北重樓地上部分的化學(xué)成分研究

姜鵬，劉艷，潘娟，劉源，許振鵬，楊炳友

(黑龍江中醫(yī)藥大學(xué)，黑龍江 哈爾濱 150040)

北重樓(ParisverticillataM.Bieb.)為百合科(Liliaceae)重樓屬(Paris)植物，其藥用部位為根莖，臨床多用于治療高熱抽搐、熱病煩躁、咽喉腫痛、疔癤腫毒、毒蛇咬傷等[1-2]。近年來(lái)，因重樓具有資源分布的廣泛性、生物活性的多樣性使其受到國(guó)內(nèi)外學(xué)者的關(guān)注[3-5]。但對(duì)于北重樓各方面的研究報(bào)道較少，從很大程度上限制了對(duì)重樓這一藥用資源更深入的研究應(yīng)用。北重樓主要分布在黃河以北地區(qū)，以東三省為主，資源比較豐富，但在采收期時(shí)，由于地上部分生長(zhǎng)較快，大量被丟棄，造成了嚴(yán)重的資源浪費(fèi)。本文對(duì)北重樓地上部分的正丁醇層進(jìn)行了系統(tǒng)研究，通過(guò)多種色譜及波譜學(xué)方法從中分離并鑒定其化學(xué)成分。

1 儀器與材料

旋轉(zhuǎn)蒸發(fā)儀(EYELA公司)；AV-600型超導(dǎo)核磁共振波譜儀(Bruker公司)；Q-TOF(ESI)高分辨質(zhì)譜儀(Waters公司)；中壓制備(布奇公司)；制備型高效液相色譜(島津公司)；分析型高效液相色譜(Waters公司)；Shim-pack GIST C18分析柱(5 μm，20 mm×250 mm，島津公司)；Sephadex LH-20(GE Healthcare公司)；反相ODS(YMC公司)；柱色譜硅膠(200～300目)(青島海洋化工廠);薄層色譜硅膠(青島海洋化工廠)；色譜甲醇(默克公司)。

北重樓地上部分藥材于2019年6月采收于黑龍江省尚志市帽兒山，經(jīng)黑龍江中醫(yī)藥大學(xué)藥學(xué)院樊銳鋒教授鑒定為北重樓(ParisverticillataM.Bieb.)。原植物標(biāo)本(20190806)保存于黑龍江中醫(yī)藥大學(xué)中藥化學(xué)實(shí)驗(yàn)室。

2 提取與分離

北重樓地上部分藥材50.5 kg(干燥)，以70%乙醇為溶劑，加熱回流提取3次，每次2 h，減壓回收溶劑，最終得到提取物浸膏4 kg。將浸膏經(jīng)水分散，分別采用乙酸乙酯和水飽和正丁醇依次進(jìn)行萃取，并將得到的萃取液分別濃縮至浸膏狀，最終得到正丁醇萃取部位浸膏400 g。取315 g的正丁醇層浸膏經(jīng)正相硅膠柱色譜進(jìn)行分離，以二氯甲烷-甲醇(100∶1→0∶1)系統(tǒng)為流動(dòng)相進(jìn)行梯度洗脫，將得到的洗脫液進(jìn)行反復(fù)的TLC檢識(shí)合并，最終共得到10個(gè)組分即Fr.A～Fr.J。Fr.F經(jīng)ODS柱色譜，凝膠柱色譜以及制備型HPLC分離得到化合物1(5.6 mg)、3(3.5 mg)、4(3.2 mg)、9(3.0 mg)、11(3.0 mg)、12(4.5 mg)。Fr.G經(jīng)ODS柱色譜，凝膠柱色譜以及制備型HPLC分離得到化合物2(2.5 mg)、5(5.0 mg)、6(4.0 mg)、7(2.5 mg)、8(5.0 mg)、10(4.2 mg)、13(3.6 mg)、14(4.4 mg)。

