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    開口箭根莖中甾體化合物的研究

    2014-01-10 04:21:00寧德生蔣麗華劉金磊李典鵬潘爭紅
    關(guān)鍵詞:氫譜波譜硅膠

    寧德生,蔣麗華,劉金磊,李典鵬,潘爭紅*

    1廣西壯族自治區(qū)中國科學院廣西植物研究所 廣西植物功能物質(zhì)研究與利用重點實驗室,桂林 541006;2廣西中醫(yī)藥大學,南寧 530001

    開口箭(Tupistra chinensis Bak.)系百合科鈴蘭族開口箭屬植物,全球約有20 種,我國有12 種[1]。主要分布在我國四川、湖北、云南和廣西等地。開口箭常用于治療頭痛咳嗽、咽喉腫痛、風濕痹痛等病癥,具有多種生物活性。藥理實驗結(jié)果顯示,開口箭具有較強的抗炎[2,3]、抗菌[4]、抗腫瘤[5,6]、免疫調(diào)節(jié)[7]和抑制動脈粥樣硬化斑形成[8]等生理作用;但目前對開口箭化學成分研究還不夠深入,活性成分的物質(zhì)基礎(chǔ)不明確,妨礙了開口箭的開發(fā)利用,因此深入研究開口箭化學成分是非常有意義的,可為該植物的開發(fā)應用提供物質(zhì)基礎(chǔ)。此次研究從該植物中分離得到9個化合物,其中3-epi-neoruscogenin-3-β-D-glucopyranoside、3-epi-ruscogenin-3-β-D-glucopyranoside 和convallagenin B 首次從該植物中分離得到。

    1 儀器與材料

    瑞士Bruker DRX-600 MHz 超導核磁共振儀;BS110S 賽多利斯電子天平,北京賽多利斯天平有限公司;Agilent 1200 半制備型高效液相色譜儀,Eclipse XDB-C18(9.4 ×250 mm,5 μm);硅膠(200~300 目)及TLC 檢測用硅膠GF254板(青島海洋化工廠);Sephadex LH-20 為瑞士Amershan Biosciences公司生產(chǎn);高效液相用試劑為色譜純,其他所用試劑均為分析純。

    開口箭根莖購自安徽省亳州藥材市場,由潘爭紅副研究員鑒定并保存標本于本室。

    2 提取與分離

    圖1 化合物1~9 的化學結(jié)構(gòu)式Fig.1 Structures of compounds 1-9

    干燥的開口箭根莖約4.8 Kg,粉碎至粗粉,用95%的乙醇浸提3 次,提取液減壓濃縮,用水分散后依次用石油醚、乙酸乙酯、正丁醇萃取。將乙酸乙酯萃取物(214 g)進行100~200 目硅膠柱層析,石油醚-丙酮(1∶0→0∶1)梯度洗脫,得到6個組分Fr.1~Fr.6。Fr.3 反復進行硅膠柱層柱(200~300 目)后,用Sephadex LH-20(氯仿/甲醇,1∶1,v/v)凝膠柱純化,得到化合物8(160 mg)、5(120 mg)和6(82 mg)。Fr.4 經(jīng)硅膠柱層析,氯仿-甲醇(9∶1→0∶1)梯度洗脫,再經(jīng)HPLC 制備(甲醇/水,40%~100%,v/v)純化,得到化合物3(60 mg)、4(3 mg)和7(115 mg)。Fr.5 經(jīng)Sephadex LH-20(甲醇)凝膠柱層析,再用HPLC 制備(甲醇/水,40%~100%,v/v)純化,得到化合物9(40 mg)、1(31 mg)和2(5 mg)。

