2 0 0 0 日本産カギカズラの塩基成分とその化学変換に関する研究
- 著者
- 萩庭 丈寿 坂井 進一郎 相見 則郎 山中 悦二 新間 信夫
- 出版者
- 公益社団法人 日本薬学会
- 雑誌
- YAKUGAKU ZASSHI (ISSN:00316903)
- 巻号頁・発行日
- vol.93, no.4, pp.448-452, 1973-04-25 (Released:2008-05-30)
- 参考文献数
- 12
- 被引用文献数
- 21 33
In the reinvestigation of the constituents of Uncaria rhynchophylla MIQ. (Japanese name "kagikazura"), the presence of two oxindole alkaloids, corynoxeine and isocorynoxeine, was demonstrated, besides the reported rhynchophylline and isorhynchophylline.3) Furthermore, four indole alkaloids were newly isolated ; hirsutine, hirsuteine, dihydrocorynantheine, and corynantheine. A chemical structural evidence of hirsutine was obtained from its epimerization to dihydrocorynantheine with acetic acid catalysis.
- 著者
- 山中 悦二 君塚 ゆみ子 相見 則郎 坂井 進一郎 萩庭 丈寿
- 出版者
- 公益社団法人 日本薬学会
- 雑誌
- YAKUGAKU ZASSHI (ISSN:00316903)
- 巻号頁・発行日
- vol.103, no.10, pp.1028-1033, 1983-10-25 (Released:2008-05-30)
- 参考文献数
- 8
- 被引用文献数
- 12 27
Quantitative analysis of the tertiary alkaloids in various parts of Uncaria rhynchophylla MIQ. was made by use of high performance liquid chromatography (HPLC). The best result was obtained in the following conditions : column ; Radial Pak C8 and mobile phase ; CH3CN-0.05M AcONH4 buffer (pH 4.0) [90 : 10]. The result revealed that the constitution of the alkaloids varied markedly depending on the botanical parts examined. While oxindole alkaloids (1, 2, 3 and 6) occupy ca. 97% of total alkaloids in hook, small stem and leaf, respectively, content of indole alkaloids (mainly 8 and 10) is almost exclusive (ca. 96%) in the bark of underground part. In the bark of aerial part both oxindole and indole alkaloids were found to be contained in nearly equal amounts. The alkaloidal content is very low in the wood (aerial or underground part) but the content ratios of rare alkaloids (4 and 7) to the total alkaloids are higher than the other parts.
- 著者
- 萩庭丈寿 坂井 進一郎 相見 則郎 山中 悦二 新間 信夫
- 出版者
- 公益社団法人日本薬学会
- 雑誌
- 薬学雑誌 (ISSN:00316903)
- 巻号頁・発行日
- vol.93, no.4, pp.448-452, 1973-04
- 被引用文献数
- 2
In the reinvestigation of the constituents of Uncaria rhynchophylla MIQ. (Japanese name "kagikazura"), the presence of two oxindole alkaloids, corynoxeine and isocorynoxeine, was demonstrated, besides the reported rhynchophylline and isorhynchophylline.^<3)> Furthermore, four indole alkaloids were newly isolated ; hirsutine, hirsuteine, dihydrocorynantheine, and corynantheine. A chemical structural evidence of hirsutine was obtained from its epimerization to dihydrocorynantheine with acetic acid catalysis.
- 著者
- 伊藤 豊 矢野 真吾 渡辺 和夫 山中 悦二 相見 則郎 坂井 進一郎
- 出版者
- The Pharmaceutical Society of Japan
- 雑誌
- Chemical and Pharmaceutical Bulletin (ISSN:00092363)
- 巻号頁・発行日
- vol.38, no.6, pp.1702-1706, 1990-06-25 (Released:2008-03-31)
- 参考文献数
- 16
- 被引用文献数
- 10 19
We investigated the selectivities and structure requirements for alpha-1 and alpha-2 adrenoceptor blocking activities of yohimbine (YO) and its 12 related analogs, such as β-yohimbine (β-YO), dihydrocorynantheine (DHC) and (-)indoloquinolizidine ((-)IQ). The affinity of YO analogs to alpha-adrenoceptor was assessed by measuring their blockade of pressor responses to epinephrine in pithed rats. Among YO structure groups, the potency order was YO>DHC=β-YO>geissoschizine methylether>14β-hydroxy YO>14β-benzoyloxy YO (inactive). (-)IQ was slightly less potent than YO, but much stronger than (+)IQ. Among (±)IQ structure groups, the potency order was (±)IQ>(±)1, 12b-trans-1-hydroxy IQ»(±)1, 12b-cis-1-hydroxy IQ (imactive). (±)Borrerine was active, but (±)desmethylborrerine was inactive. The alpha-1 blocking activities of the four compounds YO, β-YO, DHC and (-)IQ, were assessed in experiments of pressor responses to methoxamine in pithed rats and contractile responses to methoxamine in the rat vas deferens. The potency order was (-)IQ>YO>DHC>β-YO. Furthermore, the alpha-2 blocking activities of the four analogs were assessed in experiments of pressor responses to clonidine and inhibition of electrically driven cardioacceleration by clonidine, in pithed rats. The potency order was YO>β-YO>(-)IQ>DHC. Based on the potency ratio between alpha-1 and alpha-2 blocking activities, DHC or YO was most selective for alpha-1 or alpha-2 subtype, respectively, among the four YO analogs. These results suggest that the A, B, C and D rings of YO analogs and their planarity are necessary for the affinity to alpha-adrenoceptors and that the predominant conformation of the carboxymethyl or hydroxy group on the E ring of YO structure determines the selectivity for alpha-1 and alpha-2 blocking activities.
