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        五味子莖葉的化學成分研究

        2021-04-17 21:47:41趙倩倩張少軍萬閩歌曹云剛
        中草藥 2021年23期
        關鍵詞:無定形波譜五味子

        趙倩倩,張少軍,萬閩歌,劉 琦,曹云剛*,何 瑞*

        五味子莖葉的化學成分研究

        趙倩倩1,張少軍1,萬閩歌2,劉 琦3,曹云剛1*,何 瑞3*

        1. 陜西科技大學食品與生物工程學院,陜西 西安 710000 2. 陜西國際商貿(mào)學院醫(yī)藥學院,陜西 西安 710000 3. 西安阿房宮藥業(yè)股份有限公司,陜西 西安 710000

        對五味子莖葉的化學成分進行研究。利用大孔吸附樹脂、葡聚糖凝膠、硅膠柱色譜、半制備高效液相色譜等多種色譜方法分離純化,根據(jù)理化性質(zhì)及波譜數(shù)據(jù)對化合物進行結構鑒定。從五味子莖葉75%丙酮提取物中分離得到15個化合物,分別鑒定為schisanlatone C(1)、henrischinin B(2)、henrischinin C(3)、schisanlactone B(4)、schizandronic acid(5)、kadnanolactone C(6)、rubrisandrin C(7)、異戈米辛O(8)、(?)-gomisin M(9)、met A-III(10)、五味子醇甲(11)、戈米辛R(12)、4--methylsaurucinol H(13)、(3,5,6,7)-5,6-epoxy-3-hydroxy-7-megastigmen-9-one(14)、(6,9)-9-hydroxy-4,6-megastigmadien-3-one(15)。化合物5~7、13~15為首次從該植物中分離得到,其中化合物13~15為首次從五味子屬植物中分離得到。

        五味子;三萜;木脂素;異戈米辛O;五味子醇甲;戈米辛R

        五味子(Turcz.) Baill.為五味子屬Michx. 植物干燥成熟果實,是我國傳統(tǒng)中藥,具有收斂固澀、益氣生津、補腎寧心之功效[1]。研究結果表明,五味子莖葉中含有與果實類似的化學成分,4年生以上藤莖中五味子甲素、五味子乙素含量均高于果實[2]。五味子果實研究的相對較多也較為成熟,鑒于五味子莖葉中也含有類似的化學成分,因而越來越受到人們的關注。目前從五味子莖葉中分離得到的化合物主要為三萜和木脂素類化合物,這些化合物普遍具有抗病毒、抗細胞毒、抗肝炎、抗艾滋病病毒等活性[1-5]。本實驗對五味子莖葉的化學成分進行了系統(tǒng)研究,從其75%丙酮提取物中共分離鑒定了15個化合物,schisanlatone C(1)、henrischinin B(2)、henrischinin C(3)、schisanlactone B(4)、schizandronic acid(5)、kadnanolactone C(6)、rubrisandrin C(7)、異戈米辛O(-gomisin O,8)、(?)-gomisin M(9)、met A-III(10)、五味子醇甲(gomisin A,11)、戈米辛R(gomisin R,12)、4--methylsaurucinol H(13)、(3,5,6,7)-5,6-epoxy-3-hydroxy-7-megastigmen-9- one(14)、(6,9)-9-hydroxy-4,6-megastigmadien-3- one(15)?;衔?~3、6為環(huán)阿屯烷型三萜,化合物4、5為羊毛脂烷型三萜,化合物7~12為聯(lián)苯環(huán)辛烯型木脂素,化合物13為四氫呋喃型木脂素?;衔?~7、13~15為首次從該植物中分離得到,其中化合物13~15為首次從五味子屬植物中分離得到。該研究為五味子藥材的綜合開發(fā)利用及藥物研發(fā)提供理論參考。

        1 儀器與材料

        GCMS-TQ8030質(zhì)譜儀(日本島津公司);Bruker ADVANCE Ⅲ 400 MHz核磁共振波譜儀(美國Bruker公司);Waters 1525半制備型高效液相色譜儀(美國Waters公司);色譜柱:SunFire(C18,150 mm×4.6 mm,5 μm,);葡聚糖凝膠LH-20(Amersham Biosciences);薄層色譜硅膠(GF254,10~40 μm)以及正相柱色譜所用的硅膠(200~300目),青島海洋化工廠;大孔樹脂HP-20(日本三菱公司)。

        五味子莖葉于2014年8月采自陜西省寶雞鳳縣的秦嶺山,由蘭州大學藥學院李建銀教授鑒定為五味子屬植物五味子(Turcz.) Baill.。植物標本(20140824-01)存放于蘭州大學化學化工學院國家重點實驗室天然有機研究室。

