YAKUGAKU ZASSHI
Online ISSN : 1347-5231
Print ISSN : 0031-6903
ISSN-L : 0031-6903
72 巻, 5 号
選択された号の論文の44件中1~44を表示しています
  • p-Acetamino-o-alcoxybenzaldehyde Thiosemicarbazoneの合成
    宮武 一夫
    1952 年 72 巻 5 号 p. 601-603
    発行日: 1952/05/25
    公開日: 2010/02/19
    ジャーナル フリー
    Thiosemicarbazones of p-acetaminobenzaldehyde, which possess antibacterial action against tubercle bacilli, were prepared with methoxy and ethoxy group in its ortho position by the application of thiosemicarbazide to p-acetamino-o-alcoxybenzaldehyde, or by the reduction and acetylation of the product obtained by the application of thiosemicarbazide to p-nitro-o-alcoxybenzaldehyde.
  • Thiosemicarbazone類の新合成法
    宮武 一夫
    1952 年 72 巻 5 号 p. 604-606
    発行日: 1952/05/25
    公開日: 2010/02/19
    ジャーナル フリー
    In accordance with a new synthetic procedure whereby thiosemicarbazone is derived through azine compounds, p-acetamino- and p-acetamino-o-alcoxy- benzaldehyde thiosemicarbazone were prepared. In this reaction, aminobenzaldazine (IV), obtained by the reduction of nitrobenzaldazine (III) or by direct application of hydrazine to aminobenzaldehyde (V) without its isolation, is acetylated to acetaminobenzaldazine (VII) and followed by application of thiosemicarbazide. Generally, aminobenzaldehydes are unstable and, therefore, the present method is applicable to the syntheses of these thiosemicarbazones.
  • アセトニトリルの合成
    石黒 武雄, 北村 英一, 久保田 晴壽, 田畑 乃武夫
    1952 年 72 巻 5 号 p. 607-610
    発行日: 1952/05/25
    公開日: 2010/02/19
    ジャーナル フリー
    The product obtained by the condensation of acetylene and ammonia differs in ratio of pyridine bases and acetonitrile by the kind of catalyst used. The yield ratios of these two substances are naturally affected by the difference in temperature but, from the values of this yield ratio, the catalysts were found to be divided into two groups. By the use of a certain combination of the catalysts of these two groups, it was found possible to obtain the best conditions for maximum yield of acetonitrile. For example, by the passage of an equal mixture of acetylene and ammonia gas through a catalyst composed of 80% kaolin and 20% zinc oxide, heated to 400°, over 91% of the condensation product will be acetonitrile, less than 0.8% being pyridine bases. The life of this catalyst is very long, and can be used repeatedly by reactivation.
  • 2-Amino-1,3,4-thiadiazole類とα-Bromo-acetophenone類との反應について
    松川 泰三, 伴 彰一
    1952 年 72 巻 5 号 p. 610-614
    発行日: 1952/05/25
    公開日: 2010/02/19
    ジャーナル フリー
    By heating 2-amino-(5-substituted)-1, 3, 4-thiadiazoles and (p-nitro)-α-bromoacetophenone in alcoholic solution, 2-amino-3-(p-nitro)-phenacyl-(5-substituted)-2, 3-dihydro-1, 3, 4-thiadiazole hydrobromides are obtained in a good yield. By boiling the latter in water, new heterocyclic compounds are obtained as (2-substituted)-6-(p-nitro)-phenyl-imidazo-[2, 1-b]-thiadiazoles.
  • アンチピリン及びp-フェネチヂンのヂアルキルアミノアチルアミノ誘導体について
    高橋 酉藏, 千田 重男
    1952 年 72 巻 5 号 p. 614-616
    発行日: 1952/05/25
    公開日: 2010/02/19
    ジャーナル フリー
    Twelve kinds of dialkylaminoacylamino compounds were prepared by the application of dialkylamine to halogenoacylamino derivatives obtained by the condensation of halogenoacyl halides with 4-aminoantipyrine or p-phenetidine. These compounds were prepared for use as analgesics.
