YAKUGAKU ZASSHI
Online ISSN : 1347-5231
Print ISSN : 0031-6903
ISSN-L : 0031-6903
81 巻 , 4 号
選択された号の論文の36件中1~36を表示しています
  • 富田 真雄, 渡辺 恭男, 富田 真次, 古川 宏
    1961 年 81 巻 4 号 p. 469-473
    発行日: 1961/04/25
    公開日: 2010/02/19
    ジャーナル フリー
    Alkaloidal components of domestic lotus (Nelumbo nucifera GAERTN.) were examined. Alkaloids were found in the leaves, petiole, and cotyledons in the fruit but not in the edible rhizome. All the alkaloids found are in a free state and dissolve in organic solvents, there being no presence of water-soluble quaternary bases. Roemerine (II) and nuciferine (I) were isolated as the tertiary, non-phenolic bases, and a new base, nornuciferine (III), as the tertiary phenolic base, from the leaves. Roemerine (II) and nornuciferine (III) were isolated from the petiole but not nuciferine (I) (cf. Table I). These experimental results indicated that the main alkaloids of lotus are all tertiary bases of the aporphine type.
  • 百瀬 勉, 合屋 周次郎
    1961 年 81 巻 4 号 p. 474-478
    発行日: 1961/04/25
    公開日: 2010/02/19
    ジャーナル フリー
    The structure, absorption spectrum, and stability of copper chelate compounds of 5-hydroxy-6-aryl-1, 4-naphthoquinone were examined. The copper chelates consisted of 1 atom of copper and 2 moles of 5-hydroxy-6-acyl-1, 4-naphthoquinone, and had the structure shown in Table II. The chelates were soluble in organic solvents such as ether, acetone, benzene, and chloroform, but less soluble in ethanol and insoluble in water. They had the absorption maxima at 530-532mμ in their visible spectra, whereas the corresponding quinones had the maxima at 414 and 330-334mμ.
    The chelates were labile in aqueous ethanol solution and became stable with increasing concentration of ethanol. The order of their stability was 4<10<9<7, 8<5, 6 in 99% ethanol and 10<9<4<8<7<6<5 in 90% ethanol in respect to the carbon number of the aryl group in the side chain.
  • 長岡 達
    1961 年 81 巻 4 号 p. 479-483
    発行日: 1961/04/25
    公開日: 2010/02/19
    ジャーナル フリー
    1) Bromination of 3-vinyl-4-chloroquinaldine compounds (I) with 1 mole of bromine affords 3-(1, 2-dibromoethyl)-4-chloroquinaldine compounds (II) with bromine addition on the vinyl group.
    2) Further bromination of (II) results in bromine substitution of the methyl group and 2-bromomethyl-3-(1, 2-dibromomethyl)-4-chloroquinoline compounds (VII) are formed.
    3) Further bromination of the methyl group in (VIII) was attempted but 2-tribromomethyl compound was not formed.
    4) (II) was further derived to pyrrolo [2, 3-c] quinaldine, furo[2, 3-c]quinaldine, 2, 3-dihydro-3-hydroxy[3, 2-c]quinaldine, and tribromocyclopenta[b]quinoline compounds.
  • 長岡 達
    1961 年 81 巻 4 号 p. 484-489
    発行日: 1961/04/25
    公開日: 2010/02/19
    ジャーナル フリー
    Application of one mole of bromine to 4-chloro-2-methyl-3-vinyl-8-quinolinol (I) in a suitable solvent results in stepwise bromination, each product precipitating out as crystals insoluble in the solvent.
    1) (I) forms a monobromo compound, 5-bromo-4-chloro-2-methyl-3-vinyl-8-quinolinol (II), in glacial acetic acid solution.
    2) (II) forms 5, 7-dibromo compound (V) in chloroform.
    3) (V) forms a tetrabromo compound, 3-(1, 2-dibromoethyl)-5, 7-dibromo compound (VIII) in carbon tetrachloride solution.
    4) (VIII) forms a hexabromo compound, 2-dibromomethyl-3-(1, 2-dibromoethyl)-5, 7-dibromo compound (IX) in chloroform solution.
    5) Further bromination of the methyl group in (IX) was attempted but 2-tribro-methyl compound was not produced.
  • 亀谷 富士夫
    1961 年 81 巻 4 号 p. 489-491
    発行日: 1961/04/25
    公開日: 2010/02/19
    ジャーナル フリー
    Analysis of pyridine, 2-picoline, piperidine, and 2-pipecoline by gas chromatography was examined. Specific retention volume of each base to pyridine was measured in each column of triethanolamine, diethanolamine, Silicone 550, and liquid paraffin. It was found that one of the columns by itself could not separate the foregoing four bases. Approximately complete separation of these four kinds of bases was effected by connection of 3-m. column of triethanolamine or diethanolamine and 1.5-m. column of Silicone 550 in series, with the column temperature of 120°. In accordance with the proposal of Jones and Kieselbach, relative peak separation, relative peak sharpness, and resolution of this combined column were calculated.
