YAKUGAKU ZASSHI
Online ISSN : 1347-5231
Print ISSN : 0031-6903
ISSN-L : 0031-6903
84 巻, 6 号
選択された号の論文の28件中1~28を表示しています
  • 1(2H)-Phthalazone類のニトロ化について
    金原 三郎
    1964 年 84 巻 6 号 p. 483-489
    発行日: 1964/06/25
    公開日: 2010/02/19
    ジャーナル フリー
    Nitration of 1(2H)-phthalazone (XIV) and its 4-substituted derivatives was carried out with potassium nitrate and conc. sulfuric acid. XIV formed 5-nitro compound and a minute amount of 8-nitro compound. 4-Methyl-1(2H)-phthalazone (I) chiefly formed 8-nitro compound and a small amount of 5-nitro compound. Nitration of 4-oxo-3, 4-dihydro-1-phthalazinecarboxylic acid (XXII) in the cold gave 8- and 6-nitro compounds while nitration of XXII with heating gave 6-nitro compound and decarboxylated 4, 5-dinitro-1(2H)-phthalazone (XXVIII), which is also obtained by further nitration of 5-nitro-1(2H)-phthalazone (XV) and 5-nitro-4-oxo-3, 4-dihydro-1-phthalazinecarboxylic acid (XIX). The position of nitro group in the above compounds was determined by comparison and identification with the corresponding compounds synthesized by another route (cf. Charts 1-3).
  • Phthalazine類のニトロ化について
    金原 三郎
    1964 年 84 巻 6 号 p. 489-493
    発行日: 1964/06/25
    公開日: 2010/02/19
    ジャーナル フリー
    Nitration of phthalazine, 1-methylphthalazine, and 1-methoxyphthalazine was carried out with potassium nitrate and conc. sulfuric acid, and following results were obtained.
    1) Phthalazine (I) afforded 5-nitrophthalazine (II) as the main product, with 5-nitro-1(2H)-phthalazone (III) as the by-product. II forms two kinds of methiodide and their oxidation respectively gave 2-methyl-5-nitro-1(2H)-phthalazone (VII) and 2-methyl-6-nitro-1(2H)-phthalazone (VIII).
    2) 1-Methylphthalazine (X) formed 1-methyl-5-nitrophthalazine (XI) with 4-methyl-8-nitro-1(2H)-phthalazone (XII) as a by-product. Oxidation of 5-nitro-1, 3-dimethylphthala-zinium iodide (XIII), formed from XI, gave 8-nitro-2, 4-dimethyl-1(2H)-phthalazone (XV).
    3) 1-Methoxyphthalazine (XVI) formed 1-methoxy-5-nitrophthalazine (XVII) with 5-nitro-1(2H)-phthalazone (XVIII) as a by-product.
  • 1,2-Benzisothiazoline 1,1-Dioxide類の合成
    新田 義博, 新藤 実, 高須 哲雄, 磯野 千冬
    1964 年 84 巻 6 号 p. 493-497
    発行日: 1964/06/25
    公開日: 2010/02/19
    ジャーナル フリー
    Chlorosulfonation of 3-chlorobenzylamine hydrochloride with chlorosulfonic acid gives two kinds of labile products (II and V). Treatment of these two products with ammonia gives 5-chloro-1, 2-benzisothiazoline 1, 1-dioxide (III) from II and 5-chloro-1, 2-benzisothiazoline-6-sulfonamide 1, 1-dioxide (VI) from V. Reduction of III gives 1, 2-benzisothiazoline 1, 1-dioxide (VII) whose oxidation with potassium permanganate gives saccharine. Similar oxidation of III gives 5-chlorosaccharin (IX). The structure of III was confirmed from these experiments. Infrared spectra of these compounds were measured. III and VI showed diuretic action in mice.
