连花清瘟胶囊的化学成分研究(Ⅲ)
|
摘要
目的对连花清瘟胶囊化学成分进行系统研究,以期阐明该复方的物质基础。方法连花清瘟胶囊总浸膏经大孔树脂吸附,对30%乙醇洗脱部分采用中低压色谱和高压制备液相色谱对其进行分离和纯化,根据化合物的光谱数据对化学结构进行鉴定。结果连花清瘟胶囊总浸膏中分离得到18个化合物,分别鉴定为连翘酯苷A(1)、连翘酯苷I(2)、连翘酯苷H(3)、lugrandoside(4)、isolugrandoside(5)、ferruginoside A(6)、lianqiaoxinoside C(7)、calceolarioside C(8)、连翘酯苷E(9)、ferruginosideB(10)、D-苦杏仁苷(11)、L-苦杏仁苷(12)、sambunigrin(13)、cornoside(14)、4-hydroxy-4-methylenecarbomethoxy-cyclohexa-2,5-dienone(15)、鹅掌楸苷(16)、甘草素-7-O-β-D-葡萄糖苷(17)、3,4-二羟基苯甲醛(18)。结论化合物2～8、10、13～18均为首次从连花清瘟胶囊总浸膏中分离得到,化合物4～6、10、15、16均未见从复方单味药中分离的报道;首次采用二维核磁波谱技术,对化合物8在DMSO-d6溶剂中的核磁数据进行了归属;系统地阐述了连花清瘟胶囊总浸膏大极性部位的化学组成,进一步丰富了连花清瘟胶囊的化学信息。
Objective To study the chemical constituents of Lianhua Qingwen Capsule and illuminate its substance foundation.Methods The compounds were isolated and purified by LPLC and preparative HPLC from the 30% ethanol fraction of Lianhua Qingwen Capsule macroporous resin column chromatography. Their chemical structures were elucidated by the spectral analyses.Results 18 compounds were isolated and identified as forsythoside A(1), forsythoside I(2), forsythoside H(3), lugrandoside(4),isolugrandoside(5), ferruginoside A(6), lianqiaoxinoside C(7), calceolarioside C(8), forsythoside E(9), ferruginoside B(10),D-amygdaloside(11), L-amygdaloside(12), sambunigrin(13), cornoside(14), 4-hydroxy-4-methylenecarbomethoxy-cyclohexa-2,5-dienone(15), liriodendrin(16), liquiritigenin-7-O-β-D-glucopyranoside(17), and 3,4-dihydroxy benzaldehyde(18). Conclusion Compounds 2—8, 10, and 13—18 are isolated from Lianhua Qingwen Capsule for the first time, and compounds 4—6, 10, 15, and16 are isolated from single herb in Lianhua Qingwen Capsule compound for the first time. The spectral data in DMSO-d6 solution of compound 8 are reported firstly with 2 D NMR spectral data. The above results show the high polar chemical constitutions of Lianhua Qingwen Capsule, which provides more chemical information of Lianhua Qingwen Capsule.
Objective To study the chemical constituents of Lianhua Qingwen Capsule and illuminate its substance foundation.Methods The compounds were isolated and purified by LPLC and preparative HPLC from the 30% ethanol fraction of Lianhua Qingwen Capsule macroporous resin column chromatography. Their chemical structures were elucidated by the spectral analyses.Results 18 compounds were isolated and identified as forsythoside A(1), forsythoside I(2), forsythoside H(3), lugrandoside(4),isolugrandoside(5), ferruginoside A(6), lianqiaoxinoside C(7), calceolarioside C(8), forsythoside E(9), ferruginoside B(10),D-amygdaloside(11), L-amygdaloside(12), sambunigrin(13), cornoside(14), 4-hydroxy-4-methylenecarbomethoxy-cyclohexa-2,5-dienone(15), liriodendrin(16), liquiritigenin-7-O-β-D-glucopyranoside(17), and 3,4-dihydroxy benzaldehyde(18). Conclusion Compounds 2—8, 10, and 13—18 are isolated from Lianhua Qingwen Capsule for the first time, and compounds 4—6, 10, 15, and16 are isolated from single herb in Lianhua Qingwen Capsule compound for the first time. The spectral data in DMSO-d6 solution of compound 8 are reported firstly with 2 D NMR spectral data. The above results show the high polar chemical constitutions of Lianhua Qingwen Capsule, which provides more chemical information of Lianhua Qingwen Capsule.