  • 赤木 満洲雄, 青木 勇
    1961 年 81 巻 4 号 p. 492-495
    発行日: 1961/04/25
    公開日: 2010/02/19
    ジャーナル フリー
    Antioxidant action was examined with 5 kinds of 3-(alkylthio)propionic acid, 6 kinds of its oxidation product, 8 kinds of 3-(arylthio)propionic acid, 9 kinds of its oxidation product, 5 kinds of mercaptal, 4 kinds of 4-thiol derivatives of butyric acid, and 6 kinds of ω-alkoxy derivatives of lower fatty acids, using high-unit vitamin A codliver oil as the substrate. For the sake of comparison, synergistic action of α-tocopherol was tested with commercial propyl gallate (PG) and nordihydroguaiaretic acid (NDGA). 3-Thiol derivatives of propionic acid indicated antioxidant effect against vitamin A but their oxidation products were all ineffective, the activity descending in the order -S-, -SO-, and -SO2-. All the ω-alkoxy derivatives of lower fatty acids were ineffective, as were also 4-thiol derivatives of butyric acid, although 3-thiol derivative of propionic acid alone was effective. All mercaptal derivatives were effective and α-tocopherol intensified the potency of samples. Antibacterial tests of these compounds showed them to be all ineffective.
  • 北沢 豊吉, 内藤 正之, 吉田 富佐男, 丸山 昌子
    1961 年 81 巻 4 号 p. 496-498
    発行日: 1961/04/25
    公開日: 2010/02/19
    ジャーナル フリー
    Separatory determination of methyltestosterone and ethisterone in mixed hormone tablet containing methyltestosterone, ethisterone, and ethynylestradiol was examined. For their separation, column chromatography was employed, the benzene solution of the hormones was passed through a column of alumina and the column was eluted with a mixture (9:91) of acetone-benzene to desorb methyltestosterone. Ethisterone was desorbed by elution with ethanol-benzene (30:70) mixture. The hydroquinone-Kober method (HK method) was used for the determination of methyltestosterone and ethisterone was determined by colorimetry, using sulfuric acid-ethanol mixture (9:10 by volume). The amount of ethynylestradiol was so small that it failed to react with the coloring reagent and did not interfere in this determination.
  • 宇野 豊三, 安田 博幸, 近藤 尚志
    1961 年 81 巻 4 号 p. 499-502
    発行日: 1961/04/25
    公開日: 2010/02/19
    ジャーナル フリー
    Colorimetric determination of cycloserine is made by addition of phosphotungstic-phosphomolybdic acid reagent (the so-called Folin-Ciocalteu's reagent) to the aqueous solution of cycloserine, basification of this solution with sodium carbonate, and measurement of the optical density of the resultant blue solution at 770mμ. The concentration of cycloserine is calculated from the regression equation. The value obtained by this method was found to agree well with those obtained by biological assay and by ultraviolet absorption method.
  • 久保田 晴寿, 秋田 正
    1961 年 81 巻 4 号 p. 502-506
    発行日: 1961/04/25
    公開日: 2010/02/19
    ジャーナル フリー
    Heating of benzenesulfonyl chloride (I) and hydrazine hydrate in ethanol results in the formation of benzenesulfinic acid (IV), while the use of diethylene glycol as a solvent and heating at 180-200° gave diphenyl disulfide (VT) in a good yield, accompanied with a small amount of thiophenol (VII). Various reaction conditions were examined for this reaction and the reaction was assumed to proceed by the route shown in Chart 1. The low yield of (VII) is probably due to the formation of (VI) from (VII) by autoxidation by the alkalinity of hydrazine. The reaction of hydrazine with diphenyl sulfone, diphenyl disulfone, benzenesulfonic acid, and benzenesulfonamide resulted in the reduction of diphenyl disulfone alone to (VI) and others were not reduced. (VI) was also obtained when (I) was reacted with methyihydrazine and phenylhydrazine instead of hydrazine hydrate.