  • 田中 邦喜, 須川 利男
    1952 年 72 巻 5 号 p. 616-620
    発行日: 1952/05/25
    公開日: 2010/02/19
    ジャーナル フリー
    It has been found possible to determine the kind of alkaloids contained in ergots by the use of paper partition chromatography. Development of the chromatogram with butanol acidified with acetic acid gives ergometrine or elymoclavine, agroclavine and peptide-type alkaloids in different positions which gave characteristic coloration with the Ehrlich reagent. Furthermore, ergometrine and elymoclavine were separatory determined by development with pyridine-butanol solution. By the application of this procedure with total alkaloids extracted from natural ergots, following results were obtained:
  • 田中 邦喜, 須川 利男
    1952 年 72 巻 5 号 p. 620-623
    発行日: 1952/05/25
    公開日: 2010/02/19
    ジャーナル フリー
    Peptide-type alkaloids contained in ergot were decomposed, and the amino and α-keto acids obtained were examined by paper partition chromatography. From the chromatograms the following results were obtained:
  • 羽野 壽, 田村 三郎
    1952 年 72 巻 5 号 p. 623-626
    発行日: 1952/05/25
    公開日: 2010/02/19
    ジャーナル フリー
    General pharmacological properties of 10 kinds of isoquinoline series compounds of safrol were examined from whcih it was found that bis-(3-methyl-6, 7-methylenedioxyisoquinolyl-1-methyl)-methylamine trihydrochloride possessed the strongest papaverinelike activity of relaxing smooth muscles with the less toxicity. The compound effected decreasing of tonus and motility on isolated intestines and in situ, lowered blood pressure and increased resipiration by intravenous injection, with no influence on the heart.
  • ニトロ馬尿酸の合成
    宮武 一夫, 加賀 愼一郎
    1952 年 72 巻 5 号 p. 627-629
    発行日: 1952/05/25
    公開日: 2010/02/19
    ジャーナル フリー
    Hydrolysis of p-nitrohippuric ester by the ordinary method results in the decomposition of the acid amide linkage of the molecule to form p-nitrobenzoic acid. Such linkage in o- and m-nitrohippuric esters is so stable that they form, by this hydrolysis, o- and m-nitrohippuric acids. Hydrolysis of p-nitrohippuric ester with potassium carbonate gives, by almost quantitative yields, p-nitrohippuric acid which comes in two kinds of crystals, i.e. one of m. p. 250° (decomp.) which precipitates out at pH 7-4 by neutralization of the potassium carbonate solution with hydrochloric acid, and the other of m. p. 131-132°, which precipitates out at below pH 3. It was found that the former crystals are those of a molecular compound composed of 1 mole of p-nitrohippuric acid with 1 mole of potassium p-nitrohippurate. The formation of such molecular compound was not seen with o- and m-nitrohippuric acids.
  • 宮武 一夫, 角尾 元三
    1952 年 72 巻 5 号 p. 630-631
    発行日: 1952/05/25
    公開日: 2010/02/19
    ジャーナル フリー
    Catalytic reduction of 2-methyl-4-amino-5-cyanopyrimidine (VII) in hydrogen chloridesaturated glacial acetic acid, with palladium-carbon as the catalyst, results in the formation of 2-methyl-4-amino-5-hydroxymethylpyrimidine (XII) as long as a suitable amount of water is present and the reaction temperature is maintained at around 45°. The mechanism of this reaction was clarified by the fact that a 5-aldehyde compound (XI) was obtained from the reaction system. The formation of (XI) was rather small in this case, but the use of Raney nickel as a catalyst and the reaction carried out in methanol resulted in formation of a Shiff's base (X) which could be decomposed to (XI). No formation of (XII) was witnessed in this case.
  • 宮武 一夫
    1952 年 72 巻 5 号 p. 632-634
    発行日: 1952/05/25
    公開日: 2010/02/19
    ジャーナル フリー
    In order to obtain antimalarial sulfa drugs, three kinds of sulfanilamide derivatives, (IV), (V) and (VI) were obtained by the respective condensation of sulfanilamide with δ-diethylamino-α-methylbutylamine (III), 2-methoxy-6, 9-dichloroacridine (I) and 6-methoxy-8-aminoquinoline (II), but none of the compounds prepared were found to be effective against malaria. N1-Sulfanil-3, 5-dibromoanilide, obtained by the hydrolysis of an acetyl condensate (X) of N4-acetylsulfanilamide and 1, 3, 5-tribromobenzene (IX), by a new synthetic method, was found to be effective against malaria.
  • α, π-Dihalocamphorの発烟硫酸による異性化 その1 x,x´-Dihalocamphorの生成
    西川 正元
    1952 年 72 巻 5 号 p. 634-637
    発行日: 1952/05/25
    公開日: 2010/02/19
    ジャーナル フリー
    Treatment of four kinds of α, π-dihalo-d-camphor, i.e. α, π-dichloro-, -dibromo-, α-chloro-π-bromo- and α-bromo-π-chloro-d-camphor, with fuming sulfuric acid results in isomerization to give levorotatory x, x′-dihalocamphors in approximately 30% yield. With the exception of x, x′-dichlorocamphor, which was found identical with the dichlorocamphor of unknown structure obtained by Uyeyanagi, all the three dihalocamphors are new substances of unknown structure. This isomerization also proceeds with chlorosulfonic acid but more incompletely than by fuming sulfuric acid.
