卷柏化学成分研究

【作者】 史社坡；

【导师】 冯卫生；

【作者基本信息】 河南中医学院 ， 药物化学， 2003， 硕士

【摘要】 本论文分两部分。 第一部分:提取分离与结构鉴定。说明了本研究所用仪器与试剂及提取分离过程。采用70%含水丙酮提取、系统溶剂萃取,得乙醚部位、醋酸乙酯部位、正丁醇部位、水部位。将乙醚和醋酸乙酯部位分别拌样上硅胶柱,反复柱层析;正丁醇部位分别进行Diaion HP-20、Toyopearl HW-40、MCI Gel CHP-20、Sephadex LH-20、硅胶等柱层析及制备薄层层析,结果共分离得到25个化合物。根据化合物的理化性质及UV、HRFAB-MS、ESI-MS、IR、¹HNMR、¹³CNMR、¹H-¹H COSY、HMQC、HMBC等波谱分析方法,鉴定了20个化合物的结构,分别为:β-谷甾醇（JB-Y-1）、十六烷酸（JB-Y-5）、十一烷酸（JB-Y-6）、穗花杉双黄酮（JB-Y-7）、4-O-[2-羟基-3-（4-羟基苯基）-6-羟甲基苯基]-苯丙炔酸（JB-Y-8）、丁香脂素（JB-Y-9）、2,3-二氢-5,7,4′,5″,7″,3′″,4′″-七羟基-8,8″-双黄酮（JB-E-2）、扁柏双黄酮（JB-E-4）、（7S,8R）-二氢-7-（3,5-二甲氧基-4-羟基苯基）-8-羟甲基-3′-甲氧基-1′-乙酰基-苯骈呋喃（JB-E-5）、新柳杉双黄酮（JB-E-9）、芫花素（JB-E-14）、1-O-β-D-2-[2-羟基-3-甲氧基-5-（1-乙醇基）苯基]-3-（4-羟基-3,5-二甲氧基苯基）-丙醇-葡萄糖苷（JB-A-1）、丁香酸（JB-A-2）、芹菜素-6,8-二-C-β-葡萄糖苷（JB-A-3）、咖啡酰基环己六醇（JB-A-4）、熊果苷（JB-A-5）、7,8-二氢-7-（4-羟基-3,5-二甲氧基苯基）-8-羟甲基-[1′-（7′-羟基）乙基-5′-甲氧基]苯骈呋喃-4-β-葡萄糖苷（JB-A-11）、鸟苷（JB-A-18）、1-（4-羟基-3-甲氧基苯基）丙三醇（JB-A-19）、腺苷（JB-A-20）。其中4-O-[2-羟基-3-（4-羟基苯基）-6-羟甲基苯基]-苯丙炔酸、（7S,8R）-二氢-7-（3,5-二甲氧基-4-羟基苯基）-8-羟甲基-3′-甲氧基-1′-乙酰基-苯骈呋喃、1-O-β-D-2-[2-羟基-3-甲氧基-5-（1-乙醇基）苯基]-3-（4-羟基-3,5-二甲氧基苯基）-丙醇-葡萄糖苷、7,8-二氢-7-（4-羟基-3,5-二甲氧基苯基）-8-羟甲基-[1′-（7′-羟基乙基）-5′-甲氧基]苯骈呋喃-4-β-葡萄糖苷四个化合物暂定为新化合物;其余化合物除穗花杉双黄酮、扁柏双黄酮以外均为首次从卷柏中分离得到。 第二部分:卷柏中腺苷的含量测定。采用反相高效液相色谱法对卷柏中腺苷的含量进行了初步的探讨,并对新疆、河北、安徽、河南四个产地的卷柏中腺苷含量进行了比较,为建立其质量标准提供参考。色谱柱选用SHIM-PACK CLC-ODS柱,流动相为水:甲醇（100:2）:检测波长260nm;室温下对腺苷含量进行测定。结果表明,在1～8μg范围内线性关系较好,相关系数r=0.9993,平均回收率为96.70%,RSD为0.93%。本法灵敏、简便、准确,重现性较好。更多还原