  • Aminomethylbenzenesulfonamide類の合成
    新田 義博, 新藤 実, 藤森 東一, 磯野 千冬
    1964 年 84 巻 6 号 p. 498-503
    発行日: 1964/06/25
    公開日: 2010/02/19
    ジャーナル フリー
    Chlorosulfonation of N-(3-chlorobenzyl)acetamide (I), followed by ammonolysis of its product gives 2-acetamidomethyl-4-chlorobenzenesulf onamide (III) and hydrolysis of III with hydrochloric acid gives 2-aminomethyl-4-chlorobenzenesulf onamide hydrochloride (IV). Fusion of IV with the free base (V) results in cyclization to form 5-chloro-1, 2-benzisothiazoline 1, 1-dioxide (VI), which is the new compound reported in the preceding paper and the position of the chlorosulfonation is now determined. o-Aminomethylbenzenesulfonamide hydrochloride (VII) and its free base (VIII) are obtained by the catalytic reduction of IV over 10% palladium-carbon. Reaction of V and ethyl orthoformate gives 7-chloro-2, 5-dihydro-1, 2, 4-benzothiadiazepine 1, 1-dioxide (IX).
    On the other hand, sulfamylation of N-(4-chlorobenzyl)acetamide (X) gives 5-acetamidomethyl-2-chlorobenzenesulfonamide (XII), which is converted to 5-aminomethyl-2-chlorobenzenesulfonamide hydrochloride (XIII) and its free base (XIV). Similar reaction of N-(2-chlorobenzyl)acetamide (XXI) gives 3-acetamidomethyl-4-chlorobenzenesulfonamide (XXIII), 3-aminomethyl-4-chlorobenzenesulfonamide hydrochloride (XXIV), and its free base (XXV). Oxidation of XIV and XXV gives the corresponding benzoic acid derivatives (XV and XXVI) which were identified.
    It is concluded from these experiments that the chlorosulfonation of chlorobenzylamines is dependent on the orienting effect of the chlorine atom and not to that of the aminomethyl group. XIII. and XIV showed a fairly strong diuretic action in rats.
  • 梅本 進
    1964 年 84 巻 6 号 p. 504-508
    発行日: 1964/06/25
    公開日: 2010/02/19
    ジャーナル フリー
    In order to test anti-convulsant action, ethoxycarbonylhydantoins were synthesized from the sodium salt of hydantoins and ethyl chloroformate. It was found during this synthesis that treatment of 3-ethoxycarbonyl derivatives of 5, 5-diphenyl-, 5-ethyl-5-phenyl-, 5, 5-dimethyl-, and 5-benzyl-hydantoins with sodium hydride resulted in the rearrangement of ethoxycarbonyl group to 1-position but no such rearrangement occurred in 3-ethoxycarbonyl-5-benzylidenehydantoin.
  • 梅本 進
    1964 年 84 巻 6 号 p. 509-512
    発行日: 1964/06/25
    公開日: 2010/02/19
    ジャーナル フリー
    3-Acylhydantoins were prepared from hydantoins and their rearrangement reaction with sodium hydride was examined. 3-Acetyl-, 3-phenylacetyl-, and 3-benzoyl-5, 5-diphenylhydantoins, and 3-acetyl derivatives of 5-ethyl-5-phenyl-, 5, 5-dimethyl-, and 5-benzyl-hydantoins underwent rearrangement with sodium hydride to give their corresponding 1-substituted derivatives but not 3-acetyl-5-benzylidenehydantoin.
  • 島村 芳三, 三宅 良一
    1964 年 84 巻 6 号 p. 512-516
    発行日: 1964/06/25
    公開日: 2010/02/19
    ジャーナル フリー
    The report that Cu⋅Cr-O catalyst hydrogenated higher unsaturated acids of whale oil and other fats to the point of oleic acid series acids at 180° under atmospheric pressure was confirmed by prolongation of working period with Tsubaki oil which consists mainly of oleic acid.
    Allowable high temperatures to preserve this selectivity were determined by volumetric and bubbling procedures, leading to the same conclusions that oleic acid series acids were subjected, though very slowly, to saturation at 230°, while a reduction of carboxylic group started at 260°, along with complete saturation of carbon-carbon double bond, both at minor but fairly appreciable rates.
  • スルファミン類と血清アルブミンとの結合の機構について
    中垣 正幸, 古賀 直文, 寺田 弘
    1964 年 84 巻 6 号 p. 516-521
    発行日: 1964/06/25
    公開日: 2010/02/19
    ジャーナル フリー
    The binding ability of crystalline bovine serum albumin was examined with several commonly used sulfonamides; sulfisomidine, sulfathiazole, sulfadimethoxine, sulfaphenazole and sulfisoxazole. The relationship between the amount of sulfonamides bound to bovine serum albumin and concentration of the sulfonamide solution at equilibrium is represented by a Langmuir-type equation. In order to study its mechanism, the binding of sulfamonomethoxine with bovine serum albumin was further examined, and in comparison with that of sulfadimethoxine, the effect of methoxyl group on the binding was discussed. Then the relationship between the charge of bovine serum albumin and its binding capacity for these six sulfonamides was examined and the standard binding affinity of sulfonamides was estimated to be about 6kcal/mole. It was concluded that in the binding of the albumin with sulfonamide, electrostatic force is the most important factor and the dissociation constant of sulfonamide affects the binding.