  • 久保田 晴寿, 秋田 正
    1961 年 81 巻 4 号 p. 507-511
    発行日: 1961/04/25
    公開日: 2010/02/19
    ジャーナル フリー
    The new method of synthesis reported in the previous paper of this series*1 was applied to alkane-, aralkane-, and arene-sulfonyl chlorides and the objective disulfides were obtained. In general, the yield of disulfide was good from arenesulfonyl chloride but in the case of o-tolyl o-toluenesulfonyl chloride, a fairly large amount of insufficiently reduced o-tolyl o-toluenesulfonthiolate was produced. In arenesulfonyl chloride with a nitro group, the reduction progressed to produce the amino compound and further to thiol compound, but the presence of halogen and carboxyl did not affect the reaction, respective disulfide being produced. In the case of phenylmetha-nesulfonyl chloride, the reaction differed according to reaction conditions and the reaction at a high temperature was found to effect desulfurization-decomposition of the disulfide produced. This method is thought to be a reduction method which can be applied to a wide range according to reaction conditions.
  • 久保田 晴寿, 秋田 正
    1961 年 81 巻 4 号 p. 511-515
    発行日: 1961/04/25
    公開日: 2010/02/19
    ジャーナル フリー
    The method for synthesis of disulfides reported in an earlier paper*1 was applied to 2-, 3-, and 4-pyridinesulfonyl chloride and 3-, 4-, 5-, 6-, and 8-quinolinesulfonyl chloride. It was thereby found that sulfonyl chlorides of these heterocyclic compounds, with the exception of 4-pyridinesulfonyl chloride, were all reduced to the corresponding disulfides. 4-Pyridinesulfonyl chloride produced 4, 4′-thiodipyridine alone and not 4, 4′-dithiodipyridine. 3- and 4-Quinolinesulfonyl chloride were prepared by passage of chlorine through conc. hydrochloric solution of the corresponding quinolinethiols.
  • 久保田 晴寿, 秋田 正
    1961 年 81 巻 4 号 p. 515-518
    発行日: 1961/04/25
    公開日: 2010/02/19
    ジャーナル フリー
    Antibacterial action was examined in dithiodipyridines, dithiodiquinolines and their quaternary salts, and pyridine- and quinolinethiols against Staphylococcus aureus, Streptococcus hemolyticus S-8, Escherichia coli, Shigella flexneri, and Candida albicans. Minimum inhibitory concentration of these compounds was around 50γ/cc. and none indicated the anticipated antibacterial activity.
  • 秋田 正
    1961 年 81 巻 4 号 p. 518-521
    発行日: 1961/04/25
    公開日: 2010/02/19
    ジャーナル フリー
    Application of hydrazine hydrate to fluorescein, at ordinary and high temperature, afforded a compound of m.p. 280°(decomp.), the same as that obtained by Orndorff. Assuming that fluorescein takes the p-quinone type under these reaction conditions, six kinds of structural formula were assumed for the reaction product. From the reactivity of hydrazine hydrate, synthesis of fluorescein hydrazide and various derivatives, and from infrared absoption spectrum, this compound was considered to be a fluorescein hydrazide and its structure was established. A compound thought to be fluorescein imide was prepared by deamination and the presence of an amino group was confirmed.
  • 久保田 晴寿, 秋田 正
    1961 年 81 巻 4 号 p. 521-526
    発行日: 1961/04/25
    公開日: 2010/02/19
    ジャーナル フリー
    By heating phenolphthalein and hydrazine hydrate in diethylene glycol, two kinds of crystalline product, (A) of m. p. 266-267° and (B) of m. p. 255-256°, were obtained. (B) alone was obtained when phenolphthalein was allowed to stand with hydrazine hydrate at ordinary temperature or when warm hydrazine hydrate was added. The structure of these two substances was determined through the preparation of their derivatives and from their infrared and ultraviolet absorption spectra.
  • 安江 政一, 加藤 義成
    1961 年 81 巻 4 号 p. 526-528
    発行日: 1961/04/25
    公開日: 2010/02/19
    ジャーナル フリー
    A new glycoside, lyoniside, C27H36O12⋅5H2O, was extracted in 0.28% yield from the intact wood of Lyonia ovalifolia var. elliptica. Methylation followed by hydrolysis of lyoniside furnished lyoniresinol dimethyl ether and xylose. The wood also contained toxic substance found in several kinds of the Ericaceae plants and one was isolated as impure crystals of m. p. 225-235°.
