延胡索的化学成分研究
摘要
延胡索又名元胡,为罂粟科(Papaveraceae)荷包丹亚科紫堇属植物(Corydalis yanhusuoW.T.Wang)的干燥块茎,生于低海拔的旷野草丛或缓坡林缘,分布于河南、陕西等南部以及江苏、安徽、浙江、湖北等地。历代本草均有记载。延胡索在我国药典中作为民间用药用于治疗疼痛。现今以延胡索为名的药材有很多种,为了对其进行质量控制,本论文对其化学成分进行了研究。
本文对中药延胡索85%的乙醇回流提取物进行了化学成分研究,利用硅胶、氧化铝吸附柱色谱、凝胶柱色谱和ODS反相吸附柱色谱等分离方法,对其中的成分进行了分离鉴定,从中分离得到了18个化合物,根据化合物的理化性质以及光谱数据确定了其中16个化合物的结构,分别为:四氢紫堇萨明(tetrahydrocorysamine,1),四氢黄连碱(tetrahydrocoptisine,即延胡索丁素,2),四氢紫堇碱(tetrahydrocorydaline,即延胡索甲素,3),四氢巴马亭(tetrahydropalmatine,即延胡索乙素,4),去氢紫堇碱(dehydrocorydaline,即去氢延胡索甲素,5),氧海罂粟碱(oxoglaucine,6),降氧化北美黄连次碱(noroxyhydrastinine,7),6-丙酮基-5,6-二氢血根碱(6-acetonyl-5,6-dihydrosanguinarine,8),四氢小檗碱(tetrahydroberberine,9),麦角甾-4-烯-3-酮(ergosta-4-en-3-one,10),δ-乙酰鸟氨酸(δ-acetylornithine,11),山嵛酸(docosanoic acid,12),β-谷甾醇(β-sitosterol,13),胡萝卜苷(daucosterol,14),香草酸(vanillic acid,15),对羟基苯甲酸(p-hydroxybenzoic acid,16)。其中化合物1,6,7,8,11为首次从该植物中分离得到,化合物10,12,15,16为首次从该属植物中分离得到,并且分离得到了反式阿魏酸酯的同系物(反式阿魏酸二十二烷醇酯、反式阿魏酸二十烷醇酯和反式阿魏酸十八烷醇酯)的混合物,也为首次从该属植物中分离得到。
Yanhusuo is the bulb of the Corydalis yanhusuo W.T.Wang and lives in anhui、jiangsu、hubei and zhejiang etc.It embodied in Chinese pharmacopoeia was used in folk medicine to treat ache. Many genera from the Corydalis were also used with the name of Yanhusuo.In order to control the quality of Yanhusuo,the chemical constituents of Corydalis yanhusuo W.T.Wang were studies.
The dried bulbs of Corydalis yanhusuo W.T.Wang were extracted with 85%EtOH.The extract was subjected to Silica gel,Al_2O_3 chromatography repeatedly.Eightteen compounds were obtained and the structures of sixteen compounds were elucidated on the basis of spectroscopic analysis and physico-chemical properties.They were tetrahydrocorysamine(1),tetrahydrocoptisine (2),tetrahydrocorydaline(3),tetrahydropalmatine(4),dehydrocorydaline(5),oxoglaucine(6),norox yhydrastinine(7),6-acetonyl-5,6-dihydrosanguinarine(8),tetrahydroberberine(9),ergosta-4-en-3-one( 10),δ-acetylornithine(11),docosanoic.acid(12),β-sitosterol(13),daucosterol(14),vanillic.acid(15),p-h ydroxybenzoic acid(16).Compounds 1,6,7,8,11were obtained from this plant for the first time, compounds 10,12,15,16 were obtained from the genus for the first time,the mixture of homolog of trans-ferulic acid ester(trans-docosanoylferulate、trans-eicosanolferulate and trans-octodecanol ferulate)was also obtained from the genus for the first time.
