YAKUGAKU ZASSHI
Online ISSN : 1347-5231
Print ISSN : 0031-6903
ISSN-L : 0031-6903
84 巻 , 10 号
選択された号の論文の26件中1~26を表示しています
  • 津田 恭介, 伊藤 四十二
    1964 年 84 巻 10 号 p. 905-910
    発行日: 1964/10/25
    公開日: 2010/02/19
    ジャーナル フリー
  • 高橋 酉蔵, 藤村 一, 浜島 好男
    1964 年 84 巻 10 号 p. 911-917
    発行日: 1964/10/25
    公開日: 2010/02/19
    ジャーナル フリー
    In order to remove the side effects from N, N-dimethyl-2-(3-camphorylamino) acetamide and N, N-dimethyl-2-[N-(3-camphoryl)-methylamino] acetamide, which have good analgesic action, hydroxyl groups were introduced into the 9- and 10-positions of the camphor ring. The resulting products, N, N-dimethyl-2-[(9-hydroxy-3-camphoryl)amino] acetamide (VII) and N, N-dimethyl-2-[(10-hydroxy-3-camphoryl)amino] acetamide (XIX), and their N-methylated compounds (X and XXVI) were found to have excellent analgesic action with a much lower toxicity. Some examinations were made on the steric configuration of their intermediates, 3-amino-9- and -10-hydroxycamphor (VI and XVIII). In the presence of alkali, XVIII formed 3, 3′-dihydro-bis-(2-borneno) [2, 3-b:2′, 3′-e]pyrazine-10, 10′-diol (XXI), while its acid hydrolysis reverted it to XVIII. Oxidation of XXI gave pyrazine (XXII) while its reduction gave piperazine (XXIII).
  • 高橋 酉蔵, 藤村 一, 浜島 好男
    1964 年 84 巻 10 号 p. 918-929
    発行日: 1964/10/25
    公開日: 2010/02/19
    ジャーナル フリー
    Synthesis of the derivatives of camphoric acid, one of the biological metabolites of camphor, was carried out since 3-amino-9- and 3-amino-10-hydroxycamphor derivatives had less toxicity than 3-aminocamphor. Starting with camphorimide (V), camphorimidoacetic, -2-propionic, and -3-propionic acids (XXVII, XXVIII, XXIX), 20 kinds of their alkylamides, and 6 kinds of N-alkyl- and N-aralkyl-camphorimides were synthesized. Of these, N, N-dimethyl-2-camphorimido-acetamide (XVIII) and -propionamide (XXIV) showed the best analgesic effect.
    Pharmacological tests were made on 24 kinds of alkyl, aralkyl, and acyl derivatives of 3-aza-1, 8, 8-trimethyl-bicyclo [3.2.1] octan-2-one (VI) and 3-aza-1, 8, 8-trimethylbicyclo-[3.2.1] octane (VII), and on newly synthesized 3-dimethyl (or diethyl) aminomethylborneol benzoate (LXXIX, LXXX) but none showed any promising effect.
  • 西村 温樹
    1964 年 84 巻 10 号 p. 930-938
    発行日: 1964/10/25
    公開日: 2010/02/19
    ジャーナル フリー
    Compounds having the structure of 1-phenyl-2-(disubstituted amino) ethylisothiuronium type, such as 1-phenyl-2-dimethylaminopropyl- or -piperidinoethyl- and 1, 2-diphenyl-2-dimethylaminoethyl-isothiouronium salts, undergo deamination when heated in alcohol or water and form vinylisothiouronium type compounds such as 1-phenylpropenyl-, 1-phenylvinyl-, and 1, 2-diphenylvinyl-isothiouronium salts. The decomposition reaction is inhibited by an acid and promoted by a base. Some considerations were made on the mechanism of this decomposition reaction by measuring the deamination rate constant by ultraviolet spectrum or optical rotation.
    Vinylisothiouronium salt derivatives, the product of deamination, were found to be hydrolyzed, easily by alkali but difficultly by acid, to the corresponding ketone compound, such as propiophenone from 1-phenylpropenylisothiouronium salt, and thiourea.
