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[摘要] 目的 研究宽叶大戟的化学成分。方法 采用硅胶柱层析法、Sephadex LH20凝胶柱层析法,对宽叶大戟全草体积分数95%乙醇提取物的氯仿萃取部分进行分离,根据理化性质和波谱数据确定各化合物的结构。结果 分离并鉴定了8个化合物,分别为:三十二烷酸(1)、蒲公英醇(2)、α波甾醇(3)、羽扇豆醇(4)、β谷甾醇(5)、白桦酸(6)、齐墩果酸(7)和桦木醇(8)。结论 化合物1-4为首次从宽叶大戟中分离得到。
[关键词] 宽叶大戟;化学成分;提取;分离;结构鉴定
中图分类号:R284.1 文献标识码:A 文章编号:
宽叶大戟(Euphorbia latifolia Meyer ex Ledeb.)为大戟科大戟属多年生草本植物。产于新疆伊犁、塔城至哈巴河,生于海拔1 000~1 500 m的河谷、草甸、林缘及灌丛,主要分布于中亚和西伯利亚。张雷红等从宽叶大戟中分离得到了三萜、黄酮等成分。本研究从宽叶大戟体积分数95%乙醇提取物的氯仿萃取部分分离得到了8个化合物,分别鉴定为三十二烷酸(1)、蒲公英醇(2)、α波甾醇(3)、羽扇豆醇(4)、β谷甾醇(5)、白桦酸(6)、齐墩果酸(7)和桦木醇(8)。其中化合物1-4为首次从宽叶大戟中分离得到。
一、 仪器、试剂与药材
宽叶大戟药材于2007年7月采自新疆阿爾泰地区,经中国医学科学院药用植物研究所李国强副研究员鉴定为Euphorbia latifolia Meyer ex Ledeb.。 FisherJohns型显微熔点仪(温度未校正),PerkinElmer 241旋光仪,PerkinElmer 983G 红外光谱仪,AutospecUltimaETOF质谱仪,INOVA500核磁共振仪。柱色谱硅胶、薄层色谱硅胶板(青岛海洋化工厂),Sephadex LH20(Pharmacia公司),其余试剂均为分析纯。
二、提取与分离
取宽叶大戟全草8.2 kg,粉碎,以体积分数95%乙醇提取3次,每次2 h,过滤,合并滤液,浓缩得乙醇浸膏。浸膏加适量水成混悬液,依次用石油醚、三氯甲烷、乙酸乙酯及正丁醇萃取,浓缩得5个不同极性部分。三氯甲烷萃取物经反复硅胶柱层析和Sephadex LH20凝胶柱层析得化合物1(15 mg)、2(8 mg)、3(9 mg)、4(14 mg)、5(25 mg)、6(12 mg)、7(20 mg)、8(10 mg)。
三、结构鉴定
化合物1:白色粉末,mp 73~75 ℃。EIMS m/z(%): 480 (M+),一系列失去14 amu的碎片离子峰,129(51),111 (20),97 (38),85 (42),73 (66),60 (40),57 (89),44 (100)。经与文献对照,鉴定为三十二烷酸。
化合物2:无色针晶,mp 190~193 ℃,LibermannBurchard 反应呈阳性。IR νmax (KBr): 3 400,2 910,
2 850,1 630,1 450,1 380,1 040,880。EIMS m/z (%):426 (M+,70),408 (15),357 (10),249 (20),218 (90),207 (100),204 (20),189 (90),121 (25)。1HNMR (CDCl3,500 MHz) δ:4.43 (1H,m,H3 ),4.6l (2H,m,H21),0.80-1.20之间有7个甲基信号。与对照品比较,混合熔点不下降,TLC检测Rf值一致。根据以上数据及文献鉴定为蒲公英醇。
化合物3:无色针晶,mp 154~156 ℃。EIMS m/z (%): 412 (M+,66),397 (M+CH3,16),369 (M+CH3CO,21),351 (5),300 (19),271 (失去侧链,100),255 (36),246 (21),231 (13),229 (21),213 (14),81 (76),69 (40)。