  • 安江 政一, 加藤 義成
    1961 年 81 巻 4 号 p. 529-532
    発行日: 1961/04/25
    公開日: 2010/02/19
    ジャーナル フリー
    Methylation followed by hydrolysis of lyoniside (I) affords xylose and lyoniresinol dimethyl ether (II), C24H32O8. Oxidation of (II) with chromium trioxide in glacial acetic acid gave 2, 6-dimethoxy-p-benzoquinone while the same oxidation in pyridine gave two kinds of γ-lactone with the same molecular composition. The latter lactones indicated the presence of asymmetrically substituted 1, 4-butylene glycol. Oxidation of (II) with potassium permanganate in pyridine and decarboxylation of the acid (V), m. p. 187°, C20H22O9, so obtained gave 2, 3, 3′, 4′, 5′-hexamethoxybenzophenone (VI), which was identified by admixture with the compound prepared by a different route. Treatment of (I) with p-nitrobenzenediazonium chloride and methylation of the dye so obtained gave 3, 4, 5-trimethoxy-4′-nitroazobenzene (VII), which was identified with the compound obtained by the same treatment of syringic acid. These results indicate that (I) is a 5-substituted pyrogallol 1, 3-dimethyl ether. (II) possesses two alcoholic hydroxyls but no phenolic hydroxyl, and xylose must have been attached to one of them. Formula (I) is therefore proposed for lyoniside from the foregoing chemical evidences and from biosynthetic consideration.
  • 増田 克忠
    1961 年 81 巻 4 号 p. 533-536
    発行日: 1961/04/25
    公開日: 2010/02/19
    ジャーナル フリー
    Application of ketonic reagents such as hydroxylamine, thiosemicarbazide, hydrazine, and phenylhydrazine, at room temperature to the aqueous solution of thiamine base, obtained from thiamine hydrochloride and 2 molar equivalents of alkali hydroxide, affords, with evolution of hydrogen sulfide, desulfurized products, corresponding to the oxime (V), thiosemicarbazone (VII), and phenylhydrazone (VIII) of thioketone. Reaction with hydrazine produced the base itself and the reaction with phenylhydrazine (XIV) and (X), produced by derivation of (VIII) to its salt and cyclization with liberation of one mole of water. Thiamine homolog (II) also underwent the same reaction and the reaction of thiamine and isonicotinic acid hydrazine afforded similar desulfurized product (XXI).
  • 増田 克忠
    1961 年 81 巻 4 号 p. 536-540
    発行日: 1961/04/25
    公開日: 2010/02/19
    ジャーナル フリー
    Application of ammonia to aqueous solution of thiamine base at room temperature results in desulfurization-substitution reaction with evolution of hydrogen sulfide, as reported in the preceding paper. Identity of this product with 1-[(2-methyl-4-amino-5-pyrimidinyl)methyl]-4-(2-hydroxyethyl)-5-methylimidazole (III) was clear from its chemical properties and the identity of the product (VII) from the thiamine homolog, 3-[(2-methyl-4-amino-5-pyrimidinyl)methyl]-4, 5-dimethylthiazolium chloride (VI), by its similar reaction with ammonia, with the product obtained from 2-methyl-4-amino-5-bromomethylpyrimidine salt (IV) and 4, 5-dimethylimidazole (VIII). However, the product obtained by Erlenmeyer and others from (IV) and 4-(2-hydroxyethyl)-5-methylimidazole (V) was not identical with (III) and it was considered that there is a possibility that a position isomer (III′) would be produced in nonsymmetric imidazole like (V). Therefore, synthesis of (III′) was carried out by the route shown in Chart 2.
  • 増田 克忠
    1961 年 81 巻 4 号 p. 540-544
    発行日: 1961/04/25
    公開日: 2010/02/19
    ジャーナル フリー
    Application of aliphatic primary amines to aqueous solution of the thiamine base at room temperature was found to effect desulfurization-substitution, as in previous work, to produce N-(1-methyl-2-alkylamino-4-hydroxy-1-butenyl)-N-[(2-methyl-4-amino-5-pyrimidinyl)methyl]formamide (III) (cf. Table I) and its salt was found to be 1-[(2-methyl-4-amino-5-pyrimidinyl)methyl]-4-(2-hydroxyethyl)-5-methylimidazolium salt (IV) (cf. Table II). This reaction did not take place with aromatic amines, secondary, or tertiary amines, and only thiothiamine and 2, 7-dimethyl-5, 6-dihydro-8-(2-hydroxyethyl)-6-formyl-9H-pyrimido[4, 5-e]-1, 4-diazepine were chiefly produced, as in the application of alkalis. Such conversion of thiazolium to imidazolium was not limited to thiamine and was also effected in 3-benzyl-4-methyl-5-(2-hydroxyethyl)-thiazolium salt (V).