  • 西村 温樹, 高松 秀二
    1964 年 84 巻 10 号 p. 938-943
    発行日: 1964/10/25
    公開日: 2010/02/19
    ジャーナル フリー
    Reaction of 2-aminopropiophenones with phosphorus pentasulfide in toluene and treatment of the toluene-insoluble products with sodium borohydride give 1-phenyl-2-aminopropanes, in which the original carbonyl had been reduced to a methylene group. Treatment of the toluene-insoluble substance in aqueous solution gives phenylacetone. This reaction was found to be common to 2-amino-ketones.
    From this toluene-insoluble substance, enamines were detected, such as 1-phenyl-2-piperidino-1-propene and 2-piperidino-1-cyclohexene, which were identified by infrared spectra and gas chromatography. It was found that these enamines were the intermediate of the above reaction.
  • 西村 温樹, 高松 秀二
    1964 年 84 巻 10 号 p. 944-955
    発行日: 1964/10/25
    公開日: 2010/02/19
    ジャーナル フリー
    1-Amino-2-propanethiol derivatives, 2, 3-diaminopropanethiol derivatives, and some aminothiol derivatives having nitrogen-containing ring were synthesized. 2, 3-Diaminopropanethiol derivatives were obtained by the application of sodium thiosulfate or thiourea to 2-chloro-1, 3-propanediamine derivatives (VI) formed from 1, 3-diamino-2-propanol derivatives (V), to form thiosulfonic acid compounds (VII) or isbthiouronium salts (XI) and their treatment with acid or alkali. Since 1, 2-diaminopropane derivative (X) was obtained from bis (2, 3-diaminopropyl) disulfide (VII) by desulfurization with Raney nickel, application of sodium thiosulfate or thiourea to VI had caused 1, 2-rearrangement reaction. It is probable that aziridinium compund is formed as an intermediate and the reagent attacks the site with less steric hindrance.
    Examination of the reaction between aminoalkylthiosulfonic acid (Bunte salt) and sodium borohydride showed that the corresponding bis (aminoalkyl) disulfide is the main product but in the case of sodium carbamoylmethylthiosulfonate derivative, thiol derivative was formed.
  • 田口 平八郎, 今関 和泉
    1964 年 84 巻 10 号 p. 955-961
    発行日: 1964/10/25
    公開日: 2010/02/19
    ジャーナル フリー
    Base II is a tertiary base obtained from Corydalis ambigua CHAM et SCHLECHT. var. amurensis MAXIM., with m.p. 144-146°, [α]D12±306.0° (CHCl3); (±) form of m.p. 190-191°, and dehydro base (iodide) of m.p. 282° (decomp.). It was assumed to be a protober-berine-type base from its ultraviolet spectrum (Fig. 1). Its nuclear magnetic resonance spectrum (Fig. 2) and analytical values indicated the presence of two methoxyls, one methylenedioxy group, and one methyl bonded to a secondary carbon. Cleavage of methylenedioxy group with phloroglucinol-sulfuric acid followed by methylation with diazomethane gave corydaline (I) (Chart 1), from which it was proved that the methoxyl and methylenedioxy group are situated at 2, 3, 9, and 10-positions, and the methyl group at 13-position. Consequently, base II must be either thalictricavine (VII) or thalictrifoline (VIII), but various properties of base II are not in agreement with those of VII or VIII, as shown in Teble II, and their infrared spectra are different (cf. Fig. 4).
    It was possible that base II is a stereoisomer of VII or VIII, and these compounds were compared in the form of an anhydro base which does not contain any asymmetric carbon atoms. As a result, dehydro-base II agreed with dehydrothalictriflinium iodide (XI) in melting point, Rf, and infrared spectrum (Fig. 5), but not with dehydrothalictricavinium iodide (X). Consequently, it was found that base II has the same planar structure as VIII with different steric configuration. The infrared spectrum (Fig. 6) of base II exhibits abosorption of trans-quinolinidine at 2700cm-1, which is not present in the spectrum of VIII. Dehydration with mercuric acetate showed that base II has a trans-quinolizidine skeleton, while VIII has the cis-quinolizidine skeleton. The dehydro-base II, obtained as the quaternary base, was found to be none other than dehydrothalictrifoline.
