邸同蓮，劉小清，吳 楠，陳孝源，范君婷，譚寧華

· 化學(xué)成分 ?

五味子中1個(gè)新的聯(lián)苯環(huán)辛烯類木脂素

邸同蓮1，劉小清2，吳 楠1，陳孝源1，范君婷3*，譚寧華1*

1. 中國藥科大學(xué)中藥學(xué)院，江蘇 南京 211198 2. 揚(yáng)子江藥業(yè)集團(tuán)北京海燕藥業(yè)有限公司，北京 102206 3. 南京醫(yī)科大學(xué)藥學(xué)院，江蘇 南京 211116

研究中藥五味子的木脂素類化學(xué)成分。采用硅膠柱色譜、中壓反相柱色譜、半制備和制備液相對五味子中富含木脂素類成分的石油醚萃取部位進(jìn)行分離、純化，通過波譜數(shù)據(jù)鑒定化合物的結(jié)構(gòu)。從五味子中分離得到了26個(gè)化合物，分別鑒定為綠葉五味子素B（1）、sphaerandrin A（2）、sieverlignan E（3）、arisanschinin G（4）、widdaranal F（5）、戈米辛A（6）、戈米辛B（7）、戈米辛D（8）、戈米辛G（9）、(?)-戈米辛K1（10）、(＋)-戈米辛K2（11）、(?)-戈米辛L1（12）、(＋)-戈米辛M1（13）、戈米辛N（14）、當(dāng)歸酰戈米辛H（15）、當(dāng)歸酰戈米辛O（16）、當(dāng)歸酰戈米辛Q（17）、苯甲酰戈米辛Q（18）、五味子醇甲（19）、五味子甲素（20）、五味子乙素（21）、五味子丙素（22）、五味子酯丙（23）、neglschisandrin E（24）、7(18)-dehydroschisandro A（25）、安五脂素（26），其中24個(gè)為聯(lián)苯環(huán)辛烯類木脂素（1～4、6～25）?；衔?為新化合物，化合物2～5為首次從該植物中分離得到。

五味子；綠葉五味子素B；聯(lián)苯環(huán)辛烯類木脂素；sphaerandrin A；sieverlignan E；arisanschinin G；widdaranal F；五味子醇甲

五味子為木蘭科植物五味子(Turcz.) Baill.的干燥成熟果實(shí)，始載于《神農(nóng)本草經(jīng)》，列為上品，習(xí)稱“北五味子”，道地產(chǎn)區(qū)為黑龍江、吉林、遼寧等地。五味子具有收斂固澀、益氣生津、補(bǔ)腎寧心等功效，可用于治療久咳虛喘、久瀉不止、津傷口渴等癥[1]。五味子中富含木脂素、萜類、揮發(fā)油、多糖、酚酸、黃酮、植物甾醇等多類成分，其中木脂素類是其特征活性成分[2]。五味子作為蘇黃止咳膠囊復(fù)方中的臣藥，研究發(fā)現(xiàn)其木脂素類成分具有舒張氣管平滑肌[3]、抗炎[4-6]、抗纖維化[7-8]、鎮(zhèn)咳平喘[9-11]的功效，可能是該中成藥發(fā)揮藥效的活性成分。前期課題組利用LC-MS技術(shù)對蘇黃止咳膠囊的化學(xué)成分進(jìn)行分析和藥材溯源，鑒定出300多個(gè)化合物[12-13]，其中包含29個(gè)木脂素并主要來源于五味子，且研究結(jié)果表明五味子醇甲是影響該藥質(zhì)量的主要成分[14]。因此本實(shí)驗(yàn)研究蘇黃止咳膠囊臣藥五味子的化學(xué)成分，有助于進(jìn)一步闡明蘇黃止咳膠囊的藥效物質(zhì)基礎(chǔ)及其質(zhì)量標(biāo)準(zhǔn)研究。

本實(shí)驗(yàn)采用硅膠柱色譜、中壓反相柱色譜、半制備和制備液相對五味子水提物富含木脂素的石油醚萃取部位進(jìn)行分離純化，共得到25個(gè)木脂素和1個(gè)倍半萜，包括24個(gè)聯(lián)苯環(huán)辛烯類木脂素（1～4、6～25），分別鑒定為綠葉五味子素B（schiviridin B，1）、sphaerandrin A（2）、sieverlignan E（3）、arisanschinin G（4）、widdaranal F（5）、戈米辛A（gomisin A，6）、戈米辛B（gomisin B，7）、戈米辛D（gomisin D，8）、戈米辛G（gomisin G，9）、(?)-戈米辛K1[(?)-gomisin K1，10]、(＋)-戈米辛K2[(+)-gomisin K2，11]、(?)-戈米辛L1[(?)-gomisin L1，12]、(＋)-戈米辛M1[(+)-gomisin M1，13]、戈米辛N（gomisin N，14）、當(dāng)歸酰戈米辛H（angeloylgomisin H，15）、當(dāng)歸酰戈米辛O（angeloylgomisin O，16）、當(dāng)歸酰戈米辛Q（angeloylgomisin Q，17）、苯甲酰戈米辛Q（benzoylgomisin Q，18）、五味子醇甲（schisandrin，19）、五味子甲素（schisandrin A，20）、五味子乙素（γ-schisandrin，21）、五味子丙素（schisandrin C，22）、五味子酯丙（schisantherin C，23）、neglschisandrin E（24）、7(18)-dehydroschisandro A（25）、安五脂素（anwulignan，26）。其中化合物1為新化合物，化合物2～5為首次從該藥材中分離得到。

1 藥材、儀器與材料

五味子（10 kg）由揚(yáng)子江藥業(yè)集團(tuán)北京海燕藥業(yè)有限公司提供，樣品（ID-210831）保存于中國藥科大學(xué)中藥學(xué)院譚寧華教授團(tuán)隊(duì)實(shí)驗(yàn)室，經(jīng)中國藥科大學(xué)中藥學(xué)院秦民堅(jiān)教授鑒定為植物五味子(Turcz.) Baill.的干燥成熟果實(shí)。