    3 結(jié)構(gòu)鑒定

    化合物1 白色固體,1H NMR(600 MHz,C5D5N)δ:3.76 (1H,dd,J=4.2,12.0 Hz,H-1),1.98 (1H,m,H-2a),1.68 (1H,m,H-2b),4.04(1H,br.s,H-3),1.70 (1H,m,H-4a),1.21 (1H,m,H-4b),5.47 (1H,d,J=5.4 Hz,H-6),1.97 (1H,m,H-7a),1.29 (1H,m,H-7b),1.60 (1H,m,H-8),1.29 (1H,m,H-9),2.28 (1H,m,H-11a),1.55(1H,m,H-11b),2.49 (1H,d,J=15.0 Hz,H-12a),2.24 (1H,m,H-12b),1.17 (1H,m,H-14),1.97 (1H,m,H-15a),1.30 (1H,m,H-15b),4.45(1H,m,H-16),1.74 (1H,t,J=7.2 Hz,H-17),0.84 (3H,s,H-18),1.03 (3H,s,H-19),1.93 (1H,m,H-20),0.95 (3H,d,J=7.2 Hz,H-21),1.71(1H,m,H-23),2.51 (1H,m,H-24a),2.25 (1H,m,H-24b),4.26 (1H,d,J=12.0 Hz,H-26a),3.82(1H,d,J=12.0 Hz,H-26b),4.77 (1H,br.s,H-27a),4.74 (1H,br.s,H-27b),4.32 (1H,d,J=7.8 Hz,H-1'),3.16 (1H,t,J=7.8 Hz,H-2'),3.34(1H,m,H-3'),3.27 (1H,m,H-4'),3.25 (1H,m,H-5'),3.85 (1H,dd,J=2.4,12.0 Hz,H-6'a),3.65 (1H,dd,J=5.4,12.0 Hz,H-6'b);13C NMR(150 MHz,C5D5N)δ:76.2 (d,C-1),36.6 (t,C-2),75.4 (d,C-3),41.3 (t,C-4),139.8 (s,C-5),125.5(d,C-6),33.0 (t,C-7),33.7 (d,C-8),51.6 (d,C-9),44.9 (s,C-10),24.9 (t,C-11),39.1 (t,C-12),41.1 (s,C-13),58.0 (d,C-14),33.0 (t,C-15),82.5 (d,C-16),64.1 (d,C-17),17.0 (q,C-18),13.3 (q,C-19),42.8 (d,C-20),14.9 (q,C-21),110.7 (s,C-22),34.0 (t,C-23),29.5 (t,C-24),145.2 (s,C-25),65.8 (t,C-26),108.9 (t,C-27),102.9 (d,C-1'),74.9 (d,C-2'),78.2 (d C-3'),71.6 (d,C-4'),77.9 (d,C-5'),62.8 (t,C-6')。本文首次列出化合物1 完整的碳、氫譜數(shù)據(jù),并與文獻[9]的氫譜數(shù)據(jù)一致,故鑒定化合物1 為3-epi-neoruscogenin-3-β-D-glucopyranoside。

