YAKUGAKU ZASSHI
Online ISSN : 1347-5231
Print ISSN : 0031-6903
ISSN-L : 0031-6903
83 巻 , 7 号
選択された号の論文の20件中1~20を表示しています
  • エステル型高分子誘導体
    伊田 忠夫, 高橋 省二, 野田 和夫, 内海 勇
    1963 年 83 巻 7 号 p. 663-671
    発行日: 1963/07/25
    公開日: 2010/02/19
    ジャーナル フリー
    Various O-acyithiamines were prepared by the oxidation of O-acrylate, O-methacrylate, O-crotonate, and O-undecylenate of thiothiamine and high-molecular derivatives of thiamine were obtained by their polymerization. Copolymer of these with vinyl compounds was also prepared.
    Oral administration of these high-molecular derivatives in man and measurement of the amount of thiamine excreted in the urine showed that the total amount excreted during 24 hours was 1/2 to 1/4 of that after administration of thiamine hydrochloride. The peak of excretion appeared much later, 7-12 hours later than that of thiamine, and indicated the lasting effect of high-molecular derivatives. Of these derivatives, those with smaller molecular weight were excreted in larger amount, and copolymers were excreted in larger amount than homopolymers. Greater urinary excretion was found in basic comonomers than acid comonomers among these copolymers.
    These experimental results showed the same tendency as that shown by hydrolysis of high molecular derivatives with alkali or diastase. O-Methacryloyl derivative was not hydrolyzed by alkali or diastase but was hydrolyzed in vivo to be excreted into urine in a similar manner as the other derivatives.
  • アセビの花のトリテルペノイド その1
    近藤 嘉和, 竹本 常松
    1963 年 83 巻 7 号 p. 671-673
    発行日: 1963/07/25
    公開日: 2010/02/19
    ジャーナル フリー
    Triterpenoid components were examined in the flowers of Pieris japonica (THUNBERG) D. DON, and β-amyrin, oleanolic acid, ursolic acid, and β-sitosterol were isolated and identified. In addition, a hitherto unknown neutral triterpenoid (C32H52O2, m. p. 188-189°) was isolated. Its infrared spectrum suggested the presence of endo-methylene group and the spectrum was similar to that of lupeol acetate except for the region of 1000-1100cm-1. It was therefore assumed that this new triterpenoid is its epimer with respect to its 3-hydroxyl group but no evidence has yet been obtained.
  • ホツツジの成分 その1
    近藤 嘉和, 永谷 富子, 武内 康義, 竹本 常松
    1963 年 83 巻 7 号 p. 674-676
    発行日: 1963/07/25
    公開日: 2010/02/19
    ジャーナル フリー
    The present series of work was carried out in order to extract and isolate poisonous component from the leaves of Tripetaleia paniculata SIEB. et ZUCC. Presence of grayanotoxin series substance was assumed from the toxic symptoms of the leaves to mice and such a fraction was obtained but did not crystallize. At the same time, hexa-consane (?), 1-triacontanol, 1-octacosanoi, ursolic acid, and quercetin were separated and identified. Presence of kaempferol was observed in paper chromatography. A new triterpenoid of m. p. 210-211°, C30H50O (acetate, m. p. 210.5-211°), was also isolated.
  • TrilobineおよびIsotrilobineの構造 その15 EpistephanineよりIsotrilobine Antipodeの合成
    富田 真雄, 古川 宏
    1963 年 83 巻 7 号 p. 676-679
    発行日: 1963/07/25
    公開日: 2010/02/19
    ジャーナル フリー
    Y. Inubushi and K. Nomura reported a ring cleavage reaction of natural isotrilobine with sodium in liquid ammonia and represented its structure by II. In the present paper authors showed that the demethylation and dehydration of N-methyldihydroepistephanine (V) with hydrobromic acid followed by O-methylation gave O-methylanhydrodemethyl-N-methyldihydroepistephanine (VIII) (picrate, m. p. 188-189° (decomp.), [α]D -226.7° (acetone)), which is the antipode of natural isotrilobine (cf. Table I).
  • 2,3,4,4a,5,6-Hexahydro-1H-pyrazino[1,2-a]quinolineの新合成法
    永田 正典, 山崎 高応
    1963 年 83 巻 7 号 p. 679-682
    発行日: 1963/07/25
    公開日: 2010/02/19
    ジャーナル フリー
    2-Aminomethylquinoline was converted to the corresponding haloacetyl compound (V, VI), followed by cyclization to the corresponding quinolinium salt (VII) by warming in a sealed tube at 90° for 2hr. The salt (VII) was then reduced with lithium aluminum hydride to 2, 3, 4, 4a, 5, 6-hexahydro-1H-pyrazino [1, 2-a] quinoline (IV), identified with the authentic specimen. The compound (IV) was also prepared by the reduction of I with lithium aluminium hydride.
