YAKUGAKU ZASSHI
Online ISSN : 1347-5231
Print ISSN : 0031-6903
ISSN-L : 0031-6903
83 巻, 2 号
選択された号の論文の30件中1~30を表示しています
  • 1-Methyl-3- and 4-methoxycarbonylpyridinium IodidesのNaBH4による還元
    木下 洋夫, 浜名 政和, 川崎 敏男
    1963 年 83 巻 2 号 p. 115-120
    発行日: 1963/02/25
    公開日: 2010/02/19
    ジャーナル フリー
    In the reduction of 1-methyl-3- and 4-methoxycarbonylpyridinium iodides in methanol by NaBH4, it was found that the 4-substitute gave only 1, 2, 5, 6-tetrahydropyridine, and that the 3-substitute gave 1, 2, 5, 6-tetrahydropyridine and 1, 6-dihydropyri dine compounds. When this reaction was carried out in sodium hydroxide methanol, no tetrahydro compound was obtained, but 1, 2- and 1, 6-dihydro compounds were obtained. When the molar ratio of pyridinium salt to NaBH4 was varied, the product was examined quantitatively and the dihydro derivative isolated was found not to undergo NaBH4 reduction in methanol.
    The result showed that the reductive reaction of pyridinium salt by NaBH4 was taken place at the first stage, between pyridinium cation and BH4 anion, followed by the reaction between dihydro compound produced and BH3. When the methoxy carbonyl group was present at the terminal of the double bond in enamine part of the dihydro compound, and when the reaction was taken place in sodium hydroxide alkali medium, any reduction into tetrahydro compound by BH3 has not been found to take place. This fact may be explained by the following reactivity with BH3
    OH->>N-CH=CH->MeOH>N-CH=C-COOMe
  • 1-Methyl-3-methoxycarbonyldihydropyridinesのB2H6による還元
    木下 洋夫, 川崎 敏男
    1963 年 83 巻 2 号 p. 120-122
    発行日: 1963/02/25
    公開日: 2010/02/19
    ジャーナル フリー
    The reductive reaction of 1-methyl-3-methoxycarbonyl-1, 2, -1, 4- and -1, 6-dihydropyridines by B2H6 (diborane) in methanol was examined and it was found that 1, 2-dihydro compound was reduced to 1, 2, 5, 6-tetrahydro compound, but that 1, 4- and 1, 6-dihydro compounds did not undergo any reduction.
    This fact support the previously reported assumption on the studies in reductive process of 1-methyl-3- and -4-methoxycarbonylpyridinium iodides by NaBH4.
  • 1-Methyl-3-cyanopyridinium Iodideと1,3-Dimethylpyridinium IodideのNaBH4による還元
    木下 洋夫, 川崎 敏男
    1963 年 83 巻 2 号 p. 123-126
    発行日: 1963/02/25
    公開日: 2010/02/19
    ジャーナル フリー
    In order to know the influence of the substitute at the 3-position in the reduction of pyridinium salt by NaBH4, the reduction of 1-methyl-3-cyanopyridinium iodide and 1, 3-dimethylpyridinium iodide by NaBH4 was carried out. It was found that the former gave quite a similar type of reductive product to that of 3-methoxycarbonyl derivative but the latter gave a different type of reductive product. This difference might be considered that the cyano group possess the same electro-philic property to the methoxycarbonyl group but the methyl group might possess electron-donor properties. Therefore, the influence of the substitute in the reaction may be controlled by rather electronic behavior than steric configuration.
  • 1-Methyl-2-methoxycarbonylpyridinium IodideのNaBH4による還元
    木下 洋夫, 川崎 敏男
    1963 年 83 巻 2 号 p. 126-130
    発行日: 1963/02/25
    公開日: 2010/02/19
    ジャーナル フリー
    The reduction of 1-methyl-2-methoxycarbonylpyridinium iodide by NaBH4 in methanol gave 1-methyl-2-methoxycarbonyl-1, 2, 3, 6-tetrahydropyridine and 1-methyl-2-methoxy-carbonyl-1, 6-dihydropyridine and the reduction in sodium hydroxide alkali methanol gave only 1, 6-dihydro compound. The reduction of 2-methoxycarbonyl derivative (I) by NaBH4 gave, different from the case of the 3- or 4-substitute, 1, 6-dihydro compound firstly, reduced only from Ib structure, a part of which will be further reduced to 1, 2, 3, 6-tetrahydro compound.
    The structure of tetrahydro compound has been determined by the NMR measurement of its methyl iodide salt in heavy water and that of dihydro compound by the IR spectrum analysis.
