夏夢雯 , 寧德生, 黃思思, 程　玲, 呂仕洪，羅　蕾, 潘爭紅*

( 1. 廣西植物功能物質(zhì)研究與利用重點實驗室，廣西壯族自治區(qū)中國科學(xué)院 廣西植物研究所, 廣西 桂林 541006；2. 云南師范大學(xué) 化學(xué)化工學(xué)院，昆明 650500 )

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石山巴豆枝葉的化學(xué)成分研究

夏夢雯1, 2, 寧德生1, 黃思思1, 程玲1, 2, 呂仕洪1，羅蕾2, 潘爭紅1*

( 1. 廣西植物功能物質(zhì)研究與利用重點實驗室，廣西壯族自治區(qū)中國科學(xué)院 廣西植物研究所, 廣西 桂林 541006；2. 云南師范大學(xué) 化學(xué)化工學(xué)院，昆明 650500 )

石山巴豆(Crotoneuryphyllus)為大戟科(Euphorbiaceae)巴豆屬(Croton)植物，主要分布于西南各省的巖溶石山地區(qū)，民間用于殺蟲和治療跌打損傷。為了闡明其化學(xué)物質(zhì)基礎(chǔ)，該研究采用硅膠柱層析、Sephadex LH-20、HPLC等方法對石山巴豆枝葉醇提物進(jìn)行分離純化。結(jié)果表明：共分離得到16個化合物，分別鑒定為異毛葉巴豆萜 (1), jatrophoidin (2), 山藿香定 (3), 異山藿香素 (4), 山藿香素 (5), 賴百當(dāng)-13-烯-8,15-二醇 (6), 7-酮基-β-谷甾醇 (7), (22E)-5α,8β-表二氧麥角甾-6,22-二烯-3β-醇 (8), 豆甾烷-4-烯-6β-醇-3-酮 (9), 齊墩果烷-12-烯-2α,3β-二醇 (10), 東莨菪內(nèi)酯 (11), 催吐蘿芙木醇 (12), lyratol F (13), 羅布麻酚A (14), 芹菜素 (15), 金色酰胺醇酯 (16)。所有化合物均為首次從該植物中分離得到，其中化合物8-16為首次從巴豆屬中發(fā)現(xiàn)。

石山巴豆, 化學(xué)成分, 二萜, 甾醇, 結(jié)構(gòu)鑒定

石山巴豆(Crotoneuryphyllus)為大戟科(Euphorbiaceae)巴豆屬(Croton)植物，主要分布于我國西南各省，其中在廣西石山地區(qū)十分常見。種子供藥用，其性味辛、熱，有大毒，作峻瀉藥，外用于惡瘡、疥廯等；根、葉入藥，治風(fēng)濕骨痛等；民間用枝、葉作殺蟲藥或毒魚等(China Flora Editorial Board, 1996)。吳新安等(2004)研究表明二萜及其內(nèi)酯類、酚類是該屬植物的主要化學(xué)成分，其中二萜化合物最常見，為該屬植物抗癌、抗炎、殺蟲等活性的有效成分。迄今為止關(guān)于石山巴豆化學(xué)成分和藥理活性的研究尚未見報道。在前期的研究中，我們發(fā)現(xiàn)石山巴豆枝葉的粗提物有明顯的抗癌作用。為了填補該植物的化學(xué)研究空白，同時為該植物的藥用提供理論基礎(chǔ)，本研究對石山巴豆枝葉的化學(xué)成分進(jìn)行了研究，共分離鑒定了16個化合物，結(jié)構(gòu)類型涉及萜類(單萜、二萜、三萜)、甾醇、黃酮、香豆素、酰胺等，其中化合物8-16為首次從巴豆屬中發(fā)現(xiàn)。

1　材料與方法

1.1 材料與儀器

石山巴豆(Crotoneuryphyllus)采自廣西平果縣，由廣西植物研究所呂仕洪副研究員鑒定并保存于廣西植物功能物質(zhì)研究與利用重點實驗室。

硅膠(100～200目、200～300目)及TLC檢測用的硅膠GF254(青島海洋化工廠)；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；LC/MS-IT-TOF system (Shimadzu, Tokyo, Japan)；瑞士Bruker AVANCE Ⅲ HD-500 MHz 超導(dǎo)核磁共振儀；所有試劑均為分析純。

