|
作者:田学军 李红霞 陈玉 王晓琼
【摘要】 目的对灯心草Juncus effusus L.石油醚和醋酸乙酯提取物的化学成分进行研究。方法运用正相和反相硅胶柱层析对灯心草石油醚和醋酸乙酯提取物进行分离纯化,并用波谱技术鉴定其结构。结果从灯心草石油醚提取物分得2个甾体化合物 stigmast4en6βol3one (1), (24R)stigmast4ene3one (2),从醋酸乙酯提取物分得两个二氢菲类化合物juncusol (3)和efffusol (4)。结论 化合物1和2均为首次从灯心草属植物中分得。
【关键词】 灯心草 灯心草属 甾体化合物
Abstract:ObjectiveTo investigate the chemical constituents of the stem of Juncus effusus L. MethodsThe constituents were isolated by normal-phase and reverse-phase silica gel column chromatography from the P.E. and EtOAc extract. Their structures were elucidated by spectral analysis. ResultsTwo steroid compounds were isolated from P.E. extract and identified as stigmast4en6βol3one (1), (24R)stigmast4ene3one (2), two 9,10dihydrophenanthrene compounds were isolated from EtOAc extract and identified as juncusol (3) and efffusol (4).ConclusionCompound 1 and 2 were isolated from Juncaceae plant for the first time.
Key words:Juncus effusus L.; Juncaceae; Steroids
灯心草Juncus effusus L.是灯心草科(Juncaceae)灯心草属(Juncus)多年生草本植物。通常生长在草甸、沼泽、水边及阴湿的环境中。在我国,灯心草是用于治疗失眠、发烧并具有清热利尿功效的传统药物[1]。国外学者的研究发现灯心草中的菲类化合物具有很强的抗菌、抗氧化、抗肿瘤及抗藻类的活性[2~3]。中国有丰富的灯心草植物资源,仅湖北植物志记入的就有12种[1],但对其研究相当贫乏。由于同种不同产地的植物资源及其化学成分及含量也有很大的差异,我们对湖北产灯心草(Juncus effusus L.)进行了细致的分离提取鉴定工作,在前文我们已报道了7个化合物的分离与结构鉴定[4~5],为进一步寻找新的生物活性成分,充分开发我国的药用植物资源,我们又从灯心草石油醚和醋酸乙酯提取物中分得4个化合物,经波谱解析,其结构分别鉴定为stigmast4en6βol3one (1), (24R)stigmast4ene3one (2),juncusol (3)和efffusol (4)。本文报道了这4个化合物的分离和结构鉴定,结构式见图1。其中化合物1,2为首次从灯心草属植物中分得。
1 R = H, BOH 3 R = CH3
2R=H2 4R=H
图1 化合物1~4的结构(略)
1 仪器与材料
Varian INOVA-300Hz型核磁共振仪(TMS内标);柱层析用硅胶为青岛海洋化工厂生产的200~300目硅胶、硅胶H和日本YMC公司生产的RP-18反相硅胶(50 μm);薄层硅胶板(GF254)为青岛海洋硅胶干燥剂厂生产;所用溶剂均为分析纯,由天津博迪化学试剂有限公司生产。灯心草购于武汉红十字药材公司,经我院万定荣主任药师鉴定为灯心草Juncus effusus L.的干燥茎髓。
2 提取与分离
灯心草干燥茎髓10 kg粉碎后用95%乙醇浸泡,真空抽滤得滤液,减压旋蒸,得乙醇提取物166 g。将乙醇提取物依次用石油醚、醋酸乙酯、正丁醇萃取。将得到的石油醚提取物8.5 g进行硅胶柱层析,用石油醚-丙酮梯度洗脱,TLC检测合并相同流份,再经反复正相和反相硅胶柱层析得到化合物1 (68.7 mg ),2 (82.6 mg)。将得到的醋酸乙酯提取物55 g进行硅胶柱层析,用石油醚-丙酮梯度洗脱,TLC检测合并相同流份,流份21~30分别合并,并记作Fr2130, Fr2130经反复正相和反相硅胶柱色谱分离得到化合物3(13.2 mg)、4(18.3 mg)。
3 结构鉴定