  • 岩城 利一郎, 安井 卓三, 三村 明
    1964 年 84 巻 10 号 p. 961-966
    発行日: 1964/10/25
    公開日: 2010/02/19
    ジャーナル フリー
    Detailed examinations were made on the protective action of adrenergic agents, barium agents, histamine agents, and compounds possessing chemical structure related to adrenaline against the irreversible suppressor of alkylation like dibenamine and irreversible antagonistic action of SH inhibitors like mercuric chloride, using the Magnus method employing isolated vascular series of a guinea pig. As shown in Fig. 2, action of 10-6M of dibenzamine against adrenergic receptor was selectively protected by adrenergic agents but the protection of barium chloride and histamine was non-selective. Dibenzamine in 10-4M concentration attacked the receptor of adrenaline, histamine, and barium chloride. There were no substances that showed protective action against the former two, but adrenergic agents and barium agents showed protection against the latter. The action of SH inhibitors like mercuric chloride against adrenergic receptor cannot be considered as specific, from the result of their protective action.
  • 田村 善蔵, 渡辺 光夫, 岩崎 憲太郎, 粕谷 芳代
    1964 年 84 巻 10 号 p. 967-971
    発行日: 1964/10/25
    公開日: 2010/02/19
    ジャーナル フリー
    Structural form of the -+N2 group in 1-diazo-2-naphthol (V) and 2-diazo-1-naphthol (VI), and their 4-sulfonic acids (III and IV) in solid and in water-perchloric acid solution was studied from their infrared and ultraviolet absorption spectra. In the solid state, V and VI took the quinonoid form, and their perchlorate took the diazonium form, while III and IV were in the diazonium form and their metal salts, the quinonoid form. Ultraviolet absorption of the solid form also showed difference of quinonoid and diazonium types.
    Ultraviolet absorption spectra of these compounds were measured in water-perchloric acid solution and acidity of their phenolic hydroxyls was compared from the ratio of the quinonoid and diazonium forms and its relation to the concentration of perchloric acid. It was thereby found that their acidity is much stronger than that of known p-diazophenol (pKa=3.40), their pKa being less than 1. The acidity of these hydroxyls increased in the order of V, III, VI, and IV.
  • 山名 月中, 古池 宏, 水上 勇三, 本谷 千枝, 院瀬見 義弘
    1964 年 84 巻 10 号 p. 971-973
    発行日: 1964/10/25
    公開日: 2010/02/19
    ジャーナル フリー
    By the technique of counter current distribution method, an intermediate product of the degradative reaction of chlorothiazide in alkaline solution was isolated. The chemical structure of this product was clarified as N-(2-amino-4-chloro-5-sulfamoylphenylsulfonyl)-formamide. This reaction appears to go through this compound as the only degradative intermediate.
  • 山名 月中, 水上 勇三, 市村 藤雄, 古池 宏
    1964 年 84 巻 10 号 p. 974-976
    発行日: 1964/10/25
    公開日: 2010/02/19
    ジャーナル フリー
    A simplified method for the calculation of the rate constants for the first-order reaction of scheme D←A⇔B→C, from experimental data, has been studied. From the determination of rate constants for the degradative reaction of chlorothiazide in alkaline solution, a possible formulation of this reaction was concluded according to this method.
  • 佐々木 正, 兼松 顕, 大瀬 誠子
    1964 年 84 巻 10 号 p. 977-983
    発行日: 1964/10/25
    公開日: 2010/02/19
    ジャーナル フリー
    Some diphenyl derivatives were visualized, imitating the A and C rings in the morphine skeleton with the C ring substituted with a phenyl group, as shown in Table I. On the assumption that the angle of A and C rings is necessary for these compounds to show analgesic action by their contact with the cells in the action site, examinations were made for the syntheses of 9-substituted 9, 10-dihydrophenanthrene and 5-substituted 9, 10-dihydro-5H-dibenzo [a, b] cycloheptene.