1.2 提取與分離

干燥的石山巴豆枝葉15 kg，用95%的乙醇浸提3次，將提取液濃縮至無醇味，將浸膏分散于水中，分別用石油醚，乙酸乙酯，正丁醇萃取，得到3個部分。乙酸乙酯部分(400 g)經(jīng)硅膠柱層析(100～200目)，用石油醚-乙酸乙酯(25∶1～0∶1)梯度洗脫，得到5個組分Fr. B1～Fr. B5。Fr. B2經(jīng)過反復(fù)硅膠柱層析(200～300目，石油醚-乙酸乙酯9∶1～0∶1梯度洗脫)，分別得到化合物6(5 mg)、7(50 mg)、8(35 mg)、9(35 mg)和10(15 mg)。Fr. B3經(jīng)重結(jié)晶得到化合物1(115 mg)，母液經(jīng)過反復(fù)硅膠柱(200～300目，石油醚-丙酮9∶1～0∶1梯度洗脫)和凝膠Sephadex LH-20層析 (氯仿-甲醇, 1∶1)，分別得到化合物2(8 mg)、3(13 mg)、4(15 mg)、5(20 mg)和16(95 mg)。Fr. B4經(jīng)過硅膠柱(200～300目)，石油醚-丙酮(9∶1～0∶1)梯度洗脫后，重結(jié)晶得到化合物15(55 mg)，母液經(jīng)HPLC半制備(乙腈/水，50%～65%，v/v)純化，分別得到化合物11(12 mg)、12(20 mg)、13(30 mg)和14(8 mg)。

2　結(jié)構(gòu)鑒定

化合物1ESI-MS (m/z) 327 [M+H]+，分子式為C19H18O5。1H NMR (500 MHz, CDCl3)δ: 4.89 (1H, m, H-6), 2.24 (1H, m, H-10), 5.02 (1H, t,J= 1.5 Hz, H-11), 5.17 (1H, s, H-14), 1.14 (3H, d,J= 4.0 Hz, Me-17);13C NMR (125 MHz, CDCl3)δ: 23.8 (C-1), 21.1 (C-2), 20.1 (C-3), 127.7 (C-4), 162.3 (C-5), 76.4 (C-6), 35.5 (C-7), 36.6 (C-8), 57.7 (C-9), 37.0 (C-10), 103.8 (C-11), 147.1 (C-12), 115.5 (C-13), 107.2 (C-14), 144.5 (C-15), 141.5 (C-16), 13.7 (C-17), 172.6 (C-18), 177.4 (C-20)。以上數(shù)據(jù)與Chatterjee et al(1978)的報道一致，故鑒定為異毛葉巴豆萜 (isocrotocaudin)。

化合物2ESI-MS (m/z) 409 [M+Na]+，分子式為C21H22O7。1H NMR (500 MHz, CDCl3)δ: 5.25 (1H, m, H-6), 2.72 (1H, m, H-1), 2.66 (1H, m, H-11), 2.44 (1H, m, H-8), 5.43 (1H, m, H-12), 6.37 (1H, m, H-14), 7.26 (1H, s, H-15), 7.45 (1H, s, H-16), 3.80 (3H, s, COOCH3), 1.01 (3H, d,J= 5.5 Hz, Me-17);13C NMR (125 MHz, CDCl3)δ: 29.3 (C-1), 20.8 (C-2), 20.0 (C-3), 129.5 (C-4), 158.0 (C-5), 78.3 (C-6), 35.1 (C-7), 33.9 (C-8), 52.5 (C-9), 56.4 (C-10), 37.1 (C-11), 72.0 (C-12), 124.6 (C-13), 108.0 (C-14), 144.4 (C-15), 139.7 (C-16), 17.8 (C-17), 172.5 (C-18), 170.8 (C-19), 174.7 (C-20), 53.3 (COOMe)。以上數(shù)據(jù)與Mbwambo et al(2009)的報道一致，故鑒定為jatrophoidin。