  • 2-(p-Methoxyphenylamino)acetohydroxamic Acid, 2-(p-Methoxyphenylamino)acetamide誘導体の合成について
    近藤 薫, 早崎 孝財
    1963 年 83 巻 2 号 p. 130-134
    発行日: 1963/02/25
    公開日: 2010/02/19
    ジャーナル フリー
    2-(p-methoxyphenylamino)acetohydroxamic acid (IIa) and 2-[N-(p-methoxyphenyl)-phenylsulfonamido]acetohydroxamic acid (IIb) were obtained by reacting N-(p-methoxyphenyl)glycine ethyl ester (Ia) and N-(p-methoxyphenyl)-N-phenylsulfonylglycine ethyl ester (Ib) with hydroxylamine. when Ia and Ib were reacted with methanolic ammonia under pressure, 2-(p-methoxyphenylamino)acetanilide (IIIa) and 2-[N-(p-methoxyphenyl)phenylsulfonamido]acetamide (IIIb) were obtained.
    IIa is also obtainable by reacting either IIIa or N-(p-methoxyphenyl)glycine hydrazide (IVa) with hydroxylamine hydrochloride. On the other hand, IIIa and IIIb are also obtainable either by the reaction of methanolic ammonia under pressure, or by reacting IVa and N-(p-methoxyphenyl)-N-phenylsulfonylglycine hydrazide (IVb) with potassium ferricyanate. When IIa and IIb were reacted with benzenesulfonyl chloride in pyridine, they gave the substance VII, m. p. 176° (decomp.), which was assumed to be 1, 3-bis{[N-(p-methoxyphenyl)phenylsulfonamido]methyl}urea by the qualitative and elemental analysis. If VII was treated with hydrazinehydrate, it decomposed into N-(p-methoxyphenyl)benzenesulfonamide.
  • 14H-Dibenzo[a,j]xanthene誘導体について
    岡林 一蔵
    1963 年 83 巻 2 号 p. 135-138
    発行日: 1963/02/25
    公開日: 2010/02/19
    ジャーナル フリー
    2-Diethylaminoethyl 14H-dibenzo[a, j]xanthene-14-acetate hydrochloride (IV) was synthesized through 14H-dibenzo[a, j]xanthene-14-acetic acid (III) from 14H-dibenzo[a, j]xanthen-14-ol (II), the starting material, prepared by the treatment of dibenzo[a, j]xanthylium perbromide (I) in ethanolic potassium hydroxide solution.
    II was condensed with monoethyl malonate, diethyl malonate, cyanoacetic acid and ethyl cyanoacetate to afforded ethyl hydrogen 14H-dibenzo[a, j]xanthene-14-malonate (V), diethyl 14H-dibenzo [a, j]xanthene-14-malonate (VI), α-cyano-14H-dibenzo[a, j]xanthene-14-acetic acid (VII) and ethyl α-cyano-14H-dibenzo[a, j]xanthene-14-acetate (VIII) respectively. It was found that the anti-acetylcholine action, anti-histaminic action, as well as anti-barium hydrochloride action of IV were considerably weak with the corresponding xanthene-9-acetic acid ester.
  • キノリン誘導体について その9
    浜田 喜樹, 杉原 久義
    1963 年 83 巻 2 号 p. 138-142
    発行日: 1963/02/25
    公開日: 2010/02/19
    ジャーナル フリー
    4-Thiocyanato-8-quinalinol (III) was obtained by the rhodanation of either 8-quinolinol or 3′-chloro-4′-thiocyanatoacetanilide (II) which was prepared from the acetylation of 3-chloro-1-amino-4-chiocyanatobenzene (I) with acetic anhydride with sodium thiocyanate in methanol, but the rhodanation of 5-sulfanilyl-8-quinolinol and 5-chloro-7-iodo-8-quinolinol with either sodium thiocyanate in methanol or ammonium thiocyanate in acetic acid ended in the recovery of the starting materials. 5-Thiocyanatoquinoline (V) was synthesized by the rhodanation of 8-aminoquinoline with ammonium thiocyanate, followed by the deamination of 5-thiocyanato-8-aminoquinoline (IV). On the other hand, the compound obtained from 5-aminoquinoline by the Sandmeyer reaction was identical with V. 6-Chloro-8-aminoquinoline was rhodanized to 5-thiocyanato-6-chloro-8-aminoquinoline (VI) with ammonium thiocyanate.