1HNMR (CDCl3,500 MHz) δ: 5.17 (1H,m,H7),5.15 (1H,dd,J=15.0,9.0 Hz,H22),5.03 (1H,dd,J=15.0,8.5 Hz,H23),3.58 (1H,m,H3),1.02 (3H,d,J=9.5 Hz,H21),0.85 (3H,d,J=6.5 Hz,H26),0.820.80 (3H×3,H19,27,29),0.55 (3H,s,H18); 13CNMR(CDCl3,125 MHz) δ: 37.2 (C1),31.5 (C2),71.2 (C3),38.1 (C4),40.3 (C5),29.7 (C6),117.5 (C7),139.6 (C8),49.5 (C9),34.3 (C10),21.6 (C11),39.5 (C12),43.3 (C13),55.2 (C14),23.0 (C15),28.5 (C16),56.0 (C17),12.1 (C18),13.0 (C19),40.8 (C20),21.4 (C21),138.2 (C22),129.5 (C23),51.3 (C24),31.9 (C25),21.1 (C26),19.0 (C27),25.4 (C28),12.2 (C29)。根据以上数据并与文献比较,鉴定为α波甾醇。
4:无色针晶,mp 178~180 ℃。EIMS m/z (%): 426 [M]+,426 (65),411 (16),408 (21),393 (8),383 (3),218 (45),207 (47),203 (35),189 (57),175 (23),147 (25),135 (50); 1HNMR (CDCl3,500 MHz) δ: 4.68 (1H,d,J=3.0 Hz,H30a),4.56 (1H,d,J=3.0 Hz,H30b),3.20 (1H,dd,J=12.0,5.0Hz,H3),1.68 (3H,s,29CH3),1.03,0.96,0.94,0.82,0.78,0.76 (各3H,s,23,24,25,26,27,28CH3); 13CNMR (CDCl3,125 MHz) δ: 38.7 (C1),27.4 (C2),79.0 (C3),38.8 (C4),55.3 (C5),18.3 (C6),34.3 (C7),40.8 (C8),50.4 (C9),37.1 (C10),20.9 (C11),25.1 (C12),38.0 (C13),42.8 (C14),27.4 (C15),35.6 (C16),43.0 (C17),48.0 (C18),48.3 (C19),150.9 (C20),29.8 (C21),40.0 (C22),27.9 (C23),15.4 (C24),16.1 (C25),15.9 (C26),14.5 (C27),18.0 (C28),19.3 (C29),109.3 (C30)。根据以上数据及文献鉴定为羽扇豆醇。 化合物5:无色针晶,mp 134~136 ℃。EIMS m/z:414 [M]+,396,330,329,273,255。经与对照品比较,混合熔点不下降,TLC检测Rf值一致,证明两者为同一化合物,鉴定为β谷甾醇。
化合物6:无色针晶,mp 256~258 ℃。EIMS m/z (%): 456 (M+,31),438 (12),410 (8),395 (5),248 (33),220 (21),207 (32),189 (40),175 (55),161 (52),145 (44 ),133(100),123 (71),109 (79),94 (60),77 (73),57 (76); 1HNMR (C5D5N,500 MHz) δ: 4.93 (1H,br s,H30a),4.76 (1H,br s,H30b),3.53 (1H,m,H3),3.44 (1H,br t,J=7.0 Hz,H19),2.75 (2H,m,H2),2.23 (2H,t, J=5.0 Hz,H16),0.81,1.00,1.05,1.06,1.21,1.78 (各3H,s,6個角甲基); 13CNMR (C5D5N,125 MHz) δ: 39.5 (C1),28.3 (C2),78.1 (C3),39.3 (C4),55.9 (C5),18.8 (C6),34.8 (C7),41.1 (C8),50.9 (C9),37.5 (C10),21.2 (C11),26.1 (C12),38.6 (C13),42.8 (C14),31.2 (C15),32.8 (C16),56.6 (C17),49.7 (C18),47.7 (C19),151.3 (C20),30.2 (C21),37.6 (C22),28.6 (C23),16.3 (C24),16.4 (C25),16.4 (C26),14.9 (C27),178.8 (C28),19.4 (C29),109.9 (C30)。根据以上数据及文献鉴定为白桦酸。