        2 提取與分離

        五味子莖葉9.8 kg干燥后粉碎,70%丙酮浸泡3次,每次7 d。合并后減壓蒸餾得粗浸膏水溶液,用醋酸乙酯萃取,減壓蒸餾得粗膏220.7 g,用少量甲醇溶解后進行大孔樹脂柱色譜,甲醇-水(3∶7、5∶5、8∶2、9∶1、10∶0)梯度洗脫。大孔樹脂90%部分洗脫液減壓蒸餾得到粗樣品59.2 g。該部分樣品進行硅膠柱色譜,石油醚-丙酮(20∶1、10∶1、5∶1、2∶1、1∶1、0∶1)梯度洗脫,得到6個組分(Fr. A~F)。

        Fr. C(3.1 g)進行反相硅膠柱色譜,甲醇-水(5∶5、6∶4、7∶3、8∶2、9∶1、1∶0)梯度洗脫,共得到6個組分Fr. C1~C6。Fr. C2和Fr. C3分別經(jīng)葡聚糖凝膠經(jīng)甲醇洗脫后得到5個組分,后用半制備高效液相色譜[甲醇-水(3∶7),2 mL/min]進行純化,依次得到化合物1(2.2 mg,R=26 min)、2(3.2 mg,R=35 min)、3(10.2 mg,R=31 min)、4(2.0 mg,R=50 min)、5(2.5 mg,R=16 min)、6(2.2 mg,R=40 min)。

        Fr. D(2.7 g)、Fr. E(3.3 g)經(jīng)薄層色譜檢測所含的化合物相似,合并后進行反相硅膠柱色譜,甲醇-水(6∶4、7∶3、8∶2、9∶1、1∶0)為洗脫劑進行梯度洗脫,得到5個組分Fr. D1~D5。Fr. D2和Fr. D3有白色固體析出,醋酸乙酯重結晶后得到化合物8(11.2 mg)、9(8.7 mg)、10(21.7 mg),合并母液后進行硅膠柱色譜,氯仿-醋酸乙酯(1∶0~0∶1)為洗脫劑進行梯度洗脫,后經(jīng)葡聚糖凝膠以甲醇為洗脫劑洗脫得到3個組分,半制備高效液相色譜 [甲醇-水(1∶3),2 mL/min]進行純化,分別得到化合物7(2.4 mg,R=17.5 min)、11(1.2 mg,R=22 min)、12(2.1 mg,R=25 min)、13(3.9 mg,R=33 min)。半制備高效液相色譜 [甲醇-水(1∶6),2 mL/min]進行純化,分別得到化合物14(5.2 mg,R=22 min)、15(5.1 mg,R=29 min)。

        3 結構鑒定

        化合物1:白色無定形粉末狀固體;1H-NMR (400 MHz, CDCl3): 6.68 (1H, d,= 12.2 Hz, H-1), 5.82 (1H, d,= 12.2 Hz, H-2), 6.61 (1H, d,= 6.1 Hz, H-24), 6.21 (1H, s, H-19), 4.30 (1H, dd,= 3.6, 12.8 Hz, H-22), 2.49 (1H, m, H-5), 1.92 (3H, s, Me-27), 1.52 (3H, s, Me-29), 1.40 (3H, s, Me-30), 1.30 (3H, s, Me-21), 1.12 (3H, s, Me-28), 0.92 (3H, s, Me-18);13C-NMR (100 MHz, CDCl3): 143.1 (C-1), 117.7 (C-2), 167.2 (C-3), 80.54 (C-4), 49.3 (C-5), 39.7 (C-6), 26.7 (C-7), 150.3 (C-8), 129.0 (C-9), 139.4 (C-10), 28.3 (C-11), 30.5 (C-12), 45.5 (C-13), 52.3 (C-14), 30.6 (C-15), 25.2 (C-16), 48.5 (C-17), 17.6 (C-18), 143.6 (C-19), 75.0 (C-20), 21.5 (C-21), 82.6 (C-22), 21.7 (C-23), 139.2 (C-24), 128.2 (C-25), 165.6 (C-26), 16.6 (C-27), 27.2 (C-28), 26.2 (C-29), 29.2 (C-30)。以上波譜數(shù)據(jù)與文獻報道一致[6],故鑒定化合物1為schisanlatone C。