    IV and VI were reacted with acetic anhydride to 5-thiocyanate-8-acetamidoquinoline (VII) and 5-thiocyanato-6-chloro-8-acetamidoquinoline (VIII). 6-Thiocyanatoquinoline (XI) and 6-chloro-8-thiocyanatoquinoline (XII) were obtained by the rhodanation of 5-aminoquinoline and 5-amino-6-chloroquinoline with ammonium thiocyanate, followed by the deamination of 5-amino-6-thiocyanatoquinoline (IX) and 5-amino-6-chloro-8-thiocyanatoquinoline (X). On the other hand, the products synthesized by the Sandmeyer reaction of 6-aminoquinoline and 6-chloro-8-aminoquinoline were identical with XI and XII. 4-Methyl-6-nitrothiocarbostyril and 2-methyl-8-chloro-4-quinolinethiol were reacted into 2-methylthio-4-methyl-6-nitroquinoline (XIII) and 2-methyl-4-methylthio-8-chloroquinoline (XIV) by methyl iodide.
    Quinaldinic acid acylhydrazide (XVI)-(XIX) were prepared by reacting quinaldinic acid hydrazide (XV) with acetyl chloride, benzoyl chloride, p-nitrobenzoyl chloride and cinnamoyl chloride. Anti-candida activities of these compounds, I-IV, VI, VIII-XI and XVI-XIX were examined.
  • トリニトロベンゼンによる強心配糖体の比色定量
    百瀬 勉, 松隈 ときよ, 大倉 洋甫, 中村 由美子
    1963 年 83 巻 2 号 p. 143-147
    発行日: 1963/02/25
    公開日: 2010/02/19
    ジャーナル フリー
    A sensitive colorimetric method was devised for determination of cardiac glycosides, oleandrin (I), digoxin (II), digitoxin (III), and ouabain (IV), with 1, 3, 5-trinitrobenzene as a color developing agent in sodium carbonate solution. The addition of sodium dihydrogenphosphate reduced the intensity of blank color.
    The test solution was prepared by dissolving I, II, or III in dimethylformamide, and IV in water. To 1.0ml. of the test solution, 0.5ml. of 0.1% solution of trinitrobenzene and 0.5ml. of sodium carbonate solution were successively added, and the mixture was warmed at 42±1°, protected from light. After cooling in an ice-water bath, 0.12% solution of sodium dihydrogenphosphate was added to the mixture to make 5.0ml., and the developed color was measured at the absorption maximum of 460 mμ, with a reagent blank, which followed the Beer's rule in a concentration range of 0 to 100γ/ml. The appropriate concentration of sodium carbonate was 0.2% for I, 0.3% for III, and 0.35% for II and IV. The optimum heating time for the color development was 20 minutes for I, II, and III, and 25 minutes for IV.
    Some active methylene compounds interfered with this coloration. Polyphenols, creatinine, indole, and androsterone gave a strong coloration with this reagent. Standard deviation of the method in a concentration of 50γ/ml. of the glycoside is given in Table I, compared with the J. P. method.
  • 2-Heteroaryl-ω-(5-nitro-2-furyl) polyenoic Acid類の合成
    西海枝 東雄, 田中 昭
    1963 年 83 巻 2 号 p. 147-153
    発行日: 1963/02/25
    公開日: 2010/02/19
    ジャーナル フリー
    2-Thienyl-ω-(5-nitro-2-furyl) acrylic acid, 2-furyl-ω-(5-nitro-2-furyl) acrylic acid and also corresponding seventeen acid amides were synthesized. In case of the synthesis of 2-furyl-3-(5-nitro-2-furyl) acrylic acid by Perkin reaction, cis and trans crystalline isomers were obtained, whose conformations were determined on the basis of their dipole moments. Ultraviolet absorption spectra of the above mentioned compounds were also determined.
  • ThalicberineおよびO-Methylthalicberineの構造 その5
    富松 利明, 加納 蓉子
    1963 年 83 巻 2 号 p. 153-158
    発行日: 1963/02/25
    公開日: 2010/02/19
    ジャーナル フリー
    The structure of thalicberine and O-methylthalicberine, the new tertiary bases of Thalictrum thunbergii DC. (Japanese name “Aki-karamatsu”), had been indicated as Ia and Ib but the type of its ether bonding constituting the diphenyl ether binding two isoquinoline rings was so exceptional that further examinations were made to prove this structure.