Shimadzu UV-2600i型紫外光譜儀（日本Shimadzu有限公司）；Bruker AV-400型核磁共振儀（德國Bruker公司）；Rudolph Autopl IV型旋光儀（美國Rudolph有限公司）；Bruker Tensor-27型紅外光譜儀（德國Bruker公司）；Japan Jasco J810型圓二光譜儀（日本分光JASCO公司）；Angilent 1260-6230 TOF液質(zhì)聯(lián)用儀（美國Angilent公司）；Waters XevoTQD質(zhì)譜儀（美國Waters公司）；LC 3000 Ⅰ型制備型HPLC（北京創(chuàng)新通恒科技有限公司）。半制備型液相色譜柱、制備型液相色譜柱以及分析型液相色譜柱分別為YMC-Pack ODS-A C18柱系列（250 mm×10 mm，5 μm，日本YMC公司）、YMC-Pack ODS-A C18柱系列（250 mm×20 mm，5 μm，日本YMC公司）、Waters ACQUITY UPLCHSS T3色譜柱（100 mm×2.1 mm，1.8 μm，美國Waters公司）。柱色譜硅膠（100～200、200～300目）以及GF254薄層板（青島裕明源硅膠試劑廠）；反相材料Lichroprep RP-18（40～63 μm，美國Merck公司）；顯色劑為5%硫酸乙醇溶液；實(shí)驗(yàn)所用試劑均為分析純（無錫市亞盛集團(tuán)化學(xué)試劑有限公司）和色譜純（美國TEDIA公司和Merck公司）；LC-MS級甲酸（德國Sigma-Aldrich公司）。

2 提取與分離

干燥的五味子10 kg，粉碎，用10倍量的水煎煮3次，每次1 h，水提液減壓濃縮得浸膏。浸膏以水溶解，用石油醚、醋酸乙酯、正丁醇依次萃取3～4次，萃取液減壓濃縮得各萃取部位浸膏。各萃取部位浸膏經(jīng)TLC、LC-MS檢測，確定所需木脂素類成分主要集中在石油醚萃取部位。然后石油醚部位（80.4 g）首先通過硅膠柱色譜（200～300目硅膠），以石油醚-醋酸乙酯（10∶0～0∶10）梯度洗脫，減壓濃縮，TLC、LC-MS檢測合并，得到6個(gè)流分（Fr. 1～6）。

Fr. 2（5.936 g）經(jīng)硅膠柱色譜，以石油醚-醋酸乙酯5個(gè)梯度（80∶1、40∶1、20∶1、10∶1、0∶1）進(jìn)行洗脫，利用TLC和LC-MS檢測，合并獲得7個(gè)亞流分（Fr. 2-1～2-7）。Fr. 2-3（473 mg）經(jīng)反復(fù)硅膠柱色譜及制備型HPLC（75%乙腈）純化得到化合物16（34 mg，R＝51.6 min）、22（18 mg，R＝38.8 min）、26（33 mg，R＝23.1 min）。Fr. 2-5（3.7 g）經(jīng)反復(fù)硅膠柱色譜及制備型HPLC（72%乙腈）純化得到化合物14（958 mg，R＝33.0 min）、21（304 mg，R＝35.3 min）。Fr. 3（22.555 g）經(jīng)硅膠柱色譜，石油醚-醋酸乙酯（50∶1、40∶1、20∶1、10∶1、5∶1、3∶1、0∶1）梯度洗脫，得到9個(gè)亞流分（Fr. 3-1～3-9）。Fr. 3-5（5.385 g）經(jīng)反復(fù)硅膠柱色譜及制備型HPLC（60%乙腈）純化得到化合物1（8 mg，R＝33.6 min）、5（56 mg，R＝41.6 min）、10（16 mg，R＝27.6 min）、11（10 mg，R＝24.9 min）、12（19 mg，R＝54.0 min）、13（35 mg，R＝55.8 min）、20（206 mg，R＝29.6 min）、24（22 mg，R＝21.0 min）、25（16 mg，R＝22.5 min）。Fr. 3-7（8.056 g）經(jīng)反復(fù)硅膠柱色譜及制備型HPLC（60%乙腈）純化得到化合物9（24 mg，R＝36.6 min）。Fr. 4（22.91 g）經(jīng)硅膠柱色譜，石油醚-醋酸乙酯（20∶1、10∶1、5∶1、3∶1、0∶1）梯度洗脫，得到5個(gè)亞流分Fr. 4-1～4-5。Fr. 4-2（2.474 g）經(jīng)制備型HPLC（60%乙腈）純化得到化合物4（6 mg，R＝38.2 min）、6（252 mg，R＝19.1 min）、7（51 mg，R＝34.5 min）、17（217 mg，R＝26.5 min）、23（21 mg，R＝31.4 min）。Fr. 4-3（15.896 g）經(jīng)RP-18中壓反相柱色譜，甲醇-水（30%～100%）梯度洗脫，利用TLC和LC-MS檢測合并，得到4個(gè)亞流分Fr. 4-3-1～4-3-4，其中Fr. 4-3-2（10.202 g）經(jīng)檢測為化合物19（10.202 g）。Fr. 4-3-3（1.802 g）經(jīng)制備型HPLC（60%乙腈）純化得到化合物2（15 mg，R＝19.7 min）、3（21 mg，R＝23.8 min）、8（71 mg，R＝15.8 min）、15（608 mg，R＝25.6 min）、18（57 mg，R＝27.1 min）。

3 結(jié)構(gòu)鑒定

化合物1：黃色固體（甲醇），易溶于三氯甲烷。[α]20 D＋82.1°（0.067，MeOH），HR-ESI-MS（/519.197 31 [M＋Na]+；計(jì)算值519.198 94），可確定化合物1分子式為C28H32O8，不飽和度為13。紫外光譜顯示其在225 nm處有最大吸收，表明化合物結(jié)構(gòu)中存在較強(qiáng)的共軛系統(tǒng)。紅外光譜在3398、1641、1456、1396、1033 cm?1處有吸收，提示分子中含有苯環(huán)、羰基、雙鍵。化合物1的1H-NMR和13C-NMR譜（表1）與schiviridin A[15]較為相似，提示其為聯(lián)苯環(huán)辛烯類木脂素。

化合物1的1H-NMR譜（表1）顯示2個(gè)芳環(huán)質(zhì)子信號H6.73 (1H, s), 6.48 (1H, s)；1個(gè)連酯基質(zhì)子信號H6.42 (1H, s)；1個(gè)亞甲二氧基質(zhì)子信號H5.99 (1H, d,= 1.4 Hz), 5.97 (1H, d,= 1.4 Hz)；2個(gè)末端烯氫質(zhì)子信號H4.83 (1H, s), 4.60 (1H, s)；4個(gè)甲氧基質(zhì)子信號H3.88 (3H, s), 3.84 (3H, s), 3.78 (3H, s), 3.61 (3H, s)；1個(gè)次甲基質(zhì)子信號H2.58 (1H, overlapped)；1個(gè)亞甲基質(zhì)子信號H2.54 (1H, overlapped), 2.24 (1H, dd,= 12.2, 9.6 Hz)；1個(gè)甲基質(zhì)子信號H1.21 (3H, d,= 6.8 Hz)；還具有偶合系統(tǒng)的質(zhì)子信號H5.95 (1H, m), 1.87 (3H, dq,= 7.2, 1.6 Hz), 1.51 (3H, q,= 1.6 Hz)，結(jié)合13C-NMR譜（表1）的酯基碳(C166.3) 和烯碳(C139.6, 127.5)，以及1H-1H COSY譜中H-3/H-4相關(guān)信號，可以推導(dǎo)為當(dāng)歸?；盘?。13C-NMR結(jié)合HSQC譜顯示化合物1中有28個(gè)碳信號，包括4個(gè)甲氧基、3個(gè)甲基、1個(gè)亞甲二氧基、2個(gè)亞甲基、5個(gè)次甲基、12個(gè)季碳、1個(gè)酯基。