  • α, π-Dihalocamphorの発烟硫酸による異性化その2 x,x´-Dihalocamphorの母核
    西川 正元
    1952 年 72 巻 5 号 p. 637-639
    発行日: 1952/05/25
    公開日: 2010/02/19
    ジャーナル フリー
    Reduction of x, x′-dichlorocamphor with sodium and alcohol results in the formation of l-borneol, while reduction of x, x′-dibromocamphor with zinc dust and acetic acid yields l-camphor. From these experimental results, it was assumed that the parent skeleton of x, x′-dichloro- and x, x′-dibromo-camphor is the l-camphor.
  • α, π-Dihalocamphorの発烟硫酸による異性化 その3 x,x´-Dihalocamphorの樟腦酸誘導体
    西川 正元
    1952 年 72 巻 5 号 p. 640-643
    発行日: 1952/05/25
    公開日: 2010/02/19
    ジャーナル フリー
    The four kinds of x, x′-dihalocamphor, i.e. x, x′-dichloro-, x, x′-dibromo-, x, x′-chloro-bromo- and x, x′-bromochrorocamphors, were oxidized with selenium dioxide in acetic anhydride to camphorquinone compounds, and further to camphoric acid and camphoric anhydrides by oxidation with hydrogen peroxide. From the results obtained, it was concluded that the all four dihalocamphors do not possess halogen atoms in the 3- and 4-positions, and that all the four halocamphors possessed identical structures.
  • α, π-Dihalocamphorの発烟硫酸による異性化 その4 x,x´-Chlorobromocamphor及びx,x´-Bromochlorocamphorの亞鉛末, 酢酸による還元反應
    西川 正元
    1952 年 72 巻 5 号 p. 643-645
    発行日: 1952/05/25
    公開日: 2010/02/19
    ジャーナル フリー
    Reduction of x, x′-chlorobromo-and x, x′-bromochloro-camphors with zinc dust in acetic acid resulted in the elimination of bromine atom alone to yield monochlorocamphors, from the former, (I), m.p. 170°, [α]D17: -32° (in EtOH), and from the latter, (II), m.p. 138-139°, [α]D17: -96° (in CHCl3). By comparison with trans-π-chloro-d-camphor, (II) was found to be trans-π-chloro-l-camphor, while (I) was assumed to be 6-or cis-π-chlorocamphor since it was different from any of the six known monochlorocamphors.
  • α, π-Dihalocamphorの発烟硫酸による異性化 その5 χ-Chlorocamphor
    西川 正元
    1952 年 72 巻 5 号 p. 646-651
    発行日: 1952/05/25
    公開日: 2010/02/19
    ジャーナル フリー
    Oxidation of χ-chlorocamphor with chromic acid gives 6-oxocamphor, while oxidation with selenium oxide followed by further oxidation with hydrogen peroxide gives 6-chloro-l(+)-camphorquinone and 5-chloro-l(+)-camphoric acid, from which it was confirmed that the original χ-chloro compound is the 6-chloro-l-camphor. Summarization of the results described in Reports I to VI is as follows. Treatment of α, π-dihalo-d-camphor with fuming sulfuric acid results in perfect optical rearrangement of the nucleus to l-camphor, with attendant migration of the halogen atom at α-position to 6-position, forming 6-trans-π-dihalo-l-camphor. This has also confirmed the fact that the dichlorocamphor obtained by Uyeyanagi is 6-trans-π-dichloro-l-camphor, which in turn clarified that 6-halo-l-camphor-π-sulfonic acid is formed as a byproduct during π-sulfonation of α-halo-d-camphor. The experimental results show that a total of 19 new compounds have been synthesized including, 6-chloro-l-camphor, four kinds of 6-trans-π-dihalo-l-camphor and their oxidation products, and that a third rule for the optical transition of camphor has been found, following those previously discovered by Asahina and the others, and by Houben, et al.
  • 2,3-Dihydroxy-cyclohexylacetic Acid Lactone置換体の合成
    阿部 泰夫, 角 正夫
    1952 年 72 巻 5 号 p. 652-655
    発行日: 1952/05/25
    公開日: 2010/02/19
    ジャーナル フリー
    Addition of bromine and hypobromous acid to the double bond between C2 and C3 of [cyclohexen-(2)-yl]-acetic acid derivatives (A) results in the formation, chiefly, of the lactones of 2-hydroxy-3-bromo- and 2-bromo-3-hydroxycyclohexylacetic acid derivatives, hydrolyses of which gives the lactones of 2, 3-dihydroxycyclohexylacetic acid homologs. Similar reactions were found to take place with chlorine derivatives. The lactones thus obtained were found to be identical with the hydroxylation products obtained by organic peracid oxidation of the starting materials (A) described in Report IV and V. Some considerations were given for this reaction mechanism.