    O-Methylthalicberine methylmethine (II) was oxidized with ozone to (A) and (B) fragments. (B) afforded 4-methoxy-3, 4′-dihydroxybenzaldehyde (III) and aldehydic acids (IVa) and (IVb) as crystals. (A) afforded a diamino-dialdehyde, which was obtained as its dimethiodide (VIII) of m. p. 235°(decomp.), C27H40O6N2I⋅H2O. It was submitted to the second Hofmann degradation, followed by catalytic and Clemmensen reductions, and derived to X, whose infrared spectrum (in CS2) agreed with that of synthesized 2-methoxy-4-methyl-5-ethylphenyl 2-methyl-3-ethyl-5, 6-dimethoxy-phenyl ether. The whole route of this synthesis is indicated in Chart 1.
    Ozone oxidation of O-methyloxyacanthine methylmethine (XII) by the route shown in Chart 2 afforded, as the basic decomposition product, a diamino-dialdehyde as its dimethiodide (XIV) of m. p. 245°(decomp.), C27H40O6N2I2⋅H2O. The infrared spectrum (in Nujol) of this dimethiodide (XIV) was entirely different from that of VIII, derived from O-methythalicberine methylmethine (II).
    The present series of experiments has proved unequivocally that thalicberine and O-methylthalicberine are represented as Ia and Ib, respectively.
  • ThalicberineおよびO-Methyl-thalicberineの構造 その6
    藤田 栄一, 富松 利明, 加納 蓉子
    1963 年 83 巻 2 号 p. 159-161
    発行日: 1963/02/25
    公開日: 2010/02/19
    ジャーナル フリー
    In order to elucidate the structure of the substance III, derived from the basic decomposition product of ozone oxidation of O-methylthalicberine methylmethine (I), synthesis of 2-methoxy-4-methyl-5-ethylphenyl 2-methyl-3-ethyl-5, 6-dimethoxyphenyl ether (II) was carried out.
    One of the starting materials, 3-bromo-4-methyl-5-ethyl-1, 2-dimethoxybenzene (VIII), was synthesized from isovanillin (III) by its Clemmensen reduction to IV, introduction of acetyl group by the Friedel-Crafts reaction, Clemmensen reduction of its products to VI, bromination to VII, and finally by O-methylation to VIII. The other substance XVI was synthesized from m-cresol (IX) by its acetylation to X, Fries rearrangement followed by Clemmensen reduction to XII, and O-methylation to 3-methyl-4-ethylanisole (XIII), which was reduced and hydroxyl group introduced through diazotization. The position of this hydroxyl group was confirmed through the negative Gibbs reaction and identity of the infrared spectrum (in CHCl3) of the O-methyl ether (XVII) of this substance with that of O-methyl ether (XVII) of VI synthesized by a known method.
    The Ullmann condensation of these 3-bromo-4-methyl-5-ethyl-1, 2-dimethoxybenzene (VIII) and 2-methoxy-4-methyl-5-ethylphenol (XVI) gave the desired substance (II).
  • Berberine Phenolbetaineの還元成績体の構造
    竹本 常松, 近藤 嘉和, 近藤 一恵
    1963 年 83 巻 2 号 p. 162-165
    発行日: 1963/02/25
    公開日: 2010/02/19
    ジャーナル フリー
    Treatment of berberine phenolbetaine (I) with acetic acid and zinc dust afforded colorless prisms of C20H21O4N (II), m. p. 169-171° and colorless feather shaped crystals of C20H21O4N (III), m. p. 180-181°. Both products showed ultraviolet spectra at λmaxEtOH 285mμ (log ε 3.71) but different infrared spectra (CHCl3). II was identified with trans-2, 3-methylenedioxy-9, 10-dimethoxy-5, 6, 13, 13a-tetrahydro-8H-dibenzo [a, g] quinolizine (m. p. 171-172°). On the basis of ultraviolet, infrared and nuclear magnetic resonance spectra, III was regarded to be a stereoisomer which possesses the same skeleton as that of II. III was presumed to have cis-quinolizidine structure, since it is already shown that II possesses trans-quinolizidine structure. As their infrared spectra in the region 2700-2800cm-1 did not provide a definite conclusion, their nuclear magnetic resonance spectra were determined in the two component solvent system. Since the proton exchange rate between nitrogen of the compound and trifluoroacetic acid in its solution of pyridine-trifluoroacetic acid system alters depending upon its shielding, the determination of the shift of proton signal of trifluoroacetic acid may indicate their conformational difference. Of their 3 mole% trifluoroacetic acid-pyridine solution proton signal in III shifted at higher field by 35.83 c. p. s. than that of II. It follows, therefore, from these results that III possesses a cis-quinolizidine structure.