    化合物2 白色固體,1H NMR(600 MHz,C5D5N)δ:3.76 (1H,dd,J=4.2,12.0 Hz,H-1),1.98,(1H,m,H-2a),1.68 (1H,m,H-2b),4.04(1H,br.s,H-3),1.70 (1H,m,H-4a),1.21 (1H,m,H-4b),5.47 (1H,d,J=5.4 Hz,H-6),1.97 (1H,m,H-7a),1.29 (1H,m,H-7b),1.60 (1H,m,H-8),1.29 (1H,m,H-9),2.28,(1H,m,H-11a),1.55(1H,m,H-11b),2.49 (1H,d,J=15.0 Hz,H-12),2.24 (1H,m,H-12),1.97 (1H,m,H-15a),1.30(1H,m,H-15b),4.39 (1H,m,H-16),1.74 (1H,t,J=7.2 Hz,H-17),0.81 (3H,s,H-18),1.03 (3H,s,H-19),1.93 (1H,m,H-20),0.95 (3H,d,J=7.2 Hz,H-21),1.56 (1H,m,H-25),3.44 (1H,dd,J=9.6,3.0 Hz,H-26a),3.32 (1H,t,J=9.6 Hz,H-26b),0.79 (3H,d,J=6.6 Hz,H-27),4.32 (1H,d,J=7.8 Hz,H-1'),3.16 (1H,t,J=7.8 Hz,H-2'),3.34 (1H,m,H-3'),3.27 (1H,m,H-4'),3.25(1H,m,H-5'),3.85 (1H,dd,J=2.4,12.0 Hz,H-6'a),3.65 (1H,dd,J=5.4,12.0 Hz,H-6'b);13C NMR (150 MHz,C5D5N)δ:76.2 (d,C-1),36.6 (t,C-2),75.4 (d,C-3),41.3 (t,C-4),139.8 (s,C-5),125.5 (d,C-6),33.0 (t,C-7),33.7 (d,C-8),51.6(d,C-9),44.9 (s,C-10),24.9 (t,C-11),39.1 (t,C-12),41.1 (s,C-13),58.0 (d,C-14),33.0 (t,C-15),82.2 (d,C-16),64.0 (d,C-17),17.0 (q,C-18),13.3 (q,C-19),42.8 (d,C-20),14.9 (q,C-21),110.6 (s,C-22),34.0 (t,C-23),29.8 (t,C-24),31.6 (d,C-25),67.8 (t,C-26),17.5 (q,C-27),102.9 (d,C-1'),74.9 (d,C-2'),78.2 (d,C-3'),71.6 (d,C-4'),77.9 (d,C-5'),62.8 (t,C-6')。本文首次列出化合物2 完整的碳、氫譜數(shù)據(jù),并與文獻[9]的氫譜數(shù)據(jù)一致,故鑒定化合物2 為3-epiruscogenin-3-β-D-glucopyranoside。

    化合物3 白色針晶,1H NMR(600 MHz,C5D5N)δ:4.21 (1H,br.s,H-1),2.53 (1H,dt,J=15.0,2.5 Hz,H-2a),2.10 (1H,dt,J=15.0,2.5 Hz,H-2b),4.57 (1H,m,H-3),4.27 (1H,d,J=2.4 Hz,H-4),2.47,(1H,dt,J=13.2,3.0 Hz,H-6a),1.70 (1H,dt,J=13.2,3.0 Hz,H-6b),4.60(1H,m,H-16),0.88 (3H,s,H-18),1.60 (3H,s,H-19),1.10 (3H,d,J=7.2 Hz,H-21),2.72 (1H,td,J=13.2,5.4 Hz,H-24ax),2.25 (1H,d,J=13.2 Hz,H-24eq),4.48 (1H,d,J=12.0 Hz,H-26ax),4.04 (1H,d,J=12.0 Hz,H-26eq),4.82(1H,s,H-27a),4.78 (1H,s,H-27b);13C NMR (150 MHz,C5D5N)δ:73.7 (d,C-1),33.4 (t,C-2),71.1 (d,C-3),68.0 (d,C-4),78.3 (s,C-5),30.4 (t,C-6),28.4 (t,C-7),35.0 (d,C-8),45.7 (d,C-9),45.4(s,C-10),21.4 (t,C-11),40.0 (t,C-12),40.6 (s,C-13),56.2 (d,C-14),32.2 (t,C-15),81.4 (d,C-16),63.0 (d,C-17),16.6 (q,C-18),13.8 (q,C-19),41.9 (d,C-20),14.9 (q,C-21),109.4 (s,C-22),33.2 (t,C-23),28.9 (t,C-24),144.4 (s,C-25),65.0 (t,C-26),108.6 (t,C-27)。以上波譜數(shù)據(jù)與文獻[10]一致,故鑒定化合物3 為ranmogenin A。