化合物1:无色针晶,分子式C29H48O2 其波谱数据如下:1H-NMR(300 MHz,CDCl3)δ5.81 (1H, s, H-4),4.35 (1H, m, H-6), 0.74 (3H, s, H3-18) , 1.37(3H, s, H3-19), 0.94 (3H,d, J = 7.2Hz, H3-21,), 0.85 (3H, d, J = 6.6Hz, H3-26), 0.83 (3H, d, J = 6.6 Hz, H3-27), 0.87 (3H, t, J =7.2Hz , H3-29)。13C-NMR(75 MHz,CDCl3)δ37.3(t,C-1),34.5(t,C-2),200.6(s,C-3),126.5(d,C-4),168.8(s,C-5),73.5(d,C-6),38.8(t,C-7),30.0(d, C-8),54.0(d, C-9),38.2(s, C-10),21.2(t, C-11),39.8(t, C-12),42.7(s, C-13),56.1(d, C-14),24.4(t, C-15),28.4(t, C-16),56.3 (d, C-17), 12.2(q, Me-18), 19.7(q, Me-19), 36.3(d, C-20), 19.0(q, Me-21), 34.1 (t, C-22), 26.4 (t, C-23), 46.1(d, C-24), 29.4 (d, C-25), 20.0 (q, Me-26), 19.3 (q, Me-27), 23.3(t, C-28), 12.2(q, Me-29)以上波谱数据与文献[6]报道的stigmast-4-en-6β-ol-3-one数据一致,故鉴定1为 stigmast-4-en-6β-ol-3-one。 作者:田学军 李红霞 陈玉 王晓琼
【摘要】 目的对灯心草Juncus effusus L.石油醚和醋酸乙酯提取物的化学成分进行研究。方法运用正相和反相硅胶柱层析对灯心草石油醚和醋酸乙酯提取物进行分离纯化,并用波谱技术鉴定其结构。结果从灯心草石油醚提取物分得2个甾体化合物 stigmast4en6βol3one (1), (24R)stigmast4ene3one (2),从醋酸乙酯提取物分得两个二氢菲类化合物juncusol (3)和efffusol (4)。结论 化合物1和2均为首次从灯心草属植物中分得。
【关键词】 灯心草 灯心草属 甾体化合物
Abstract:ObjectiveTo investigate the chemical constituents of the stem of Juncus effusus L. MethodsThe constituents were isolated by normal-phase and reverse-phase silica gel column chromatography from the P.E. and EtOAc extract. Their structures were elucidated by spectral analysis. ResultsTwo steroid compounds were isolated from P.E. extract and identified as stigmast4en6βol3one (1), (24R)stigmast4ene3one (2), two 9,10dihydrophenanthrene compounds were isolated from EtOAc extract and identified as juncusol (3) and efffusol (4).ConclusionCompound 1 and 2 were isolated from Juncaceae plant for the first time.
Key words:Juncus effusus L.; Juncaceae; Steroids
灯心草Juncus effusus L.是灯心草科(Juncaceae)灯心草属(Juncus)多年生草本植物。通常生长在草甸、沼泽、水边及阴湿的环境中。在我国,灯心草是用于治疗失眠、发烧并具有清热利尿功效的传统药物[1]。国外学者的研究发现灯心草中的菲类化合物具有很强的抗菌、抗氧化、抗肿瘤及抗藻类的活性[2~3]。中国有丰富的灯心草植物资源,仅湖北植物志记入的就有12种[1],但对其研究相当贫乏。由于同种不同产地的植物资源及其化学成分及含量也有很大的差异,我们对湖北产灯心草(Juncus effusus L.)进行了细致的分离提取鉴定工作,在前文我们已报道了7个化合物的分离与结构鉴定[4~5],为进一步寻找新的生物活性成分,充分开发我国的药用植物资源,我们又从灯心草石油醚和醋酸乙酯提取物中分得4个化合物,经波谱解析,其结构分别鉴定为stigmast4en6βol3one (1), (24R)stigmast4ene3one (2),juncusol (3)和efffusol (4)。本文报道了这4个化合物的分离和结构鉴定,结构式见图1。其中化合物1,2为首次从灯心草属植物中分得。