化合物7:白色粉末,mp 178~180 ℃。EIMS m/z (%): 456 (M+,9),248 (28),297 (31),203 (100),189 (17) ; 1HNMR (C5D5N,500 MHz) δ: 5.72 (1H,br s,H11),3.45 (1H,m,H3),0.89,0.94,1.00,1.02,1.05,1.22,1.24 (各3H,s,7 个角甲基); 13CNMR (C5D5N,125 MHz)δ: 38.5 (C1),27.7 (C2),77.7 (C3),38.7 (C4),55.4 (C5),18.4 (C6),32.5 (C7),39.1 (C8),47.7 (C9),36.9 (C10),23.4 (C11),122.6 (C12),144.4 (C13),41.6 (C14),27.7 (C15),23.2 (C16),46.3 (C17),40.7 (C18),46.1 (C19),30.7 (C20),33.8 (C21),32.5 (C22),27.9 (C23),15.3 (C24),15.1 (C25),17.1 (C26),25.8 (C27),179.8 (C28),32.9 (C29),23.4 (C30)。与对照品比较,混合熔点不下降,TLC检测Rf值一致,再根据文献鉴定为齐墩果酸。
化合物8:白色粉末,mp 253~255 ℃。1HNMR (CDCl3,500 MHz) δ: 0.77 (3H,s),0.84 (3H,s),0.99 (3H,s),1.27 (3H,s),1.69 (3H,s),3.18 (1H,dd,J=11.0,5.1 Hz,H3),3.79 (1H,d,J=10.9 Hz,H28a),3.34 (1H,d, J=10.9 Hz,H28b),4.69 (1H,d,J=2.1 Hz,H30a),4.59 (1H,d,J=2.1 Hz,H30b); 13CNMR (CDCl3,125 MHz) δ: 38.7 (C1),27.4 (C2),79.0 (C3),38.9 (C4),55.3 (C5),18.3 (C6),34.2 (C7),41.0 (C8),50.4 (C9),37.2 (C10),20.8 (C11),25.2 (C12),37.3 (C13),42.7 (C14),29.2 (C15),25.2 (C16),40.9 (C17),48.8 (C18),47.8 (C19),150.5 (C20),29.8 (C21),34.2 (C22),28.0 (C23),15.3 (C24),16.0 (C25),16.1 (C26),14.8 (C27),60.6 (C28),19.1 (C29),110.0 (C30)。根据以上数据及文献鉴定为桦木醇。
参考文献:
1、邹忠杰,龚梦鹃??,宽叶大戟化学成分的研究,论文网,2010.10
[关键词] 宽叶大戟;化学成分;提取;分离;结构鉴定
中图分类号:R284.1 文献标识码:A 文章编号:
宽叶大戟(Euphorbia latifolia Meyer ex Ledeb.)为大戟科大戟属多年生草本植物。产于新疆伊犁、塔城至哈巴河,生于海拔1 000~1 500 m的河谷、草甸、林缘及灌丛,主要分布于中亚和西伯利亚。张雷红等从宽叶大戟中分离得到了三萜、黄酮等成分。本研究从宽叶大戟体积分数95%乙醇提取物的氯仿萃取部分分离得到了8个化合物,分别鉴定为三十二烷酸(1)、蒲公英醇(2)、α波甾醇(3)、羽扇豆醇(4)、β谷甾醇(5)、白桦酸(6)、齐墩果酸(7)和桦木醇(8)。其中化合物1-4为首次从宽叶大戟中分离得到。
一、 仪器、试剂与药材
宽叶大戟药材于2007年7月采自新疆阿爾泰地区,经中国医学科学院药用植物研究所李国强副研究员鉴定为Euphorbia latifolia Meyer ex Ledeb.。 FisherJohns型显微熔点仪(温度未校正),PerkinElmer 241旋光仪,PerkinElmer 983G 红外光谱仪,AutospecUltimaETOF质谱仪,INOVA500核磁共振仪。柱色谱硅胶、薄层色谱硅胶板(青岛海洋化工厂),Sephadex LH20(Pharmacia公司),其余试剂均为分析纯。
二、提取与分离
取宽叶大戟全草8.2 kg,粉碎,以体积分数95%乙醇提取3次,每次2 h,过滤,合并滤液,浓缩得乙醇浸膏。浸膏加适量水成混悬液,依次用石油醚、三氯甲烷、乙酸乙酯及正丁醇萃取,浓缩得5个不同极性部分。三氯甲烷萃取物经反复硅胶柱层析和Sephadex LH20凝胶柱层析得化合物1(15 mg)、2(8 mg)、3(9 mg)、4(14 mg)、5(25 mg)、6(12 mg)、7(20 mg)、8(10 mg)。
三、结构鉴定