    化合物4 白色針晶,1H NMR (600 MHz,C5D5N)δ:4.21 (1H,br.s,H-1),2.53 (1H,dt,J=15.0,2.5 Hz,H-2a),2.10 (1H,dt,J=15.0,2.5 Hz,H-2b),4.57 (1H,m,H-3),4.27 (1H,d,J=2.4 Hz,H-4),2.47 (1H,dt,J=13.2,3.0 Hz,H-6a),1.70 (1H,dt,J=13.2,3.0 Hz,H-6b),4.60(1H,m,H-16),0.87 (3H,s,H-18),1.59 (3H,s,H-19),1.15 (3H,d,J=7.2 Hz,H-21),2.70 (1H,td,J=13.2,5.4 Hz,H-24a),2.24 (1H,d,J=13.2 Hz,H-24b),3.48 (1H,d,J=10.8 Hz,H-26a),3.36 (1H,d,J=10.8 Hz,H-26b),1.07 (3H,d,J=7.2 Hz,H-27);13C NMR (150 MHz,C5D5N)δ:73.7 (d,C-1),33.4 (t,C-2),71.1 (d,C-3),68.0(d,C-4),78.3 (s,C-5),30.4 (t,C-6),28.4 (t,C-7),35.0 (d,C-8),45.7 (d,C-9),45.4 (s,C-10),21.4 (t,C-11),40.0 (t,C-12),40.6 (s,C-13),56.2 (d,C-14),32.2 (t,C-15),81.1 (d,C-16),62.8 (d,C-17),16.5 (q,C-18),13.8 (q,C-19),42.4 (d,C-20),14.8 (q,C-21),109.7 (s,C-22),26.1 (t,C-23),26.3 (t,C-24),27.5 (d,C-25),65.1 (t,C-26),16.2 (q,C-27)。以上波譜數(shù)據(jù)與文獻[11]一致,故鑒定化合物4 為convallagenin B。

    化合物5 白色無定形粉末,1H NMR(600 MHz,C5D5N)δ:4.52 (1H,dd,J=11.4,4.2 Hz,H-1),4.36 (1H,br.s,H-3),5.66 (1H,d,J=6.0 Hz,H-6),4.49 (1H,m,H-16),0.92 (3H,s,H-18),1.34 (3H,s,H-19),1.05 (3H,d,J=7.2 Hz,H-21),4.46 (1H,d,J=12.6 Hz,H-26a),4.03 (1H,d,J=12.0 Hz,H-26b),4.81 (1H,s,H-27a),4.78(1H,s,H-27b);13C NMR (150 MHz,C5D5N)δ:75.3 (d,C-1),40.8 (t,C-2),66.5(d,C-3),41.1(t,C-4),140.1 (s,C-5),124.5 (d,C-6),32.8 (t,C-7),32.3 (d,C-8),51.2 (d,C-9),44.6 (s,C-10),24.3 (t,C-11),40.5 (t,C-12),40.2 (s,C-13),57.0 (d,C-14),32.3 (t,C-15),81.4 (d,C-16),63.1 (d,C-17),16.6 (q,C-18),13.2 (q,C-19),41.8 (d,C-20),14.9 (q,C-21),109.4 (s,C-22),33.2 (t,C-23),28.9 (t,C-24),144.5 (s,C-25),64.9 (t,C-26),108.6 (t,C-27)。以上波譜數(shù)據(jù)與文獻[12]一致,故鑒定化合物5 為3-epineoruscogenin。