本文对中药延胡索85%的乙醇回流提取物进行了化学成分研究,利用硅胶、氧化铝吸附柱色谱、凝胶柱色谱和ODS反相吸附柱色谱等分离方法,对其中的成分进行了分离鉴定,从中分离得到了18个化合物,根据化合物的理化性质以及光谱数据确定了其中16个化合物的结构,分别为:四氢紫堇萨明(tetrahydrocorysamine,1),四氢黄连碱(tetrahydrocoptisine,即延胡索丁素,2),四氢紫堇碱(tetrahydrocorydaline,即延胡索甲素,3),四氢巴马亭(tetrahydropalmatine,即延胡索乙素,4),去氢紫堇碱(dehydrocorydaline,即去氢延胡索甲素,5),氧海罂粟碱(oxoglaucine,6),降氧化北美黄连次碱(noroxyhydrastinine,7),6-丙酮基-5,6-二氢血根碱(6-acetonyl-5,6-dihydrosanguinarine,8),四氢小檗碱(tetrahydroberberine,9),麦角甾-4-烯-3-酮(ergosta-4-en-3-one,10),δ-乙酰鸟氨酸(δ-acetylornithine,11),山嵛酸(docosanoic acid,12),β-谷甾醇(β-sitosterol,13),胡萝卜苷(daucosterol,14),香草酸(vanillic acid,15),对羟基苯甲酸(p-hydroxybenzoic acid,16)。其中化合物1,6,7,8,11为首次从该植物中分离得到,化合物10,12,15,16为首次从该属植物中分离得到,并且分离得到了反式阿魏酸酯的同系物(反式阿魏酸二十二烷醇酯、反式阿魏酸二十烷醇酯和反式阿魏酸十八烷醇酯)的混合物,也为首次从该属植物中分离得到。
Yanhusuo is the bulb of the Corydalis yanhusuo W.T.Wang and lives in anhui、jiangsu、hubei and zhejiang etc.It embodied in Chinese pharmacopoeia was used in folk medicine to treat ache. Many genera from the Corydalis were also used with the name of Yanhusuo.In order to control the quality of Yanhusuo,the chemical constituents of Corydalis yanhusuo W.T.Wang were studies.
The dried bulbs of Corydalis yanhusuo W.T.Wang were extracted with 85%EtOH.The extract was subjected to Silica gel,Al_2O_3 chromatography repeatedly.Eightteen compounds were obtained and the structures of sixteen compounds were elucidated on the basis of spectroscopic analysis and physico-chemical properties.They were tetrahydrocorysamine(1),tetrahydrocoptisine (2),tetrahydrocorydaline(3),tetrahydropalmatine(4),dehydrocorydaline(5),oxoglaucine(6),norox yhydrastinine(7),6-acetonyl-5,6-dihydrosanguinarine(8),tetrahydroberberine(9),ergosta-4-en-3-one( 10),δ-acetylornithine(11),docosanoic.acid(12),β-sitosterol(13),daucosterol(14),vanillic.acid(15),p-h ydroxybenzoic acid(16).Compounds 1,6,7,8,11were obtained from this plant for the first time, compounds 10,12,15,16 were obtained from the genus for the first time,the mixture of homolog of trans-ferulic acid ester(trans-docosanoylferulate、trans-eicosanolferulate and trans-octodecanol ferulate)was also obtained from the genus for the first time.
引文
[1]国家药典委员会.中华人民共和国药典(2005版)一部.北京:人民卫生出版社.2005:94
[2]苏志云.中国的紫堇属延胡索亚属的分类、分布、演化趋势及其用途.云南植物研究.1985,7(3):253
[3]刘慎谔.东北草本植物志.第Ⅳ卷.北京:科学出版社,1980:16
[4]李书心.辽宁植物志上册.沈阳:辽宁科学出版社,1988:596,604,59,600
[5]郝近大.延胡索古今用药品种的连续与变迁.中国中药杂志.1993,18(1):7
[6]田明.近年来中药延胡索的研究简介[J].中医药学报,1996,(3):39-40.