- 著者
- 伊藤 豊 矢野 真吾 渡辺 和夫 山中 悦二 相見 則郎 坂井 進一郎
- 出版者
- 公益社団法人日本薬学会
- 雑誌
- Chem Pharm Bull (Tokyo) (ISSN:00092363)
- 巻号頁・発行日
- vol.38, pp.1702-1706, 1990
- 被引用文献数
- 2
We investigated the selectivities and structure requirements for alpha-1 and alpha-2 adrenoceptor blocking activities of yohimbine (YO) and its 12 related analogs, such as β-yohimbine (β-YO), dihydrocorynantheine (DHC) and (-)indoloquinolizidine ((-)IQ). The affinity of YO analogs to alpha-adrenoceptor was assessed by measuring their blockade of pressor responses to epinephrine in pithed rats. Among YO structure groups, the potency order was YO>DHC=β-YO>geissoschizine methylether>14β-hydroxy YO>14β-benzoyloxy YO (inactive). (-)IQ was slightly less potent than YO, but much stronger than (+)IQ. Among (±)IQ structure groups, the potency order was (±)IQ>(±)1,12b-trans-1-hydroxy IQ≫(±)1,12b-cis-1-hydroxy IQ (imactive). (±)Borrerine was active, but (±)desmethylborrerine was inactive. The alpha-1 blocking activities of the four compounds YO, β-YO, DHC and (-)IQ, were assessed in experiments of pressor responses to methoxamine in pithed rats and contractile responses to methoxamine in the rat vas deferens. The potency order was (-)IQ>YO>DHC>β-YO. Furthermore, the alpha-2 blocking activities of the four analogs were assessed in experiments of pressor responses to clonidine and inhibition of electrically driven cardioacceleration by clonidine, in pithed rats. The potency order was YO>β-YO>(-)IQ>DHC. Based on the potency ratio between alpha-1 and alpha-2 blocking activities, DHC or YO was most selective for alpha-1 or alpha-2 subtype, respectively, among the four YO analogs. These results suggest that the A, B, C and D rings of YO analogs and their planarity are necessary for the affinity to alpha-adrenoceptors and that the predominant conformation of the carboxymethyl or hydroxy group on the E ring of YO structure determines the selectivity for alpha-1 and alpha-2 blocking activities.
1 0 0 0 OA 3-Ethyloxindole誘導体の合成とそのアミド部分の反応性について
- 著者
- 坂井 進一郎 山中 悦二 横溝 理 松本 緑
- 出版者
- 公益社団法人 日本薬学会
- 雑誌
- YAKUGAKU ZASSHI (ISSN:00316903)
- 巻号頁・発行日
- vol.95, no.12, pp.1511-1516, 1975-12-25 (Released:2008-05-30)
- 参考文献数
- 10
- 被引用文献数
- 1 2
It has been found that a reaction of the cyclic imino ether in gardneramine (I) with MeI afforded N-methylated oxindole (III). Synthesis of a compound (XIV)) having a cyclic imino ether system and its reaction with MeI are described. An alcohol (X) was prepared by the Michael reaction of N-acetyl-3-ethyloxindole (VII) with ethyl acrylate, followed by LiA1H4 reduction. On treatment with p-toluenesulfonyl chloride in pyridine, X afforded a tosylate (XI) and a chloride (XII). The imino ether (XIV), synthesised by the reaction of XII with potassium t-butoxide in dimethyl sulfoxide-benzene (1 : 1), reacted with MeI to afford N-methyl-3-(3-iodopropyl)oxindole (XX). The reductive dehalogenation of XX with NaBH4/Me2SO gave N-methyl-3-ethyl-3-propyloxindole (XXI), which was identical with the authentic sample prepared from XII by a different route.