    1) 9, 10-Dihydro-9-phenanthrenecarboxylic acid (IV) was obtained in a good yield by the reduction of 9-phenanthrenecarboxylic acid (X) with sodium amalgam. Curtius reaction of the azide of IV afforded ethyl 9, 10-dihydro-9-phenanthrenecarbamate (XIV) but this substance was extremely labile and underwent decomposition on being left at room temperature to form phenanthrene. The acid amide compounds (XVII and XVIII) of IV were stable.
    2) Reaction of 5-amino-10, 11-dihydro-5H-dibenzo [a, b] cycloheptene (XXII) with methyl iodide in the presence of alkali gave 5-dimethylamino compound (XXIII). Amination of 10-bromo compound (XXV) was attempted in order to obtain 10-dimethylamino compound but the product was found to be 5H-dibenzo [a, b] cyclohepten-5-one (XXVI).
  • 加来 天民, 久保田 和彦, 村上 元, 浅田 泉
    1964 年 84 巻 10 号 p. 983-988
    発行日: 1964/10/25
    公開日: 2010/02/19
    ジャーナル フリー
    3-Substituted 2-benzoxazolinone and 2-substituted thiobenzoxazole, in which the substituent was piperidinoethyl or diethylaminoethyl, were synthesized and their pharmacological action was comparatively examined. These compounds showed similar activity and had local anesthetic action equal to or better than procaine. Both compounds have but weak anticonvulsant and antihistamine actions. These compounds depressed the blood pressure of a rabbit without affecting its respiration but this action was not affected by pretreatment with atropine.
  • 金子 秀彦, 中村 清, 永井 保嵩
    1964 年 84 巻 10 号 p. 988-992
    発行日: 1964/10/25
    公開日: 2010/02/19
    ジャーナル フリー
    By the Grignard reaction of cotarnine hydriodide (IV) or by the condensation of cotarnine (II) with acetophenone derivative and subsequent reactions shown in Chart 2, 1-benzyl- and 1-phenethylhydrocotarnine derivatives were prepared. Condensation of α, β-unsaturated ketone and cyclization with mineral acid afforded 1, 3, 4, 6, 7, 11b-hexahydro-2H-benzo[a]quinolizin-2-one methobromides (XXII and XXIII), as shown in Chart 3.
  • 藤川 福二郎, 平井 邦夫, 中谷 義煕, 今西 きぬ子, 内藤 益一, 津久間 俊次
    1964 年 84 巻 10 号 p. 993-998
    発行日: 1964/10/25
    公開日: 2010/02/19
    ジャーナル フリー
    A total of 93 kinds of compound were synthesized in order to clarify the relationship between the chemical structure of phenylthiourea derivatives and their antibacterial action against human-type tubercle bacilli H37Rv.
    1) Carboxyl group introduced into the benzene ring, irrespective of their position of ortho, meta, or para, does not show any antibacterial activity.
    2) Esteriflcation of the carboxyl group introduced into the benzene ring showed no antibacterial action when a substituent is in the ortho-position, when R in R-NH-CSNH COOEt is an aryl, but showed antibacterial action when the substituent is in the para-position and when R is an alkyl group, although no great difference in the antibacterial action was observed with increasing number of carbon atoms in the alkyl group from 3, 4, to 6.
    3) Thiocarbanilide with substituents in para- and para-prime positions showed antibacterial activity, while those with substituents in the two ortho or ortho and meta-prime positions had no such activity. Although the number of compounds examined was small, those with substituents in ortho and para-prime, two meta positions, or meta and para-prime positions seem to acquire antibacterial activity.
    4) Some of the compounds of R-NHCSNH- show antibacterial activity according to the kind and position of the substituent R′, although no great difference was found by the change of carbon number from 3, 4, to 6 in the alkyl group R.
    5) Phenylthiourea derivatives have no cross-resistance with INAH, PAS, or streptomycin.