3 結(jié)構(gòu)鑒定

3.1 化合物1

白色無(wú)定形粉末。HR-ESI-MS m/z: 373.222 6 [M+H]+，分子式為C19H32O7。1H-NMR (CD3OD, 600 MHz) δ：1.97 (1H, d, J = 17.3 Hz, H-2a), 2.46 (1H, d, J = 17.3 Hz, H-2b), 5.80 (1H, s, H-4), 1.99 (1H, m, H-6), 1.97 (1H, m, H-7), 1.64 (2H, m, H-8), 3.88 (1H, m, H-9), 1.18 (3H, d, J = 6.2 Hz, H-10), 1.00 (3H, s, H-11), 1.08 (3H, s, H-12), 2.04 (3H, d, J = 0.8 Hz, H-13), 4.32 (1H, d, J = 7.8 Hz, H-1′), 3.13 (1H, m, H-2′), 3.35 (1H, m, H-3′), 3.26 (2H, m, H-4′, H-5′), 3.85 (1H, m, H-6′a), 3.64 (1H, dd, J = 11.7,6.0 Hz, H-6′b)。13C-NMR (CD3OD, 150 MHz) δ：37.4 (C-1), 48.1 (C-2), 202.5 (C-3), 125.4 (C-4), 170.1 (C-5), 52.4 (C-6), 26.9 (C-7), 37.8 (C-8), 75.5 (C-9), 19.9 (C-10), 27.6 (C-11), 29.0 (C-12), 25.0 (C-13), 102.1 (C-1′), 75.2 (C-2′), 78.2 (C-3′), 71.8 (C-4′), 77.9 (C-5′), 62.9 (C-6′)。上述數(shù)據(jù)與文獻(xiàn)[6]報(bào)道基本一致，故鑒定為byzantionoside B。

3.2 化合物2

白色無(wú)定形粉末。HR-ESI-MS m/z: 387.201 9 [M+H]+，分子式為C19H30O8。1H-NMR (CD3OD, 600 MHz) δ：2.50 (1H, d, J = 16.8 Hz, H-2a)，2.14 (1H, d, J = 16.8 Hz, H-2b), 5.85 (1H, s, H-4), 5.86 (2H, m, H-7, H-8), 4.41 (1H, m, H-9), 1.28 (3H, d, J = 6.4 Hz, H-10), 1.03 (3H, s, H-11), 1.02 (3H, s, H-12), 1.91 (3H, s, H-13), 4.32 (1H, d, J = 7.8 Hz, H-1′), 3.15 (1H, t, J = 7.8 Hz, H-2′), 3.36 (1H, m, H-3′), 3.24 (2H, m, H-4′, H-5′), 3.84 (1H, dd, J = 12.5,2.0 Hz, H-6′a), 3.61 (1H, dd, J = 12.5,5.5 Hz, H-6′b)。13C-NMR (CD3OD, 150 MHz) δ：42.5 (C-1), 50.7 (C-2), 201.2 (C-3), 127.2 (C-4), 167.3 (C-5), 80.0 (C-6), 131.6 (C-7), 135.3 (C-8), 77.3 (C-9), 21.2 (C-10), 23.4 (C-11), 24.7 (C-12), 19.6 (C-13), 102.8 (C-1′), 75.3 (C-2′), 78.2 (C-3′), 71.7 (C-4′), 78.1 (C-5′), 62.9 (C-6′)。上述數(shù)據(jù)與文獻(xiàn)[7]報(bào)道基本一致，故鑒定為vomifoliol 9-O-β-D-glucopyranoside。