化合物1:白色粉末,mp 73~75 ℃。EIMS m/z(%): 480 (M+),一系列失去14 amu的碎片离子峰,129(51),111 (20),97 (38),85 (42),73 (66),60 (40),57 (89),44 (100)。经与文献对照,鉴定为三十二烷酸。
化合物2:无色针晶,mp 190~193 ℃,LibermannBurchard 反应呈阳性。IR νmax (KBr): 3 400,2 910,
2 850,1 630,1 450,1 380,1 040,880。EIMS m/z (%):426 (M+,70),408 (15),357 (10),249 (20),218 (90),207 (100),204 (20),189 (90),121 (25)。1HNMR (CDCl3,500 MHz) δ:4.43 (1H,m,H3 ),4.6l (2H,m,H21),0.80-1.20之间有7个甲基信号。与对照品比较,混合熔点不下降,TLC检测Rf值一致。根据以上数据及文献鉴定为蒲公英醇。
化合物3:无色针晶,mp 154~156 ℃。EIMS m/z (%): 412 (M+,66),397 (M+CH3,16),369 (M+CH3CO,21),351 (5),300 (19),271 (失去侧链,100),255 (36),246 (21),231 (13),229 (21),213 (14),81 (76),69 (40)。1HNMR (CDCl3,500 MHz) δ: 5.17 (1H,m,H7),5.15 (1H,dd,J=15.0,9.0 Hz,H22),5.03 (1H,dd,J=15.0,8.5 Hz,H23),3.58 (1H,m,H3),1.02 (3H,d,J=9.5 Hz,H21),0.85 (3H,d,J=6.5 Hz,H26),0.820.80 (3H×3,H19,27,29),0.55 (3H,s,H18); 13CNMR(CDCl3,125 MHz) δ: 37.2 (C1),31.5 (C2),71.2 (C3),38.1 (C4),40.3 (C5),29.7 (C6),117.5 (C7),139.6 (C8),49.5 (C9),34.3 (C10),21.6 (C11),39.5 (C12),43.3 (C13),55.2 (C14),23.0 (C15),28.5 (C16),56.0 (C17),12.1 (C18),13.0 (C19),40.8 (C20),21.4 (C21),138.2 (C22),129.5 (C23),51.3 (C24),31.9 (C25),21.1 (C26),19.0 (C27),25.4 (C28),12.2 (C29)。根据以上数据并与文献比较,鉴定为α波甾醇。
4:无色针晶,mp 178~180 ℃。EIMS m/z (%): 426 [M]+,426 (65),411 (16),408 (21),393 (8),383 (3),218 (45),207 (47),203 (35),189 (57),175 (23),147 (25),135 (50); 1HNMR (CDCl3,500 MHz) δ: 4.68 (1H,d,J=3.0 Hz,H30a),4.56 (1H,d,J=3.0 Hz,H30b),3.20 (1H,dd,J=12.0,5.0Hz,H3),1.68 (3H,s,29CH3),1.03,0.96,0.94,0.82,0.78,0.76 (各3H,s,23,24,25,26,27,28CH3); 13CNMR (CDCl3,125 MHz) δ: 38.7 (C1),27.4 (C2),79.0 (C3),38.8 (C4),55.3 (C5),18.3 (C6),34.3 (C7),40.8 (C8),50.4 (C9),37.1 (C10),20.9 (C11),25.1 (C12),38.0 (C13),42.8 (C14),27.4 (C15),35.6 (C16),43.0 (C17),48.0 (C18),48.3 (C19),150.9 (C20),29.8 (C21),40.0 (C22),27.9 (C23),15.4 (C24),16.1 (C25),15.9 (C26),14.5 (C27),18.0 (C28),19.3 (C29),109.3 (C30)。根据以上数据及文献鉴定为羽扇豆醇。 化合物5:无色针晶,mp 134~136 ℃。EIMS m/z:414 [M]+,396,330,329,273,255。经与对照品比较,混合熔点不下降,TLC检测Rf值一致,证明两者为同一化合物,鉴定为β谷甾醇。