1 R = H, BOH 3 R = CH3
2R=H2 4R=H
图1 化合物1~4的结构(略)
1 仪器与材料
Varian INOVA-300Hz型核磁共振仪(TMS内标);柱层析用硅胶为青岛海洋化工厂生产的200~300目硅胶、硅胶H和日本YMC公司生产的RP-18反相硅胶(50 μm);薄层硅胶板(GF254)为青岛海洋硅胶干燥剂厂生产;所用溶剂均为分析纯,由天津博迪化学试剂有限公司生产。灯心草购于武汉红十字药材公司,经我院万定荣主任药师鉴定为灯心草Juncus effusus L.的干燥茎髓。
2 提取与分离
灯心草干燥茎髓10 kg粉碎后用95%乙醇浸泡,真空抽滤得滤液,减压旋蒸,得乙醇提取物166 g。将乙醇提取物依次用石油醚、醋酸乙酯、正丁醇萃取。将得到的石油醚提取物8.5 g进行硅胶柱层析,用石油醚-丙酮梯度洗脱,TLC检测合并相同流份,再经反复正相和反相硅胶柱层析得到化合物1 (68.7 mg ),2 (82.6 mg)。将得到的醋酸乙酯提取物55 g进行硅胶柱层析,用石油醚-丙酮梯度洗脱,TLC检测合并相同流份,流份21~30分别合并,并记作Fr2130, Fr2130经反复正相和反相硅胶柱色谱分离得到化合物3(13.2 mg)、4(18.3 mg)。
3 结构鉴定
化合物1:无色针晶,分子式C29H48O2 其波谱数据如下:1H-NMR(300 MHz,CDCl3)δ5.81 (1H, s, H-4),4.35 (1H, m, H-6), 0.74 (3H, s, H3-18) , 1.37(3H, s, H3-19), 0.94 (3H,d, J = 7.2Hz, H3-21,), 0.85 (3H, d, J = 6.6Hz, H3-26), 0.83 (3H, d, J = 6.6 Hz, H3-27), 0.87 (3H, t, J =7.2Hz , H3-29)。13C-NMR(75 MHz,CDCl3)δ37.3(t,C-1),34.5(t,C-2),200.6(s,C-3),126.5(d,C-4),168.8(s,C-5),73.5(d,C-6),38.8(t,C-7),30.0(d, C-8),54.0(d, C-9),38.2(s, C-10),21.2(t, C-11),39.8(t, C-12),42.7(s, C-13),56.1(d, C-14),24.4(t, C-15),28.4(t, C-16),56.3 (d, C-17), 12.2(q, Me-18), 19.7(q, Me-19), 36.3(d, C-20), 19.0(q, Me-21), 34.1 (t, C-22), 26.4 (t, C-23), 46.1(d, C-24), 29.4 (d, C-25), 20.0 (q, Me-26), 19.3 (q, Me-27), 23.3(t, C-28), 12.2(q, Me-29)以上波谱数据与文献[6]报道的stigmast-4-en-6β-ol-3-one数据一致,故鉴定1为 stigmast-4-en-6β-ol-3-one。
化合物2:无色针晶,分子式C29H48O 其波谱数据如下:1H-NMR(300 MHz,CDCl3)δ 0.71(3H, s, H3-18), 0.83(3H, d, J= 6.9Hz, H3-27),0.87 (3H, d, J = 6.9Hz, H3-26),0.85 (3H, t,J = 6.6Hz, H3-29),0.93 (3H, d,J = 6.6Hz, H3-21) ,1.18 (3H, s, H3-19) ,5.72 (1H, s, H-4)。13C-NMR(75 MHz,CDCl3)δ35.9(t,C-1),34.2(t ,C-2),199.9(s,C-3),124.0(d,C-4),172.0(s,C-5), 33.2(t,C-6), 32.3(t,C-7),36.3(d ,C-8), 54.1(d ,C-9),38.8(s,C-10),21.3(t,C-11),40.0(t,C-12),42.6(s,C-13),56.1(d,C-14), 24.4(t,C-15),28.4(t,C-16),56.2 (d,C-17),12.2 (q, Me-18), 17.6 (q, Me-19), 35.9(d, C-20), 18.9 (q, Me-21), 34.1 (t, C-22) 26.3 (d, C-23), 46.0 (t, C-24), 29.4 (d, C-25), 20.1(q, Me-26), 19.3 (q, Me-27), 23.3(t, C-28), 12.2 (q, Me-29), 以上波谱数据与文献[6,7]报道的(24R)-stigmast-4-ene-3-one的数据一致,故鉴定2为 (24R)-stigmast-4-ene-3-one。