3.3 化合物3

白色無(wú)定形粉末。HR-ESI-MS m/z: 389.217 5 [M+H]+，其分子式為C19H32O8。1H-NMR (CD3OD, 600 MHz) δ：5.82 (1H, s, H-2), 2.61 (1H, d, J = 17.9 Hz, H-6a), 2.14 (1H, d, J = 17.9 Hz, H-6b), 2.03 (1H, m, H-7a), 1.81 (1H, m, H-7b), 1.75 (1H, m, H-8a), 1.48 (1H, m, H-8b), 3.81 (1H, m, H-9), 1.17 (3H, d, J = 6.2 Hz, H-10), 1.09 (3H, s, H-11), 1.00 (3H, s, H-12), 2.03 (3H, s, H-13), 4.30 (1H, d, J = 7.9 Hz, H-1′), 3.12 (1H, dd, J = 9.2,7.9 Hz, H-2′), 3.31 (1H, o, H-3′), 3.25 (2H, m, H-4′, H-5′), 3.86 (1H, dd, J = 11.9,2.1 Hz, H-6′a), 3.64 (1H, dd, J = 11.9,5.2 Hz, H-6′b)。13C-NMR (CD3OD, 150 MHz) δ：201.1 (C-1), 126.7 (C-2), 171.7 (C-3), 79.3 (C-4), 42.9 (C-5), 51.1 (C-6), 34.9 (C-7), 33.6 (C-8), 76.2 (C-9), 20.1 (C-10), 24.1 (C-11), 24.7 (C-12), 21.7 (C-13), 102.3 (C-1′), 75.2 (C-2′), 78.2 (C-3′), 71.8 (C-4′), 78.0 (C-5′), 62.9 (C-6′)。上述數(shù)據(jù)與文獻(xiàn)[8]報(bào)道基本一致，故鑒定為dihydrovomifoliol-O-β-D-glucopyranoside。

3.4 化合物4

白色無(wú)定形粉末。HR-ESI-MS m/z: 389.217 5 [M+H]+，分子式為C19H32O8。1H-NMR (CD3OD, 600 MHz) δ：2.15 (1H, d, J = 17.3 Hz, H-2a), 2.57 (1H, d, J = 17.3 Hz, H-2b), 2.17 (1H, d, J = 17.3 Hz, H-4a), 2.53 (1H, d, J = 17.3 Hz, H-4b), 1.73 (1H, m, H-6), 1.49 (1H, m, H-7a), 1.84 (1H, m, H-7b), 1.70 (1H, m, H-8a), 1.78 (1H, m, H-8b), 3.94 (1H, m, H-9), 1.21 (3H, d, J = 6.2 Hz, H-10), 1.08 (3H, s, H-11), 3.55 (1H, dd, J = 7.8,2.5 Hz, H-12a), 3.57 (1H, d, J = 7.8 Hz, H-12b), 1.31 (3H, s, H-13), 4.33 (1H, d, J = 7.8 Hz, H-1′), 3.14 (1H, dd, J = 9.2,7.8 Hz, H-2′), 3.36 (1H, o, H-3′), 3.25 (2H, m, H-4′, H-5′), 3.85 (1H, dd, J = 11.5,1.3 Hz, H-6′a), 3.61 (1H, dd, J = 11.5,5.6 Hz, H-6′b)。13C-NMR (CD3OD, 150 MHz) δ：44.8 (C-1), 49.9 (C-2), 212.4 (C-3), 50.6 (C-4), 85.6 (C-5), 54.8 (C-6), 22.1 (C-7), 37.7 (C-8), 75.9 (C-9), 20.0 (C-10), 20.9 (C-11), 79.5 (C-12), 25.2 (C-13), 102.3 (C-1′), 75.2 (C-2′), 78.2 (C-3′), 71.9 (C-4′), 78.0 (C-5′), 63.0 (C-6′)。上述數(shù)據(jù)與文獻(xiàn)[9]報(bào)道基本一致，故鑒定為macarangioside F。