表1 化合物1的1H-NMR和13C-NMR數(shù)據(jù)(400/100 MHz, CDCl3)

1H-1H COSY譜中（圖1），H-8與H-9、H-17相關(guān)，表明C-8、C-9、C-17相連。HMBC譜中（圖1）顯示，H-6 (H6.42) 與C-4、C-5、C-7、C-8、C-16、C-18、C-1相關(guān)；H-9 (H2.24, 2.54) 與C-11、C-8、C-10、C-15、C-7存在相關(guān)信號；芳環(huán)H-4 (H6.73) 與C-2、C-3、C-16相關(guān)，芳環(huán)氫H-11 (H6.48) 與C-12、C-13、C-15相關(guān)；這些相關(guān)信號提示含有聯(lián)苯環(huán)辛烯類木脂素的基本骨架。其中，H-6與C-1存在相關(guān)信號，表明C-6位是當(dāng)歸酰基取代；H-6還與C-18相關(guān)，顯示末端烯鍵連接在C-7位；亞甲二氧基H5.99、5.97分別與C-2、C-3相關(guān)，表明亞甲二氧基與C-2、C-3連接；4個(gè)甲氧基H3.61、3.78、3.84、3.88分別與C-14、C-1、C-13、C-12相關(guān)，確定了甲氧基的連接位置。綜上所述，化合物1的平面結(jié)構(gòu)得以確定。

化合物1的立體結(jié)構(gòu)利用CD光譜和ROESY譜來確定。文獻(xiàn)報(bào)道型聯(lián)苯環(huán)辛烯類木脂素的CD光譜在215～225 nm為正Cotton效應(yīng)，在235～255 nm為負(fù)Cotton效應(yīng)，而型的CD光譜則相反[15]?；衔?的實(shí)驗(yàn)ECD光譜顯示在222 nm有正Cotton效應(yīng)，在243 nm有負(fù)Cotton效應(yīng)，表明1是型聯(lián)苯環(huán)辛烯類木脂素。同時(shí)，ROESY譜中（圖1）H-4/H-6、H-6/H-18相關(guān)，顯示H-4、H-6和H-18處于同側(cè)；H-11/H-8、H-8/H-9β相關(guān)，也顯示H-8、H-9β和H-11處于同側(cè)。最后，通過計(jì)算ECD和實(shí)驗(yàn)ECD比較（圖2），確定其絕對構(gòu)型為6、8。與已知化合物schiviridin A[15]的結(jié)構(gòu)進(jìn)行比對，二者苯環(huán)上的4個(gè)甲氧基和亞甲二氧基取代位置存在差異，且schiviridin A的絕對構(gòu)型是6、8。因此，化合物1的結(jié)構(gòu)鑒定為(a)-(5,7)- 5,6,7,8-四氫-1,11,12,13-四甲氧基-7-甲基-6-亞甲苯并[3,4]環(huán)辛基[1,2:4,5]苯并[1,2-f][1,3]二氧-5-基(2)-2-甲基-丁烯酸酯。經(jīng)SciFinder檢索為未見文獻(xiàn)報(bào)道的新化合物，命名為綠葉五味子素B（schiviridin B）。

圖1 化合物1的結(jié)構(gòu)及其主要1H-1H COSY、HMBC和ROESY相關(guān)信號

圖2 化合物1的計(jì)算ECD和實(shí)驗(yàn)ECD圖譜

化合物2：白色晶體（甲醇）；[α]20 D?42.3°(0.052，MeOH)；C27H32O9；ESI-MS/: 523.25 [M＋Na]+。1H-NMR (400 MHz, CDCl3): 6.86 (1H, s, H-4), 5.51 (1H, s, H-6), 2.00 (1H, m, H-8), 2.26 (1H, dd,= 14.1, 9.6 Hz, H-9β), 2.18 (1H, dd,= 14.1, 1.3 Hz, H-9α), 6.48 (1H, s, H-11), 1.14 (3H, d,= 7.1 Hz, H-17), 1.36 (3H, s, H-18), 5.95 (1H, m, H-3), 1.84 (3H, dq,= 7.3, 1.5 Hz, H-4), 1.42 (3H, d,= 1.5 Hz, H-5), 3.55 (3H, s, 1-OCH3), 3.93 (3H, s, 2-OCH3), 3.93 (3H, s, 3-OCH3), 5.97 (1H, d,= 1.4 Hz, 12, 13-OCH2O), 5.89 (1H, d,= 1.4 Hz, 12, 13-OCH2O), 5.15 (1H, s, 14-OH)；13C-NMR (100 MHz, CDCl3): 150.9 (C-1), 142.0 (C-2), 152.6 (C-3), 111.5 (C-4), 132.5 (C-5), 84.8 (C-6), 72.3 (C-7), 42.6 (C-8), 36.6 (C-9), 135.7 (C-10), 102.2 (C-11), 148.6 (C-12), 133.6 (C-13), 136.7 (C-14), 118.5 (C-15), 120.0 (C-16), 20.0 (C-17), 28.4 (C-18), 166.2 (C-1), 126.9 (C-2), 140.1 (C-3), 15.9 (C-4), 18.8 (C-5), 61.5 (1-OCH3), 61.3 (2-OCH3), 56.1 (3-OCH3), 101.4 (12, 13-OCH2O)。以上數(shù)據(jù)與文獻(xiàn)報(bào)道對比基本一致[16]，鑒定化合物2為sphaerandrin A。