        化合物2:白色無定形粉末狀固體;1H-NMR (400 MHz, CDCl3): 6.65 (1H, d,= 12.2 Hz, H-1), 5.81 (1H, d,= 12.2 Hz, H-2), 6.22 (1H, s, H-19), 4.56 (1H, s, H-22), 0.75, 1.06, 1.39, 1.53, 1.72, 2.11 (各3H, s, 6×Me);13C-NMR (100 MHz, CDCl3): 143.6 (C-1), 118.2 (C-2), 166.6 (C-3), 80.2 (C-4), 49.3 (C-5), 39.5 (C-6), 28.2 (C-7), 150.5 (C-8), 129.2 (C-9), 139.7 (C-10), 26.6 (C-11), 30.2 (C-12), 44.7 (C-13), 51.8 (C-14), 31.2 (C-15), 27.6 (C-16), 48.6 (C-17), 17.5 (C-18), 143.8 (C-19), 48.5 (C-20), 33.2 (C-21), 85.5 (C-22), 34.1 (C-23), 46.0 (C-24), 82.7 (C-25), 170.1 (C-26), 26.2 (C-27), 27.1 (C-28), 26.0 (C-29), 29.1 (C-30), 170.3, 21.3 (OAc)。以上波譜數(shù)據(jù)與文獻報道一致[7],故鑒定化合物2為henrischinin B。

        化合物3:白色無定形粉末狀固體;1H-NMR (400 MHz, CDCl3): 6.12 (1H, d,= 12.4 Hz, H-1), 6.17 (1H, d,= 12.4 Hz, H-2), 2.32 (1H, dd,= 12.6, 4.6 Hz, H-5), 0.78 (3H, s, H-18), 0.78~0.86 (1H, d,= 4.6 Hz, H-19), 1.02~1.08 (1H, d,= 4.6 Hz, H-19β), 2.26~2.35 (1H, m, H-20), 4.56 (1H, br s, H-22), 2.52~2.57 (1H, t,= 4.4 Hz, H-24), 1.73 (3H, s, H-27), 0.76 (3H, s, H-28), 1.30 (3H, s, H-29), 1.32 (3H, s, H-30);13C-NMR (100 MHz, CDCl3): 151.2 (C-1), 120.7 (C-2), 166.9 (C-3), 84.0 (C-4), 46.6 (C-5), 23.7 (C-6), 24.2 (C-7), 44.8 (C-8), 33.5 (C-9), 28.7 (C-10), 32.8 (C-11), 28.6 (C-12), 45.7 (C-13), 48.9 (C-14), 35.2 (C-15), 28.8 (C-16), 50.2 (C-17), 18.3 (C-18), 31.8 (C-19), 49.2 (C-20), 30.1 (C-21), 85.1 (C-22), 33.6 (C-23), 46.9 (C-24), 74.3 (C-25), 177.2 (C-26), 28.8 (C-27), 18.6 (C-28), 22.2 (C-29), 29.2 (C-30)。以上波譜數(shù)據(jù)與文獻報道一致[7],故鑒定化合物3為henrischinin C。

        化合物4:白色粉末狀無定形固體;1H-NMR (400 MHz, CDCl3): 0.91 (3H, s, Me-18), 0.56 (1H, d,= 4.0 Hz, H-19α), 0.77 (1H, d,= 4.0 Hz, H-19β), 0.89 (3H, d,= 3.6 Hz, Me-21), 6.08 (1H, t,= 6.8 Hz, H-24), 1.90 (3H, s, Me-27), 1.06 (3H, s, Me-28), 1.09 (3H, s, Me-29), 0.98 (3H, s, Me-30);13C-NMR (100 MHz, CDCl3): 35.7 (C-1), 37.2 (C-2), 216.8 (C-3), 50.2 (C-4), 48.5 (C-5), 21.6 (C-6), 28.5 (C-7), 47.7 (C-8), 21.1 (C-9), 26.2 (C-10), 26.7 (C-11), 35.7 (C-12), 45.3 (C-13), 48.5 (C-14), 33.2 (C-15), 26.7 (C-16), 52.3 (C-17), 18.5 (C-18), 29.6 (C-19), 36.2 (C-20), 18.2 (C-21), 32.5 (C-22), 25.6 (C-23), 147.0 (C-24), 125.8 (C-25), 173.2 (C-26), 20.6 (C-27), 19.5 (C-28), 22.2 (C-29), 20.5 (C-30)。以上波譜數(shù)據(jù)與文獻報道一致[8],故鑒定化合物4為schizandronic acid。