  • 13-Oxy誘導体の還元
    近藤 嘉和, 永谷 富子, 竹本 常松
    1963 年 83 巻 2 号 p. 166-168
    発行日: 1963/02/25
    公開日: 2010/02/19
    ジャーナル フリー
    Reduction of 13-hydroxy-2, 3-methylenedioxy-9, 10-dimethoxy-5, 6-dihydrobenzo[a]-acridizinium chloride (III) with zinc and acetic acid afforded trans-2, 3-methylenedioxy-9, 10-dimethoxy-5, 6, 13, 13a-tetrahydro-8H-dibenzo [a, g] quinolizine (IIa) and cis-2, 3-methylenedioxy-9, 10-dimethoxy-5, 6, 13, 13a-tetrahydro-8H-dibenzo[a, g]quinolizine (IIb). A similar reduction of 13-methoxy-2, 3-methylenedioxy-9, 10-dimethoxy-5, 6-dihydrobenzo[a]acridizinium iodide (IV) gave only II a which is formed by the elimination of methoxy group at 13-position of IV. Sodium borohydride reduction of III and IV in methanol afforded 2, 3-methylenedioxy-9, 10-dimethoxy-5, 6, 13, 13a-tetrahydro-8H-dibenzo[a, g]quinolizin-13-ol (V) and 13-methoxy-2, 3-methylenedioxy-9, 10-dimethoxy-5, 6, 13, 13a-tetrahydro-8H-dibenzo[a, g]quinolizine (VI) (m. p. 200-201° in vacuo), respectively. Reduction of 8-acetonyl-13-hydroxy-2, 3-methylenedioxy-9, 10-dimethoxy-5, 6, 13, 13a-tetrahydro-8H-dibenzo[a, g]quinolizine (VII) with zinc dust and acetic acid gave IIa, but in case of α-methyl-13-hydroxy-2, 3-methylenedioxy-9, 10-dimethoxy-5, 6, 13, 13a-tetrahydro-8H-dibenzo[a, g]quinolizine-8-methanol (VIII) and V the same reduction afforded starting materials. Therefore, it follows from these results that the mechanisms of dehydroxylation and demethoxylation with zinc and acetic acid differ from that of hydrogenolysis of benzyl alcohol type compounds via their tetrahydro-derivatives.
  • 森山 弘明
    1963 年 83 巻 2 号 p. 169-171
    発行日: 1963/02/25
    公開日: 2010/02/19
    ジャーナル フリー
    Condensation of acetylenedicarboxylic acid with urea in conc. sulfuric acid gave Δ5, α-hydantoinacetic acid (II), which on heating in aqueous 1N potassium hydroxide was converted into 4-uracilcarboxylic acid (III). Condensation of acetylenedicarboxylic acid with thiourea proceeded more smoothly to afforded 2-thio-Δ5, α-hydantoinacetic acid (IV) which was also converted into 2-thio-4-uracilcarboxylic acid (V). Condensation of dimethyl acetylenedicarboxylate with thiourea proceeded even in water solution to give methyl 2-thio-Δ5, α-hydantoinacetate (VI) which changed into V on heating in 2N potassium hydroxide.
  • 多塩基性酸エステル類とアミン類との縮合反応 その2 Diethyl 2-Cyano-3-methylglutarateとHomoveratrylamineとの溶融縮合成績体について
    亀谷 哲治, 柳瀬 良文, 小林 良介
    1963 年 83 巻 2 号 p. 171-174
    発行日: 1963/02/25
    公開日: 2010/02/19
    ジャーナル フリー
    The condensation product of 1 mole of diethyl 2-cyano-3-methylglutarate with 1 mole of homoveratrylamine, on purification by alumina chromatography afforded monoamide (I) and imide (V). When the former was cyclized with phosphorus oxychloride, isoquinoline derivative having an exo-double bond (IV) and a lactam (III) were resulted. The latter imide (V) was also obtained by the action of sodium ethoxide on amide (I). When the same reaction was carried out with 2 mole of ester and 1 mole of amine, diamide (VI), imide (V) and a product of unknown structure were obtained. Cyclization of diamide (VI) with phosphorus oxychloride gave isoquinoline derivative, whose probable structure would be represented by VIIa on the basis of its infrared spectrum.