化合物3ESI-MS (m/z) 351 [M+Na]+，分子式為C19H20O5。1H NMR (500 MHz, CDCl3)δ: 2.04 (1H, m, H-1α), 2.00 (1H, m, H-2α), 2.35 (2H, m, H-3β, 7β), 5.01 (1H, m, H-6α), 3.27 (1H, m, H-10α), 2.60 (1H, m, H-11B), 5.36 (1H, t,J=7.0, 13.5 Hz, H-12), 6.35 (1H, t,J= 2.0 Hz, H-14), 7.43 (1H, s, H-15), 7.44 (1H, s,H-16), 1.35 (3H, d,J= 6.0 Hz, Me-17);13C NMR (125 MHz, CDCl3)δ: 23.5 (C-1), 21.5 (C-2), 20.2 (C-3), 127.9 (C-4), 162.3 (C-5), 76.2 (C-6), 35.8 (C-7), 38.8 (C-8), 52.2 (C-9), 35.9 (C-10), 39.1 (C-11), 72.0 (C-12), 125.4 (C-13), 108.0 (C-14), 144.5 (C-15), 139.6 (C-16), 14.4 (C-17), 172.7 (C-18), 177.7 (C-20)。以上數(shù)據(jù)與Rodriguez et al(2004)的報道一致，故鑒定為山藿香定 (teucvidin)。

圖 1　化合物1-16的結(jié)構(gòu)圖Fig. 1　Structure of compounds 1-16

化合物4ESI-MS (m/z) 351 [M+Na]+，分子式為C19H20O5。1H NMR (500 MHz, CDCl3)δ: 4.82 (1H, d,J= 11.0 Hz, H-6), 2.93 (1H, m, H-10), 2.71 (1H, m, H-11), 5.49 (1H, d,J= 7.0 Hz, H-12), 6.35 (1H, s, H-14), 7.43 (1H, s, H-15), 7.46 (1H, s, H-16), 1.08 (3H, d,J= 5.5 Hz, Me-17);13C NMR (125 MHz, CDCl3)δ: 23.1 (C-1), 22.5 (C-2), 19.2 (C-3), 125.2 (C-4), 166.1 (C-5), 77.0 (C-6), 34.2 (C-7), 39.0 (C-8), 47.3 (C-9), 37.8 (C-10), 40.7 (C-11), 71.8 (C-12), 126.2 (C-13), 107.9 (C-14), 144.7 (C-15), 138.9 (C-16), 19.2 (C-17), 173.1 (C-18), 176.9 (C-20)。以上數(shù)據(jù)與Mbwambo et al(2009)的報道一致，故鑒定為異山藿香素 (isoteucvin)。

化合物5ESI-MS (m/z) 351 [M+Na]+，分子式為C19H20O5。1H NMR (500 MHz, CDCl3)δ: 4.77 (1H, m, H-6β), 2.69 (1H, m, H-10β), 2.56 (2H, m, H-11A, 11B), 5.46 (1H, t,J= 7.0, 15.0 Hz, H-12), 6.39 (1H, s, H-14), 7.44 (1H, s, H-15), 7.46 (1H, s, H-16), 1.07 (3H, d,J= 6.0 Hz, Me-17);13C NMR (125 MHz, CDCl3)δ: 24.9 (C-1), 21.8 (C-2), 19.7 (C-3), 126.6 (C-4), 161.7 (C-5), 78.4 (C-6), 35.4 (C-7), 36.0 (C-8), 53.6 (C-9), 42.2 (C-10), 41.0 (C-11), 71.9 (C-12), 125.0 (C-13), 108.1 (C-14), 144.4 (C-15), 139.7 (C-16), 17.1 (C-17), 173.2 (C-18), 175.8 (C-20)。以上數(shù)據(jù)與Rodriguez et al(2004)的報道一致，故鑒定為山藿香素 (teucvin)。