        化合物5:白色無定形粉末狀固體;1H-NMR (400 MHz, CDCl3): 6.12 (1H, d,= 12.2 Hz, H-1), 5.96 (1H, d,= 12.2 Hz, H-2), 2.44 (1H, m, H-5), 1.85 (1H, m, H-6a), 0.81 (1H, m, H-6b), 1.47 (1H, m, H-7a), 1.22 (1H, m, H-7b), 1.80 (1H, m, H-8), 1.56~1.65 (1H, m, H-11a), 2.07 (1H, m, H-11b), 1.67 (1H, m, H-12a), 1.70 (1H, m, H-12b), 1.58-1.62 (1H, m, H-15a), 1.77 (1H, m, H-15b), 1.35-1.45 (2H, m, H-16), 1.58~1.62 (1H, m, H-17), 0.99 (3H, s, Me-18), 1.26 (1H, d,= 5.2 Hz, H-19a), 1.03 (1H, d,= 5.2 Hz, H-19b), 2.06 (1H, m, H-20), 0.99 (3H, d,= 6.6 Hz, Me-21), 4.46 (1H, m, H-22), 2.13 (1H, m, H-23a), 2.37 (1H, m, H-23b), 6.60 (1H, m, H-24), 1.92 (3H, s, Me-27), 0.90 (3H, s, Me-28), 1.37 (3H, s, Me-29), 1.35 (3H, s, Me-30);13C-NMR (100 MHz, CDCl3): 150.7 (C-1), 120.6 (C-2), 167.5 (C-3), 84.6 (C-4), 46.5 (C-5), 24.7 (C-6), 29.1 (C-7), 45.1 (C-8), 33.6 (C-9), 28.7 (C-10), 32.1 (C-11), 32.5 (C-12), 48.9 (C-13), 45.2 (C-14), 26.6 (C-15), 35.3 (C-16), 48.0 (C-17), 16.6 (C-18), 24.2 (C-19), 39.2 (C-20), 13.5 (C-21), 80.7 (C-22), 23.9 (C-23), 139.6 (C-24), 128.5 (C-25), 166.6 (C-26), 17.2 (C-27), 19.1 (C-28), 29.2 (C-29), 21.9 (C-30)。以上波譜數(shù)據(jù)與文獻報道一致[9],故鑒定化合物5為schisanlactone B。

        化合物6:白色無定型粉末狀固體;1H-NMR (400 MHz, CDCl3): 1.66 (1H, m, H-1β), 1.76 (1H, m, H-1α), 2.62 (1H, m, H-2α), 2.55 (1H, m, H-2β), 1.98 (1H, m, H-5), 1.56 (1H, m, H-6β), 2.09 (1H, m, H-6α), 1.47 (1H, m, H-7β), 1.72 (1H, m, H-7α), 1.71 (1H, m, H-11α), 1.66 (1H, m, H-11β), 2.12 (1H, m, H-12α), 2.00 (1H, m, H-12β), 1.23 (2H, m, H-15), 1.41 (1H, m, H-16α), 2.05 (1H, m, H-16β), 1.52 (1H, m, H-17), 0.76 (3H, s, Me-18), 1.23 (3H, s, Me-19), 2.02 (1H, m, H-20), 0.99 (3H, d,= 6.8 Hz, Me-21), 4.50 (1H, m, H-22), 2.38 (1H, m, H-23), 6.63 (1H, m, H-24), 1.91 (3H, s, Me-27), 0.88 (3H, s, Me-28), 1.53 (3H, s, Me-29), 1.44 (3H, s, Me-30);13C-NMR (100 MHz, CDCl3): 36.7 (C-1), 32.6 (C-2), 174.5 (C-3), 86.2 (C-4), 49.6 (C-5), 23.7 (C-6), 27.2 (C-7), 134.2 (C-8), 133.5 (C-9), 39.7 (C-10), 31.2 (C-11), 21.3 (C-12), 44.3 (C-13), 49.7 (C-14), 31.2 (C-15), 26.1 (C-16), 46.0 (C-17), 15.8 (C-18), 20.2 (C-19), 39.7 (C-20), 13.6 (C-21), 80.2 (C-22), 23.1 (C-23), 139.2 (C-24), 128.2 (C-25), 166.8 (C-26), 17.6 (C-27), 24.7 (C-28), 30.8 (C-29), 26.2 (C-30)。以上波譜數(shù)據(jù)與文獻報道一致[10],故鑒定化合物6為kadnanolactone C。