  • 犬伏 康夫
    1952 年 72 巻 5 号 p. 656-657
    発行日: 1952/05/25
    公開日: 2010/02/19
    ジャーナル フリー
    Reduction of 3, 4:5, 6-dibenzo-(1, 2-pyrone) (I) with lithium aluminum hydride yields 1-hydroxymethyl-1′-hydroxybiphenyl (II) from which 3, 4:5, 6-dibenzo-(1, 2-pyrane) (IV) was obtained via 1-bromomethyl-1′-hydroxybiphenyl (III). Ultraviolet absorption spectra of (I) and (IV) were compared with the absorption curves of 1-acetoxy-3-n-amyl-6, 6, 9-trimethyl-6-dibenzopyran (VI) and 3-acetoxy-2-n-amyl-6, 6, 9-trimethyl-6-dibenzopyran (VII) synthesized by Adams, et al.
  • 炭水素分析に於ける可動炉延長効果並びに空気焼却法に就いて その1
    穗積 啓一郎, 今枝 一男, 田中 原子
    1952 年 72 巻 5 号 p. 658-661
    発行日: 1952/05/25
    公開日: 2010/02/19
    ジャーナル フリー
    In the determination of carbon and hydrogen by the Pregl method, it had been thought that the oxygen stream was indispensable. However, the authors have obtained a good result by the use of ordinary air stream, by the elongation of the heating tube at the moving furnace, with added advantage of simplifying the process with moving furnace and eliminating the danger of inflammation of samples. The purification of air is also very simple and in most cases, ordinary air of the analysis room can be used as it is. Moreover, weighing of the absorption tubes can be made without any considerations for specially designed tubes or for weighing time. The total time required for hydrogen and carbon determination by this method is 40 minutes.
  • 炭水素分析に於ける可動炉延長効果並びに空気燒却法に就いて その2
    穗積 啓一郎, 今枝 一男, 田中 原子
    1952 年 72 巻 5 号 p. 661-664
    発行日: 1952/05/25
    公開日: 2010/02/19
    ジャーナル フリー
    The simplified method of analysis as described in the foregoing paper gives many added advantages over previously practiced method but, at the same time, it requires sufficient experimental evidence for the complete oxidation of samples. Experimental and statistical evidences were obtained to show that the present method is equal to or better than the method hereto practiced.
  • 4,6-Diaminochinolinの簡易合成法
    中山 巖
    1952 年 72 巻 5 号 p. 665-667
    発行日: 1952/05/25
    公開日: 2010/02/19
    ジャーナル フリー
    The 4, 6-diaminoquinoline is an important intermediate compound in the manufacture of sulfen system pharmaceuticals. Tschitschibabin prepared 4-amino-6-nitroquinoline by the direct nitration of 4-aminoquinoline but it has later been clarified by Jensch and Simpson that the so-called 4-amino-6-nitroquinoline was a mixture of 6-nitro-, 3(?)-nitro- and 3, 6-dinitro compounds. As a result of the simplification of 4-aminoquinoline by the recent discovery of the simple synthetic procedure for 4-nitroquinoline, and by the comparative examination of the nitration of 4-amino- and 4-hydroxy-quinolines with that of their N-oxides, it was found that by preliminary obstruction of the 3-position with an atom which could easily be removed later, such as the bromine, with subsequent nitration with sulfuric and nitric acid at below 10° would give 3-bromo-4-amino-6-nitroquinoline, m.p. 286°, with a good yield. Reduction of this compound will give 4, 6-diaminoquinoline with an yield of 52% against 4-amino-quinoline.
  • n-アルキル硫酸アルカリ及びn-アルキルスルフォン酸アルカリの抗菌作用に就いて
    高田 善之, 宇野 蓊, 松田 敏雄
    1952 年 72 巻 5 号 p. 667-669
    発行日: 1952/05/25
    公開日: 2010/02/19
    ジャーナル フリー
    Antibacterial action against Staphylococcus aureus, Escherichia coli, and Bacillus subtilis was tested with alkali salts of alkyl sulfates and alkyl sulfonates possessing straight chain, odd-numbered carbons in the range of C8 to C18. The growth inhibitory action of alkali salts of alkyl sulfates was found to be the most strongest in the range of C12 to C16, showing strong inhibition against growth of Gram positive, Staph. aureus and B. subtilis, but the action was weak against Gram negative, Esch. coli. The action of alkali salts of alkyl sulfonates was very weak against both Gram positive and negative organisms.
  • 1-p-Nitrophenyl-2-amino-1,3-propanediolの合成
    宮本 益雄
    1952 年 72 巻 5 号 p. 669-672
    発行日: 1952/05/25
    公開日: 2010/02/19
    ジャーナル フリー
    Nitration of the threo-N-acetylated and erythro-N-benzoylated compounds of 1-phenyl-1-methoxy-2-amino-3-propanol with nitric and sulfuric acids results in the nitration of the hydroxyls in the p- and 3-positions of the benzene nucleus, and their hydrolysis with hydrochloric acid gives threo- and erythro-1-p-nitrophenyl-1-methoxy-2-amino-3-propanol hydrochloride. Solvation of threo-3-p-nitrophenyl-3-methoxy-2-acetamido-1-propyl nitrate in hot water results in the formation of threo-1-p-nitrophenyl-1-methoxy-2-amino-3-acetoxypropane nitrate whose treatment with alkali gives. threo-1-p-nitrophenyl-1-methoxy-2-acetamido-3-propanol. The hydrolysis of the latter with hydrochloric acid gives threo-1-p-nitrophenyl-1-methoxy-2-amino-3-propanol hydrochloride, in a good yield.