化合物3：白色晶體（甲醇）；[α]20 D＋126.6°(0.064，MeOH)；C28H36O8；ESI-MS/: 501.25 [M＋H]+。1H-NMR (400 MHz, CDCl3): 6.55 (1H, s, H-4), 2.71 (1H, d,= 13.7 Hz, H-6α), 2.33 (1H, d,= 13.7 Hz, H-6β), 1.89 (1H, m, H-8), 2.69 (1H, dd,= 14.2, 1.8 Hz, H-9α), 2.41 (1H, dd,= 14.2, 7.6 Hz, H-9β), 6.68 (1H, s, H-11), 0.85 (3H, d,= 7.3 Hz, H-17), 1.24 (3H, s, H-18), 6.82 (1H, m, H-3), 1.71 (3H, overlapped, H-4), 1.69 (3H, overlapped, H-5), 3.50 (3H, s, 1-OCH3), 3.83 (3H, s, 2-OCH3), 3.87 (3H, s, 3-OCH3), 3.82 (3H, s, 13-OCH3), 3.90 (3H, s, 14-OCH3)；13C-NMR (100 MHz, CDCl3): 152.0 (C-1), 140.5 (C-2), 152.6 (C-3), 110.3 (C-4), 133.2 (C-5), 40.8 (C-6), 72.1 (C-7), 42.1 (C-8), 34.4 (C-9), 133.9 (C-10), 112.9 (C-11), 142.8 (C-12), 140.0 (C-13), 151.8 (C-14), 123.3 (C-15), 123.1 (C-16), 16.0 (C-17), 30.0 (C-18), 165.9 (C-1), 128.1 (C-2), 138.3 (C-3), 12.2 (C-4), 14.5 (C-5), 61.0 (1-OCH3), 61.1 (2-OCH3), 56.2 (3-OCH3), 60.8 (13-OCH3), 56.2 (14-OCH3)。以上數(shù)據(jù)與文獻(xiàn)報(bào)道對比基本一致[17]，鑒定化合物3為sieverlignan E。

招聘需求人數(shù)規(guī)模度指標(biāo)用來表征崗位的人數(shù)需求緊缺度，即崗位在同行業(yè)中的人數(shù)需求緊缺情況。計(jì)算方法是先對招聘需求實(shí)際人數(shù)進(jìn)行修正，修正值為招聘需求人數(shù)和發(fā)布頻率的比值。招聘需求人數(shù)規(guī)模度指標(biāo)為崗位招聘需求人數(shù)修正值和崗位所在細(xì)分領(lǐng)域內(nèi)招聘需求人數(shù)修正值總和的比值。發(fā)布頻率指標(biāo)用于表征崗位招聘需求在時(shí)間上的緊缺程度，意思是平均每家公司每天發(fā)布的崗位需求情況，計(jì)算方法是招聘發(fā)布公司數(shù)量和發(fā)布天數(shù)的乘積比招聘發(fā)布條數(shù)。

化合物4：白色晶體（甲醇）；[α]20 D?24.1°(0.058，MeOH)；C22H28O6；ESI-MS/: 411.36 [M＋Na]+。1H-NMR (400 MHz, CDCl3): 6.37 (1H, s, H-4), 2.24 (1H, dd,= 13.3, 9.4 Hz, H-6β), 2.04 (1H, d,= 13.3 Hz, H-6α), 1.81 (1H, m, H-7), 1.89 (1H, m, H-8), 2.56 (1H, dd,= 13.5, 7.4 Hz, H-9β), 2.44 (1H, d,= 13.5, 1.9 Hz, H-9α), 6.66 (1H, s, H-11), 0.73 (3H, d,= 7.1 Hz, H-17), 1.00 (3H, d,= 7.1 Hz, H-18), 5.74 (1H, s, 1-OH), 3.87 (3H, s, 2-OCH3), 3.90 (3H, s, 3-OCH3), 5.68 (1H, s, 12-OH), 3.93 (3H, s, 13-OCH3), 3.60 (3H, s, 14-OCH3)；13C-NMR (100 MHz, CDCl3): 146.7 (C-1), 133.5 (C-2), 151.9 (C-3), 104.0 (C-4), 140.0 (C-5), 35.6 (C-6), 41.0 (C-7), 33.9 (C-8), 38.9 (C-9), 135.5 (C-10), 113.8 (C-11), 147.9 (C-12), 137.7 (C-13), 150.3 (C-14), 121.6 (C-15), 115.9 (C-16), 12.6 (C-17), 22.0 (C-18), 61.2 (2-OCH3), 55.9 (3-OCH3), 61.2 (13-OCH3), 60.6 (14-OCH3)。以上數(shù)據(jù)與文獻(xiàn)報(bào)道對比基本一致[18]，鑒定化合物4為arisanschinin G。

化合物5：白色針晶（甲醇）；[α]20 D?82.6°(0.086，MeOH)；C15H22O2；ESI-MS/: 235.25 [M＋H]+。1H-NMR (400 MHz, CDCl3): 2.24 (2H, m, H-1), 7.10 (1H, m, H-2), 2.34 (1H, m, H-4a), 1.84 (1H, m, H-4b), 1.54 (2H, m, H-5), 1.78 (1H, m, H-8a), 1.19 (1H, m, H-8b), 2.08 (1H, m, H-9a), 1.41 (1H, m, H-9b), 2.16 (2H, m, H-10), 4.86 (1H, s, H-12a), 4.36 (1H, s, H-12b), 0.88 (3H, s, H-13), 0.85 (3H, s, H-14)；13C-NMR (100 MHz, CDCl3): 30.1 (C-1), 142.2 (C-2), 128.9 (C-3), 21.8 (C-4), 23.7 (C-5), 45.0 (C-6), 37.3 (C-7), 37.0 (C-8), 25.6 (C-9), 32.1 (C-10), 148.5 (C-11), 110.9 (C-12), 23.2 (C-13), 25.0 (C-14), 173.0 (C-15)。以上數(shù)據(jù)與文獻(xiàn)報(bào)道對比基本一致[19]，鑒定化合物5為widdaranal F。

化合物6：白色晶體（甲醇）；[α]20 D＋59.5°(0.074，MeOH)；C23H28O7；ESI-MS/: 439.26 [M＋Na]+。1H-NMR (400 MHz, CDCl3): 6.61 (1H, s, H-4), 2.67 (1H, d,= 13.5 Hz, H-6α), 2.35 (1H, d,= 13.5 Hz, H-6β), 2.00 (1H, s, 7-OH), 1.85 (1H, m, H-8), 2.57 (1H, dd,= 14.1, 1.6 Hz, H-9α), 2.32 (1H, dd,= 14.1, 7.4 Hz, H-9β), 6.47 (1H, s, H-11), 0.81 (3H, d,= 7.3 Hz, H-17), 1.25 (3H, s, H-18), 3.51 (3H, s, 1-OCH3), 3.90 (3H, s, 2-OCH3), 3.91 (3H, s, 3-OCH3), 5.96 (2H, s, 12, 13-OCH2O), 3.83 (3H, s, 14-OCH3)；13C-NMR (100 MHz, CDCl3): 152.2 (C-1), 140.8 (C-2), 152.4 (C-3), 110.4 (C-4), 132.1 (C-5), 40.6 (C-6), 71.7 (C-7), 42.1 (C-8), 33.8 (C-9), 132.6 (C-10), 106.1 (C-11), 148.0 (C-12), 135.0 (C-13), 141.3 (C-14), 121.9 (C-15), 124.2 (C-16), 15.9 (C-17), 30.2 (C-18), 60.7 (1-OCH3), 61.1 (2-OCH3), 56.1 (3-OCH3), 101.0 (12, 13-OCH2O), 59.8 (14-OCH3)。以上數(shù)據(jù)與文獻(xiàn)報(bào)道對比基本一致[20]，鑒定化合物6為gomisin A。