  • 増田 克忠
    1961 年 81 巻 4 号 p. 544-548
    発行日: 1961/04/25
    公開日: 2010/02/19
    ジャーナル フリー
    Thiol-type thiamine forms a desulfurization-substitution product (II) by reaction with acetamidine but this reaction does not take place with guanidines due to their strong alkalinity and the product formed was a new compound, Substance X, C16H26O3N4S, obtained by application of 4 molar equivalents of sodium hydroxide to the thiamine salt (I). Application of 2-3 molar equivalents of sodium hydroxide to (I) produces thiothiamine or diazepine compound (III) and it is interesting that the reaction of (I) differs so markedly by the difference in the quantity of alkali. This chemical reaction was examined in thiazolium compounds other than thiamine and a compound of the same system as Substance X was found to be formed from thiazolium compounds with 2-hydroxyethyl group in 5-position by the action of strong alkali. Substance X is formed almost quantitatively by alkaline reaction of the diazepine compound (III) and 3-mercapto-5-hydroxy-2-pentanone (X).
  • 増田 克忠
    1961 年 81 巻 4 号 p. 549-554
    発行日: 1961/04/25
    公開日: 2010/02/19
    ジャーナル フリー
    The new compound, Substance X, formed from thiamine hydrochloride and 4 molar equivalents of sodium hydroxide, forms an N-acylated compound by introduction of acyl group into the amino group in 4-position of the pyrimidine ring by acylation. It is decomposed into 2-methyl-4-amino-5-pyrimidinylmethanesulfonic acid (VIII) and Substance Y (C10H17O2NS) by the action of sodium sulfite, and Substance Y forms an N-monoacetate by acetylation. The structure of Substance X was assumed to be 2-(2-hydroxyethyl)-3-hydroxy-3, 4a-dimethyl-4-[(2-methyl-4-amino-5-pyrimidinyl)-methyl]perhydrofuro[3, 2-b]-1, 4-thiazine (IX) from the fact that it is produced quantitatively from the diazepine compound (II) and α-mercapto-ketone compound (III) in the presence of alkali, some thiazole compounds possessing 2-hydroxyethyl group in 5-position have tendency to undergo facile cyclization to a tetrahydrofuran ring, and from other reactions. Consequently, formula (X) is proposed for the Substance Y and (XI) to its monoacetylated compound. The dihydro compound obtained by reduction of Substance X would be given the formula (XII) and its acetylation products would be (XIII) and (XIV). Docomposition of (XII) with sulfite would give (VIII) and (XV), and acylation of (XV) would produce (XVI). Attempted preparation of (IX) by deformylation of (XIX) was not effected.
  • 中込 孟也
    1961 年 81 巻 4 号 p. 554-557
    発行日: 1961/04/25
    公開日: 2010/02/19
    ジャーナル フリー
    Nitration of 3-methoxypyridazine 1-oxide afforded three kinds of product. One was a molecular compound of 3-methoxypyridazine 1-oxide and 3-methoxy-4-nitropyridazine 1-oxide, and the others were 3-methoxy-6-nitropyridazine 1-oxide and 3-methoxy-6-nitropyridazine. The molecular compound was separated into its componental parts by treatment with an acid or by adsorption chromatography over alumina or Florisil.
  • 中沖 太七郎, 森田 直賢, 伊勢谷 篤弘
    1961 年 81 巻 4 号 p. 558-559
    発行日: 1961/04/25
    公開日: 2010/02/19
    ジャーナル フリー
    Extraction of fresh leaves of Lonicera japonica THUNB. with methanol and treatment of the methanolic extract with lead acetate afforded pale yellow microneedles, m.p. 218°, [α]D19 -83.5°, C27H30O15⋅2H2O, in 0.01% yield. This substance was named lonicerin. Hydrolysis of lonicerin with 5% sulfuric acid gave luteolin, rhamnose, and glucose. Permethylation of lonicerin followed by hydrolysis afforded 3′, 4′, 5-tri-O-methylluteolin. It follows, therefore, that the sugar is bonded at the 7-position and that lonicerin is luteolin 7-rhamnoglucoside.
  • 古川 清太郎, 相馬 信夫
    1961 年 81 巻 4 号 p. 559-565
    発行日: 1961/04/25
    公開日: 2010/02/19
    ジャーナル フリー
    A component of the essential oil, obtained from the root of Aristolochia debilis SIEB. et Zucc., named aristolone, was assigned the molecular formula of C15H22O. Its catalytic, Wolff-Kischner, and lithium aluminium hydride reduction respectively afforded dihydroaristolone, C15H24O, deoxoaristolone, C15H24, and aristolol, C15H24O. Examination of the absorption spectra of these products suggested the presence of a double bond on one side and cyclopropane ring on the other side, conjugated with the ketone group in aristolone. Dehydrogenation of aristolone afforded 5-methyl-2-naphthol, while that of deoxoaristolone and aristolol gave 1-methylnaphthalene. It was thereby found that aristolone has a hydronaphthalene skeleton, that the ketone group is in its 2-position, and one methyl group is in 5-position. From these data, formula (VIII) or (IX) is proposed as the partial structure for aristolone.