引文
[1]张爱华,孙晖,闫广利,等.“血清药物化学-药代(效)动力学-系统生物学”三维整合体系研究中药复方的构建及其在茵陈蒿汤分析中的应用[J].中国中药杂志,2013,38(21):3786-3789.
[2]沙孟晨,张海珠,何琴,等.基于微量量热法的连花清瘟胶囊质量一致性评价方法的建立[J].中草药,2017,48(11):2202-2206.
[3]吕宏,欧阳张宁,王俊,等.连花清瘟胶囊联合左氧氟沙星治疗肺炎的临床研究[J].现代药物与临床,2018,33(9):2294-2297.
[4]李伟,郗红娟.连花清瘟胶囊治疗急性上呼吸道感染的临床观察[J].科技信息,2014(15):377-400.
[5]邹龑,黄天泓.连花清瘟胶囊治疗流行性感冒临床效果观察[J].现代医药卫生,2015,31(4):590-592.
[6]李宝法,张长青,付敏,等.连花清瘟胶囊治疗甲型H1N1流感临床研究[J].医药论坛杂志,2009,30(23):91-92.
[7]毕丹,孙云波,宋联强,等.连花清瘟胶囊化学成分研究(I)[J].中草药,2018,49(4):795-800.
[8]张创峰,沈硕,宋联强,等.连花清瘟胶囊的化学成分研究(II)[J].中草药,2018,49(14):3222-3225.
[9]范毅,陈玲,朱杰,等.连翘叶化学成分[J].中国实验方剂学杂志,2015,12(24):22-25.
[10]Wang F N,Ma Z Q,Liu Y,et al.New phenylethanoid glycosides from the fruits of Forsythia suspense(Thunb.)Vahl[J].Molecules,2009,14(3):1324-1331.
[11]郑晓珂,李军,冯卫生,等.石胆草的苯乙醇苷类成分研究[J].中草药,2002,33(10):19-21.
[12]林生,刘明韬,王素娟,等.小蜡树的粉苷及苯乙醇苷类成分[J].中国中药杂志,2010,35(8):992-996.
[13]Xia Y G,Yang B Y,Liang J,et al.Caffeoyl phenylethanoid glycosides from unripe fruits of Forsythia suspensai[J].Chem Nat Compd,2015,51(4):656-659.
[14]Nicoletti M,Galeffi C,Messana I,et al.Phenylpropanoid glycosides from Calceolaria hypericina[J].Phytochemistry,1988,27(2):639-641.
[15]Endo K,Hikino H.Structures of rengyol,rengyoxide and rengyolone,new cyclohexylethane derivatives from Forsythia suspensa fruits[J].Can J Chem,1984,62(9):2011-2014.
[16]Calis I,Tasdemir D,Sticher O,et al.Phenylethanoid glycosides from Digitalis ferruginea subsp.farruginea(=D.aurea LINDLEY)(Scrophulariaceae)[J].Chem Pharm Bull,1999,47(9):1305-1307.
[17]萧伟,谢雪,宋亚玲,等.一种苦杏仁苷的制备方法:中国,CN105461765A[P].2016-04-06.
[18]刘华,沈娟娟,张东明,等.江香薷极性成分的研究[J].中国实验方剂学杂志,2010,16(8):84-86.
[19]Hong M L,Jin K K,Jai M J,et al.Analysis of the inhibitory activity of Abeliophyllum distichum leaf constituents against aldose reductase by using high-speed counter current chromatography[J].Arch Pharm Res,2013,36(9):1104-1112.
[20]Muhammad P,Ahmad S,Nawaz H R,et al.New acetylated quinols from Ajuga parviflora[J].Fitoterapia,1999,70(3):229-232.
[21]Lami N,Kadota S,Kikuchi T,et al.Constituents of the roots of Boerhaavia diffusa L.III.Identification of Ca2+channel antagonistic compound from the methanol extract[J].Chem Pharm Bull,1991,39(6):1551-1555.
[22]赫军,张迅杰,马秉智,等.白英水提取物的化学成分研究[J].中国药学杂志,2015,50(23):2035-2038.
[23]Jin Q H,Lee C,Lee J W,et al.Chemical constituents from the fruits of Prunus mume[J].Nat Prod Sci,2012,18(3):200-203.
[24]Kang H S,Choi J H,Cho W K,et al.A sphingolipid and tyrosinase inhibitors from the fruiting body of Phellinus linteus[J].Arch Pharm Res,2004,27(7):742-750.
[25]Trimbak B M,Tushar M K,Ramakrishna G B.Oxidative decarboxylation of arylacetic acids in water:One-pot transition-metal-free synthesis of aldehydes and ketones[J].Tetrahedron Lett,2017,58(29):2822-2825.