  • 中垣 正幸, 古賀 直文, 岩田 修造, 寺田 弘
    1964 年 84 巻 10 号 p. 998-1003
    発行日: 1964/10/25
    公開日: 2010/02/19
    ジャーナル フリー
    According to the results that the scattered light at the direction of 45° had two maximum points, the soluble protein of crude cortex was fractionated into three fractions; αa (precipitate at pH 5.5), αb (precipitate at pH 5.0 after αa was removed), and βc (supernatant after αa and αb were removed). The chromatographic pattern from DEAR-cellulose, electrophoresis diagram, and sedimentation diagram of each fraction were also studied.
  • 湊 顕, 小木曾 健人
    1964 年 84 巻 10 号 p. 1003-1008
    発行日: 1964/10/25
    公開日: 2010/02/19
    ジャーナル フリー
    In order to examine the biochemical activity of copper, copper-casein was prepared by the following two methods.
    1) 2% Copper sulfate solution was reacted with 2% casein solution, while keeping the solution at pH 9.5 with the addition of sodium hydroxide, and the mixture was allowed to stand at room temperature for 12 hours. In order to remove unreacted copper, isoelectric point (pH 4.8) precipitation was repeated twice and purified copper-casein was obtained.
    2) Electrolysis was carried out in an electrolytic cell divided into four compartments with three porcelain plates (Fig. 1), with casein solution placed in A, copper sulfate in B, and water in C and D, with direct current of 100 v.
    Copper content of copper-casein thus obtained was 0.74% by the first method and 0.54% by the second method.
    Bonding of casein and copper was examined by spectrophotometry and by the equilibrium dialysis method. It was found that the affinity of casein to copper increased with increasing pH and absorption maximum of copper-casein shifted to the lower wave-length side. Increase in bound copper per mole of casein with increasing pH was found around pH 5.8 by the dialysis method. Increase in bound copper with dissociation of carboxyl group can be considered but changes in the absorption spectrum and dissociation constants suggested that groups other than carboxyl, such as amino and imidazole, took part in the binding of copper.
  • 掛見 喜一郎, 有田 隆一, 端(旧横田) 幹子
    1964 年 84 巻 10 号 p. 1009-1012
    発行日: 1964/10/25
    公開日: 2010/02/19
    ジャーナル フリー
    Ultraviolet absorption spectra of 5-iodo-2′-deoxyuridine (IDU) and its decomposition products, 5-iodouracil (IU), 2′-deoxyuridine (DU), and uracil (U), show different absorption maxima according to changes in the reaction of the solution. This nature was utilized in the separatory determination of IDU and IU without the interference of DU and U. The procedure is as follows:
    TO 4ml. of the sample solution, 1ml. of buffer solution (pH 5) is added and absorbancy of this solution is measured at 290mμ. Another 4ml. of the sample solution, added with 1ml, of buffer solution (pH 11.5), is measured at 310mμ. Concentration of IDU and IU is calculated from these two observed values. Optimal concentration of the sample is 5-25γ/ml. of IDU and 4-20γ/ml. of IU. Standard deviation of the values was σ±0.62% (n=11).
    Determination of IDU in an ointment is carried out by dissolving the sample in chloroform, and IDU and IU extracted with water, using this aqueous extract as sample solution.
  • 須山 正, 金尾 清造
    1964 年 84 巻 10 号 p. 1012-1014
    発行日: 1964/10/25
    公開日: 2010/02/19
    ジャーナル フリー
    3-Methylthiopropylamine, obtained by decarboxylation of DL-methionine with tetralin, showed the same boiling point as that of the sample obtained by Schneider and agreed in the boiling point of the base and melting point of the hydrochloride of the sample obtained by following the method of Akabori, Kaneko, and others. The product was obtained in 90% yield. 3-Nitrotyramine, obtained by decarboxylation of 3-nitro-L-tyrosine, and its hydrochloride showed the same melting point as that of the sample obtained by nitration of tyramine by Waser. 4-Methoxyphenethylamine, obtained from L-tyrosine methyl ether by the same method, was identical with the sample synthesized by the Rosenmund method and was identified by mixed fusion with the reduction product of β-nitro-4-methylstyrol with lithium aluminum hydride.