化合物3:淡黄色油状物,分子式C18H18O2,1H NMR(300MHz,Me2CO-d6)δ8.16, 8.14 (2H, s, 2, 7-OH), 7.43(1H,d,J = 8.4Hz,H-4),6.80(1H,dd,J = 11.4,18.2Hz,H-12),6.73(1H,s,H-8),6.68(1H,d,J = 8.4Hz,H-3),5.45(1H,dd,J = 11.4, 2.1Hz, H-13a),5.17(1H,dd,J = 18.2, 2.1Hz,H-13b),2.67 (2H, m, H2-9 or H2-10), 2.58 (2H, m, H2-9 or H2-10), 2.24(3H,s,H3-11), 2.20(3H,s,H3-14)。13C NMR(75MHz,DMSO-d6)δ121.0(C-1),154.2(C-2),111.9(C-3),128.7(C-4),137.7(C-5),121.5(C-6),154.4(C-7),113.7(C-8),31.0(C-9),26.3(C-10),11.7(C-11),139.0(C-12),119.0(C-13),113.5(C-14),139.9(C-1a),127.3(C-4a),127.5(C-5a),137.2(C-8a)。所列数据与文献[8]报道juncusol一致,故鉴定3为juncusol。
化合物4:淡黄色油状物,分子式C17H16O2, 1H NMR(300MHz,Me2CO-d6)δ8.26, 8.24 (2H, s, 2, 7-OH), 7.20(1H,d,J = 8.9Hz,H-4),6.95(1H,dd,J = 10.9,17.4Hz,H-12),6.91(1H,d,J = 3.0Hz,H-6),6.73(1H,d,J = 3.0Hz,H-8),6.75(1H,d,J = 8.9Hz,H-3),5.65(1H,dd,J = 17.4,1.5Hz, H-13a),5.21(1H,dd,J = 10.9, 1.5Hz,H-13b),2.67 (2H, m, H2-9 or H2-10), 2.65(2H, m, H2-9 or H2-10), 2.22(3H,s,H3-11)。所列数据与文献[9]报道efffusol一致,故鉴定4为efffusol。(【参考文献】
[1] 傅书暇,郑 重. 湖北植物志[M].武汉:湖北科学技术出版社, 2001:443.
[2] 金东哲, 闵知大,孔令义,等. 灯心草科植物中二萜成分[J].国外医药:植物药分册 , 1995 , 10 (5):208.
[3] 陈 玉,杨光忠. 灯心草属植物菲类化合物结构和生物活性的研究进展[J].天然产物研究与开发, 2005 , 17 (4) :496 , 505.
[4] 李红霞,钟芳芳,陈 玉,等. 灯心草抗菌活性成分的研究[J].华中师范大学学报·自然科学版,2006,40 (2) : 205.
[5] 李红霞,陈 玉,梅之南,等. 灯心草化学成分的研究[J].中药材,2006,29 (11):1186.
[6] Greca, M. D.; Monaco, P.; Previtera, L. Stigmasterols from Typhha latifolia. J. Nat. Prod., 1990, 53 (6):1430.
[7] Gaspar, E. M. M.; Neves, H. J. C. D. Steroidal constituents from mature wheat straw . Phytochemistry, 1993, 34 (2) :523.
[8] Hanawa, F;Okamoto, M.; Towers, G. H. N. Antimicrobial DNA-binding photosensitizers from the common rush, Juncus effusus[J].Photochemistry and Photobiology, 2002, 76(1):51.
[9] Mody, N. V.; Mahmoud, I. I; Moore, J. F.; Pelletier, S. W. Constituents of Juncus effusus: the X-ray analysis of effusol diacetate. J. Nat. Prod., 1982, 45 (6):733. |
|