【Abstract】 This dissertation consists of two chapters:Chapter 1: This chapter includes two sections. The first section is about experiment. The extraction and isolation procedures of chemical constituents in Selaginella tamariscina (Beauv.)Spring was illuminated. An aqueous acetone extract of Selaginella tamariscina(Beauv.)Spring collected in Xixia county, Henan province was suspended in water, extracted by ether, ethyl acetate and n-butanol (saturated with water) respectively. The extract obtained were subjected to a combination of column chromatographies such as silica gel, Diaion HP-20, Toyopearl HW-40, MCI Gel CHP-20, Sephadex LH-20 etc. PTLC was also used to purified the compounds obtained. With such methods, 25 compounds were yielded.The second section describes the elucidation of compounds obtained fromSelaginella tamariscina (Beauv.)Spring. On the basis of spectroscopic analysis andchemical evidences, 20 compounds’ structures were determined as β-sitosterol (JB-Y-1),hexadecalic acid (JB-Y-5) , hendecylic acid (JB-Y-6) , amentoflavone (JB-Y-7) ,4-O-[2-hydroxyl-3- (4-hydroxyphenyl) -6-hydroxymethyphenyl]-phenylpropiolic acid(tamariscinic acid A, JB-Y-8), sygringaresinol(JB-Y-9), 2,3-dihydro-5,7,4’,5",7",3’",4’"-septahydroxyl-8, 8"-biflavonoids (JB-E-2), robustaflavone (JB-E-4), (7S,8R) -dihydro-7- (3,5-dimethoxyl-4-hydroxyphenyl) -8-hydroxymethyl-3’- methoxyl -1’-acetyl-benzofuran(JB-E-5), neocryptomerin (JB-E-9), genkwanin (JB-E-14), 1 -O-β-D-2-[2-hydroxyl-3-methoxyl-5-( 1 -ethanol )phenyl]-3-( 4-hydroxyl-3,5-dimethoxyphenyl)-propanol-glucopyranoside(tamariscinoside A, JB-A-1) , syringic acid (JB-A-2) , Apigenin-6,8-di-C-β-glucopyranoside(JB-A-3) , caffeoylinositol (JB-A-4) , arbutin (JB-A-5) , 7,8-dihydro-7-(4-hydroxyl-3,5-dimethoxyphenyl)-8-hydroxymethyl -[l’-7’-hydroxyethyl] -5’-methoxyl] benzofuran-4-β-glucopyranoside (tamariscinoside B,JB-A-11), guanosine (JB-A-18) ,1- (4-hydroxyl-3-methoxyphenyl) glycerol (JB-A-19)、 adenosine (JB-A-20) .Among the 20 compounds, 4-O-[2-hydroxyl-3- (4-hydroxyphenyl) -6-hydroxymethyphenyl] -phenylpropiolic acid (tamariscinic acid A, JB-Y-8), (7S,8R) -dihydro-7- (4-hydroxy-3,5-dimethoxylphenyl)-8-hydroxymethyl-3’- methoxyl -1’-acetyl-benzofuran(JB-E-5),1-O-β-D-2-[2-hydroxyl-3-methoxyl-5- (1-ethanol) phenyl]-3- (4-hydroxyl-3,5-dimethoxyphenyl) -propanol-glucopyranoside (tamariscinoside A, JB-A-1), 7,8-dihydro-7-(4-hydroxyl-3.5-dimethoxyphenyl)- 8-hydroxymethyl-[1’-7’-hydroxyethyl] -5’-methoxyl] benzofuran-4-β-glucopyranoside (tamariscinoside B, JB-A-11) were identified as novel compounds in natural products. The other compounds are all obtained from the plants for the first time except amentoflavone and robustaflvaone.Chapter 2: Determination the quantity of Adenosine in Selaginella tamariscina by RP-HPLC. To establish a RP-HPLC method for the determination of adenosine in Selaginella tamariscina, four samples collected from Xinjiang, Hebei, Anhui and Henan were detected by RP-HPLC. The chromatographic conditions includes SHIM-PACK CLC-ODS column and the mobile phase consisting of a mixture of water-methanol (100:2) for adenosine. The detection wavelength was at 260nm, and measured at room temperature. It has concluded that This method was sensitive, simple and accurate with a good linearity in the concentration range of l~8ug for adenosine. The correlation coefficient was 0.9993. The average recovery of adenosine was 96.70% with 0.93% of RSD.更多还原