[7]Lin MT,et al.The protective sffect of dl-tetrahydropalmatine against the development of amygdale kindling seizures in rats[J].Neurosci Lett,2002.320(3):113.
[8]Chang CK,et al.DL-Tetrahydropalmatine may act through inhibition of amygdalorid release of dopamine to inhibit an epileptic attack in rats[J].Neurosci Lett.2001
[9]Liao ET,Chiang SY,Lao CT,et al.Effect of Rhizoma Corydalis on focal cerebral in ischemia-reperfusion injures rats[J].Acta Pharmacol Sin,2001,22(12):1143-1148.
[10]张友容.延胡索治疗冠心病的药理实验研究[J].中草药通讯,1978,11:27.
[11]马胜兴.延胡索碱对家兔心电图的影响及其对量效关系的观察[J].中西医结合杂志,1986,6(12):743.
[12]黄泰康,主编.常用中药成分与药理手册[J].北京:中国医药科技出版社,1994,879-881.
[13]中国科学院植物研究所.中国高等植物科属检索表.1979:190
[14]刘寿山.中药研究文献摘要(1820-1961).第一版.北京:科学出版社,1963
[15]国家中医药管理局.中药大辞典[M].上海:上海科学技术出版社,2002.919.
[16]江苏中学院.现代中药学大辞典[M].北京:人民卫生出版社,2001.857.
[17]傅小勇,梁文藻,涂国士.延胡索生物碱的化学研究-Ⅶ元胡块茎中的生物碱[J].中草药,1986,17(2):5.
[18]傅小勇,梁文藻,涂国士.元胡生物碱的化学研究-Ⅱ东阳元胡地上部分的生物碱[J].药物分析杂志,1986,6(1):6.
[19]秦永祺,杨企铮,延胡索治疗冠心病有效成分的研究.天津医药.1978,10:450-453
[20]彭树林,陈维新,坂神洋次,丸茂晋吾.药用异喹啉生物碱的研究Ⅳ.峨眉紫堇生物碱.天然产物研究与开发.1992,4(2):7-13
[21]许翔鸿,王峥涛,余国奠,阮碧芳,李军.延胡索中生物碱成分的研究.中国药科大学学报.2002, 33(6):483-486
[22]Anita J.Marsaioli,Aderbal F.Magalhaes,Edmundo A.Ruveda,Francisco de A.M.Reis.~(13)C NMR analysis of some oxoaporphine alkaloids.Phytochemistry.1980,19:995-997
[23]刘川,赵守训.江苏元胡块茎中化学成分的研究.中国药科大学学报.1989,20(5):261-265
[24]唐艳丽,杨爱梅,张樱山,汪汉卿.灰绿黄堇生物碱化学成分的研究(Ⅰ).中国中药杂志.2005,30(3):195-197
[25]蔡祥海,邓德山,马云保,罗晓东.牛耳朵化学成分的研究.中草药.2005,36(4):510-511
[26]Aliou M.Balde,M.Claeys,L.A.Pieters,V.Wray and A.J.Vlietinck.FERULIC ACID ESTERS FROM STEM BARK OF PAVETTA OWARIENSIS.Photochemistry.1991,30(3):1024-1026
[27]Richard H.A.M.Janssen,Peter Wijkens,Cer Kruk,HuBertus W.A.Biessels,Francesco Menichini,Hubert G.Theuns.Assignments of ~1H And ~(13)C NMR Resenances of some isoquinoline Alkaloids.Phytochemistry.1990.29(10).3331-3339
[28]P.K.Agrawal,R.S.Thakur.~(13)C NMR Spectroscopy of Lignan and Neolignan Derivatives.Magnetic Resonance in Chemistry 23(6)389-418(1985)
[2]苏志云.中国的紫堇属延胡索亚属的分类、分布、演化趋势及其用途.云南植物研究.1985,7(3):253
[3]刘慎谔.东北草本植物志.第Ⅳ卷.北京:科学出版社,1980:16
[4]李书心.辽宁植物志上册.沈阳:辽宁科学出版社,1988:596,604,59,600
[5]郝近大.延胡索古今用药品种的连续与变迁.中国中药杂志.1993,18(1):7
[6]田明.近年来中药延胡索的研究简介[J].中医药学报,1996,(3):39-40.