        化合物7:白色粉末狀固體;1H-NMR (400 MHz, CDCl3): 6.49 (1H, s, H-4), 6.39 (1H, s, H-11), 0.86 (3H, d,= 7.2 Hz, H-17), 0.93 (3H, d,= 7.2 Hz, H-18), 3.82 (3H, s, OMe), 3.87 (3H, s, OMe), 4.25 (1H, d,= 7.2 Hz, H-6α), 5.91 (2H, s, -OCH2O-), 5.92 (2H, s, -OCH2O-);13C-NMR (100 MHz, CDCl3): 141.5 (C-1), 136.6 (C-2), 148.0 (C-3), 105.3 (C-4), 136.2 (C-5), 81.1 (C-6), 40.2 (C-7), 37.3 (C-8), 37.8 (C-9), 135.5 (C-10), 102.7 (C-11), 149.2 (C-12), 134.7 (C-13), 141.5 (C-14), 120.2 (C-15), 121.3 (C-16), 16.6 (C-17), 17.6 (C-18), 59.9 (-OMe), 59.8 (-OMe), 100.7 (-OCH2O-), 101.6 (-OCH2O-)。以上波譜數(shù)據(jù)與文獻報道一致[11],故鑒定化合物7為rubrisandrin C。

        化合物8:無色油狀物;1H-NMR (400 MHz, CDCl3): 6.51 (1H, s, H-4), 6.45 (1H, s, H-11), 5.92 (2H, s, OCH2O), 4.31 (1H, s, H-6), 1.77 (2H, d,= 4.1 Hz, H-8), 1.90~2.48 (2H, m, H-9), 0.83 (3H, d,= 6.8 Hz, H-17), 0.96 (3H, d,= 6.8 Hz, H-18);13C- NMR (100 MHz, CDCl3): 151.6 (C-1), 141.7 (C-2), 152.3 (C-3), 110.1 (C-4), 137.2 (C-5), 81.2 (C-6), 40.1 (C-7), 37.2 (C-8), 38.1 (C-9), 135.5 (C-10), 102.3 (C-11), 149.0 (C-12), 134.6 (C-13), 141.2 (C-14), 120.1 (C-15), 122.1 (C-16), 17.7 (C-17), 16.8 (C-18), 100.6 (-OCH2O), 60.7 (-OMe), 59.6 (-OMe), 60.1 (-OMe), 56.2 (-OMe)。以上波譜數(shù)據(jù)與文獻報道一致[12],故鑒定化合物8為異戈米辛O。

        化合物9:淡黃色油狀物;1H-NMR (400 MHz, CDCl3): 6.46 (1H, s, H-4), 2.47 (1H, dd,= 2.2, 13.4 Hz, H-6α), 2.55 (1H, dd,= 6.6, 13.4 Hz, H-6β), 1.87 (1H, m, H-7), 1.82 (1H, m, H-8), 2.11 (1H, dd,= 8.4, 13.0 Hz, H-9α), 2.06 (1H, brd,= 13.0 Hz, H-9β), 6.40 (1H, s, H-11), 0.96 (3H, d,= 6.6 Hz, H-17), 0.72 (3H, d,= 6.6 Hz, H-18), 3.86 (3H, s, OCH3), 3.85 (3H, s, OCH3), 3.65 (3H, s, OCH3), 5.92 (2H, s, OCH2O);13C-NMR (100 MHz, CDCl3): 146.2 (C-1), 133.5 (C-2), 151.1 (C-3), 108.5 (C-4), 136.0 (C-5), 38.8 (C-6), 33.5 (C-7), 41.3 (C-8), 35.2 (C-9), 138.1 (C-10), 101.8 (C-11), 148.5 (C-12), 132.1 (C-13), 137.2 (C-14), 116.7 (C-15), 114.2 (C-16), 21.6 (C-17), 12.5 (C-18), 61.2 (OMe), 61.2 (OMe), 56.1 (OMe), 101.2 (OCH2O)。以上波譜數(shù)據(jù)與文獻報道一致[13],故鑒定化合物9為(?)-gomisin M。