    化合物6 白色無定形粉末,1H NMR(600 MHz,C5D5N)δ:4.26 (1H,br.s,H-1),4.57 (1H,br.s,H-3),4.65 (1H,q,J=7.2 Hz,H-16),0.89(3H,s,H-18),1.58 (3H,s,H-19),1.13 (3H,d,J=7.2 Hz,H-21),4.08 (1H,d,J=11.4 Hz,H-26eq),4.52 (1H,d,J=12.0 Hz,H-26ax),4.84(1H,s,H-27a),4.80 (1H,s,H-27b);13C NMR (150 MHz,C5D5N)δ:74.0 (d,C-1),39.5 (t,C-2),67.9(d,C-3),36.6 (t,C-4),75.1(s,C-5),35.0 (t,C-6),29.9 (t,C-7),34.4 (d,C-8),45.8 (d,C-9),44.0 (s,C-10),21.5 (t,C-11),40.1 (t,C-12),40.7 (s,C-13),56.3 (d,C-14),32.2 (t,C-15),81.4 (d,C-16),63.0 (d,C-17),16.5 (q,C-18),13.8 (q,C-19),41.9 (d,C-20),14.9 (q,C-21),109.4 (s,C-22),33.2 (t,C-23),28.9 (t,C-24),144.4 (s,C-25),65.0 (t,C-26),108.7 (t,C-27)。以上波譜數(shù)據(jù)與文獻[12]一致,故鑒定化合物6 為tupichigenin E。

    化合物7 白色針晶(氯仿-甲醇),1H NMR(600 MHz,C5D5N)δ:4.33 (1H,br.s,H-1),4.41(1H,br.s,H-2),4.74 (1H,br.s,H-3),4.56 (1H,br.s,H-7),2.48 (1H,td,J=11.1,4.8 Hz,H-9),2.41 (1H,m,H-15a),1.58 (1H,m,H-15b),4.59(1H,m,H-16),1.93 (1H,t,J=6.6 Hz,H-17),0.88 (3H,s,H-18),1.47 (3H,s,H-19),1.08 (3H,d,J=6.6 Hz,H-21),2.24 (1H,m,H-24eq),2.68(1H,m,H-24ax),4.03 (1H,d,J=12.6 Hz,H-26eq),4.43(1H,d,J=12.6 Hz,H-26αx),4.77(1H,s,H-27a),4.80 (1H,s,H-27b);13C NMR (150 MHz,C5D5N)δ:76.4 (d,C-1),67.8 (d,C-2),75.4(d,C-3),71.1 (d,C-4),86.2 (s,C-5),211.1 (s,C-6),75.1 (d,C-7),40.8 (d,C-8),37.9 (d,C-9),50.1 (s,C-10),21.9 (t,C-11),39.3 (t,C-12),40.6 (s,C-13),49.2 (d,C-14),31.4 (t,C-15),81.3 (d,C-16),62.8 (d,C-17),16.2 (q,C-18),12.9 (q,C-19),42.0 (d,C-20),14.9 (q,C-21),109.4 (s,C-22),33.1 (t,C-23),28.9 (t,C-24),144.3 (s,C-25),64.9 (t,C-26),108.7 (t,C-27)。以上波譜數(shù)據(jù)與文獻[13]一致,故鑒定化合物7 為(20S,22R)-spirost-25(27)-ene-1β,2β,3β,4β,5β,7α-hexaol-6-one。

    化合物8 白色晶體(氯仿),mp.129~130 ℃,分子式C29H50O。在10%硫酸乙醇溶液中顯紫紅色,與β-谷甾醇標準品TLC 檢測Rf值一致,且混合熔點不下降。故化合物8 鑒定為β-谷甾醇。

    化合物9 白色粉末,微溶于氯仿、甲醇,易溶于吡啶。在10%硫酸乙醇溶液中顯紫紅色,與胡蘿卜苷標準品TLC 檢測Rf值一致,且混合熔點不下降。故化合物9 鑒定為胡蘿卜苷。

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    12 Pan WB,Chang FR,Wei LM,et al.New flavans spirostanol sapogenins,and a pregnane genin from Tupistra chinensis and their cytotoxicity.J Nat Prod,2003,66:161-168.

    13 Pan WB,Chang FR,Wu YC.Tupichigenin A,a new steroidal sapogenin from Tupistra chinensis.J Nat prod,2000,63:861-863.

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