3.5 化合物5

白色無(wú)定形粉末。HR-ESI-MS m/z: 391.233 2 [M+H]+，其分子式為C19H34O8。1H-NMR (CD3OD, 600 MHz) δ：1.67 (1H, t, J = 12.0 Hz, H-2a), 1.56 (1H, m, H-2b), 3.95 (1H, m, H-3), 1.80 (1H, m, H-4a), 1.49 (1H, m, H-4b), 1.94 (1H, m, H-5), 5.55 (1H, dd, J = 15.7,1.0 Hz, H-7), 5.72 (1H, dd, J = 15.7,6.0 Hz, H-8), 4.28 (1H, m, H-9), 1.23 (3H, d, J = 6.4 Hz, H-10), 0.97 (3H, s, H-11), 0.90 (3H, s, H-12), 0.81 (3H, d, J = 6.7 Hz, H-13), 4.34 (1H, d, J = 7.9 Hz, H-1′), 3.12 (1H, dd, J = 9.1,7.9 Hz, H-2′), 3.36 (1H, o, H-3′), 3.25 (2H, m, H-4′, H-5′), 3.86 (1H, dd, J = 11.9,2.1 Hz, H-6′a), 3.64 (1H, dd, J = 11.9,5.2 Hz, H-6′b)。13C-NMR (CD3OD, 150 MHz) δ：40.5 (C-1), 42.6 (C-2), 75.7 (C-3), 38.2 (C-4), 35.6 (C-5), 78.3 (C-6), 133.8 (C-7), 135.6 (C-8), 69.3 (C-9), 24.2 (C-10), 25.1 (C-11), 25.9 (C-12), 16.5 (C-13), 102.7 (C-1′), 75.2 (C-2′), 78.1 (C-3′), 71.8 (C-4′), 77.9 (C-5′), 62.9 (C-6′)。上述數(shù)據(jù)與文獻(xiàn)[10]報(bào)道基本一致，故鑒定為turpinionoside A。

3.6 化合物6

白色無(wú)定形粉末。HR-ESI-MS m/z: 405.212 5 [M+H]+，其分子式為C19H32O9。1H-NMR (CD3OD, 600 MHz) δ：1.73 (1H, ddd, J = 13.0,3.2,1.2 Hz, H-2a), 1.41 (1H, dd, J = 13.0,10.0 Hz, H-2b), 3.91 (1H, m, H-3), 2.40 (1H, dd, J = 14.7,4.9 Hz, H-4a), 1.80 (1H, dd, J = 14.7,8.3 Hz, H-4b), 7.15 (1H, d, J = 15.8 Hz, H-7), 6.18 (1H, d, J = 15.8 Hz, H-8), 2.28 (3H, s, H-10), 0.95 (3H, s, H-11), 1.20 (3H, s, H-12), 1.18 (3H, s, H-13), 4.33 (1H, d, J = 7.9 Hz, H-1′), 3.11 (1H, dd, J = 8.9,7.9 Hz, H-2′), 3.36 (1H, o, H-3′), 3.26 (2H, m, H-4′, H-5′), 3.84 (1H, dd, J = 11.9,2.1 Hz, H-6′a), 3.66 (1H, dd, J = 11.9,5.2 Hz, H-6′b)。13C-NMR (CD3OD, 150 MHz) δ：36.0 (C-1), 45.2 (C-2), 72.8 (C-3), 38.2 (C-4), 68.4 (C-5), 71.2 (C-6), 145.3 (C-7), 133.9 (C-8), 200.3 (C-9), 27.5 (C-10), 25.5 (C-11), 29.5 (C-12), 20.2 (C-13), 103.0 (C-1′), 75.2 (C-2′), 77.9 (C-3′), 71.6 (C-4′), 78.2 (C-5′), 62.7 (C-6′)。上述數(shù)據(jù)與文獻(xiàn)[11]報(bào)道基本一致，故鑒定為5β,6α-dihydroxy-3β-(β-D-glucoyranosyloxy)-7-megastigmen-9-one。