化合物6ESI-MS (m/z) 309 [M+H]+，分子式為C20H36O2。1H NMR (500 MHz, CDCl3)δ: 5.45 (1H, d,J= 4.5 Hz, H-14), 1.66 (3H, s, H3-16), 1.36 (3H, s, H3-17), 0.93 (3H, s, H3-18), 0.86 (3H, s, H3-19), 1.06 (3H, s, H3-20);13C NMR (125 MHz, CDCl3)δ: 39.4 (C-1), 16.6 (C-2), 42.2 (C-3), 33.4 (C-4), 56.1 (C-5), 18.5 (C-6), 42.4 (C-7), 73.4 (C-8), 59.0 (C-9), 39.1 (C-10), 18.4 (C-11), 43.5 (C-12), 140.6 (C-13), 123.3 (C-14), 59.6 (C-15), 24.1 (C-16), 30.4 (C-17), 33.6 (C-18), 21.8 (C-19), 15.3 (C-20)。以上數(shù)據(jù)與Albert et al(2007)的報道一致，故鑒定為賴百當(dāng)-13-烯-8，15-二醇 (labd-13E-ene-8β, 15-diol)。

化合物7ESI-MS (m/z) 451 [M+Na]+，分子式為C29H48O2。1H NMR (500 MHz, CDCl3)δ: 5.38 (1H, m, H-6), 0.64 (3H, s, H-18), 1.03 (3H, s, H-19), 0.89 (3H, m, H-21), 0.88 (3H, m, H-27), 0.85 (3H, m, H-29);13C NMR (125 MHz, CDCl3)δ: 36.5 (C-1), 31.4 (C-2), 70.7 (C-3), 42.0 (C-4), 165.2 (C-5), 126.3 (C-6), 202.4 (C-7), 45.6 (C-8), 50.2 (C-9), 38.4 (C-10), 21.4 (C-11), 38.9 (C-12), 43.3 (C-13), 50.1 (C-14), 26.5 (C-15), 28.7 (C-16), 54.9 (C-17), 12.1 (C-18), 17.5 (C-19), 36.2 (C-20), 18.9 (C-21), 34.1 (C-22), 26.3 (C-23), 46.0 (C-24), 29.3 (C-25), 19.1 (C-26), 20.0 (C-27), 23.2 (C-28), 12.1 (C-29)。以上數(shù)據(jù)與馬曉莉等(2009)的報道一致，故鑒定為7-酮基-β-谷甾醇 (7-oxo-β-sitosterol)。

化合物8ESI-MS (m/z) 429 [M+H]+，分子式為C28H44O3。1H NMR (500 MHz, CDCl3)δ: 4.02 (1H, m, H-3α), 4.89 (1H, m, H-22), 5.24 (1H, m, H-23), 0.81 (3H, s, Me-18), 0.88 (3H, s, Me-19), 1.00 (3H, d,J= 5.5 Hz, Me-21), 0.84 (3H, m, Me-26), 0.78 (3H, m, Me-27), 0,92 (3H, d,J= 3.0 Hz, Me-28);13C NMR (125 MHz, CDCl3)δ: 34.9 (C-1), 30.3 (C-2), 66.6 (C-3), 37.1 (C-4), 82.3 (C-5), 135.6 (C-6), 130.9 (C-7), 79.6 (C-8), 51.3 (C-9), 37.1 (C-10), 20.8 (C-11), 39.5 (C-12), 44.7 (C-13), 51.9 (C-14), 23.6 (C-15), 28.8 (C-16), 56.4 (C-17), 13.0 (C-18), 18.3 (C-19), 39.9 (C-20), 21.0 (C-21), 135.4 (C-22), 132.5 (C-23), 42.9 (C-24), 33.2 (C-25), 19.8 (C-26), 20.1 (C-27), 17.7 (C-28)。以上數(shù)據(jù)與姜北等(2002)的報道一致，故鑒定為(22E)-5α, 8β-表二氧麥角甾-6, 22-二烯-3β-醇 ((22E)-5α, 8β-epidioxyergosta-6, 22-dien-3β-ol)。