        化合物10:白色無定形粉末;1H-NMR (400 MHz, CDCl3): 6.63 (1H, s, H-14), 6.47 (1H, s, H-11), 2.68 (1H, d,= 13.6 Hz, H-6α), 2.33 (1H, d,= 13.6 Hz, H-6β), 2.38 (1H, dd,= 14.2, 7.0 Hz, H-9α), 2.56 (1H, dd,= 14.2, 2.2 Hz, H-9β), 1.89 (1H, m, H-8), 0.82 (3H, d,= 7.2 Hz, Me-17), 1.26 (3H, s, Me-18), 3.40 (3H, s, OMe), 3.83 (3H, s, OMe), 3.95 (3H, s, OMe), 5.97 (2H, s, OCH2O), 5.61 (1H, s, Ar-OH);13C-NMR (100 MHz, CDCl3): 145.1 (C-1), 137.3 (C-2), 146.5 (C-3), 110.3 (C-4), 127.5 (C-5), 40.3 (C-6), 71.6 (C-7), 42.2 (C-8), 33.7 (C-9), 132.6 (C-10), 106.3 (C-11), 148.3 (C-12), 135.2 (C-13), 141.5 (C-14), 121.7 (C-15), 123.2 (C-16), 15.7 (C-17), 30.2 (C-18), 101.2 (OCH2O), 60.3, 59.8, 56.2 (3×OMe)。以上波譜數(shù)據(jù)與文獻報道一致[14],故鑒定化合物10為met A-III。

        化合物11:白色無定形粉末;1H-NMR (400 MHz, CDCl3): 6.60 (1H, s, H-14), 6.45 (1H, s, H-11), 2.67 (1H, d,= 13.4 Hz, H-6α), 2.37 (1H, d,= 13.4 Hz, H-6β), 2.33 (1H, dd,= 14.0, 6.8 Hz, H-9α), 2.62 (1H, dd,= 14.0, 2.0 Hz, H-9β), 1.86 (1H, m, H-8), 0.82 (3H, d,= 7.0 Hz, Me-17), 1.22 (3H, s, Me-18), 3.52 (3H, s, OMe), 3.86 (3H, s, OMe), 3.91 (3H, s, OMe), 3.91 (3H, s, OMe), 5.93 (2H, s, OCH2O);13C-NMR (100 MHz, CDCl3): 152.1 (C-1), 140.9 (C-2), 152.5 (C-3), 110.3 (C-4), 132.5 (C-5), 40.7 (C-6), 71.7 (C-7), 42.1 (C-8), 33.8 (C-9), 132.7 (C-10), 105.7 (C-11), 147.6 (C-12), 135.2 (C-13), 141.5 (C-14), 121.6 (C-15), 124.3 (C-16), 15.5 (C-17), 30.1 (C-18), 100.6 (OCH2O), 60.7, 59.5, 61.2, 56.2 (4×OMe)。以上波譜數(shù)據(jù)與文獻報道一致[15],故鑒定化合物11為五味子醇甲。

        化合物12:為白色無定型粉末;1H-NMR (400 MHz, CDCl3): 0.89 ( 6H, d,= 6.4 Hz, Me-17, 18), 1.89-2.58 (1H, m, H-9), 1.71 (2H, m, H-7, 8), 4.28 (1H, d,= 7.2 Hz, H-6), 3.78 (3H, s, OMe), 3.92 (3H, s, OMe), 5.91 (2H, s, OCH2O), 5.96 (2H, s, OCH2O), 6.39 (1H, s, H-11), 6.49 (1H, s, H-4);13C-NMR (100 MHz, CDCl3): 141.6 (C-1), 136.6 (C-2), 148.0 (C-3), 105.3 (C-4), 136.3 (C-5), 81.3 (C-6), 40.2 (C-7), 37.2 (C-8), 38.0 (C-9), 135.6 (C-10), 102.2 (C-11), 149.3 (C-12), 134.6 (C-13), 141.5 (C-14), 120.6 (C-15), 121.2 (C-16), 16.6 (C-17), 17.5 (C-18), 60.9, 60.2, 55.8 (6×OMe)。以上波譜數(shù)據(jù)與文獻報道一致[12],故鑒定化合物12為戈米辛R。

        化合物13:無色油狀物;1H-NMR (400 MHz, CDCl3): 6.97 (1H, s, H-2), 6.87 (1H, d,= 8.2 Hz, H-5), 6.96 (1H, d,= 8.2 Hz, H-6), 4.51 (1H, m, H-7, 7′), 2.33 (1H, m, H-8, 8′), 1.07 (3H, d,= 6.6 Hz, Me-9), 6.66 (1H, s, H-2′, 6′), 1.01 (3H, d,= 6.6 Hz, Me-9′), 3.82~3.86 (15H, s, 5-OMe);13C-NMR (100 MHz, CDCl3): 134.5 (C-1), 110.0 (C-2), 149.5 (C-3), 148.3 (C-4), 111.1 (C-5), 118.9 (C-5), 87.7 (C-7), 44.7 (C-8), 13.7 (C-9), 138.6 (C-1′), 103.6 (C-2′, 6′), 153.2 (C-3′, 5′), 138.6 (C-4′), 87.2 (C-7′), 44.0 (C-8′), 13.3 (C-9′), 56.0, 56.1, 56.3, 56.3, 61.2 (5×OMe)。以上波譜數(shù)據(jù)與文獻報道一致[16],故鑒定化合物13為4--methylsaurucinol H。