[2]沙孟晨,张海珠,何琴,等.基于微量量热法的连花清瘟胶囊质量一致性评价方法的建立[J].中草药,2017,48(11):2202-2206.
[3]吕宏,欧阳张宁,王俊,等.连花清瘟胶囊联合左氧氟沙星治疗肺炎的临床研究[J].现代药物与临床,2018,33(9):2294-2297.
[4]李伟,郗红娟.连花清瘟胶囊治疗急性上呼吸道感染的临床观察[J].科技信息,2014(15):377-400.
[5]邹龑,黄天泓.连花清瘟胶囊治疗流行性感冒临床效果观察[J].现代医药卫生,2015,31(4):590-592.
[6]李宝法,张长青,付敏,等.连花清瘟胶囊治疗甲型H1N1流感临床研究[J].医药论坛杂志,2009,30(23):91-92.
[7]毕丹,孙云波,宋联强,等.连花清瘟胶囊化学成分研究(I)[J].中草药,2018,49(4):795-800.
[8]张创峰,沈硕,宋联强,等.连花清瘟胶囊的化学成分研究(II)[J].中草药,2018,49(14):3222-3225.
[9]范毅,陈玲,朱杰,等.连翘叶化学成分[J].中国实验方剂学杂志,2015,12(24):22-25.
[10]Wang F N,Ma Z Q,Liu Y,et al.New phenylethanoid glycosides from the fruits of Forsythia suspense(Thunb.)Vahl[J].Molecules,2009,14(3):1324-1331.
[11]郑晓珂,李军,冯卫生,等.石胆草的苯乙醇苷类成分研究[J].中草药,2002,33(10):19-21.
[12]林生,刘明韬,王素娟,等.小蜡树的粉苷及苯乙醇苷类成分[J].中国中药杂志,2010,35(8):992-996.
[13]Xia Y G,Yang B Y,Liang J,et al.Caffeoyl phenylethanoid glycosides from unripe fruits of Forsythia suspensai[J].Chem Nat Compd,2015,51(4):656-659.
[14]Nicoletti M,Galeffi C,Messana I,et al.Phenylpropanoid glycosides from Calceolaria hypericina[J].Phytochemistry,1988,27(2):639-641.
[15]Endo K,Hikino H.Structures of rengyol,rengyoxide and rengyolone,new cyclohexylethane derivatives from Forsythia suspensa fruits[J].Can J Chem,1984,62(9):2011-2014.
[16]Calis I,Tasdemir D,Sticher O,et al.Phenylethanoid glycosides from Digitalis ferruginea subsp.farruginea(=D.aurea LINDLEY)(Scrophulariaceae)[J].Chem Pharm Bull,1999,47(9):1305-1307.
[17]萧伟,谢雪,宋亚玲,等.一种苦杏仁苷的制备方法:中国,CN105461765A[P].2016-04-06.
[18]刘华,沈娟娟,张东明,等.江香薷极性成分的研究[J].中国实验方剂学杂志,2010,16(8):84-86.
[19]Hong M L,Jin K K,Jai M J,et al.Analysis of the inhibitory activity of Abeliophyllum distichum leaf constituents against aldose reductase by using high-speed counter current chromatography[J].Arch Pharm Res,2013,36(9):1104-1112.
[20]Muhammad P,Ahmad S,Nawaz H R,et al.New acetylated quinols from Ajuga parviflora[J].Fitoterapia,1999,70(3):229-232.
[21]Lami N,Kadota S,Kikuchi T,et al.Constituents of the roots of Boerhaavia diffusa L.III.Identification of Ca2+channel antagonistic compound from the methanol extract[J].Chem Pharm Bull,1991,39(6):1551-1555.
[22]赫军,张迅杰,马秉智,等.白英水提取物的化学成分研究[J].中国药学杂志,2015,50(23):2035-2038.
[23]Jin Q H,Lee C,Lee J W,et al.Chemical constituents from the fruits of Prunus mume[J].Nat Prod Sci,2012,18(3):200-203.
[24]Kang H S,Choi J H,Cho W K,et al.A sphingolipid and tyrosinase inhibitors from the fruiting body of Phellinus linteus[J].Arch Pharm Res,2004,27(7):742-750.
[25]Trimbak B M,Tushar M K,Ramakrishna G B.Oxidative decarboxylation of arylacetic acids in water:One-pot transition-metal-free synthesis of aldehydes and ketones[J].Tetrahedron Lett,2017,58(29):2822-2825.