  • 古川 清太郎, 小山田 浩三, 相馬 信夫
    1961 年 81 巻 4 号 p. 565-570
    発行日: 1961/04/25
    公開日: 2010/02/19
    ジャーナル フリー
    Permanganate oxidation of aristolone and deoxoaristolone, obtained by its Wolff-Kishner reduction, gave aristoic acid, C15H20O5. Treatment of aristoic acid with mineral acid afforded a kind of phenolic carboxylic acid, C11H14O3, which was assumed to be a m-hydroxybenzoic acid derivative possessing methyl and isopropyl groups, by the determination of C-methyl group and absorption spectra. Based on this assumption, 3-isopropyl-5-hydroxy-o-toluic. acid was synthesized from 2-isopropyl-4-nitrotoluene and identity of the foregoing phenolic carboxylic acid was established.
  • 古川 清太郎
    1961 年 81 巻 4 号 p. 570-573
    発行日: 1961/04/25
    公開日: 2010/02/19
    ジャーナル フリー
    From the formation of 3-isopropyl-5-hydroxy-o-toluic acid by treatment of aristoic acid, obtained by permanganate oxidation of aristolone, with mineral acid, *1 liberation of C4-monocarboxylic acid was presumed. The presence of this fragment as crotonic acid was cofirmed and a reaction system was established for oxidation of aristolone with potassium permanganate to aristoic acid and its decomposition by acid treatment into 3-isopropyl-5-hydroxy-o-toluic acid and crotonic acid. Based on these facts, the structure of cyclopropane ring and position of the methyl group in aristolone were presumed and structural formulae (V) and (VI) were respectively forwarded for aristolone and aristoic acid.
  • 浜名 政和, 山崎 企善
    1961 年 81 巻 4 号 p. 574-578
    発行日: 1961/04/25
    公開日: 2010/02/19
    ジャーナル フリー
    2-Chloropyridine 1-oxide reacts with phosphoryl chloride and forms 2, 6-dichloro-pyridine in a high yield. Reaction of 2-substituted pyridine 1-oxide and acetic anhydride fails to give normal rearrangement product, 2-chloro-, 2-ethoxy-, and 2-phenoxypyridine 1-oxides all forming 2-substituted 1-hydroxy-2(1H)-pyridones. In the case of 2-picolinic acid 1-oxide, decarboxylation takes place first, followed by formation of 2(1H)-pyridone. 2-Picolinamide 1-oxide merely forms 2-N-acetylcarbamoyl-pyridine 1-oxide. On the other hand, reaction of 2-chloro-4- or -6-methylpyridine 1-oxide with acetic anhydride chiefly gives acetoxymethyl compounds, the methyl group in these compounds being more active than the chlorine atom.
  • 宇野 豊三, 秋浜 澄行
    1961 年 81 巻 4 号 p. 579-585
    発行日: 1961/04/25
    公開日: 2010/02/19
    ジャーナル フリー
    4-Phenyl-2-thiazolecarboxaldehyde and naphtho[2, 1-d]thiazole-2-carboxaldehyde were prepared by warming 2-methyl-4-phenylthiazole and 2-methynaphtho[2, 1-d]-thiazole with iodine and pyridine to form the pyridinium salts, reacting these salts with N, N-dimethyl-p-nitrosoaniline in sodium hydroxide alkalinity to form N-p-dimethylaminophenyl-α-(4-phenyl-2-thiazolyl)nitrone and N-p-dimethylaminophenyl-α-naphtho[2, 1-d]thiazol-2-ylnitrone, and their hydrolysis with dil. hydrochloric acid.
    Heating of 2, 4-dimethyithiazole with iodine and pyridine gives 1-(4-methyl-5-iodo-2-thiazolylmethyl)pyridinium iodide which undergoes reaction with N, N-dimethyl-p-nitrosoaniline in sodium hydroxide alkalinity to form N-p-dimethylaminophenyl-α-(4-methyl-5-iodo-2-thiazolyl)nitrone, and its hydrolysis with dil. hydrochloric acid affords 4-methyl-5-iodo-2-thiazolecarboxaldehyde.
    In order to obtained organic reagents which would react with metallic ions, the aldoxime, thiosemicarbazone, 2-phenyliminomethylthiazole derivatives, benzimidazole derivatives, 2-(2-benzothiazolyl)iminomethylthiazole derivatives, and 2-benzothiazolylhydrazone were prepared from 4-phenyl-2-thiazolecarboxaldehyde, 2-benzothiazolecarboxaldehyde, naphtho[2, 1-d]thiazole-2-carboxaldehyde, and naphtho[1, 2-d]thiazole-2-carboxaldehyde. 1, 2-Bis {naphtho[1, 2-and 2, 1-d]thiazol-2-yl} -1, 2-ethenediol were prepared by the benzoin condensation of naphtho[1, 2- and 2, 1-d]thiazole-2-carboxaldehyde.