化合物7：白色晶體（甲醇）；[α]20 D?20.9°(0.067，MeOH)；C28H34O9；ESI-MS/: 537.35 [M＋Na]+。1H-NMR (400 MHz, CDCl3): 6.76 (1H, s, H-4), 5.61 (1H, s, H-6), 1.93 (1H, m, H-8), 2.29 (1H, dd,= 14.0, 9.7 Hz, H-9β), 2.13 (1H, d,= 14.0 Hz, H-9α), 6.45 (1H, s, H-11), 1.12 (3H, d,= 7.1 Hz, H-17), 1.32 (3H, s, H-18), 5.99 (1H, m, H-3), 1.84 (3H, dq,= 7.3, 1.6 Hz, H-4), 1.38 (3H, q,= 1.6 Hz, H-5), 3.72 (3H, s, 1-OCH3), 3.88 (3H, s, 2-OCH3), 3.89 (3H, s, 3-OCH3), 5.89 (1H, d,= 1.4 Hz, 12, 13-OCH2O), 5.86 (1H, d,= 1.4 Hz, 12, 13-OCH2O), 3.55 (3H, s, 14-OCH3)；13C-NMR (100 MHz, CDCl3): 152.2 (C-1), 141.8 (C-2), 152.0 (C-3), 109.9 (C-4), 130.7 (C-5), 84.5 (C-6), 72.3 (C-7), 42.5 (C-8), 36.5 (C-9), 135.3 (C-10), 102.8 (C-11), 148.8 (C-12), 134.3 (C-13), 140.6 (C-14), 121.3 (C-15), 122.3 (C-16), 19.1 (C-17), 28.2 (C-18), 166.0 (C-1), 127.2 (C-2), 140.1 (C-3), 15.8 (C-4), 19.9 (C-5), 60.8 (1-OCH3), 61.0 (2-OCH3), 55.9 (3-OCH3), 100.7 (12, 13-OCH2O), 59.2 (14-OCH3)。以上數(shù)據(jù)與文獻(xiàn)報(bào)道對比基本一致[21]，鑒定化合物7為gomisin B。

化合物8：白色晶體（甲醇）；[α]20 D?47.4°(0.076，MeOH)；C28H34O10；ESI-MS/: 553.36 [M＋Na]+。1H-NMR (400 MHz, CDCl3): 6.79 (1H, s, H-4), 5.72 (1H, s, H-6), 1.76 (1H, m, H-8), 2.37 (1H, dd,= 14.1, 8.3 Hz, H-9β), 2.00 (1H, d,= 14.1 Hz, H-9α), 6.47 (1H, s, H-11), 1.05 (3H, d,= 7.0 Hz, H-17), 1.22 (3H, s, H-18), 1.65 (1H, m, H-21), 3.71 (2H, m, H-22), 1.28 (3H, s, H-23), 1.14 (3H, d,= 7.2 Hz, H-24), 3.56 (3H, s, 1-OCH3), 3.84 (3H, s, 2-OCH3), 3.91 (3H, s, 3-OCH3), 6.00 (1H, d,= 1.4 Hz, 12, 13-OCH2O), 5.91 (1H, d,= 1.4 Hz, 12, 13-OCH2O)；13C-NMR (100 MHz, CDCl3): 152.0 (C-1), 142.5 (C-2), 152.2 (C-3), 110.9 (C-4), 130.3 (C-5), 87.6 (C-6), 72.2 (C-7), 44.0 (C-8), 36.1 (C-9), 136.5 (C-10), 102.7 (C-11), 148.6 (C-12), 137.3 (C-13), 138.4 (C-14), 121.4 (C-15), 122.6 (C-16), 19.0 (C-17), 27.6 (C-18), 177.7 (C-19), 75.0 (C-20), 37.9 (C-21), 73.0 (C-22), 24.8 (C-23), 11.4 (C-24), 60.8 (1-OCH3), 60.9 (2-OCH3), 56.1 (3-OCH3), 101.2 (12, 13-OCH2O)。以上數(shù)據(jù)與文獻(xiàn)報(bào)道對比基本一致[22]，鑒定化合物8為gomisin D。

化合物9：白色晶體（甲醇）；[α]20 D?126.5°(0.068，MeOH)；C30H32O9；ESI-MS/: 559.25 [M＋Na]+。1H-NMR (400 MHz, CDCl3): 6.77 (1H, s, H-4), 5.88 (1H, s, H-6), 2.13 (1H, m, H-8), 2.48 (1H, dd,= 14.0, 10.1 Hz, H-9β), 2.28 (1H, d,= 14.0 Hz, H-9α), 6.69 (1H, s, H-11), 1.20 (3H, d,= 7.0 Hz, H-17), 1.33 (3H, s, H-18), 7.36 (5H, overlapped, H-2～6), 3.39 (3H, s, 1-OCH3), 6.00 (2H, d,= 1.6 Hz, 2, 3-OCH2O), 3.98 (3H, s, 12-OCH3), 3.81 (3H, s, 13-OCH3), 3.14 (3H, s, 14-OCH3)；13C-NMR (100 MHz, CDCl3): 141.8 (C-1), 137.2 (C-2), 148.2 (C-3), 107.4 (C-4), 128.9 (C-5), 84.5 (C-6), 72.6 (C-7), 42.3 (C-8), 36.9 (C-9), 136.6 (C-10), 106.3 (C-11), 153.4 (C-12), 140.0 (C-13), 150.8 (C-14), 122.4 (C-15), 121.9 (C-16), 19.1 (C-17), 28.4 (C-18), 164.9 (-CO), 129.6 (C-1), 129.3 (C-2, 6), 128.2 (C-3, 5), 133.3 (C-4), 60.0 (1-OCH3), 101.5 (2, 3-OCH2O), 56.2 (12-OCH3), 60.2 (13-OCH3), 59.8 (14-OCH3)。以上數(shù)據(jù)與文獻(xiàn)報(bào)道對比基本一致[21]，鑒定化合物9為gomisin G。