  • 2,3,4,4a,5,6-Hexahydro-1H-pyrimido[1,2-a]quinoline類の合成
    永田 正典, 山崎 高応
    1963 年 83 巻 7 号 p. 682-689
    発行日: 1963/07/25
    公開日: 2010/02/19
    ジャーナル フリー
    Reaction of 2-chloroquinoline with 3-amino propanol gave 2-(3-hydroxypropylamino)-quinoline (I). I was treated with phosphoryl chloride to give the corresponding 4-aza-benzo[c]quinolizine derivative (III). III was reduced to 2, 3, 4, 4a, 5, 6-hexahydro-1H-pyrimido[1, 2-a]quinoline (IVa) over platinium oxide catalyst.
    The hydrochloride of IVa absorbed one mole of hydrogen over platinium oxide catalyst to give 1-(3-aminopropyl)-1, 2, 3, 4-tetrahydroquinoline (IVb), whose structure was elucidated by another method of its synthesis. The compound IVa was prepared also by another method, according to the following process. 2-Aminoquinoline was reacted with ethyl 3-chloropropionate to give 1, 2-dihydro-3H-pyrimido[1, 2-a]quinolin-3-one (VII), followed by its catalytic reduction over platinium oxide catalyst to give 1, 2, 4, 4a, 5, 6-hexahydro-3H-pyrimido[1, 2-a]quinolin-3-one (XIII), which was reduced with lithium aluminum hydride to IVa.
  • N-(Dimethylaminoalkyl) aniline系化合物の合成
    気賀沢 和雄, 菅原 宏, 柊木 峯治
    1963 年 83 巻 7 号 p. 689-695
    発行日: 1963/07/25
    公開日: 2010/02/19
    ジャーナル フリー
    By the reaction of N, N-dimethyl-2-chloropropylamine (or N, N-1-trimethyl-2-chloro-ethylamine), Y-C6H4NRH (Y=H, OC2H5; R=H, CH3, CH2C6H5) represented by the general formula produced a mixture of two kinds of Y-C6H4NRCH(CH3)CH2N(CH3)2 (III) and Y-C6H4NRCH2CH(CH3)N(CH3)2 (IV). A series of such compounds (III) and (IV) was synthesized aiming the analgesics shown in Table I and II. A mixture of two kinds was separated by recrystallization as maleates and picrates and the structure was determined by the method shown in Chart 2.
    In order to obtain the III-type compound, N-(1-methyl-2-dimethylaminoethyl)-p-phenetidine was prepared by the reductive reaction of p-phenetidine and CH3COCH2-N(CH3)2 in the presence of PtO2 catalyst.
  • N-(Dimethylaminoalkyl) aniline系化合物の合成と薬理作用
    気賀沢 和雄, 菅原 宏, 柊木 峯治, 府川 和永
    1963 年 83 巻 7 号 p. 696-700
    発行日: 1963/07/25
    公開日: 2010/02/19
    ジャーナル フリー
    In continuation to the previous report, aminobenzene derivatives, represented by the general formula, Y-C6H4NR-CH2CH2CH2N(CH3)2, Y-C6H4NRCH2CH2N(CH3)2 (Y=H, OC2H5; R=H, CH3, CH2C6H5, COCH3, COC6H5) being also ethylenediamine derivatives, were synthesized as is shown in Table I and II. All of the analgesic activities were examined and some of the superior derivatives to aminopyrine were shown in Table III and IV.
  • チオクト酸誘導体とビタミンB1との結合化合物の合成 その1
    出口 義雄, 中西 和夫
    1963 年 83 巻 7 号 p. 701-704
    発行日: 1963/07/25
    公開日: 2010/02/19
    ジャーナル フリー
    Both thioetic acid and thiamine play important rôle in the metabolic process of pyruvic acid and preparation of their conjugate would be significant for biological studies. The present series of synthetic work was undertaken in order to obtain such compounds.
    Attempt was first made to synthesize a compound in which the sulfur atoms in 6- and 8-positions of thioctlc acid was bonded in disulfide-form to thiamine. Application of sodium thiosulfate to methyl 6, 8-dichloroöctanoate (VI) to obtain the Bunte salt (VII) showed that chlorine in 6-position is less reactive and, by the use of the methyl ester (VIII) and amide (XIV) of 6-bromo-8-chloroöctanoic acid, the objective 6, 8-bis{2-{N-[(4-amino-2-methyl-5 -pyrimidinyl) methyl] formamido}-1-(2-hydroxyethyl) propenyldithio}-octanoic acid was obtained as its methyl ester (II) and amide (IV). Although II retained its thioctic acid activity in approximately 90% of the original acid, transition of thiamine into blood cells was hardly observed.