[7]Lin MT,et al.The protective sffect of dl-tetrahydropalmatine against the development of amygdale kindling seizures in rats[J].Neurosci Lett,2002.320(3):113.
[8]Chang CK,et al.DL-Tetrahydropalmatine may act through inhibition of amygdalorid release of dopamine to inhibit an epileptic attack in rats[J].Neurosci Lett.2001
[9]Liao ET,Chiang SY,Lao CT,et al.Effect of Rhizoma Corydalis on focal cerebral in ischemia-reperfusion injures rats[J].Acta Pharmacol Sin,2001,22(12):1143-1148.
[10]张友容.延胡索治疗冠心病的药理实验研究[J].中草药通讯,1978,11:27.
[11]马胜兴.延胡索碱对家兔心电图的影响及其对量效关系的观察[J].中西医结合杂志,1986,6(12):743.
[12]黄泰康,主编.常用中药成分与药理手册[J].北京:中国医药科技出版社,1994,879-881.
[13]中国科学院植物研究所.中国高等植物科属检索表.1979:190
[14]刘寿山.中药研究文献摘要(1820-1961).第一版.北京:科学出版社,1963
[15]国家中医药管理局.中药大辞典[M].上海:上海科学技术出版社,2002.919.
[16]江苏中学院.现代中药学大辞典[M].北京:人民卫生出版社,2001.857.
[17]傅小勇,梁文藻,涂国士.延胡索生物碱的化学研究-Ⅶ元胡块茎中的生物碱[J].中草药,1986,17(2):5.
[18]傅小勇,梁文藻,涂国士.元胡生物碱的化学研究-Ⅱ东阳元胡地上部分的生物碱[J].药物分析杂志,1986,6(1):6.
[19]秦永祺,杨企铮,延胡索治疗冠心病有效成分的研究.天津医药.1978,10:450-453
[20]彭树林,陈维新,坂神洋次,丸茂晋吾.药用异喹啉生物碱的研究Ⅳ.峨眉紫堇生物碱.天然产物研究与开发.1992,4(2):7-13
[21]许翔鸿,王峥涛,余国奠,阮碧芳,李军.延胡索中生物碱成分的研究.中国药科大学学报.2002, 33(6):483-486
[22]Anita J.Marsaioli,Aderbal F.Magalhaes,Edmundo A.Ruveda,Francisco de A.M.Reis.~(13)C NMR analysis of some oxoaporphine alkaloids.Phytochemistry.1980,19:995-997
[23]刘川,赵守训.江苏元胡块茎中化学成分的研究.中国药科大学学报.1989,20(5):261-265
[24]唐艳丽,杨爱梅,张樱山,汪汉卿.灰绿黄堇生物碱化学成分的研究(Ⅰ).中国中药杂志.2005,30(3):195-197
[25]蔡祥海,邓德山,马云保,罗晓东.牛耳朵化学成分的研究.中草药.2005,36(4):510-511
[26]Aliou M.Balde,M.Claeys,L.A.Pieters,V.Wray and A.J.Vlietinck.FERULIC ACID ESTERS FROM STEM BARK OF PAVETTA OWARIENSIS.Photochemistry.1991,30(3):1024-1026
[27]Richard H.A.M.Janssen,Peter Wijkens,Cer Kruk,HuBertus W.A.Biessels,Francesco Menichini,Hubert G.Theuns.Assignments of ~1H And ~(13)C NMR Resenances of some isoquinoline Alkaloids.Phytochemistry.1990.29(10).3331-3339
[28]P.K.Agrawal,R.S.Thakur.~(13)C NMR Spectroscopy of Lignan and Neolignan Derivatives.Magnetic Resonance in Chemistry 23(6)389-418(1985)