3.7 化合物7

白色無(wú)定形粉末。HR-ESI-MS m/z: 387.201 9 [M+H]+，其分子式為C19H30O8。1H-NMR (CD3OD, 600 MHz) δ：2.03 (2H, d, J = 12.7 Hz, H-2), 4.34 (1H, m, H-3), 2.32 (2H, d, J = 12.7 Hz, H-4), 5.90 (1H, s, H-8), 2.27 (3H, s, H-10), 1.12 (3H, s, H-11), 1.43 (3H, s, H-12), 1.37 (3H, s, H-13), 4.42 (1H, d, J = 7.9 Hz, H-1′), 3.14 (1H, dd, J = 8.9,7.9 Hz, H-2′), 3.36 (1H, o, H-3′), 3.25 (2H, m, H-4′, H-5′), 3.86 (1H, m, H-6′a), 3.68 (1H, m, H-6′b)。13C-NMR (CD3OD, 150 MHz) δ：36.9 (C-1), 48.1 (C-2), 72.6 (C-3), 46.8 (C-4), 72.5 (C-5), 120.2 (C-6), 211.1 (C-7), 101.4 (C-8), 202.2 (C-9), 27.0 (C-10), 32.5 (C-11), 29.3 (C-12), 30.9 (C-13), 102.7 (C-1′), 75.1 (C-2′), 78.2 (C-3′), 71.7 (C-4′), 77.9 (C-5′), 62.8 (C-6′)。上述數(shù)據(jù)與文獻(xiàn)[12]報(bào)道基本一致，故鑒定為austroside B。

3.8 化合物8

白色無(wú)定形粉末。HR-ESI-MS m/z: 197.117 8 [M+H]+，其分子式為C11H16O3。1H-NMR (CD3OD, 600 MHz) δ：1.52 (1H, dd, J = 14.4,3.7 Hz, H-2a), 1.98 (1H, dt, J = 14.4,2.7 Hz, H-2b), 4.20 (1H, m, H-3), 1.73 (1H, br.d, J = 4.0 Hz, H-4a), 2.40 (1H, dt, J = 13.4,2.7 Hz, H-4b), 5.74 (1H, s, H-7), 1.46 (3H, s, H-9), 1.26 (3H, s, H-10), 1.75 (3H, s, H-11)。13C-NMR (CD3OD, 150 MHz) δ：37.2 (C-1), 48.0 (C-2), 67.3 (C-3), 46.5 (C-4), 89.0 (C-5), 185.7 (C-6), 113.4 (C-7), 174.5 (C-8), 27.0 (C-9), 31.0 (C-10), 27.5 (C-11)。上述數(shù)據(jù)與文獻(xiàn)[13]報(bào)道基本一致，故鑒定為loliolide。

3.9 化合物9

白色無(wú)定形粉末。HR-ESI-MS m/z: 263.149 5 [M+H]+，分子式為C12H22O6。1H-NMR (CD3OD, 600 MHz) δ：3.53 (2H, m, H-1), 2.37 (2H, q, J = 7.2 Hz, H-2), 5.37 (1H, m, H-3), 5.45 (1H, m, H-4), 2.07 (2H, q, J = 7.5 Hz, H-5), 0.96 (3H, t, J = 7.5 Hz, H-6), 4.25 (1H, d, J = 7.8 Hz, H-1′), 3.14 (1H, dd, J = 9.0,7.9 Hz, H-2′), 3.34 (1H, o, H-3′), 3.25 (2H, m, H-4′, H-5′), 3.86 (1H, m, H-6′a), 3.66 (1H, m, H-6′b)。13C-NMR (CD3OD, 150 MHz) δ：70.5 (C-1), 28.8 (C-2), 134.5 (C-3), 125.9 (C-4), 21.6 (C-5), 14.6 (C-6), 104.4 (C-1′), 75.1 (C-2′), 78.0 (C-3′), 71.7 (C-4′), 78.2 (C-5′), 62.8 (C-6′)。上述數(shù)據(jù)與文獻(xiàn)[14]報(bào)道基本一致，故鑒定為(Z)-3-hexenyl β-D-glucopyranoside。