化合物10：白色晶體（甲醇）；[α]20 D?112.5°(0.056，MeOH)；C23H30O6；ESI-MS/: 403.30 [M＋H]+。1H-NMR (400 MHz, CDCl3): 6.54 (1H, s, H-4), 2.54 (2H, m, H-6), 1.84 (1H, overlapped, H-7), 1.84 (1H, overlapped, H-8), 2.22 (1H, dd,= 13.1, 9.4 Hz, H-9β), 2.01 (1H, dd,= 13.1, 1.3 Hz, H-9α), 6.62 (1H, s, H-11), 0.96 (3H, d,= 7.1 Hz, H-17), 0.72 (3H, d,= 7.1 Hz, H-18), 3.54 (3H, s, 1-OCH3), 3.88 (3H, s, 2-OCH3), 3.88 (3H, s, 3-OCH3), 5.86 (1H, s, 12-OH), 3.90 (3H, s, 13-OCH3), 3.55 (3H, s, 14-OCH3)；13C-NMR (100 MHz, CDCl3): 151.6 (C-1), 140.1 (C-2), 151.6 (C-3), 110.6 (C-4), 134.2 (C-5), 39.3 (C-6), 33.8 (C-7), 40.9 (C-8), 35.3 (C-9), 140.1 (C-10), 110.1 (C-11), 148.8 (C-12), 137.4 (C-13), 150.3 (C-14), 121.5 (C-15), 123.3 (C-16), 21.8 (C-17), 12.7 (C-18), 60.6 (1-OCH3), 61.1 (2-OCH3), 56.0 (3-OCH3), 61.0 (13-OCH3), 60.2 (14-OCH3)。以上數(shù)據(jù)與文獻(xiàn)報(bào)道對比基本一致[20]，鑒定化合物10為(?)-gomisin K1。

化合物11：白色晶體（甲醇）；[α]20 D＋3.8°(0.053，MeOH)；C23H30O6；ESI-MS/: 403.31 [M＋H]+。1H-NMR (400 MHz, CDCl3): 6.54 (1H, s, H-4), 2.16 (2H, m, H-6), 1.84 (1H, overlapped, H-7), 1.84 (1H, overlapped, H-8), 2.51 (2H, m, H-9), 6.62 (1H, s, H-11), 0.73 (3H, d,= 7.1 Hz, H-17), 0.99 (3H, d,= 7.1 Hz, H-18), 3.55 (3H, s, 1-OCH3), 3.89 (3H, s, 2-OCH3), 3.92 (3H, s, 3-OCH3), 5.70 (1H, s, 12-OH), 3.88 (3H, s, 13-OCH3), 3.55 (3H, s, 14-OCH3)；13C-NMR (100 MHz, CDCl3): 151.5 (C-1), 139.9 (C-2), 153.0 (C-3), 107.4 (C-4), 139.5 (C-5), 35.7 (C-6), 41.0 (C-7), 33.9 (C-8), 38.9 (C-9), 134.8 (C-10), 113.1 (C-11), 147.6 (C-12), 137.7 (C-13), 150.4 (C-14), 122.7 (C-15), 122.3 (C-16), 12.6 (C-17), 22.0 (C-18), 60.7 (1-OCH3), 61.1 (2-OCH3), 56.0 (3-OCH3), 61.1 (13-OCH3), 60.2 (14-OCH3)。以上數(shù)據(jù)與文獻(xiàn)報(bào)道對比基本一致[23]，鑒定化合物11為(＋)-gomisin K2。

化合物12：白色晶體（甲醇）；[α]20 D?5.9°(0.051，MeOH)；C22H26O6；ESI-MS/: 387.26 [M＋H]+。1H-NMR (400 MHz, CDCl3): 6.51 (1H, s, H-4), 2.51 (2H, m, H-6), 1.84 (1H, overlapped, H-7), 1.84 (1H, overlapped, H-8), 2.16 (2H, m, H-9), 6.37 (1H, s, H-11), 1.00 (3H, d,= 7.2 Hz, H-17), 0.73 (3H, d,= 7.2 Hz, H-18), 3.87 (3H, s, 1-OCH3), 5.95 (2H, d,= 1.6 Hz, 2, 3-OCH2O), 3.90 (3H, s, 12-OCH3), 3.90 (3H, s, 13-OCH3), 5.72 (1H, s, 14-OH)；13C-NMR (100 MHz, CDCl3): 141.3 (C-1), 135.1 (C-2), 148.0 (C-3), 106.6 (C-4), 133.2 (C-5), 39.1 (C-6), 34.0 (C-7), 40.9 (C-8), 35.5 (C-9), 140.1 (C-10), 104.0 (C-11), 151.8 (C-12), 133.2 (C-13), 146.8 (C-14), 115.8 (C-15), 121.4 (C-16), 22.1 (C-17), 12.4 (C-18), 59.9 (1-OCH3), 101.0 (2, 3-OCH2O), 55.8 (12-OCH3), 61.2 (13-OCH3)。以上數(shù)據(jù)與文獻(xiàn)報(bào)道對比基本一致[24]，鑒定化合物12為(?)-gomisin L1。

化合物13：白色晶體（甲醇）；[α]20 D＋3.2°(0.062，MeOH)；C22H26O6；ESI-MS/: 387.26 [M＋H]+。1H-NMR (400 MHz, CDCl3): 6.51 (1H, s, H-4), 2.14 (2H, m, H-6), 1.84 (1H, overlapped, H-7), 1.84 (1H, overlapped, H-8), 2.55 (2H, m, H-9), 6.38 (1H, s, H-11), 0.75 (3H, d,= 7.2 Hz, H-17), 0.97 (3H, d,= 7.2 Hz, H-18), 3.87 (3H, s, 1-OCH3), 5.95 (1H, d,= 1.5 Hz, 2, 3-OCH2O), 5.93 (1H, d,= 1.5 Hz, 2, 3-OCH2O), 3.91 (3H, s, 12-OCH3), 3.89 (3H, s, 13-OCH3), 5.72 (1H, s, 14-OH)；13C-NMR (100 MHz, CDCl3): 141.1 (C-1), 134.6 (C-2), 149.0 (C-3), 103.6 (C-4), 138.5 (C-5), 35.8 (C-6), 40.9 (C-7), 33.6 (C-8), 39.3 (C-9), 134.8 (C-10), 107.3 (C-11), 150.5 (C-12), 133.6 (C-13), 147.0 (C-14), 116.7 (C-15), 120.3 (C-16), 13.0 (C-17), 21.6 (C-18), 59.9 (1-OCH3), 100.9 (2, 3-OCH2O), 55.8 (12-OCH3), 61.1 (13-OCH3)。以上數(shù)據(jù)與文獻(xiàn)報(bào)道對比基本一致[25]，鑒定化合物13為(＋)-gomisin M1。

