干姜和益智仁化学成分研究
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摘要
本论文为本人三年期间攻读硕士学位的研究工作,报道两种传统姜科中药,干姜和益智仁的化学成分研究,通过使用多种分离手段和核磁、红外、紫外、质谱等结构鉴定技术,从上述两种姜科中药中共分离、鉴定了19个化合物,包括1个新化合物和1个新的天然产物。已鉴定的化合物类型主要有二苯庚烷类、姜酮类,姜辣素、黄酮、甾体等,其中二苯庚烷类成分为其主要化学成分。
第一章主要讨论干姜的化学成分,干姜为姜科植物生姜(Zingiber officinale)的新鲜根茎炮制干燥而来,其性味与功效与鲜姜明显不同,目前鲜姜化学成分研究较多,而干姜成分到目前鲜见文献报道。利用如D101大孔树脂柱,SaphadexLH-20层析柱,硅胶层析柱,MCI层析柱等手段,从该干姜的甲醇提取物中共分离、鉴定了10个化合物,其中包括1个新二苯庚烷类化合物和9个已知化合物。分别鉴定为：(4-E,6-E)-7-(3,4-dihydroxy-5-metho-xyphenyl)-1-(4-hydroxy-3-metho xyphenyl)hepta-4,6-dien-3-one(1),3,5-二酮-1,7-二-{(3-甲氧基-4-羟基)-苯基}-庚烷(2), 1-dehydro-8-gingerdione (3),6-姜酚(6-gingerol,4),姜黄素(curcumin,5),1,7-二(4-羟基-3-甲氧基苯基)庚烷-5-羟基-3酮(6),1-(4-羟基-3-甲氧基苯基)-7-(3,4-二羟基苯基)庚烷-5-羟基-3酮(7),1,7-二(4-羟基-3-甲氧基苯基)庚烷-4-烯-3-酮(8),2-甲氧基对苯二酚(9)和谷甾醇(10),其中1新化合物。
第二章详细论述了对益智仁化学成分的研究。益智仁是姜科(Zingiberaceae)植物益智(Alpinia oxyphylla Miq)的成熟果实或种子。益智为四大南药之一,具有温脾止泻摄唾,暖肾固精缩尿等功效。采用硅胶、Sephadex LH-20和MCI等柱色谱手段进行单体化合物的分离纯化,通过波谱方法,从海南产益智仁乙醇提取物中,共分离鉴定了9个已知化合物,分别为：益智酮甲(1),益智酮乙(2),杨芽黄素(3),原儿茶酸(4),4-methoxy-1,2-dihydrocyclobutabenzene (5),棕榈酸(6),谷甾醇棕榈酸脂(7),豆甾醇(8),β-胡萝卜苷(9)。化合物5、6、7、8首次在益智中分离得到,化合物5为一新天然产物。
第三章和第四章,分别对生姜和益智的化学成分和活性进行了综述。
The thesis is composed of four chapters. The first chapter focused on constitutents of dried ginger. Dried ginger is the dried rhizome of Zingiber officinale Roscoe (Zingiberaceae). Dried ginger is a kind of Chinese traditional medicine. Dried ginger is frequently prescribed in traditional Chinese medicine as a stomachic, antiemetic, antidiarrheal, expectorant, antiasthmatic, haemostatic and cardiotonic, for the treatment of gastrointestinal and respiratory diseases. To make a better exploitation of dried ginger, we had a research to the dried ginger cultivated in Anhui province on chemical constituents. By repeated column chromatography over silica gel, and Sephadex LH-20, and their structures were determined mainly by means of MS and NMR techniques, one new compounds (1), along with 9 known compounds (2-10) was isolated from the EtOAC fraction of the dried ginger and their structures were identified as follows:(4-E,6-E)-7-(3,4-dihydroxy-5-methoxyphenyl)-1-(4-hydroxy-3-methoxyphenyl)hepta-4,6-dien-3-one(1),1,7-bis(4-hydroxy-3-methoxype nyl)heptane-3,5-dione(2), 1-dehydroxy-8-Gingerdione(3),6-Gingerol(4), curcumin(5), hexahydrocurcumin(6),1-(4-dihydroxy-3-methoxy-phenyl)-7-(4,3-bisdihydrophenyl) hepane-5-dihydroxy-one(7), 1,7-bis(4-hydroxy-3-methoxyphenyl)hepane-4-dien-one (8),2-methoxyben zene-1,4-diol (9), sitosterol (10).
The second chapter was focused on study of constitutents of Alpinia oxyphylla Miq. The seeds of A. oxyphylla, belonging to Zingiberaceae, are widely distributed in South China, and used as a traditional folk medicine to treat intestinal disorders, urosis, diuresis, ulceration and dementia. To make a better exploitation of A. oxyphylla, we have a deep research to chemical constituents of A. oxyphylla Miq. cultivated in Hainan province. By repeated column chromatography over silica gel, and Sephadex LH-20, and their structures were determined mainly by means of MS and NMR techniques, a new natural compound (5), along with 8 known compounds was isolated from the EtOH estract of the seeds of Alpinia oxyphyll and their structures were identified as follows:yakuchinone A (1), yakuchinone B (2), tectochrysin (3), Protocatechuic acid (4),4-methoxy-1,2-dihydrocyclobutabenzene (5), palmiticacid (6), stigmasterol (7), sitosteryl plamiate (8), daucosterol (9).
The third and forth chapters reviewed the research progresses of chemical constituents and pharmacological activities of Zingiber officinale and Alpinia oxyphylla, respectively.