化合物9ESI-MS (m/z) 451 [M+Na]+，分子式為C29H48O2。1H NMR (500 MHz, CDCl3)δ: 5.81 (1H, s, H-4), 4.34 (1H, s, H-6), 0.74 (3H, s, Me-18), 1.37 (3H, s, Me-19), 0.93 (3H, d,J= 5.5 Hz, Me-21), 0.83 (1H, s, H-26), 0.82 (3H, d,J= 6.0 Hz, Me-27), 0.85 (3H, d,J= 6.0 Hz, Me-29);13C NMR (125 MHz, CDCl3)δ: 37.3 (C-1), 34.4 (C-2), 200.5 (C-3), 126.5 (C-4), 168.6 (C-5), 73.4 (C-6), 38.8 (C-7), 29.9 (C-8), 53.8 (C-9), 38.2 (C-10), 21.1 (C-11), 39.8 (C-12), 42.7 (C-13), 56.1 (C-14), 24.3 (C-15), 28.3 (C-16), 56.2 (C-17), 12.1 (C-18), 20.0 (C-19), 36.3 (C-20), 18.9 (C-21), 34.1 (C-22), 26.3 (C-23), 46.0 (C-24), 29.3 (C-25), 19.7 (C-26), 19.2 (C-27), 23.3 (C-28), 12.2 (C-29)。以上數(shù)據(jù)與吳少華等(2008)的報道一致，故鑒定為豆甾烷-4-烯-6β-醇-3-酮 (stigmast-4-en-6β-ol-3-one)。

化合物10ESI-MS (m/z) 465 [M+Na]+，分子式為C30H50O2。1H NMR (500 MHz, CDCl3)δ: 4.32 (1H, d,J= 12.5 Hz, H-2), 5.42 (1H, m, H-12), 1.58 (3H, s, Me-23), 0.87 (3H, s, Me-24), 1.34 (3H, s, Me-25), 1.20 (3H, s, Me-26), 1.66 (3H, s, Me-27), 0.94 (3H, s, Me-28), 1.10 (3H, s, Me-29), 1.15 (3H, s, Me-30);13C NMR (125 MHz, CDCl3)δ: 46.7 (C-1), 69.1 (C-2), 84.1 (C-3), 39.4 (C-4), 55.4 (C-5), 18.6 (C-6), 32.7 (C-7), 40.1 (C-8), 47.8 (C-9), 38.4 (C-10), 23.8 (C-11), 121.7 (C-12), 145.4 (C-13), 41.9 (C-14), 26.3 (C-15), 27.1 (C-16), 32.6 (C-17), 47.4 (C-18), 47.0 (C-19), 31.6 (C-20), 35.0 (C-21), 37.3 (C-22), 28.8 (C-23), 19.9 (C-24), 17.0 (C-25), 17.0 (C-26), 26.2 (C-27), 28.5 (C-28), 33.5 (C-29), 23.8 (C-30)。以上數(shù)據(jù)與Braca et al(2001)的報道一致，故鑒定為齊墩果烷-12-烯- 2α, 3β-二醇 (olean-12-en-2α, 3β-diol)。

化合物11ESI-MS (m/z) 193 [M+H]+，分子式為C10H8O4。1H NMR (500 MHz, (CD3)2CO)δ: 6.22 (1H, d,J= 7.5 Hz, H-3), 7.91 (1H, d,J= 8.0 Hz, H-4), 6.78 (1H, s, H-5), 7.21 (1H, s, H-8), 3.81 (3H, s, -OCH3);13C NMR (125 MHz, (CD3)2CO)δ: 160.8 (C-2), 111.8 (C-3), 144.6 (C-4), 109.6 (C-5), 145.3 (C-6), 151.2 (C-7), 102.8 (C-8), 149.6 (C-9), 110.6 (C-10), 56.1 (-CH3)。以上數(shù)據(jù)與喻蓉等(2003)的報道一致，故鑒定為東莨菪內(nèi)酯 (scopoletin)。