  • 1-(5-Nitro-2-thienyl)-6,7-dialkoxyisoquinoline誘導体の合成ならびに5-Nitro-2-置換チオフェン誘導体の抗菌性および抗バイ性について
    亀谷 哲治, 梅沢 修, 佐藤 実, 小林 富二男
    1963 年 83 巻 2 号 p. 174-179
    発行日: 1963/02/25
    公開日: 2010/02/19
    ジャーナル フリー
    Since some of 5-nitro-2-thiophenecarboxylic acid derivatives show strong antibiotic activity, several isoquinoline derivatives which possess 5-nitro-2-thienyl group were synthesized and their pharmacological action was examined. No significant activity was exhibited by any isoquinoline derivative but 5-nitro-2-thiophenecarboxaldehyde, its oxime and ethyl 5-nitro-2-thiophenecarboxylate showed considerably strong anti-syphilis activity. Also, a strong antibiotic effect was seen in two kinds of methyl 5-nitro-2-thiophenecarboxamides. The syntheses of isoquinoline derivatives were carried out by Bischler-Napieralski reaction and a simplified method of Kametani.
  • クラリンおよび関連化合物の合成研究 その2 N-[3-(2-Formyl-4,5-dimethoxyphenoxy)-4-methoxyphenethyl]acetamideのPictet-Spengler反応による成績体について (C-nor-Cularineの合成)
    亀谷 哲治, 福本 圭一郎, 小笠原 国郎
    1963 年 83 巻 2 号 p. 180-184
    発行日: 1963/02/25
    公開日: 2010/02/19
    ジャーナル フリー
    Condensation of N-(3-hydroxy-4-methoxyphenethyl)acetamide (VIII) prepared from iso-vaniline and 6-bromoveratraldehyde by Ullmann reaction afforded N-[3-(2-formyl-4, 5-dimethoxyphenoxy)-4-methoxyphenethyl]acetamide (IX). By Pictet-Spengler reaction with 20% hydrochloric acid, acetamide (IX) was cyclized and dehydrogenated to give isoquinoline (XI), the structure of which was established by various physical and chemical methods. Next, C-nor-cularine (1-methyl-6, 9, 10-trimethoxy-1, 2, 3, 11b-tetra-hydropyrido[4, 3, 2-kl]xanthene was synthesized by preparing methiodide (XII) and its reduction with NaBH4.
  • ステアリン酸アルミニウムーベンゼン溶液の構造粘性
    中垣 正幸, 西野 操
    1963 年 83 巻 2 号 p. 185-189
    発行日: 1963/02/25
    公開日: 2010/02/19
    ジャーナル フリー
    The structural viscosity of the commercial and the synthesized aluminum distear-ate by the double decomposition method in aqueous solution was measured by capilary viscosimeter in benzene. The result was that aluminum stearate in benzene solution showed the structural viscosity at a low concentration of less than 0.5g./100cc., and that the time dependency of apparent viscosity in solution was assumed to be due mainly to the change of molecular weight of aluminum stearate.
    By applying the double extrapolation method of 1/s→0 and c→0 into in η/r/c the intrinsic viscosity was calculated, and it gave exact information on the property of aluminum stearate. When the molar relationship of the intrinsic viscosity, [ηN] to aluminum and stearic acid was calculated, the maximum of [ηN] was found in a little smaller than 2 of St/Al.
  • ホウザンツヅラフジ (鉄牛入石) Cocculus sarmentosus DIELSのアルカロイド その4 水溶性第4級Aporphine型塩基Cocsarrnineの構造
    富田 真雄, 古川 宏
    1963 年 83 巻 2 号 p. 190-194
    発行日: 1963/02/25
    公開日: 2010/02/19
    ジャーナル フリー
    Tomita has previously isolated such a tertiary biscoclaurine-type base as trilobine, isotrilobine and menisarine from the root-stock of Cocculus sarmentosus DIELS (Japanese name “Hozan-tsuzurafuji”) produced in Formosa.
    From the residual mother liquior, from which the crystals mentioned above had already separated, a little amount of crystal, m. p. 155-157° was obtained and it was certified to be a bimorphism of tetrandrine (I). On the other hand, an investigation of new water-soluble quaternary base was made on this plant and a new aporphine-type base, which was named cocsarmine, was obtained. The picrate, C21H26O4N⋅C6H2-O7N3, m. p. 226-227° (decomp.), iodide, C21H26O4NI⋅3H2O-C16H10(OCH3)3(OH)NCH3CH3I⋅3H2O, m. p. 205-207° (decomp.) (185° sint.), [α]D+27.9°(EtOH). Its O-methyl derivative, C22H28O4NI, m. p. 219-221° was identical with O, O-dimethyllaurifoline (II) iodide by the mixed m. p. determination and IR analysis (CHCl3, Nujol). The O-ethyl derivative was also identical with the authentic sample of 1, 2, 9-trimethoxy-10-ethoxyapor-phine methiodide (VIII) by IR analysis (CHCl3). Thus cocsarmine has been certified to be d-N-methyl-10-hydroxy-1, 2, 9-trimethoxyaporphine (IV).