  • 須山 正, 金尾 清造
    1964 年 84 巻 10 号 p. 1014-1016
    発行日: 1964/10/25
    公開日: 2010/02/19
    ジャーナル フリー
    N-Methylphenethylamine was obtained by the decarboxylation of N-carboxymethyl-L-phenylalanine or N-methyl-L-phenylalanine. Decarboxylation of N-carboxymethyl-L-leucine or N-methyl-L-leucine gave N-methylisopentylamime. N-Methyltyramine obtained by the decarboxylation of N-carboxymethyltyramine was identical with that obtained by Goldschmidt from N-methyl-L-tyrosine.
  • 入倉 勉, 鈴江 清吾
    1964 年 84 巻 10 号 p. 1017-1021
    発行日: 1964/10/25
    公開日: 2010/02/19
    ジャーナル フリー
    In order to examine the hypoglycemic action of the compounds, 1, 1-dialkyl- and 1, 1-alkylene-4-arylsulfonylsemicarbazides, 1, 1′-alkylenebis(3-p-chlorobenzenesulfonylureas), 1-arylsulfonyl-3-bicycloureas, fluorene-substituted ureas, and 3-substituted 1-diphenyl-methoxyethylsulfonylureas were synthesized.
  • 鈴江 清吾
    1964 年 84 巻 10 号 p. 1021-1023
    発行日: 1964/10/25
    公開日: 2010/02/19
    ジャーナル フリー
    The structure of N1-(5-alkyl-1, 3, 4-thiadiazol-2-yl- or 1, 3, 4-oxadiazol-2-yl)sulfonilamide, known as the hypoglycemic substance, is similar to 1-acyl-4-arylsulfonylsemicarbazide or 1-alkyl-6-arylsulfonylbiurea, and compounds of the latter series were synthesized in order to test their hypoglycemic action.
  • 鈴江 清吾
    1964 年 84 巻 10 号 p. 1024-1026
    発行日: 1964/10/25
    公開日: 2010/02/19
    ジャーナル フリー
    Arylsulfonylureas are known to have a hypoglycemic action. Since this kind of compound is similar to 2H-1, 2, 4-benzothiadiazin-3(4H)-one 1, 1-dioxide in structure, these compounds were synthesized in order to test their hypoglycemic action. The compounds synthesized were 4-alkyl sulfonylureas and 7-[(1-pyrrolidinyl)sulfonyl]ureas.
  • 富田 真雄, 古川 宏
    1964 年 84 巻 10 号 p. 1027-1029
    発行日: 1964/10/25
    公開日: 2010/02/19
    ジャーナル フリー
    Following the previous work on the synthesis of the antipode of isotrilobine (VI) from the antipode (N-methyl-dihydroepistephanine-B) of O-methylrepandine (II), O-methylanhydrodemethylrepandine (VI) was synthesized from repandine (III), obtained by the treatment of oxyacanthine (I) with dilute hydrochloric acid, by demethylation with hydrogen bromide in acetic acid solution, dehydrative cyclization with saturated aqueous solution of hydrogen bromide, and subsequent O-methylation. The infrared spectrum (chloroform) of this free base (VI) was in complete agreement with that of natural isotrilobine. Its picrate of m. p. 188-190°, [α]D14+200° (Me2CO), was identified with isotrilobine picrate through infrared spectrum (KBr) (cf. Table I).
  • 富田 真雄, 岡本 靖子
    1964 年 84 巻 10 号 p. 1030-1031
    発行日: 1964/10/25
    公開日: 2010/02/19
    ジャーナル フリー
    Dauricine (I), the alkaloid of Menispermum dauricum DC. (Japanese name “Kohmori-kazura”), has not been isolated in crystalline form and had been obtained as methiodide or perchlorate crystals. In the present series of experiment, dauricine was obtained as a chloroform adduct, forming colorless prismatic crystals of m.p. 100-103°, [α]D16-129.5° (MeOH), C38H44O6N2⋅CHCl3, in a pure state.
  • 塩谷 俊作, 三橋 監物
    1964 年 84 巻 10 号 p. 1032-1035
    発行日: 1964/10/25
    公開日: 2010/02/19
    ジャーナル フリー
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