化合物12ESI-MS (m/z) 225 [M+H]+，分子式為C13H20O3。1H NMR (500 MHz, CDCl3)δ: 2.44 (1H, d,J= 14.0 Hz, H-2), 2.23 (1H, d,J= 14.0 Hz, H-2), 5.89 (1H, s, H-4), 5.78 (1H, d,J= 13.0 Hz, H-7), 5.82 (1H, d,J= 4.5 Hz, H-8), 4.40 (1H, m, H-9), 1.28 (3H, d,J= 6.0 Hz, Me-10), 1.00 (3H, s, Me-11), 1.06 (3H, s, Me-12), 1.88 (3H, s, Me-13);13C NMR (125 MHz, CDCl3)δ: 41.3 (C-1), 49.8 (C-2), 198.5 (C-3), 126.9 (C-4), 163.4 (C-5), 79.1 (C-6), 135.8 (C-7), 129.1 (C-8), 68.1 (C-9), 23.8 (C-10), 23.0 (C-11), 24.2 (C-12), 19.1 (C-13)。以上數(shù)據(jù)與趙雪梅等(2008)的報道一致，故鑒定為催吐蘿芙木醇(vomifoliol)。

化合物13ESI-MS (m/z) 247 [M+Na]+，分子式為C13H20O3。1H NMR (500 MHz, CDCl3)δ: 4.34 (1H, m, H-3), 5.83 (1H, s, H-8), 2.17 (3H, s, Me-10), 1.14 (3H, s, Me-11), 1.36 (3H, s, Me-12), 1.41 (3H, s, Me-13);13C NMR (125 MHz, CDCl3)δ: 36.2 (C-1), 48.8 (C-2), 63.9 (C-3), 49.0 (C-4), 72.4 (C-5), 118.8 (C-6), 198.7 (C-7), 100.9 (C-8), 209.8 (C-9), 26.5 (C-10), 29.2 (C-11), 31.0 (C-12), 31.8 (C-13)。以上數(shù)據(jù)與Miysse et al(1987)的報道一致，故鑒定為lyratol F。

化合物14ESI-MS (m/z) 247 [M+Na]+，分子式為C13H20O3。1H NMR (500 MHz, MeOD)δ: 2.13 (1H, d,J= 16.5 Hz, H-2a), 2.52 (1H, d,J= 16.5 Hz, H-2b), 6.17(1H, s, H-4), 2.69 (1H, d,J= 7.5 Hz, H-6), 5.68 (1H, m, H-7), 5.65 (1H, m, H-8), 4.28 (1H, m, H-9), 4.20 (1H, m, H2-11), 1.25 (3H, s, H3-10), 1.05 (3H, s, H3-12), 1.01 (3H, s, H3-13);13C NMR (125 MHz, MeOD)δ: 35.8 (C-1), 48.2 (C-2), 200.6 (C-3), 121.0 (C-4), 166.9 (C-5), 50.8 (C-6), 138.8 (C-7), 126.0 (C-8), 67.4 (C-9), 22.3 (C-10), 62.7 (C-11), 26.5 (C-12), 25.9 (C-13)。以上數(shù)據(jù)與李艷平(2013)的報道一致，故鑒定為羅布麻酚A (apocynol A)。

化合物15ESI-MS (m/z) 271 [M+H]+，分子式為C15H10O5。1H NMR (500 MHz, CDCl3)δ: 6.77 (1H, s, H-3), 6.19 (1H, d,J= 2.0 Hz, H-6), 6.48 (1H, d,J= 2.0 Hz, H-8), 7.92 (2H, d,J= 7.5 Hz, H-2′,6′), 6.93 (2H, d,J= 7.5 Hz, H-3′,5′), 12.95 (1H, s, 5-OH), 10.83 (1H, s, 7-OH), 10.36 (1H, s, 4′-OH);13C NMR (125 MHz, CDCl3)δ: 163.8 (C-2), 103.7 (C-3), 181.8 (C-4), 161.5 (C-5), 98.9 (C-6), 164.2 (C-7), 94.0 (C-8), 161.2 (C-9), 102.9 (C-10), 121.2 (C-1′), 128.5 (C-2′), 116.0 (C-3′), 157.3 (C-4′), 116.0 (C-5′), 128.5 (C-6′)。以上數(shù)據(jù)與王淑英(2013)的報道一致，故鑒定為芹菜素 (apigenin)。