  • 上尾 庄次郎, 藤村 一, 浅井 篤
    1963 年 83 巻 2 号 p. 195-197
    発行日: 1963/02/25
    公開日: 2010/02/19
    ジャーナル フリー
    5-(2-Haloacylamido)-3-methylisothiazoles were prepared by treatment of 5-amino-3-methylisothiazole with 2-haloacyl halides and afforded with dimethylamine, diethyl-amine, piperidine, morpholine, and pyre rolidine the corresponding 5-(2-alkylamino-acylamido)-3-methylisothiazoles respectively. Interreaction of 5-amino-3-methylthiazole and p-nitrobenzoyl chloride gave 5-(p-nitrobenzamino)-3-methylisothiazole which was reduced with iron in acetic acid to afford 5-(p-aminobenzamido)-3-methyliso thiazole. Analgesic action and toxicity of these compounds were tested and most of them especially compounds V, VI, X, and XI were found to be more effective than aminopyrine.
  • 上尾 庄次郎, 藤村 一, 浅井 篤
    1963 年 83 巻 2 号 p. 198-200
    発行日: 1963/02/25
    公開日: 2010/02/19
    ジャーナル フリー
    5-(2-Haloacylamido)-3-methylisoxazoles were prepared by treatment of 5-amino-3-methylisoxazole with 2-haloacyl halides and afforded with dimethylamine, diethylamine, piperidine, morpholine, and pyrrolidine the corresponding 5-(2-alkylaminoacylamido)-3-methylisoxazoles respectively. Examination of analgesic action and toxicity that compounds VI and XI were more favorable than aminopyrine.
  • スルファチアゾールの肝臓灌流による変化について
    宇野 豊三, 上田 道広
    1963 年 83 巻 2 号 p. 200-202
    発行日: 1963/02/25
    公開日: 2010/02/19
    ジャーナル フリー
    Change of sulfathiazole by liver perfusion was examined. Excised liver of a rabbit was placed in the perfusion apparatus, designed by Ôhashi and Kai, and perfused with a rabbit Ringer solution, added with rabbit blood which was defibrinized and added with 10mg% of sulfathiazole. Methanol was added to the perfusion liquid obtained after two hours, centrifuged, and the supernatant was submitted to paper chromatography. Comparison with authentic samples showed the presence of acetyl-sulfathiazole, sulfathiazole-N4-sulfonate, sulfathiazole-N4-glucuronide, and unchanged sulfathiazole. Another sulfathiazole-glucuronic acid conjugate found in human urine was not found in the rabbit urine.
    The metabolite spots on the paper chromatogram were separately eluted, hydrolyzed to sulfathiazole, and determined by the Bratton-Marshall method. The amount calculated in 2-hour perfusion liquid was 43% of sulfathiazole, 12.5% of acetylsulfathiazole, 2.5% of sulfathiazole-N4-sulfonate, and 42% of sulfathiazole N4-glucuronide. This experiment has shown that the chief organ for biological change of sulfathiazole is the liver.
  • 北原 一太, 田中 善正
    1963 年 83 巻 2 号 p. 203-206
    発行日: 1963/02/25
    公開日: 2010/02/19
    ジャーナル フリー
    In order to examine the physical and chemical effect of powerful radioactive rays on liquid organic compounds, especially on unsaturated fatty acids, effect of irradiation of γ-rays from cobalt-60 of 16000 curie was examined. Changes resulting from irradiation were examined by gas chromatography and by infrared absorption spectrum. Electric conductivity during irradiation was measured by a special measuring cell possessing a wide electrode area, devised by the present authors.
    No change was observed in unsaturated fatty acid esters of 18 carbon atoms when irradiated with the dose of about 106 roentgen, in oxygen-free state. Electric conductivity during the irradiation was found to be proportional to the square root of dosage rate at a constant temperature, within a range of dosage rate of 104 to 106 r/hr., but that the conductivity returned to the pre-irradiation level within a few hours upon removal of the irradiation source. This fact is considered to be of help in elucidating the mechanism of chemical reaction under radio-active ray irradiation and could also be applied for measuring a large dosage rate.