  • 百瀬 勉
    1964 年 84 巻 6 号 p. 521-525
    発行日: 1964/06/25
    公開日: 2010/02/19
    ジャーナル フリー
    An air-bath melting point apparatus (Figs. 1, 2) was designed in which an uniform temperature was maintained with electrically heated nichrome wires and a rotating fan. The rise in temperature was easily controled with a heater by turning the dial of bimetal regulator, which was set in the furnace and operated from a room temperature to 300°.
    The sample packed in a capillary tube was placed close to the horizontal side of the mercury bulb of a thermometer, and heated intermittently by turning the dial of regulator in such a way as to cause a rise in temperature of 0.5-1° per one turning in the neighborhood of the melting point, using the heater 1 for a room temperature to 100°, 2 for 100-150°, 3 for 150-200°, 4 for 200-250°, and 5 for 250-300° (Fig. 3). A preliminary heating or cooling of the furnace was very rapid as shown in the figure. The repeated determination of the melting point of several compounds (Table I) proved that the apparatus was precise enough for the usual purpose of determination.
  • 百瀬 勉, 大倉 洋甫, 小橋 一弥, 矢野 良子, 大橋 勝子, 永田 礼子, 太田 紀代子
    1964 年 84 巻 6 号 p. 525-531
    発行日: 1964/06/25
    公開日: 2010/02/19
    ジャーナル フリー
    Sodium tungustate and alum was used for the deproteinization of diluted serum to determine creatinine and creatine with picric acid or 1, 3, 5-trinitrobenzene as the color developing agent. Sulfamic acid proved to be suitable for the conversion of creatine to creatinine in a simple procedure.
    These methods of determination give the creatinine and creatine values analogous to those determined by the Folin-Wu method. Precision of the methods is shown in the tables.
  • Bisbenzylisoquinoline Alkaloidsの合成研究 (第1報) dl-3-Amino-3´-methoxy-4,4´-bis (2-methyl-6,7-dimethoxy-1,2,3,4-tetrahydro-1-isoquinolylmethyl) diphenyl Etherの合成
    亀谷 哲治, 福本 圭一郎, 呂 政府
    1964 年 84 巻 6 号 p. 532-537
    発行日: 1964/06/25
    公開日: 2010/02/19
    ジャーナル フリー
    Aztequine (I), m.p. 176°, is an alkaloid isolated in 1948 by Pallares and Garza from the leaves of a Mexican Magnoliaceae plant, yoloxochitl (Talauma mexicana DON.). As a preliminary to the total synthesis of I, synthesis of tetramethylaztequine (II) was attempted. In general, presence of an electron-attracting group like nitro in the position ortho or para to the halogen results in smooth progress of the Ullmann reaction, with a good yield. Therefore, 3-nitro-4-bromobenzaldehyde, obtained by nitration of 4-bromobenzaldehyde, and vanillin were submitted to the Ullmann reaction and 3-nitro-4-(2-methoxy-4-formylphenoxy)-benzaldehyed was obtained. Its reduction with sodium borohydride to the dialcohol, followed by chlorination and derivation to the dinitrile, and hydrolysis with conc. hydrochloric acid afforded the objective dihomo acid. Its fusion with homoveratrylamine or its Schotten-Baumann reaction gave the corresponding diamide (XXVII) whose Bischler-Napieralski reaction produced bis (3, 4-dihydroisoquinoline) derivative. Catalytic reduction of its methiodide (XXIX) finally afforded rac-3-amino-3′-methoxy-4, 4′-bis (2-methyl-6, 7-dimethoxy-1, 2, 3, 4-tetrahydro-1-isoquinolylmethyl)-diphenyl ether (XXXI). Attempt to diazotize XXXI to change the amino group into hydroxyl and its methylation to obtain II did not materialize.