  • 光学的活性threo-1-p-Nitrophenyl-2-amino-1,3-propanediolの合成
    宮本 益雄
    1952 年 72 巻 5 号 p. 672-673
    発行日: 1952/05/25
    公開日: 2010/02/19
    ジャーナル フリー
    Tartrates of dl-threo-1-p-nitrophenyl-l-methoxy-2-amino-3-propanol is formed by the application of d-tartaric acid to the methanolic or aqueous solution of the alcohol. Liberation of tartaric acid by alkali gives d-threo-1-p-nitrophenyl-1-methoxy-2-amino-3-propanol, demethylation of which, with hydrobromic acid, gives d-threo-1-p-nitrophenyl-2-amino-1, 3-propanediol.
  • 1-p-Nitrophenyl-2-amino-1,3-propanediol誘導体の立体転位について
    宮本 益雄
    1952 年 72 巻 5 号 p. 673-676
    発行日: 1952/05/25
    公開日: 2010/02/19
    ジャーナル フリー
    Application of thionyl chloride to the N-acyl and N, O-diacyl compounds of dl-1-p-nitrophenyl-2-amino-1, 3-propanediol to form
    NO2-C6H4-CH-CH (NH-Acyl)-CH2
    results in the obstruction of a steric rearrangement. If the reaction is carried out via the assumed structure of oxazoline hydrochloride, the threo and the erythro compounds undergo steric rearrangement to each other.
  • クロルアンフェニコールとエフエドリンとの立体化学的相関性及びアシルアミノエーテルの脱アルキルを伴うアシル転位について
    宮本 益雄
    1952 年 72 巻 5 号 p. 677-680
    発行日: 1952/05/25
    公開日: 2010/02/19
    ジャーナル フリー
    pseudo-N-Benzoylnorephedrine was derived from erythro-1-phenyl-1-methoxy-2-benzamido-3-propanol and confirmed that one steric reversion had taken place during this reaction. This has clarified that the threo system of chloramphenicol is identical with the pseudo system of ephedrine. The erythro system undergoes steric conversion to the threo system by the N→O acyl rearrangement of 1-phenyl-2-amino-1, 3-propanediol but the threo system was proved to be indifferent to this steric conversion. It follows, therefore, that entirely similar rules of steric conversion predominates in the case of chloramphenicol as with ephedrine.
  • テストステロンの去勢ラツテ副腎重量及び組織に及ぼす影響について
    伊藤 四十二, 玉置 文一, 坂本 秀冶, 江草 雅子
    1952 年 72 巻 5 号 p. 681-684
    発行日: 1952/05/25
    公開日: 2010/02/19
    ジャーナル フリー
    1) It was clearly confirmed by the present experiments that adrenal glands of castrated male rats were reduced in weight by the administration of testosterone.
    2) It was found that adrenal glands of castrated male rats became significantly heavier than those of the sham-operated male rats, while, by the administration of testosterone, the former were maintained in the condition of the latter, in weight and histologically.
    3) On the contrary, it was reported that, in hypophysectomized or hypophysectomized-gonadectomized male rats, adrenal gland increased in weight by testosterone. Referring to this fact, some assumptions were made to explain endocrinologically the results obtained in the present experiments.
  • ういきょう果実油の脂肪酸の研究
    黒野 吾市, 石田 知子
    1952 年 72 巻 5 号 p. 684-685
    発行日: 1952/05/25
    公開日: 2010/02/19
    ジャーナル フリー
    From the fruits (667g.) of Foeniculum vulgare L., a mixture (60g.) of fatty acids was obtained. The fractional distillation of their methyl esters yielded fraction (A) b.p.0.8 72-89° and (B) b.p.0.8 142-143°. No fatty acids were obtained from fraction (A) which yielded 3g. of neutral oil. Fraction (B) yielded some solid acid (ca. 86%) and liquid acid (ca. 14%). The solid acid was found to be petroselic acid, m. p. 32-33°, and the liquid acid yielded a small amount of 6, 7-dihydroxystearic acid and a comparatively large amount of 9, 10, 12, 13-tetrahydroxystearic acid. These results show that fatty acid composing the fruit oil of Foeniculum vulgare consists of a large amount of petroselic acid and a small amount of linoleic acid.