化合物16ESI-MS (m/z) 467 [M+Na]+，分子式為C27H28O4N2。1H NMR (500 MHz, CDCl3)δ: 4.83 (1H, m, H-2), 3.22 (2H, m, H-3), 7.28 (5H, m, H-5,9), 7.72 (2H, m, H-3′, 7′), 7.44 (2H, m, H-4′, 6′), 7.53 (2H, m, H-5′), 4.34 (1H, m, H-1″), 2.76 (2H, m, H-2″), 7.07 (2H, m, H-4″, 8″), 7.17 (2H, m, H-5″, 7″), 3.22 (2H, m, H-9″);13C NMR (125 MHz, CDCl3)δ: 170.5 (C-1), 55.1 (C-2), 38.6 (C-3), 136.8 (C-4), 128.8 (C-5, 9), 129.5 (C-6, 8), 127.2 (C-7), 167.3 (C-1′), 133.8 (C-2′), 128.7 (C-3′, 7′), 127.2 (C-4′, 6′), 132.0 (C-5′), 49.6 (C-1″), 37.6 (C-2″), 136.9 (C-3″), 128.8 (C-4″, 8″), 129.3 (C-5″, 7″), 126.9 (C-6″), 64.7 (C-9″), 170.9 (-CO-), 20.9 (-CH3)。以上數(shù)據(jù)與顧曉潔等(2007)的報道一致，故鑒定為金色酰胺醇酯 (aurantiamide acetate)。

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Chemical constituents from the branches and leaves ofCrotoneuryphyllus

XIA Meng-Wen1,2, NING De-Sheng1, HUANG Si-Si1, CHENG Ling1,2,Lü Shi-Hong1, LUO Lei2, PAN Zheng-Hong1*

( 1. Guangxi Key Laboratory of Functional Phytochemicals Research and Utilization, Guangxi Institute of Botany, Chinese Academy of Sciences,Guilin 541006, Guangxi, China; 2.FacultyofChemistryandChemicalEngineering,YunnanNormalUniversity, Kunming 650500, China )

Crotoneuryphyllus(Euphorbiaceae) is mainly distributed in the karst region of Southwest China and has been used as a folk medicine to cure traumatic injury and kill insects. In order to clarify the chemical constituents ofC.euryphyllus, the ethanol extract was separated by the chromatography (silica gel, Sephadex LH-20 and HPLC) and sixteen compounds were isolated. Their structures were elucidated as: isocrotocaudin (1), jatrophoidin (2), teucvidin (3), isoteucvin (4), teucvin (5), labd-13E-ene-8β,15-diol (6), 7-oxo-β-sitosterol (7), (22E)-5α, 8β-epidioxyergosta-6, 22-dien-3β-ol (8), stigmast-4-en-6β-ol-3-one (9), olean-12-en-2α,3β-diol (10), scopoletin (11), vomifoliol (12), lyratol F (13), apocynol A (14), apigenin (15), aurantiamide acetate (16). All compounds were firstly isolated from this plant, and compounds 8-16 were isolated from the genusCrotonfor the first time.

Crotoneuryphyllus, chemical constituents, diterpenoid, sterol, structure identification

10.11931/guihaia.gxzw201509026

2015-10-19

2015-12-29

國家自然科學(xué)基金(21102023)；廣西自然科學(xué)基金(2011GXNSFB018022)；中國科學(xué)院“西部之光”人才培養(yǎng)計劃項目(2012) [Supported by the National Natural Science Foundation of China(21102023); the Natural Science Foundation of Guangxi (2011GXNSFB018022); the West Light Foundation of the Chinese Academy of Sciences(2012)]。

夏夢雯(1989-)，女，四川雅安人，碩士研究生，研究方向為天然產(chǎn)物研究，(E-mail) 1036978486@qq.com。

潘爭紅，博士，研究員，主要從事天然產(chǎn)物化學(xué)與功能研究，(E-mail) pan7260@126.com。

Q946.91

A

1000-3142(2016)10-1186-06

夏夢雯, 寧德生, 黃思思，等. 石山巴豆枝葉的化學(xué)成分研究 [J]. 廣西植物，2016，36(10):1186-1191

XIA MW, NING DS, HUANG SS，et al. Chemical constituents from the branches and leaves ofCrotoneuryphyllus[J]. Guihaia，2016，36(10):1186-1191