  • ニトロフラン誘導体の化学構造と抗ガン作用との関係について
    三浦 孝次, 池田 政男, 大橋 富次, 岡田 いく子, 五十嵐 良子
    1964 年 84 巻 6 号 p. 537-543
    発行日: 1964/06/25
    公開日: 2010/02/19
    ジャーナル フリー
    Effect of 2-[2-(5-nitro-2-furyl) vinyl] quinoline (2-Q-ran) and 17 other compounds on mice bearing Ehrlich ascites tumor was examined. 2-Q-ran was found to have a marked antitumor action and its intraperitoneal administration in a suitable dose effected 50-day prolongation of life in all the test animals and avoided them from tumor death.
    Effect of the side chain on antitumor activity was then examined and it was found that the compounds having N-oxide, carbonamide, or two amino groups showed approximately the same effect as the parent compound and that the nitro, bromo, and acetamide groups gave a marked effect in decreasing the antitumor activity.
    Panfuran having an as-triazine and T-ran having a thiadiazole ring were both ineffective but X-ran having a quinoxaline ring had an effect comparable to that of 2-Q-ran.
    In order to elucidate the action mechanism of nitrofurylvinylquinoline derivatives, their effect on the nucleic acid and protein syntheses by Escherichia coli was examined. and it was found that the nitrofuran systems having antitumor action strongly inhibited biosynthesis of deoxyribonucleic acid, ribonucleic acid, and proteins. 4, 6-Diamino-2-Q-ran was found to inhibit ascites tumor dehydrogenase. It may be concluded that these nitrofuran derivatives show their antitumor action as the cytotoxic substance in a wide sense.
  • アミノ酸類とTetramethylpyrazine生成との関係
    足立 多平, 神谷 弘子, 小菅 卓夫
    1964 年 84 巻 6 号 p. 543-545
    発行日: 1964/06/25
    公開日: 2010/02/19
    ジャーナル フリー
    Tetramethylpyrazine was first produced by Bacillus subtilis in a medium having asparagine as the sole source of nitrogen. It was found that it is also produced when aspartic acid, alanine, glutamic acid, arginine, or peptone is used as the sole source of nitrogen.
  • Tetramethylpyrazineの定量法および生成機作について
    足立 多平, 神谷 弘子, 小菅 卓夫
    1964 年 84 巻 6 号 p. 545-548
    発行日: 1964/06/25
    公開日: 2010/02/19
    ジャーナル フリー
    As a method for detection of tetramethylpyrazine, use of ultraviolet spectrum was examined. It was assumed that acetoin would be formed as a precursur of tetramethyl-pyrazine from the result of shake culture and a mechanism was presumed for the formation of tetramethylpyrazine in a medium added with acetoin.
  • Tuberostemonineの脱水素反応の研究 その1
    上尾 庄次郎, 新宮 徹朗, 津田 喜典, 大和 譲
    1964 年 84 巻 6 号 p. 548-552
    発行日: 1964/06/25
    公開日: 2010/02/19
    ジャーナル フリー
    The alkaloid tuberostemonine, obtained from Stemona tuberosa L., was dehydrogenated over 40% palladium-asbestos to give, along with small amounts of three crystalline compounds, tuberostemonane, C20H29N, as an oil, the yield of which was raised to 70% by the use of 20% palladium-charcoal as a catalyst under selected conditions. Oxidation of tuberostemonane with chromium trioxide-pyridine complex or with potassium permanganate afforded an orange-red substance, C16H19O2N, whose ultraviolet and infrared spectra indicated that it is an isatin, suggesting that tuberostemonane possesses an indole skeleton.
  • Tuberostemonineの脱水素反応の研究 その2
    上尾 庄次郎, 新宮 徹朗
    1964 年 84 巻 6 号 p. 552-555
    発行日: 1964/06/25
    公開日: 2010/02/19
    ジャーナル フリー
    Comparative dehydrogenation studies on the relationship between the catalyst and the product from tuberostemonine revealed that crystalline dehydrogenation products rather than oily tuberostemonane can best be obtained by the use of a palladium-asbestos catalyst containing a trace of sodium carbonate.
  • Tuberostemonaneの構造
    上尾 庄次郎, 新宮 徹朗
    1964 年 84 巻 6 号 p. 555-561
    発行日: 1964/06/25
    公開日: 2010/02/19
    ジャーナル フリー
    Based on degradative and synthetic investigations, the structure of tuberostemonane, a dehydrogenation product of the alkaloid tuberostemonine, has been shown to be represented by the formula (IX).