第一章主要讨论干姜的化学成分,干姜为姜科植物生姜(Zingiber officinale)的新鲜根茎炮制干燥而来,其性味与功效与鲜姜明显不同,目前鲜姜化学成分研究较多,而干姜成分到目前鲜见文献报道。利用如D101大孔树脂柱,SaphadexLH-20层析柱,硅胶层析柱,MCI层析柱等手段,从该干姜的甲醇提取物中共分离、鉴定了10个化合物,其中包括1个新二苯庚烷类化合物和9个已知化合物。分别鉴定为：(4-E,6-E)-7-(3,4-dihydroxy-5-metho-xyphenyl)-1-(4-hydroxy-3-metho xyphenyl)hepta-4,6-dien-3-one(1),3,5-二酮-1,7-二-{(3-甲氧基-4-羟基)-苯基}-庚烷(2), 1-dehydro-8-gingerdione (3),6-姜酚(6-gingerol,4),姜黄素(curcumin,5),1,7-二(4-羟基-3-甲氧基苯基)庚烷-5-羟基-3酮(6),1-(4-羟基-3-甲氧基苯基)-7-(3,4-二羟基苯基)庚烷-5-羟基-3酮(7),1,7-二(4-羟基-3-甲氧基苯基)庚烷-4-烯-3-酮(8),2-甲氧基对苯二酚(9)和谷甾醇(10),其中1新化合物。
第二章详细论述了对益智仁化学成分的研究。益智仁是姜科(Zingiberaceae)植物益智(Alpinia oxyphylla Miq)的成熟果实或种子。益智为四大南药之一,具有温脾止泻摄唾,暖肾固精缩尿等功效。采用硅胶、Sephadex LH-20和MCI等柱色谱手段进行单体化合物的分离纯化,通过波谱方法,从海南产益智仁乙醇提取物中,共分离鉴定了9个已知化合物,分别为：益智酮甲(1),益智酮乙(2),杨芽黄素(3),原儿茶酸(4),4-methoxy-1,2-dihydrocyclobutabenzene (5),棕榈酸(6),谷甾醇棕榈酸脂(7),豆甾醇(8),β-胡萝卜苷(9)。化合物5、6、7、8首次在益智中分离得到,化合物5为一新天然产物。
第三章和第四章,分别对生姜和益智的化学成分和活性进行了综述。
The thesis is composed of four chapters. The first chapter focused on constitutents of dried ginger. Dried ginger is the dried rhizome of Zingiber officinale Roscoe (Zingiberaceae). Dried ginger is a kind of Chinese traditional medicine. Dried ginger is frequently prescribed in traditional Chinese medicine as a stomachic, antiemetic, antidiarrheal, expectorant, antiasthmatic, haemostatic and cardiotonic, for the treatment of gastrointestinal and respiratory diseases. To make a better exploitation of dried ginger, we had a research to the dried ginger cultivated in Anhui province on chemical constituents. By repeated column chromatography over silica gel, and Sephadex LH-20, and their structures were determined mainly by means of MS and NMR techniques, one new compounds (1), along with 9 known compounds (2-10) was isolated from the EtOAC fraction of the dried ginger and their structures were identified as follows:(4-E,6-E)-7-(3,4-dihydroxy-5-methoxyphenyl)-1-(4-hydroxy-3-methoxyphenyl)hepta-4,6-dien-3-one(1),1,7-bis(4-hydroxy-3-methoxype nyl)heptane-3,5-dione(2), 1-dehydroxy-8-Gingerdione(3),6-Gingerol(4), curcumin(5), hexahydrocurcumin(6),1-(4-dihydroxy-3-methoxy-phenyl)-7-(4,3-bisdihydrophenyl) hepane-5-dihydroxy-one(7), 1,7-bis(4-hydroxy-3-methoxyphenyl)hepane-4-dien-one (8),2-methoxyben zene-1,4-diol (9), sitosterol (10).
The second chapter was focused on study of constitutents of Alpinia oxyphylla Miq. The seeds of A. oxyphylla, belonging to Zingiberaceae, are widely distributed in South China, and used as a traditional folk medicine to treat intestinal disorders, urosis, diuresis, ulceration and dementia. To make a better exploitation of A. oxyphylla, we have a deep research to chemical constituents of A. oxyphylla Miq. cultivated in Hainan province. By repeated column chromatography over silica gel, and Sephadex LH-20, and their structures were determined mainly by means of MS and NMR techniques, a new natural compound (5), along with 8 known compounds was isolated from the EtOH estract of the seeds of Alpinia oxyphyll and their structures were identified as follows:yakuchinone A (1), yakuchinone B (2), tectochrysin (3), Protocatechuic acid (4),4-methoxy-1,2-dihydrocyclobutabenzene (5), palmiticacid (6), stigmasterol (7), sitosteryl plamiate (8), daucosterol (9).
The third and forth chapters reviewed the research progresses of chemical constituents and pharmacological activities of Zingiber officinale and Alpinia oxyphylla, respectively.
引文
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[1]江苏新医学院.中药大辞典(下册)[M].上海：上海科技出版社.1986.1957.
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[22]Muraoka O., FuJimoto M, Tanabe G. Absolute stereostructures of novel norcadinane and trinoreudesmane type sesquiterpenes with nitric oxide production inhibitory activity from Alpinia oxyphylla [J]. Bioorg. Med. Chem. Lett,2001,11(16):2217-2220.
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