        化合物14:無色油狀物;1H-NMR (400 MHz, CDCl3): 1.30, 1.62 (1H, each, m, H-2), 3.90 (1H, m, H-3), 2.37, 1.67 (1H, each, m, H-4), 7.05 (1H, d,= 15.6 Hz, H-7), 6.26 (1H, d,= 15.6 Hz, H-8), 2.27 (3H, s, Me-10), 1.22 (3H, s, Me-11), 0.98 (3H, s, Me-12), 1.56 (3H, s, Me-13);13C-NMR (100 MHz, CDCl3): 35.7 (C-1), 40.7 (C-2), 64.0 (C-3), 47.2 (C-4), 67.1 (C-5), 69.5 (C-6), 142.6 (C-7), 132.6 (C-8), 197.8 (C-9), 28.3 (C-10), 29.6 (C-11), 25.0 (C-12), 20.2 (C-13)。以上波譜數(shù)據(jù)與文獻報道一致[17],故鑒定化合物14為(3,5,6,7)-5,6-epoxy-3- hydroxy-7-megastigmen-9-one。

        化合物15:無色油狀物;1H-NMR (400 MHz, CDCl3): 2.30 (2H, m, H-2), 5.92 (1H, s, H-5), 5.76 (1H, t,= 7.2 Hz, H-7), 2.49 (2H, m, H-8), 3.92 (1H, m, H-9), 1.26 (3H, d,= 6.2 Hz, Me-10), 1.18 (3H, s, Me-11), 1.18 (3H, s, Me-12), 2.25 (3H, s, Me-13);13C- NMR (100 MHz, CDCl3): 40.7 (C-1), 53.0 (C-2), 199.1 (C-3), 129.0 (C-4), 144.7 (C-5), 155.9 (C-6), 126.6 (C-7), 39.8 (C-8), 68.2 (C-9), 23.5 (C-10), 28.3 (C-11), 28.2 (C-12), 24.7 (C-13)。以上波譜數(shù)據(jù)與文獻報道一致[17],故鑒定化合物15為(6,9)-9-hydroxy-4,6-megastigmadien-3-one。

        4 討論

        五味子是五味子屬植物干燥成熟果實,是我國傳統(tǒng)中藥,具有收斂固澀、益氣生津、補腎寧心之功效。研究表明,五味子莖葉中含有與果實類似的化學成分,且存在結構新穎的三萜類化合物,因而越來越受到人們的關注。本實驗對五味子莖葉的化學成分進行了系統(tǒng)研究,從其75%丙酮提取物中共分離鑒定了15個化合物,化合物1~3、6為環(huán)阿屯烷型三萜,4、5為羊毛脂烷型三萜,7~12為聯(lián)苯環(huán)辛烯型木脂素,13為四氫呋喃型木脂素,14~15為C13非異戊二烯類化合物?;衔?~7、13~15為首次從該植物中分離得到,其中化合物13~15為首次從五味子屬中分離得到的化合物。該結果對五味子莖葉化學成分的的發(fā)現(xiàn)具有重要指導意義,同時該研究為五味子藥材的綜合開發(fā)利用及藥物研發(fā)提供理論參考。

        利益沖突 所有作者均聲明不存在利益沖突

        [1] 黃妍, 劉秀, 陶薇, 等. 五味子化學成分及抗2型糖尿病活性研究進展 [J]. 中草藥, 2019, 50(7): 1739-1744.

        [2] 金銀萍, 艾軍, 夏娟, 等. 不同種質(zhì)資源五味子藤莖中4種木脂素的含量及品質(zhì)評價 [J]. 特產(chǎn)研究, 2018, 40(4): 75-78.

        [3] Liu G Z, Liu Y, Sun Y P,. Lignans and terpenoids from the leaves of[J]., 2020, 17(4): e2000035.

        [4] 任偉光, 張翠英. 五味子的研究進展及質(zhì)量標志物(Q-marker)的預測分析 [J]. 中草藥, 2020, 51(11): 3110-3116.

        [5] 王佳然, 呂曉東, 龐立健, 等. 基于《中國方劑數(shù)據(jù)庫》挖掘五味子應用的配伍規(guī)律[J]. 世界中醫(yī)藥, 2019, 14(8): 2186-2194.