  • チオクト酸誘導体とビタミンB1との結合化合物の合成 その2
    出口 義雄, 中西 和夫
    1963 年 83 巻 7 号 p. 704-707
    発行日: 1963/07/25
    公開日: 2010/02/19
    ジャーナル フリー
    Following the previous work*1 on the disulfide conjugate (I) of thioctic acid and thiamine, whose thiamine did not transit into blood cells, attempt was made to obtain compounds (IIa and IIb), in which the sulfur atom at 6- or 8-position of thioctic acid was bonded in disulfide form to thiamine and the other sulfur was in a dimer form. Methyl 8-chloro-6-hydroxyoctanoate (III), which was easily available, was converted into methyl 8-mercapto-6-bromo-octanoate (VIa) and from it, methyl 8, 8′-dithiobis[6-{2-{N-[(4-amino-2-methyl-5-pyrimidinyl)methyl]formamido}-1-(2-hydroxyethyl)propenyl-dithio}öctanoate] (IIa) was obtained. Although transition of thiamine into blood cells was observed in II, its thioctic acid activity was abnormally low.
  • チオクト酸誘導体とビタミンB1との結合化合物の合成 その3
    出口 義雄, 三浦 一子
    1963 年 83 巻 7 号 p. 708-713
    発行日: 1963/07/25
    公開日: 2010/02/19
    ジャーナル フリー
    In continuation of previous works, attempt was made to synthesize a compound in which the sulfur atom at 6-position of thioctic acid was bonded in disulfide form to thiamine and the sulfur atom in 8-position was acetylated, i.e. methyl 8-acetylthio-6-{2-{N-[(4-amino-2-methyl-5-pyrimidinyl)methyl]formamido}-1-(2-hydroxyethyl)propenyldithio}octanoate (IIIa). This compound, IIIa showed satisfactory result in thioctic acid activity and transition of its thiamine into blood cells. Among the various methods of synthesis tried, even that showing the highest yield gave the objective substance in a total yield of ca. 6% from methyl 8-chloro-6-hydroxyoctanoate (IV). It was found that the one of the reasons for this poor yield was the extremely slow reaction of the halogen atom in 6-position of methyl 8-acetylthio-6-halogenoöctanoate (VII) to form the Bunte salt (VIII) by the action of sodium thiosulfate and the fact that VIII is easily decomposed by heat.
  • 6-アシルチオ-8-クロロオクタン酸エステルの新合成法
    出口 義雄, 三浦 一子, 伊藤 真純
    1963 年 83 巻 7 号 p. 713-717
    発行日: 1963/07/25
    公開日: 2010/02/19
    ジャーナル フリー
    It had been found that derivatives of haloöctanoic acid in 6- and 8-positions differed in their behavior towards sodium thiosulfate and that the use of 8-substituted derivative would be more desirable. In the present series of work, methyl 8-chloro-6-hydroxy-octanoate was derived to methyl 8-chloro-6-tosyloxyoctanoate (VII) by the action of tosyl chloride and methyl 6-acetylthio-8-chioroöctanoate (Va) was finally synthesized in a high yield of 73% by the application of thioacetic acid and calcium hydroxide in acetone.
  • チオクト酸誘導体とビタミンB1との結合化合物の合成 その4
    出口 義雄, 三浦 一子
    1963 年 83 巻 7 号 p. 717-721
    発行日: 1963/07/25
    公開日: 2010/02/19
    ジャーナル フリー
    Starting with methyl 6-acetylthio-8-chloroöctanoate (Ia) obtained in a previous work, the objective methyl 6-acetylthio-8-{2-{N-[(4-amino-2-methyl-5-pyrimidinyl)methyl]-formamido}-1-(2-hydroxyethyl)propenyldithio}octanoate (IIIa) hydrochloride was obtained in 42% yield from methyl 8-chloro-6-hydroxyoctanoate.
    The values of thioctic acid activity of the conjugates of thioctic acid deriyatives and thiamine obtained in this series of work and transition of thiamine into blood cells, using washed blood cell suspension from a rabbit, are presented.