  • (+)-チオクト酸アミドの合成
    出口 義雄, 三浦 一子
    1964 年 84 巻 6 号 p. 562-563
    発行日: 1964/06/25
    公開日: 2010/02/19
    ジャーナル フリー
    Levorotatory thioctic acid has biological, activity and the compound has already been synthesized. (+)-Thioctamide was synthesized from (+)-6, 8-dichloroöctanoic acid (I) by the method already reported, using sodium disulfide. Its activity tested by Streptococcus faecalis 10Cl is about twice that of the racemic compound.
  • サイクラミン酸ナトリウムの比色定量における呈色色素について
    市川 正孝, 児島 昭次, 一番ケ瀬 尚
    1964 年 84 巻 6 号 p. 563-566
    発行日: 1964/06/25
    公開日: 2010/02/19
    ジャーナル フリー
    Sodium cyclamate (sodium N-cyclohexanesulfamate) is hydrolyzed in hydrochloric acid, in the presence of hydrogen peroxide, and forms cyclohexylamine. When the concentration of cyclohexylamine in the hydrolysis solution was less than 0.025%, the amine was extracted with chloroform, ethanolic solution of quinhydrone was added to it, and the mixture was warmed at 50° for 2 hours, giving cyclohexylamino-1, 4-benzoquinone (I), m. p. 96-98°. I was also obtained by the use of 1, 4-benzoquinone in place of quinhydrone.
    When the concentration of cyclohexylamine was over 0.25%, excess of manganese dioxide was added to the hydrolysis solution to decompose hydrogen peroxide, the solution adjusted to pH 9.0 with a buffer solution, and ethanolic solution of quinhydrone was added. The mixture was warmed at 50° for 15 minutes, and extracted with chloroform in hydrochloric acidity, by which 2, 5-bis(cyclohexylamino)-1, 4-benzoquinone (II), m. p. 242°, was obtained. II was also obtained by refluxing 2, 5-dimethoxy-1, 4-benzoquinone and cyclohexylamine in ethanol. I and II were identified as the colored substances obtained in the quinhydrone method for identification of sodium cyclomate.
  • 3-Methylthio-4-alkyl-5-[2-(5-nitro-2-furyl)vinyl]-1,2,4-triazoleの合成
    才川 勇
    1964 年 84 巻 6 号 p. 566-569
    発行日: 1964/06/25
    公開日: 2010/02/19
    ジャーナル フリー
    Reaction condition for cyclization of 1-[3-(5-nitro-2-furyl)acryloyl]-4-alkyl-S-methylisothiosemicarbazides (I) leading to 3-methylthio-4-alkyl-5-[2-(5-nitro-2-furyl)vinyl]-1, 2, 4-triazoles (III), was examined. The best method for preparing III was found to be boiling of dioxane solution of I in the presence of an organic acid or a base like acetic acid or piperidine. Physical properties of III are shown in Table I.
  • 山名 月中, 水上 勇三, 市村 藤雄, 古池 宏, 本谷 千枝
    1964 年 84 巻 6 号 p. 570
    発行日: 1964/06/25
    公開日: 2010/02/19
    ジャーナル フリー
  • 1964 年 84 巻 6 号 p. e1a
    発行日: 1964年
    公開日: 2010/02/19
    ジャーナル フリー
  • 1964 年 84 巻 6 号 p. e1b
    発行日: 1964年
    公開日: 2010/02/19
    ジャーナル フリー
  • 1964 年 84 巻 6 号 p. e1c
    発行日: 1964年
    公開日: 2010/02/19
    ジャーナル フリー
  • 1964 年 84 巻 6 号 p. e1d
    発行日: 1964年
    公開日: 2010/02/19
    ジャーナル フリー
  • 1964 年 84 巻 6 号 p. e1e
    発行日: 1964年
    公開日: 2010/02/19
    ジャーナル フリー
  • 1964 年 84 巻 6 号 p. e1f
    発行日: 1964年
    公開日: 2010/02/19
    ジャーナル フリー
  • 1964 年 84 巻 6 号 p. e1g
    発行日: 1964年
    公開日: 2010/02/19
    ジャーナル フリー
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