  • よろいぐさ果実油の脂肪酸の研究
    黒野 吾市, 酒井 健
    1952 年 72 巻 5 号 p. 686-687
    発行日: 1952/05/25
    公開日: 2010/02/19
    ジャーナル フリー
    From the fruits (550g.) of Angelica glabra Makino, a mixture (75g.) of fatty acids was obtained. By the fractional distillation of the methyl esters of these fatty acids, some pale yellowish green, crystalline sublimate of b.p.1.5 160°, and fractions (A) b.p.1.5 70-111°, (B) b.p.1.5 130-150°, and (C) b.p.1.5 164-166°, were obtained. No fatty acids were obtained from fraction (A) which yielded 7g. of neutral, oily substance. Fraction (B) yielded a solid acid of m.p. 60-61° which was found to be palmitic acid. Fraction (C) yielded some solid acid (ca. 35%) and liquid acid (ca. 65%). The solid acid, m.p. 27-28° yielded petroselidic acid, m.p. 53°, by elaidination from which it was found to consist of a large amount of petroselic acid with a small amount of petroseli-dic acid. The liquid acid yielded a small amount of 6, 7-dihydroxystearic acid, and a comparatively large amount of 9, 10, 12, 13-tetrahydroxystearic acid. These results show that fatty acids composing the fruit oil of Angelica glabra consist of petroselic acid, palmitic acid, a small amount of petroselidic acid and a large amount of linoleic acid. No detailed study has yet been made on the sublimate.
  • ぺーパークロマトグラフによるビタミンB1の定量
    宮木 高明, 籾山 浜子, 林 誠
    1952 年 72 巻 5 号 p. 688-692
    発行日: 1952/05/25
    公開日: 2010/02/19
    ジャーナル フリー
    Some time ago, Miyaki and the others devised a method of quantitative determination by one-dimensional paper chromatography. This utilizes the following relationship
    log[(spot length)-(initial size of spot)]=A log (amount of component)+B However, in actual usage, the following will suffice
    (spot length)=K1 log[log (dilution of a sample solution)]+K2
    It was, however, necessary to make a more detailed examination for individual case according to the amount of sample substances and determination conditions. The determination carried out with thiamine showed that, in 50-1, 000 γ range, linear relationship according to Fischer's formula, as well as the above two formulae, was found to exist between the spot length and log. (amount of thiamine). Therefore, conditions for quantitative detemination was chosen according to the design of experiment in this case, and a linear relationship was reëxamined. By the “Latin square” design and the analysis of covariance, the width of the strip was chosen as 8mm. (length, 40cm.), the ratio of the mixture of the developing solution (10%KCI: 95%EtOH) as 3:2, and solutions of thiamine hydrochloride containing 50, 100, 250, 500 and 1000 γ per cc., were submitted to this chromatographic determination. From a simple regression equation, y′=y+b(x-x), line of regression was obtained which was found to become the standard line (Tables I to IV). However, it was not entirely satisfactory from the manner of confidence limits (Fig. 1) but upon its application to Vitamin B1 injection, it could well be used for practical purposes by diluting the samples to contain 1000 or 500 γ per cc. of the solution (Table V). Examination of the relationship between the spot-length and the amount of thiamine in the 8-4000 γ per cc. range (Figs. 2-5) showed that such linear relationship by Fisher's formula was no longer applicable (Fig. 4). The most linear relationship was found with log. (spot-length)=α log (amount)+β (Fig. 5). This was found to be established with other examples and constitutes a standard in simple determinations. In the case of thiamine, however, a strict linear relationship cannot be observed, and a linear relationship was obtained from difference diagram from Fig. 2 by the calculus of finite difference (Fig. 6). This seems to be the most useful relationship to be employed. In general, determination by one-dimensional paper chromatography should be preceded by the preliminary determination of a relationship to be used for the length of spot and the amount of sample to be taken according to the conditions of quantitative determination.
  • 中島 邦雄, 和田井 收, 鳥井 宗和
    1952 年 72 巻 5 号 p. 692-693
    発行日: 1952/05/25
    公開日: 2010/02/19
    ジャーナル フリー
    Mold preventing action of the following six compounds against soy sauce was tested: Ethyl phenylcyanopyruvate, diphenylketipinic dinitrile, pulvic anhydride, vulpinic acid, pelvic acid and ethyl pulvate. None of these compounds were effective in preventing growth of molds in the range of approximately 0.001-0.005% concentrations, which may have been due to their difficult solubility in water.
  • 藤沢 俊郎, 水野 長太郎
    1952 年 72 巻 5 号 p. 694-695
    発行日: 1952/05/25
    公開日: 2010/02/19
    ジャーナル フリー
    A new method for the preparation of p-aminobenzenesulfone-N1-3, 4-dimethylbenzoylamide in good yield is described. 3, 4-Dimethylbenzimido ethyl ether, prepared from 3, 4-dimethylbenzonitrile by means of alcoholic hydrogen chloride, was converted into the corresponding amidine by treating with alcoholic ammonia, which was then condensed with acetosulfanil chloride, giving p-acetaminobenzenesulfone-N1-3, 4-dimethylbenzamidine. The latter gave p-aminobenzenesulfone-N1-3, 4-dimethylbenzoylamide on being treated with 15% hydrochloric acid.