化合物14：白色晶體（甲醇）；[α]20 D?10.3°(0.078，MeOH)；C23H28O6；ESI-MS/: 401.25 [M＋H]+。1H-NMR (400 MHz, CDCl3): 6.55 (1H, s, H-4), 2.58 (1H, dd,= 13.6, 7.2 Hz, H-6β), 2.51 (1H, dd,= 13.6, 2.4 Hz, H-6α), 1.84 (1H, overlapped, H-7), 1.84 (1H, overlapped, H-8), 2.23 (1H, dd,= 13.3, 9.4 Hz, H-9β), 2.02 (1H, dd,= 13.3, 1.5 Hz, H-9α), 6.48 (1H, s, H-11), 0.99 (3H, d,= 7.2 Hz, H-17), 0.73 (3H, d,= 7.2 Hz, H-18), 3.54 (3H, s, 1-OCH3), 3.88 (3H, s, 2-OCH3), 3.89 (3H, s, 3-OCH3), 5.94 (2H, s, 12, 13-OCH2O), 3.82 (3H, s, 14-OCH3)；13C-NMR (100 MHz, CDCl3): 151.7 (C-1), 140.1 (C-2), 151.7 (C-3), 110.7 (C-4), 134.2 (C-5), 39.2 (C-6), 33.9 (C-7), 40.8 (C-8), 35.6 (C-9), 137.9 (C-10), 103.0 (C-11), 148.8 (C-12), 134.6 (C-13), 141.2 (C-14), 121.4 (C-15), 123.4 (C-16), 21.7 (C-17), 12.9 (C-18), 60.6 (1-OCH3), 61.1 (2-OCH3), 56.0 (3-OCH3), 100.8 (12, 13-OCH2O), 59.7 (14-OCH3)。以上數(shù)據(jù)與文獻(xiàn)報(bào)道對比基本一致[26]，鑒定化合物14為gomisin N。

化合物15：白色晶體（甲醇）；[α]20 D＋2.2°(0.091，MeOH)；C28H36O8；ESI-MS/: 523.20 [M＋Na]+。1H-NMR (400 MHz, CDCl3): 6.53 (1H, s, H-4), 2.71 (1H, d,= 13.7 Hz, H-6α), 2.30 (1H, d,= 13.7 Hz, H-6β), 1.84 (1H, m, H-8), 2.67 (1H, dd,= 14.6, 1.8 Hz, H-9α), 2.38 (1H, dd,= 14.6, 7.6 Hz, H-9β), 6.66 (1H, s, H-11), 0.81 (3H, d,= 7.3 Hz, H-17), 1.21 (3H, s, H-18), 5.85 (1H, m, H-3), 1.73 (3H, overlapped, H-4), 1.72 (3H, overlapped, H-5), 3.50 (3H, s, 1-OCH3), 3.80 (3H, s, 2-OCH3), 3.83 (3H, s, 3-OCH3), 3.87 (3H, s, 12-OCH3), 3.80 (3H, s, 13-OCH3)；13C-NMR (100 MHz, CDCl3): 151.7 (C-1), 140.3 (C-2), 152.6 (C-3), 110.1 (C-4), 133.1 (C-5), 40.7 (C-6), 72.0 (C-7), 41.9 (C-8), 34.3 (C-9), 133.9 (C-10), 112.8 (C-11), 151.8 (C-12), 139.7 (C-13), 142.3 (C-14), 123.2 (C-15), 122.9 (C-16), 15.9 (C-17), 29.9 (C-18), 165.6 (C-1), 127.6 (C-2), 137.3 (C-3), 15.3 (C-4), 20.3 (C-5), 60.6 (1-OCH3), 60.9 (2-OCH3), 56.0 (3-OCH3), 56.0 (12-OCH3), 60.8 (13-OCH3)。以上數(shù)據(jù)與文獻(xiàn)報(bào)道對比基本一致[20]，鑒定化合物15為angeloylgomisin H。

化合物16：白色晶體（甲醇）；[α]20 D＋20.8°(0.051，MeOH)；C28H34O8；ESI-MS/: 521.26 [M＋Na]+。1H-NMR (400 MHz, CDCl3): 6.75 (1H, s, H-4), 5.75 (1H, d,= 8.5 Hz, H-6), 1.89 (1H, m, H-7), 1.89 (1H, m, H-8), 2.18 (2H, m, H-9), 6.40 (1H, s, H-11), 0.94 (3H, d,= 6.9 Hz, H-17), 0.83 (3H, d,= 6.9 Hz, H-18), 5.92 (1H, overlapped, H-3), 1.84 (3H, d,= 7.2 Hz, H-4), 1.57 (3H, s, H-5), 3.51 (3H, s, 1-OCH3), 3.88 (3H, s, 2-OCH3), 3.89 (3H, s, 3-OCH3), 5.92 (2H, m, 12, 13-OCH2O), 3.80 (3H, s, 14-OCH3)；13C-NMR (100 MHz, CDCl3): 151.9 (C-1), 141.7 (C-2), 151.9 (C-3), 111.2 (C-4), 132.9 (C-5), 80.9 (C-6), 37.1 (C-7), 37.3 (C-8), 37.9 (C-9), 135.2 (C-10), 102.4 (C-11), 148.8 (C-12), 134.6 (C-13), 142.0 (C-14), 121.7 (C-15), 123.7 (C-16), 18.0 (C-17), 15.7 (C-18), 167.1 (C-1), 128.1 (C-2), 138.2 (C-3), 15.7 (C-4), 20.2 (C-5), 60.5 (1-OCH3), 61.0 (2-OCH3), 56.1 (3-OCH3), 100.1 (12, 13-OCH2O), 59.4 (14-OCH3)。以上數(shù)據(jù)與文獻(xiàn)報(bào)道對比基本一致[27]，鑒定化合物16為angeloylgomisin O。

化合物17：白色晶體（甲醇）；[α]20 D?8.8°(0.068，MeOH)；C29H38O9；ESI-MS/: 553.34 [M＋Na]+。1H-NMR (400 MHz, CDCl3): 6.78 (1H, s, H-4), 5.73 (1H, s, H-6), 1.90 (1H, m, H-8), 2.33 (1H, dd,= 14.0, 9.8 Hz, H-9β), 2.18 (1H, d,= 14.0 Hz, H-9α), 6.53 (1H, s, H-11), 1.15 (3H, d,= 7.1 Hz, H-17), 1.31 (3H, s, H-18), 5.94 (1H, m, H-3), 1.80 (3H, dq,= 7.4, 1.7 Hz, H-4), 1.29 (3H, q,= 1.7 Hz, H-5), 3.50 (3H, s, 1-OCH3), 3.80 (3H, s, 2-OCH3), 3.88 (3H, s, 3-OCH3), 3.87 (3H, s, 12-OCH3), 3.86 (3H, s, 13-OCH3), 3.55 (3H, s, 14-OCH3)；13C-NMR (100 MHz, CDCl3): 152.2 (C-1), 141.0 (C-2), 152.0 (C-3), 110.1 (C-4), 130.4 (C-5), 84.3 (C-6), 72.4 (C-7), 42.2 (C-8), 36.8 (C-9), 136.6 (C-10), 107.3 (C-11), 153.2 (C-12), 140.0 (C-13), 150.9 (C-14), 122.3 (C-15), 122.5 (C-16), 19.2 (C-17), 28.2 (C-18), 166.0 (C-1), 127.0 (C-2), 142.0 (C-3), 15.7 (C-4), 19.9 (C-5), 60.6 (1-OCH3), 60.9 (2-OCH3), 55.9 (3-OCH3), 56.2 (12-OCH3), 60.8 (13-OCH3), 60.3 (14-OCH3)。以上數(shù)據(jù)與文獻(xiàn)報(bào)道對比基本一致[28-29]，鑒定化合物17為angeloylgomisin Q。

