 正夫
    1965 年 85 巻 4 号 p. 371-374
    発行日: 1965/04/25
    公開日: 2010/02/19
    ジャーナル フリー
    Hydrogenation of 2-methyl-1, 2, 3, 4-tetrahydro-5-isoquinolinol (I) under high temperature and high pressure in the presence of Raney-nickel was reinvestigated and a new compound, cis-2-methyldecahydro-5-isoquinolinol (II), m.p. 90-92° (methiodide, m.p. 210-212°) and two trans-2-methyldecahydro-5-isoquinolinols (IIIa and IIIb) were obtained in the ratio of 4:4:1. On the other hand, in the presence of a catalyst of platinum oxide, phenolic base (I) was hydrogenated to give cis-2-methyldecahydroisoquinoline (IV) and cis-2-methyldecahydro-5-isoquinolinol acetate (V) in the production ratio of approximately 1:1. However, in the hydrogenation of 2-methyl-1, 2, 3, 4-tetrahydro-5-isoquinolinol acetate, cis decahydro base (IV) was produced exclusively. The oxidation of cis alcoholic base (II) by chromium trioxide-pyridine complex afforded only trans-2-methyloctahydro-5(1H)-isoquinolinone (VII).
  • 知母の成分Chimoninについて
    森田 直賢, 清水 嶺夫, 福田 昌子
    1965 年 85 巻 4 号 p. 374-375
    発行日: 1965/04/25
    公開日: 2010/02/19
    ジャーナル フリー
    One of the components in Timo, Anemarrhenae Rhizoma, was known to be flavonoid compound, C22H18O11⋅2H2O, m.p. 257-258° by Nakaoki and coworkers. While Shimada and coworkers reported later that it would be a xanthon derivative, C19H18O11 and perhaps mangiferin or something concerned with it, but it had not been exactly recognized since now. It was identified to be mangiferin by the authors using UV, IR, X-ray analysis etc.
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