  • 藤沢 俊郎, 出口 義雄
    1952 年 72 巻 5 号 p. 696-698
    発行日: 1952/05/25
    公開日: 2010/02/19
    ジャーナル フリー
    The second method for the preparation of p-aminobenzenesulfone-N1-3, 4-dimethylbenzoylamide is described. 3, 4-Dimethylbenzimido ethyl ether was condensed with p-acetaminobenzenesulforiamide and p-nitrobenzenesulfonamide yielding p-acetaminobenzeneselfone-N1-3, 4-dimethylbenzamidine and p-nitrobenzenesulfone-N1-3, 4-dimethylbenzamidine, respectively. The former, on treatment with 15% hydrochloric acid, yielded p-aminobenzenesulfone-N1-3, 4-dimethylbenzoylamide, while the latter yielded the same compound by the simultaneous reduction and hydrolysis of the N4-acetyl group by treatment with tin and hydrochloric acid.
  • アミヂン類の合成 その1
    藤沢 俊郎, 出口 義雄
    1952 年 72 巻 5 号 p. 698-699
    発行日: 1952/05/25
    公開日: 2010/02/19
    ジャーナル フリー
    The third method of synthesis for p-aminobenzenesulfone-N1-3, 4-dimethylbenzoylamide consists in treating 3, 4-dimethylbenzimido ethyl ether with sulfanilamide by which the N1-amido group reacts preferentially giving p-aminobenzenesulfone-N1-3, 4-dimethylbenzamidine which was then hydrolyzed to the final objective product. p-Aminobenzenesulfone-N1-acetamide was also prepared in the similar manner.
  • (第2報) 桂皮酸誘導体の合成
    栗原 藤三郎, 丹羽 弘司
    1952 年 72 巻 5 号 p. 700-702
    発行日: 1952/05/25
    公開日: 2010/02/19
    ジャーナル フリー
    Seven kinds of alkamine esters of p-alkylmercaptocinnamic acid were prepared in order to examine the efficacy of thioalkyl group as the local anesthetic group and the influence of the unsaturated bonding in the alkamine side-chain. Of the compounds synthesized, β-piperidylethyl and γ-diethylaminopropyl p-ethylmercaptocinnamate hydrochlorides were most effective, being slightly better than cocaine as a local anesthesia against rabbit cornea and possessing no irritating action. On the other hand, four kinds of compounds were synthesized in which local anesthetic group was introduced into the β-position of the hydrocinnamic acid but none showed any anesthetic action.
  • ヒノキ酸の精製及び一般性状
    奧田 治
    1952 年 72 巻 5 号 p. 703-705
    発行日: 1952/05/25
    公開日: 2010/02/19
    ジャーナル フリー
    Hinokiic acid, m. p. 166°, [α]D30=-90.35°, was obtained in 0.08% yield from the acid portion of the leaf oil Hinoki, Chamaecyparis obtusa Endl. by extraction with alkali solutions. Hinokiic acid is an unsaturated carboxylic acid of sesquiterpene series, having a rational formula of C14H21COOH, and gives a methyl ester of m. p. 107°, ethyl ester of m. p. 47.5-48°, b. p.3.5 150°, and an amide of m. p. 125°. It is indifferent to boiling with 50% caustic soda, with 30% sulfuric acid, with glacial acetic acid, or by Bertram-Waldaum hydration, but yields an oily product when heated with 50% sulfuric acid in acetic acid solution.
  • 二重結合に対する附加反應成績体
    奧田 治
    1952 年 72 巻 5 号 p. 705-709
    発行日: 1952/05/25
    公開日: 2010/02/19
    ジャーナル フリー
    Hinokiic acid reacts with hydrogen halide to produce oily addition products (II) and (III). Absorbing 1 mole of bromine, the acid produces a dibromohinokiic acid (IV), C14H21Br2COOH, which partly melts at 50-55°, and then at 110-113°, and seems to be a mixture of isomers. By catalytic hydrogenation with PdO, hinokiic acid absorbs 2 moles of hydrogen to yield a dihydroisohinokiic acid (V), m. p. 154°, [α]D13=+77.13°. Reduction with PtO2-catalyst produces tetrahydrohinokiic acid, m. p. 143-144°, [α]D20=+61.29°, which is also obtained by the further hydrogenation of the dihydro compound using PtO2 as a catalyst. From these result, it is assumed that hinokiic acid possesses a tricyclic skeleton and a double bond. Dihydroisohinokiic acid is formed primarily by the saturation of the double bond and the tetrahydro acid seems to be a dicyclic compound formed by the secondary reduction accompanied by the fission of the bridged ring, such as the cyclopropane type. As hinokiic acid is reduced by Bouveault-Blanc's reaction to produce dihydrohinokiic acid (VII), m. p. 92-93°, [α]D13=-22.96°, which is an isomer of the dihydroisohinokiic acid, the double bond is found to be situated on the α, β-position to the carboxyl group. The ester of hinokiic acid is also reduced by Bouveault-Blanc's reaction to hinokilol (VIII), C14H21CH2OH, b. p. 4.5 142-143°, [α]D22=-14.59°, which is oxidized to hinokiic acid by CrO3 via hinokilal (IX), C14H21CHO, and also to dihydroisohinokilol (X), C14H23CH2OH, b. p. 4 130-132°, [α]D22=+7.69°, by the hydrogenation with PdO catalyst.