3.10 化合物10

白色無(wú)定形粉末。HR-ESI-MS m/z: 417.176 1 [M+H]+，分子式為C19H28O10。1H-NMR (CD3OD, 600 MHz) δ：7.25 (4H, m, H-2, H-3, H-5, H-6), 7.16 (1H, m, H-4), 2.93 (2H, m, H-7), 3.75 (2H, m, H-8), 4.28 (1H, d, J = 7.8 Hz, H-1′), 3.16 (1H, dd, J = 8.9,7.8 Hz, H-2′), 3.38 (1H, m, H-3′), 3.25 (2H, m, H-4′, H-5′), 3.88 (1H, d, J = 2.3 Hz, H-6′a), 3.68 (1H, m, H-6′b), 4.99 (1H, d, J = 2.4 Hz, H-1″), 4.04 (1H, m, H-2″), 3.96 (2H, m, H-4″), 3.55 (2H, s, H-5″)。13C-NMR (CD3OD, 150 MHz) δ：140.1 (C-1), 129.4 (C-2, C-6), 130.1 (C-3, C-5), 127.2 (C-4), 37.3 (C-7), 71.9 (C-8), 104.5 (C-1′), 75.0 (C-2′), 78.0 (C-3′), 71.7 (C-4′), 76.9 (C-5′), 68.7 (C-6′), 111.0 (C-1″), 78.1 (C-2″), 80.6 (C-3″), 75.1 (C-4″), 65.6 (C-5″)。上述數(shù)據(jù)與文獻(xiàn)[15]報(bào)道基本一致，故鑒定為icariside D1。

3.11 化合物11

白色無(wú)定形粉末。HR-ESI-MS m/z: 403.160 4 [M+H]+, 分子式為C18H26O10。1H-NMR (CD3OD, 600 MHz) δ：7.41 (2H, m, H-2, H-6), 7.32 (2H, m, H-3, H-5), 7.26 (1H, m, H-4), 4.64 (1H, d, J = 11.8 Hz, H-7a), 4.88 (1H, d, J = 11.8 Hz, H-7b), 4.32 (1H, d, J = 7.8 Hz, H-1′), 3.14 (1H, dd, J = 8.9,7.8 Hz, H-2′), 3.38 (1H, m, H-3′), 3.25 (2H, m, H-4′, H-5′), 3.88 (1H, m, H-6′a), 3.68 (1H, m, H-6′b), 5.04 (1H, d, J = 2.5 Hz, H-1″), 4.01 (1H, m, H-2″), 3.98 (2H, m, H-4″), 3.58 (2H, s, H-5″)。13C-NMR (CD3OD, 150 MHz) δ：139.0 (C-1), 129.3 (C-2, C-3, C-5, C-6), 128.7 (C-4), 71.6 (C-7), 103.2 (C-1′), 75.0 (C-2′), 78.0 (C-3′), 71.9 (C-4′), 77.0 (C-5′), 68.7 (C-6′), 111.0 (C-1″), 78.1 (C-2″), 80.6 (C-3″), 75.1 (C-4″), 65.6 (C-5″)。上述數(shù)據(jù)與文獻(xiàn)[16]報(bào)道基本一致，故鑒定為icariside F2。

3.12 化合物12

白色無(wú)定形粉末。HR-ESI-MS m/z: 268.104 6 [M+H]+，分子式為C10H13N5O4。1H-NMR (C5D5N, 600 MHz) δ：8.61 (1H, s, H-2), 8.36 (1H, s, H-8), 6.71 (1H, d, J = 5.8 Hz, H-1′), 5.06 (1H, m, H-2′), 5.49 (1H, t, J = 5.5 Hz, H-3′), 4.76 (1H, dd, J = 5.5,2.7 Hz, H-4′), 4.31 (1H, dd, J = 12.4,2.7 Hz, H-5′a), 4.13 (1H, dd, J = 12.4,2.7 Hz, H-5′b)。13C-NMR (C5D5N, 150 MHz) δ：153.2 (C-2), 150.0 (C-4), 121.3 (C-5), 157.5 (C-6), 140.4 (C-8), 90.7 (C-1′), 75.4 (C-2′), 72.3 (C-3′), 87.7 (C-4′), 62.9 (C-5′)。上述數(shù)據(jù)與文獻(xiàn)[17]報(bào)道基本一致，故鑒定為adenosine。