  • 宇野 豊三, 秋浜 澄行
    1961 年 81 巻 4 号 p. 585-590
    発行日: 1961/04/25
    公開日: 2010/02/19
    ジャーナル フリー
    Twenty-three kinds of hydrazine derivatives of thiazole were synthesized and their utility as organic reagent was examined. Characteristic coloration was found to occur by the reaction of 2, 2′-hydrazodithiazole and 2-hydrazinothiazole derivatives with Fe (III), Cu (II), Ag (I), Hg (II), Pt (IV), Au (III), and Pd (II) ions, 2, 2′-azodithiazole derivatives with Pd (II) ion alone, 2-(2-acetylhydrazino)thiazole derivatives with Co (II), Ni (II), Mn (II), Fe (III), Cu (II), Ag (I), Hg (II), Au (III), and Pd (II) ions, 2-(2, 2-diacetylhydrazino)thiazole and 2-(1, 2, 2-triacetylhydrazino)thiazole derivatives with Au (III) and Pd (II) ions, benzaldehyde 2-benzothiazolylhydrazone derivatives with Co (II), Ni (II), Cd (II), Cu (II), Ag (I), Hg (II), Au (III), and Pd (II) ions, and 1-(2-benzothiazolyl)-4-phenyl-3-thiosemicarbazide derivatives with Co (II), Cu (II), Bi (III), Au (III), Pd (II), and Pb (II). Limit of detection of these metal ions by these reagents was examined by spot test and examinations were also made on interfering ions and their removal. It was thereby found that 2-hydrazino-4-phenylthiazole was excellent spot test reagent for Cu (II) ion, 2-(2-acetylhydrazino)-4-methylthiazole for Fe (III) ion, and 2, 2′-azobis(4-methylthiazole) for Pd (II) ion.
  • 田中 信夫, 中垣 正幸
    1961 年 81 巻 4 号 p. 591-596
    発行日: 1961/04/25
    公開日: 2010/02/19
    ジャーナル フリー
    Kinetic studies were made on the decarboxylation reaction of p-aminosalicylic acid in a wide range of pH up to 11.6. The relationship between the logarithm of the reaction rate constant, k, and pH is shown in Fig. 2 where the curve is indicated by the solid line, having the minimum value of k in the range of pH 9.2-9.5. This curve is represented by equation (5) which gives a curve indicated by the dotted line in Fig. 2. The same experiments were carried out on aqueous solution of p-aminosalicylic acid of pH 1.90, 2.90, and 3.90, with the addition of propylene glycol, polyvinylpyrrolidone, or a surface-active agent as a stabilizer. As indicated in Table I, propylene glycol has no such stabilizing effect (lowering of k/k0) but such effect was found in polyvinylpyrrolidone. Experiments carried out with polyoxyethylene monolauryl ether of the polymerization degree of 9 and 25, and polyoxyethylene monoöleate ester of the polymerization degree of 22, and their results are given in Figs, 4, 5, and 6. It was found from these experiments that, at the same pH and same molar concentration, the greater was the stabilization effect, the higher the HLB.
  • 田中 信夫, 中垣 正幸
    1961 年 81 巻 4 号 p. 597-600
    発行日: 1961/04/25
    公開日: 2010/02/19
    ジャーナル フリー
    Following the previous report on the reaction velocity constant k to changes in pH in aqueous solution with constant ionic strength, in the decarboxylation reaction of p-aminosalicylic acid, experiments were carried out on variation in the concentration of sodium p-aminosalicylate and the minimum rate of decomposition was obtained in 0.5M concentration, as shown in Fig. 1. Various amounts of acetic acid-sodium acetate buffer were tested at a constant pH, as indicated in Table III, and the value of b=1.098 of equation (1) was obtained. The effect of the concentration of p-aminosalicylate was tested and the values of kobs. listed in Table I were obtained. From kobs. of 0.3M solutions at various temperatures, functions of temperature and H3O+ concentration were calculated and the values were interpolated in equation (2), from which equation (2′) was obtained. From this equation, kcalc. was calculated. The values of Eobs., ΔH, ΔS, and ΔR at various temperatures were calculated from Eyring's absolute reaction rate theory and the values became the lowest at 0.5M concentration, as indicated in Table II.