化合物6:无色针晶,mp 256~258 ℃。EIMS m/z (%): 456 (M+,31),438 (12),410 (8),395 (5),248 (33),220 (21),207 (32),189 (40),175 (55),161 (52),145 (44 ),133(100),123 (71),109 (79),94 (60),77 (73),57 (76); 1HNMR (C5D5N,500 MHz) δ: 4.93 (1H,br s,H30a),4.76 (1H,br s,H30b),3.53 (1H,m,H3),3.44 (1H,br t,J=7.0 Hz,H19),2.75 (2H,m,H2),2.23 (2H,t, J=5.0 Hz,H16),0.81,1.00,1.05,1.06,1.21,1.78 (各3H,s,6個角甲基); 13CNMR (C5D5N,125 MHz) δ: 39.5 (C1),28.3 (C2),78.1 (C3),39.3 (C4),55.9 (C5),18.8 (C6),34.8 (C7),41.1 (C8),50.9 (C9),37.5 (C10),21.2 (C11),26.1 (C12),38.6 (C13),42.8 (C14),31.2 (C15),32.8 (C16),56.6 (C17),49.7 (C18),47.7 (C19),151.3 (C20),30.2 (C21),37.6 (C22),28.6 (C23),16.3 (C24),16.4 (C25),16.4 (C26),14.9 (C27),178.8 (C28),19.4 (C29),109.9 (C30)。根据以上数据及文献鉴定为白桦酸。
化合物7:白色粉末,mp 178~180 ℃。EIMS m/z (%): 456 (M+,9),248 (28),297 (31),203 (100),189 (17) ; 1HNMR (C5D5N,500 MHz) δ: 5.72 (1H,br s,H11),3.45 (1H,m,H3),0.89,0.94,1.00,1.02,1.05,1.22,1.24 (各3H,s,7 个角甲基); 13CNMR (C5D5N,125 MHz)δ: 38.5 (C1),27.7 (C2),77.7 (C3),38.7 (C4),55.4 (C5),18.4 (C6),32.5 (C7),39.1 (C8),47.7 (C9),36.9 (C10),23.4 (C11),122.6 (C12),144.4 (C13),41.6 (C14),27.7 (C15),23.2 (C16),46.3 (C17),40.7 (C18),46.1 (C19),30.7 (C20),33.8 (C21),32.5 (C22),27.9 (C23),15.3 (C24),15.1 (C25),17.1 (C26),25.8 (C27),179.8 (C28),32.9 (C29),23.4 (C30)。与对照品比较,混合熔点不下降,TLC检测Rf值一致,再根据文献鉴定为齐墩果酸。
化合物8:白色粉末,mp 253~255 ℃。1HNMR (CDCl3,500 MHz) δ: 0.77 (3H,s),0.84 (3H,s),0.99 (3H,s),1.27 (3H,s),1.69 (3H,s),3.18 (1H,dd,J=11.0,5.1 Hz,H3),3.79 (1H,d,J=10.9 Hz,H28a),3.34 (1H,d, J=10.9 Hz,H28b),4.69 (1H,d,J=2.1 Hz,H30a),4.59 (1H,d,J=2.1 Hz,H30b); 13CNMR (CDCl3,125 MHz) δ: 38.7 (C1),27.4 (C2),79.0 (C3),38.9 (C4),55.3 (C5),18.3 (C6),34.2 (C7),41.0 (C8),50.4 (C9),37.2 (C10),20.8 (C11),25.2 (C12),37.3 (C13),42.7 (C14),29.2 (C15),25.2 (C16),40.9 (C17),48.8 (C18),47.8 (C19),150.5 (C20),29.8 (C21),34.2 (C22),28.0 (C23),15.3 (C24),16.0 (C25),16.1 (C26),14.8 (C27),60.6 (C28),19.1 (C29),110.0 (C30)。根据以上数据及文献鉴定为桦木醇。
参考文献:
1、邹忠杰,龚梦鹃??,宽叶大戟化学成分的研究,论文网,2010.10