  • 1-Methyl-3-methoxycarbonyldihydropyridine類のKMnO4酸化
    木下 洋夫, 大山 和子
    1963 年 83 巻 2 号 p. 207-209
    発行日: 1963/02/25
    公開日: 2010/02/19
    ジャーナル フリー
    It was found that 1-methyl-3-methoxycarbonyl-1, 6-dihydropyridine was oxidized by KMnO4 into 1-methyl-5-methoxycarbonyl-2(1H)-pyridone in cold acetone in comparatively better yield.
    Following to this method, 2(1H)-pyridone compound was prepared from the corresponding 1, 4-dihydro compound but any pyridone compound 1-methyl-3-methoxy-carbonyl-1, 2, 5, 6-tetrahydropyridine did not undergo the oxidation in this condition.
  • ホウ酸塩の経口投与による臓器内ホウ素およびリンの消長と脂質分画におけるホウ素およびリンの分布
    赤木 満洲雄, 三沢 隆行, 金島 弘恭
    1963 年 83 巻 2 号 p. 209-212
    発行日: 1963/02/25
    公開日: 2010/02/19
    ジャーナル フリー
    It was found that boron level in the organs of guinea pigs, given orally in a single dose of borate, reached a peak 2 hours after in the kidney, and after 3 hours in the liver and brain, About 12 hours after the boron level in the brain was the lowest but after about 24 hours, it was the highest amongst these three organs, In a period of 6 hours, in which the boron level in the brain and liver was the highest, the phosphorus level in these two organs was the lowest, but the phosphorus level in the kidney had a tendency to rise slowly for the next 12 hours. The boron level for lipid fractions of the brain and liver was also examined.
  • Tetrahydroberberine N-Oxideの合成
    近藤 嘉和, 竹本 常松
    1963 年 83 巻 2 号 p. 213-214
    発行日: 1963/02/25
    公開日: 2010/02/19
    ジャーナル フリー
    In order to examine pharmacological effect of a suitable, water soluble derivative of 2, 3-methylenedioxy-9, 10-dimethoxy-5, 6, 13, 13a-tetrahydro-8H-dibenzo [a, g] quinolizine (tetrahydroberberine), N-oxide was prepared. N-Oxide gave colorless prisms (I), m. p. 188-190°(decomp.) and cubes (II), m. p. 218-219°(decomp.) and the former was transformed to the latter during crystallization. Infrared spectra of both products are identical. Both could be reduced with zinc dust and acetic acid but resisted to a reduction wih sodium sulfite, sodium thiosulfate and sodium borohydride.
  • アオグスモドキMachilus Pseudolongifolia HAYATAのアルカロイド
    盧 盛徳
    1963 年 83 巻 2 号 p. 214-216
    発行日: 1963/02/25
    公開日: 2010/02/19
    ジャーナル フリー
    Examinations on the alkaloids of Machilus pseudolongifolia HAYATA (Lauraceae) (Japanese name “Aogusumodoki”) indicated the presence of two new phenolic base, L-(-)-N-norarmepavine (I) and dl-N-norarmepavine. Besides, a small amount of oxalate crystal, m. p. 188-189°(decomp.) has been obtained as a non-phenolic base.
  • キンコウボクMichelia Champaca LINN. のアルカロイド
    楊 藏雄, 蕭 振亜
    1963 年 83 巻 2 号 p. 216-218
    発行日: 1963/02/25
    公開日: 2010/02/19
    ジャーナル フリー
    An investigation of basic component from Michelia Champaca LINN (Japanese name “Kin-Koboku”) gave ushinsunine (I) and oxoushinsunine (liriodenine) (II) as a tertiary non-phenolic base, as well as magnoflorine (III) and unknown base, m. p. 260°(decomp.) as a water-soluble quaternary base, which were isolated to picrate, respectively. Both ushinsunine (I) and oxoushinsunine (II) were found to distribute populary, especially in Michelia genus.
  • Masao Tomita, Tsang-Hsiung Yang, K. N. Gaind, S. K. Baveja
    1963 年 83 巻 2 号 p. 218
    発行日: 1963/02/25
    公開日: 2010/02/19
    ジャーナル フリー
    Machiline, an alkaloid of Machilus macrantha NEES. (Lauraceae) was confirmed as identical with dl-coclaurine (III).
  • ヒキノ ヒロシ, 曳野 靖子, 加藤 紘子, 竹下 保義, 竹本 常松
    1963 年 83 巻 2 号 p. 219-220
    発行日: 1963/02/25
    公開日: 2010/02/19
    ジャーナル フリー
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