3.13 化合物13

白色無(wú)定形粉末。HR-ESI-MS m/z: 267.102 1 [M+H]+, 分子式為C17H14O3。1H-NMR (CD3OD, 600 MHz) δ：7.64 (1H, d, J = 15.9 Hz, H-1), 6.37 (1H, d, J = 15.9 Hz, H-2), 5.81 (1H, d, J = 12.8 Hz, H-4), 6.90 (1H, d, J = 12.8 Hz, H-5), 7.47 (2H, d, J = 8.6 Hz, H-2′, H-6′), 6.80 (2H, d, J = 8.6 Hz, H-3′, H-5′), 7.65 (2H, d, J = 8.6 Hz, H-2″, H-6″), 6.72 (2H, d, J = 8.6 Hz, H-3″, H-5″)。13C-NMR (CD3OD, 150 MHz) δ：147.3 (C-1), 115.8 (C-2), 173.2 (C-3), 160.2 (C-4), 143.5 (C-5), 127.2 (C-1′), 131.3 (C-2′), 115.8 (C-3′), 161.2 (C-4′), 115.8 (C-5′), 131.3 (C-6′), 127.2 (C-1″), 133.9 (C-2″, C-6″), 114.6 (C-3″, C-5″), 116.8 (C-4″)。上述數(shù)據(jù)與文獻(xiàn)[18]報(bào)道基本一致，故鑒定為kinsenone。

3.14 化合物14

白色無(wú)定形粉末。HR-ESI-MS m/z: 282.279 7 [M+H]+，分子式為C18H35NO。1H-NMR (CD3OD, 600 MHz) δ：2.18 (2H, t, J = 7.4 Hz, H-2), 1.59 (2H, t, J = 7.4 Hz, H-3), 1.29 (20H, m, H-4～H-7, H-12～H-17), 2.01 (2H, m, H-8), 5.33 (1H, t, J = 4.6 Hz, H-9), 5.33 (1H, t, J = 4.6 Hz, H-10), 2.01 (2H, m, H-11), 0.89 (3H, t, J = 7.0 Hz, H-18)。13C-NMR (CD3OD, 150 MHz) δ：179.3 (C-1), 36.5 (C-2), 26.9 (C-3), 30.3 (C-4), 30.4 (C-5, C-6), 30.8 (C-7), 28.1 (C-8), 130.8 (C-9), 130.8 (C-10), 28.1 (C-11), 30.6 (C-12, C-13, C-15), 30.7 (C-14), 33.1 (C-16), 23.7 (C-17), 14.4 (C-18)。上述數(shù)據(jù)與文獻(xiàn)[19]報(bào)道基本一致，故鑒定為9(Z)-octadecenamide。

4 結(jié)果與討論

本研究對(duì)北重樓地上部分正丁醇層進(jìn)行了系統(tǒng)的化學(xué)成分分離，共得到14個(gè)化合物，包括8個(gè)萜類化合物byzantionoside B (1)、vomifoliol 9-O-β-D-glucopyranoside (2)、dihydrovomifoliol-O-β-D-glucopyranoside (3)、macarangioside F (4)、turpinionoside A (5)、5β,6α-dihydroxy-3β-(β-D-glucoyranosyloxy)-7-megastigmen-9-one (6)、austroside B (7)、loliolide (8)，4個(gè)糖苷類化合物(Z)-3-hexenyl β-D-glucopyranoside (9)、icariside D1 (10)、icariside F2 (11)、adenosine (12)和2個(gè)其他類化合物kinsenone (13)、9(Z)-octadecenamide (14)。其中化合物1～7、10、11、14為首次從百合科植物中分離得到，化合物8、9為首次從重樓屬植物中分離得到。本研究進(jìn)一步豐富了北重樓地上部分的化學(xué)成分，為深入挖掘北重樓的藥效物質(zhì)基礎(chǔ)，合理利用其藥用資源提供了科學(xué)依據(jù)。