  • 保存剤のガスクロマトグラフィー
    井口 定男, 山本 孫兵衛, 青山 敏信
    1963 年 83 巻 7 号 p. 721-723
    発行日: 1963/07/25
    公開日: 2010/02/19
    ジャーナル フリー
    Separatory detection of preservatives by gas chromatography was examined. A mixture of sorbic acid, benzoic acid, salicylic acid, dehydroacetic acid, menadione, and methyl, ethyl, butyl, and propyl p-hydroxybenzoate was separated completely into the componental compounds without any pretreatment, under the conditions of 30% DC 550 silicone on Celite 545, at 190°, with carrier gas of hydrogen. Salicylic acid tended to undergo thermal decomposition and phenol peak sometimes appeared in the product but no such decomposition occurred in other compounds.
  • 百瀬 勉, 稲葉 顕
    1963 年 83 巻 7 号 p. 724-725
    発行日: 1963/07/25
    公開日: 2010/02/19
    ジャーナル フリー
    3, 6-Dinitrophthalic acid underwent degradation with aqueous sodium hydroxide at a room temperature in about 60 days to 3-hydroxy-6-nitrophthalic acid, which gave a yellow color in alkaline medium. The degradation also occurred gradually in aqueous sodium carbonate, but the acid was very stable when it was stored in tablets mixed with anhydrous alkali carbonate.
  • ピリダゾン誘導体よりピラゾロン誘導体への縮環反応
    牧 敬文, 木津 弘子, 小畑 和永
    1963 年 83 巻 7 号 p. 725-728
    発行日: 1963/07/25
    公開日: 2010/02/19
    ジャーナル フリー
    1-Phenyl-3, 5-dichloro-6(1H)-pyridazinone (IV) was converted into 1-phenyl-3-hydroxy-pyrazolecarboxylic acid (VI) by treatment with alkali hydroxide solution. The structure of VI was established mainly from infrared spectra of VI and its derivatives. The mechanism of this ring-contraction reaction was assumed.
  • 4-Thienyl-3-buten-2-one誘導体の合成ならびに抗菌作用について
    藤川 福二郎, 平井 邦夫, 沢田 乙吉, 後藤 淳子, 内藤 益一, 津久間 俊次
    1963 年 83 巻 7 号 p. 728-731
    発行日: 1963/07/25
    公開日: 2010/02/19
    ジャーナル フリー
    Nineteen kinds of 4-thienyl-3-buten-2-one derivatives were synthesized and their antibacterial activity was examined with a sensitive strain of human-type tubercle bacilli H37Rv and a strain resistant to INH, PAS, and streptomycin. Thiosemicarbazone, 4-methyl-, 4-ethyl, and 4-allyl-thiosemicarbazones of 4-thienyl-3-buten-2-one showed antibacterial activity against both sensitive and resistant strains at 6.25γ/ml. and salicyloylhydrazone at 12.5γ/ml., while 4-propyyl-, 4-butyl-, 4-(p-tolyl)-, 4-(o-methoxyphenyl)-, 4-(p-methoxyphenyl)-thiosemicarbazones, p-hydroxybenzoylhydrazone, p-aminobenzoylhydrazone, phenylhydrazone, and p-nitrophenylhydrazone at 25γ/ml.
  • ハナヒリノキのトリテルペノイド
    近藤 嘉和, 杉山 淑美, 土出 百合子, 竹本 常松
    1963 年 83 巻 7 号 p. 731-733
    発行日: 1963/07/25
    公開日: 2010/02/19
    ジャーナル フリー
    Ursolic acid and oleanolic acid were isolated and identified newly from Leucothoe Grayana MAXIM. (Japanese name, “Hanahirinoki”), besides a paraffin, considered to be nonacosane or triacontane.
  • チオクトイルアミノ酸の合成
    出口 義雄, 三浦 一子
    1963 年 83 巻 7 号 p. 733-737
    発行日: 1963/07/25
    公開日: 2010/02/19
    ジャーナル フリー
    In the previous report, the synthesis of thioctamide which shows normal ultraviolet absorption spectra was reported. In this report, a comparison between the synthetic method of N-thioctoylamino acid and the other method which have been known so far, has been made. Especially, N-thioctoylamino acid (methionine, glycine, valine and glutamic acid) which indicates normal ultraviolet absorption spectra was obtained from the reaction of thioctoyl chloride and amino acid ester easily in a better yield.
  • Flavonoid Constituents in the Leaves of Acer palmatum THUNBEAG
    有富 正和
    1963 年 83 巻 7 号 p. 737-740
    発行日: 1963/07/25
    公開日: 2010/02/19
    ジャーナル フリー
    Besides vitexin, saponaretin, orientin, and homo-orientin have now been isolated in pure state from the leaves of Acer palmatum THUNBERG and identified as such.
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