  • 田中 信夫, 中垣 正幸
    1961 年 81 巻 4 号 p. 600-603
    発行日: 1961/04/25
    公開日: 2010/02/19
    ジャーナル フリー
    As it had been recognized that the reaction rate varied with concentration of sodium p-aminosalicylate, the state of solution was examined in the aqueous solution of the salt, especially on the density and viscosity. Specific gravity was measured in the range of temperatures at 20-40° and equations (5), (6), (7), (8), and (9) were obtained. Calculations were made on the apparent molal and ionic volumes and the values approximately agreed with those of p-aminosalicylic acid calculated from X-ray diffraction. Viscosity of sodium p-aminosalicylate solution was measured and relationship between ηred. and concentration was plotted in a graph. As indicated in Fig. 2, a specificity was found in the curve at around 0.5M concentration. Using the absolute reaction rate theory of Eyring, ΔFV, ΔHV, and ΔSV at 20° were calculated and, as shown in Table II, ΔHV and ΔSV were found to increase suddenly at 0.5M concentration. From these results, sodium p-aminosalicylate is considered to take a pseudomicelle structure in the solution at a concentration above 0.5M and this is thought to be related to the reaction rate.
  • 田中 信夫
    1961 年 81 巻 4 号 p. 604-607
    発行日: 1961/04/25
    公開日: 2010/02/19
    ジャーナル フリー
    Electric conductivity of aqueous solution of sodium p-aminosalicylate was measured and physicochemical properties of the salt was examined. Electric conductivity was measured at 25° with a diluted aqueous solution of 0.1M to 0.005M, and Λ0 in equation (3) was calculated by the method of Shedlovsky. Relationship between Λ0 and C, as indicated in Fig. 2, gave a straight line and Λ0′ increased below 0.01M concentration, which is thought to be due to hydrolysis of sodium p-aminosalicylate. The value of Λ0=81.7 was obtained. Ionic electroconductivity of p-aminosalicylic acid ion was calculated as 31.6, which was used to obtain ionic radius, γs, of 2.9 Å. This value is smaller than the ionic volume calculated from the specific gravity. Measurement of Λ in a concentrated solution of from 0.1M to near saturation gave the values shown in Fig. 3, from which Λ was calculated and indicated by a graph in Fig. 4. Equation (9) was calculated for ηΛ by the use of absolute reaction rate theory of Eyring and proportionation to one-third power of the volume of moving unit (V) gave the lowest value at 0.5M concentration, at every temperature, as indicated in Table I. This concentration is the same as the concentration at which the reaction rate shows the lowest value and at which viscosity shows abnormality. It is therefore considered that some change occurs in the dissolved state in the aqueous solution of sodium p-aminosalicylate at this concentration and this may be somewhat related to the reaction rate.
  • 高橋 酉蔵, 松岡 晉
    1961 年 81 巻 4 号 p. 608-612
    発行日: 1961/04/25
    公開日: 2010/02/19
    ジャーナル フリー
    Cyclohexanone was submitted to the Strecker reaction, 1-(1-methyl or -ethylamino)-cyclohexanecarbonitrile (I or II) so obtained was acylated (III to IX), and hydrolyzed with conc. sulfuric acid to form 1-(N-methyl- or -ethyl-acylamino)cyclohexanecarboxylic acid (X to XVII). Their esters (XXVII to XXXI), esters of 2-(diethylamino- or -piperidino) ethanol (XXXII to XXXV), and amides (XXXVI to XLIII) were also prepared. Reaction of aminonitrlle (I) with haloacyl halides gave 1-[N-methyl-(2-haloacyl)amino] cyclohexanecarbonitrile (XVIII and XIX) which were reacted with dialkylamine, piperidine, morpholine, or N, N-diethyl-1, 3-propanediamines to form the corresponding 1-[N-methyl-(2-dialkylaminoacyl)amino] cyclohexanecarbonitriles (XX to XXVI).
  • 浜名 政和, 山崎 企善
    1961 年 81 巻 4 号 p. 612-615
    発行日: 1961/04/25
    公開日: 2010/02/19
    ジャーナル フリー
    Reaction of 2-chloropyridine 1-oxide and various nucleophilic reagents was carried out to prepare various 2-substituted pyridine 1-oxides. This reaction was found to be generally applicable for synthesis of 2-substituted pyridine 1-oxides.
  • 井上 正敏, 斎藤 隆子
    1961 年 81 巻 4 号 p. 615-618
    発行日: 1961/04/25
    公開日: 2010/02/19
    ジャーナル フリー
    Differential thermal analysis was carried out on sulfanilamide, sulfathiazole, bromovalerylurea, and bromodiethylacetylurea, and thermal abnormality was found in all these compounds by transition of crystal form. It was also found that bromodiethylacetylurea has a γ-form, besides α- and β-forms, which is labile at a high temperature. The γ-form is stable at above ca. 90° and this was also confirmed by powder X-ray method at the time of heating.
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