1 0 0 0 OA A Convenient Synthesis of 1, 2, 3, 4, 6, 7, 12, 12b-Octahydroindolo-[2, 3-α]quinolizine Derivatives
- 著者
- 山中 悦二 成嶋 真弓 犬飼 邦江(旧姓長島) 坂井 進一郎
- 出版者
- The Pharmaceutical Society of Japan
- 雑誌
- Chemical and Pharmaceutical Bulletin (ISSN:00092363)
- 巻号頁・発行日
- vol.34, no.1, pp.77-81, 1986-01-25 (Released:2008-03-31)
- 参考文献数
- 12
- 被引用文献数
- 7 13
Convenient syntheses of 1, 2, 3, 4, 6, 7, 12, 12b-octahydroindolo[2, 3-α]quinolizine derivatives (4a, b) and a relatd unsaturated lactam (14) are described. The condensation of tryptamine (1) with 8a, b (prepared from 7a, b by decarboethoxylation), followed by treatment with alkali gave the lactams (4a, b), respectively. The stereochemistry of 4b was determined by conversion to the known cis- and trans-compounds (5b). The condensation of 1 with the sulfenylated ester (10), which was prepared in two ways, followed by treatment with alkali gave the lactams (12a, b). Oxidation of 12a, b with m-chloroperbenzoic acid gave the sulfoxides (13) which were heated at 50°C to give the lactams (14, 15) and the pyridone (16).
- 著者
- 山中 悦二 丸田 悦子 笠松 里江 相見 則郎 坂井 進一郎 / / TANOMJIT SUPAVITA J. DAVID PHILLIPSON
- 出版者
- The Pharmaceutical Society of Japan
- 雑誌
- Chemical and Pharmaceutical Bulletin (ISSN:00092363)
- 巻号頁・発行日
- vol.34, no.9, pp.3713-3721, 1986-09-25 (Released:2008-03-31)
- 参考文献数
- 21
- 被引用文献数
- 4 6
Oxidation of the enamine (6) with dibenzoyl peroxide followed by reduction with NaBH4 gave the benzoate (8), which was converted to the cis-hydroxyl compound (9), while hydroboration-oxidation of 6 gave the trans-isomer (11). Treatment of a mixture of the enamines (13 and 14) with dibenzoyl peroxide/NaBH4 gave the benzoates (15 and 16), which were converted to 14α-hydroxy-3-isorauniticine (17) and the acetal (18), respectively. Hydroboration-oxidation of 13 gave 14α-hydroxyrauniticine (2), which was found to be identical with the natural alkaloid whose structure had erroneously been proposed as 14β-hydroxy-3-isorauniticine (4).
- 著者
- 伊藤 豊 矢野 真吾 渡辺 和夫 山中 悦二 相見 則郎 坂井 進一郎
- 出版者
- 公益社団法人 日本薬学会
- 雑誌
- CHEMICAL & PHARMACEUTICAL BULLETIN (ISSN:00092363)
- 巻号頁・発行日
- vol.38, no.6, pp.1702-1706, 1990
- 被引用文献数
- 19
We investigated the selectivities and structure requirements for alpha-1 and alpha-2 adrenoceptor blocking activities of yohimbine (YO) and its 12 related analogs, such as β-yohimbine (β-YO), dihydrocorynantheine (DHC) and (-)indoloquinolizidine ((-)IQ). The affinity of YO analogs to alpha-adrenoceptor was assessed by measuring their blockade of pressor responses to epinephrine in pithed rats. Among YO structure groups, the potency order was YO>DHC=β-YO>geissoschizine methylether>14β-hydroxy YO>14β-benzoyloxy YO (inactive). (-)IQ was slightly less potent than YO, but much stronger than (+)IQ. Among (±)IQ structure groups, the potency order was (±)IQ>(±)1, 12b-trans-1-hydroxy IQ»(±)1, 12b-cis-1-hydroxy IQ (imactive). (±)Borrerine was active, but (±)desmethylborrerine was inactive. The alpha-1 blocking activities of the four compounds YO, β-YO, DHC and (-)IQ, were assessed in experiments of pressor responses to methoxamine in pithed rats and contractile responses to methoxamine in the rat vas deferens. The potency order was (-)IQ>YO>DHC>β-YO. Furthermore, the alpha-2 blocking activities of the four analogs were assessed in experiments of pressor responses to clonidine and inhibition of electrically driven cardioacceleration by clonidine, in pithed rats. The potency order was YO>β-YO>(-)IQ>DHC. Based on the potency ratio between alpha-1 and alpha-2 blocking activities, DHC or YO was most selective for alpha-1 or alpha-2 subtype, respectively, among the four YO analogs. These results suggest that the A, B, C and D rings of YO analogs and their planarity are necessary for the affinity to alpha-adrenoceptors and that the predominant conformation of the carboxymethyl or hydroxy group on the E ring of YO structure determines the selectivity for alpha-1 and alpha-2 blocking activities.