        [6] Liu J S, Huang M F. On the structures of Schisanlactone C and Schisanlactone D, two new triterpene lactones from. [J]., 1984, 42(5): 464-469.

        [7] Xue Y B, Yang J H, Li X N,. Henrischinins A-C: Three new triterpenoids from[J]., 2011, 13(6): 1564-1567.

        [8] Takahashi K, Takani M. Studies on constituents of medicinal plants. XIV. Constituents ofMax. (I) [J]., 1975, 23(3): 538-542.

        [9] Liu J S, Huang M F, Ayer W A,. Schisanlactone B, a new triterpenoid from asp [J]., 1983, 24(23): 2355-2358.

        [10] Yang J H, Wen J, Du X,. Triterpenoids from the stems ofananosma [J]., 2010, 66(46): 8880-8887.

        [11] Ikeya Y, Taguchi H, Yosioka I. The constituents ofBaill. XII. Isolation and structure of a new lignan, gomisin R, the absolute structure of wuweizisu C and isolation of schisantherin D [J]., 1982, 30(9): 3207-3211.

        [12] Ikeya Y, Ookawa N, Taguchi H,. The constituents ofBaill. XI. The structures of three new lignans, angeloylgomisin O, and angeloyl- and benzoylisogomisin O [J]., 1982, 30(9): 3202-3206.

        [13] Hu D, Yang Z, Yao X,. Dibenzocyclooctadiene lignans fromand their inhibitory activity on NO production in lipopolysaccharide-activated microglia cells [J]., 2014, 104: 72-78.

        [14] An R B, Oh S H, Jeong G S,. Gomisin J with protective effect against t-BHP-induced oxidative damage in HT22 cells from[J]., 2006, 12(3): 134-137.

        [15] Taguchi H, Ikeya Y. The constituents ofBaill. The structures of two new lignans, gomisin F and G, and the absolute structures of gomisin A, B, and C [J]., 1977, 25(2): 364-366.

        [16] Sawasdee K, Chaowasku T, Lipipun V,. New neolignans and a lignan fromfragrans, and their anti-herpetic and cytotoxic activities [J]., 2013, 54(32): 4259-4263.

        [17] D'Abrosca B, DellaGreca M, Fiorentino A,. Structure elucidation and phytotoxicity of C13nor-isoprenoids from[J]., 2004, 65(4): 497-505.

        Study on chemical constituents of stems and leaves of

        ZHAO Qian-qian1, ZHANG Shao-jun1, WAN Min-ge2, LIU Qi3, CAO Yun-gang1, HE Rui3

        1. College of Food and Biological Engineering, Shaanxi University of Science and Technology, Xi’an 710000, China 2. College of Medicne, Shaanxi Institute of International Trade & Commerce, Xi’an 710000, China 3. Xi’an Efanggong Pharmaceutical Co., Ltd., Xi’an 710000, China

        To study the chemical constituents of the stems and leaves of.The isolation and purification were carried out by macroporous resin, Sephadex LH-20, silica gel column chromatography, semi-preparative HPLC. Their structures were elucidated on the basis of physicochemical properties and spectroscopic data.Fifteen compounds were isolated and elucidated from, their structures were identified as: schisanlatone C (1), henrischinin B (2), henrischinin C (3), schisanlactone B (4), schizandronic acid (5), kadnanolactone C (6), rubrisandrin C (7),-gomisin O (8), (?)-gomisin M (9), met A-III (10), gomisin A (11), gomisin R (12), 4--methylsaurucinol H (13), (3,5,6,7)-5,6- epoxy-3-hydroxy-7-megastigmen-9-one (14), and (6,9)-9-hydroxy-4,6-megastigmadien-3-one (15).Compounds 5-7 and 13—15 are isolated fromfor the first time. Compounds 13—15 are isolated from the genusfor the first time.

        (Turcz.) Baill.; triterpenes; lignans;-gomisin O;gomisin A; gomisin R

        R284.1

        A

        0253 - 2670(2021)23 - 7111 - 06

        10.7501/j.issn.0253-2670.2021.23.005

        2021-03-14

        陜西省科技廳基金資助項目(2019JQ-252)

        趙倩倩(1989—),女,山東德州人,講師,博士,研究方向為天然產(chǎn)物化學。E-mail: zhaoqianqian@sust.edu.cn

        何 瑞(1987—),男,陜西乾縣人,主管藥師,碩士,研究方向為中草藥物質(zhì)基礎研究。E-mail: 316199551@qq.com

        曹云剛(1985—),男,山西運城人,副教授,博士。E-mail: caoyungang@sust.edu.cn

        [責任編輯 王文倩]

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