  • γ-ピコリンよリイソニコチン酸の合成
    石黒 武雄, 内海 勇
    1952 年 72 巻 5 号 p. 709-711
    発行日: 1952/05/25
    公開日: 2010/02/19
    ジャーナル フリー
    Catalytic vapor-phase oxidation was carried out with the fraction (I) of b. p. 142-143° obtained by the fractional distillation of pyridine bases, with γ-picoline (II) isolated in a pure state as its oxalate from (I), and with γ-picoline (III), b. p. 140-145°, synthetically prepared from acetylene and ammonia. Catalyst used was V2O5 with the addition of a small amount of MoO3, CrO3 and WO3. The yield of isonicotinic acid was far better from (III) than from (I), but about the same from (II) or (III). This seems to be due to the presence of β-picoline and 2, 6-lutidine in (I), which are not formed in the synthetic procedure of (III). Catalytic oxidation of (I) results in the formation, in a minute amount, of a product possessing an odor of bitter almond oil. This was confirmed to have been nitrobenzene formed by the catalytic oxidation of aniline which is present in a very minute amount in (I). Such change was not witnessed in the case of (III).
  • ピリヂン塩基, 特にα-ピコリンの合成
    石黒 武雄, 板谷 元一, 久保田 晴壽, 田畑 乃武夫
    1952 年 72 巻 5 号 p. 711-715
    発行日: 1952/05/25
    公開日: 2010/02/19
    ジャーナル フリー
    Catalyst and reaction conditions were studied for the formation of α-picoline alone in larger yields by the synthetic preparation of pyridine bases from acetylene and ammonia. The best catalyst was found to be cadmium phosphate. The use of known catalysts, such as CdO, ZnO, Al2O3 and Cr2O3, results in the increased formation of acetonitrile as the reaction temperature increases, with attendant decrease of pyridine bases. Cadmium phosphate is not easily affected by temperature, and selectively gives a larger yield of α-picoline fraction. For example, using a catalyst of cadmium phosphate and Fuller's earth, at a temperature of 300°, approximately one-half of the fractional distillate of the condensation product is α-picoline, and only a very small amount of acetonitrile portion is obtained. There is no marked increase of acetonitrile even at a temperature between 350 to 400°.
  • 太田 達男, 奧田 治, 宮崎 利夫
    1952 年 72 巻 5 号 p. 716
    発行日: 1952/05/25
    公開日: 2010/02/19
    ジャーナル フリー
  • 中林 利平
    1952 年 72 巻 5 号 p. 717-718
    発行日: 1952/05/25
    公開日: 2010/02/19
    ジャーナル フリー
  • Diquinoline-5,6-dioxideの合成
    富田 真雄, 吉田 則運
    1952 年 72 巻 5 号 p. 718
    発行日: 1952/05/25
    公開日: 2010/02/19
    ジャーナル フリー
  • 岩山 陽治
    1952 年 72 巻 5 号 p. 719-720
    発行日: 1952/05/25
    公開日: 2010/02/19
    ジャーナル フリー
    Santonin is led to desmotroposantonin to which diazobenzenesulfonic acid is coupled to form an orange red dye. The colored solution is utilized for the colorimetric determination of santonin of which 0.2 to 1mg. can be determined.
  • 川谷 豊彦
    1952 年 72 巻 5 号 p. 721-722
    発行日: 1952/05/25
    公開日: 2010/02/19
    ジャーナル フリー
    Concerning the scientific name of “Mibuyomogi”, the sole santonin source in Japan at the present moment, it has generally been referred to as Artemisia monogyna Waldst. et Kit., but the writer has pointed out, from cytogenetical and morphological studies, that it is erroneous, and at the same time he has determined that its true scientific name should be A. maritima L. (sensu stricto) (=A. maritima L. ssp. maritima Gams). “Mibuyomogi” and A. monogyna belong to two cytogenetically and morphologically distinct species of Artemisia.
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