化合物18：白色晶體（甲醇）；[α]20 D?115.9°(0.063，MeOH)；C31H36O9；ESI-MS/: 575.14 [M＋Na]+。1H-NMR (400 MHz, CDCl3): 6.83 (1H, s, H-4), 5.97 (1H, s, H-6), 2.14 (1H, m, H-8), 2.48 (1H, dd,= 14.1, 10.0 Hz, H-9β), 2.28 (1H, d,= 14.1 Hz, H-9α), 6.68 (1H, s, H-11), 1.20 (3H, d,= 7.1 Hz, H-17), 1.34 (3H, s, H-18), 7.35 (5H, overlapped, H-2～6), 3.16 (3H, s, 1-OCH3), 3.57 (3H, s, 2-OCH3), 3.97 (3H, s, 3-OCH3), 3.89 (3H, s, 12-OCH3), 3.88 (3H, s, 13-OCH3), 3.38 (3H, s, 14-OCH3)；13C-NMR (100 MHz, CDCl3): 152.3 (C-1), 142.1 (C-2), 152.0 (C-3), 110.3 (C-4), 130.1 (C-5), 84.5 (C-6), 72.6 (C-7), 42.4 (C-8), 36.9 (C-9), 136.5 (C-10), 107.2 (C-11), 153.2 (C-12), 140.1 (C-13), 150.7 (C-14), 122.5 (C-15), 122.6 (C-16), 19.1 (C-17), 28.2 (C-18), 165.0 (-CO), 129.3 (C-1), 129.6 (C-2, 6), 128.2 (C-3, 5), 133.3 (C-4), 60.2 (1-OCH3), 60.9 (2-OCH3), 56.0 (3-OCH3), 56.2 (12-OCH3), 60.8 (13-OCH3), 59.9 (14-OCH3)。以上數(shù)據(jù)與文獻(xiàn)報(bào)道對比基本一致[28]，鑒定化合物18為benzoylgomisin Q。

化合物19：白色晶體（甲醇）；[α]20 D＋87.1°(0.124，MeOH)；C24H32O7；ESI-MS/: 455.36 [M＋Na]+。1H-NMR (400 MHz, CDCl3): 6.59 (1H, s, H-4), 2.63 (1H, d,= 13.4 Hz, H-6β), 2.34 (1H, d,= 13.4 Hz, H-6α), 1.97 (1H, s, 7-OH), 1.85 (1H, m, H-8), 2.57 (1H, dd,= 14.2, 1.8 Hz, H-9α), 2.35 (1H, dd,= 14.2, 7.7 Hz, H-9β), 6.51 (1H, s, H-11), 0.79 (3H, d,= 7.3 Hz, H-17), 1.23 (3H, s, H-18), 3.51 (3H, s, 1-OCH3), 3.85 (3H, s, 2-OCH3), 3.88 (3H, s, 3-OCH3), 3.86 (3H, s, 12-OCH3), 3.86 (3H, s, 13-OCH3), 3.56 (3H, s, 14-OCH3)；13C-NMR (100 MHz, CDCl3): 151.8 (C-1), 140.7 (C-2), 152.4 (C-3), 110.4 (C-4), 131.9 (C-5), 40.8 (C-6), 71.8 (C-7), 41.8 (C-8), 34.2 (C-9), 133.9 (C-10), 110.0 (C-11), 152.0 (C-12), 140.1 (C-13), 151.6 (C-14), 124.2 (C-15), 122.7 (C-16), 15.9 (C-17), 29.9 (C-18), 60.7 (1-OCH3), 61.0 (2-OCH3), 56.0 (3-OCH3), 55.9 (12-OCH3), 61.0 (13-OCH3), 60.6 (14-OCH3)。以上數(shù)據(jù)與文獻(xiàn)報(bào)道對比一致[20]，鑒定化合物19為schisandrin。

化合物20：白色針晶（甲醇）；[α]20 D＋9.3°(0.086，MeOH)；C24H32O6；ESI-MS/: 417.36 [M＋H]+。1H-NMR (400 MHz, CDCl3): 6.55 (1H, s, H-4), 2.59 (1H, dd,= 13.5 , 7.3 Hz, H-6β), 2.06 (1H, d,= 13.5 Hz, H-6α), 1.85 (1H, overlapped, H-7), 1.85 (1H, overlapped, H-8), 2.50 (1H, d,= 13.2 Hz, H-9α), 2.28 (1H, dd,= 13.2 , 9.5 Hz, H-9β), 6.54 (1H, s, H-11), 0.74 (3H, d,= 7.1 Hz, H-17), 1.00 (3H, d,= 7.1 Hz, H-18), 3.59 (3H, s, 1-OCH3), 3.87 (3H, s, 2-OCH3), 3.89 (3H, s, 3-OCH3), 3.88 (3H, s, 12-OCH3), 3.88 (3H, s, 13-OCH3), 3.59 (3H, s, 14-OCH3)；13C-NMR (100 MHz, CDCl3): 151.4 (C-1), 139.9 (C-2), 152.7 (C-3), 107.0 (C-4), 139.0 (C-5), 35.4 (C-6), 40.6 (C-7), 33.6 (C-8), 39.0 (C-9), 133.8 (C-10), 110.3 (C-11), 151.5 (C-12), 139.6 (C-13), 151.3 (C-14), 123.2 (C-15), 122.2 (C-16), 12.5 (C-17), 21.7 (C-18), 60.4 (1-OCH3), 60.8 (2-OCH3), 55.7 (3-OCH3), 55.7 (12-OCH3), 60.8 (13-OCH3), 60.4 (14-OCH3)。以上數(shù)據(jù)與文獻(xiàn)報(bào)道對比基本一致[20]，鑒定化合物20為schisandrin A。

化合物21：白色晶體（甲醇）；[α]20 D0°(0.084，MeOH)；C23H28O6；ESI-MS/: 401.30 [M＋H]+。1H-NMR (400 MHz, CDCl3): 6.54 (1H, s, H-4), 2.31 (1H, dd,= 13.2, 9.6 Hz, H-6β), 2.04 (1H, dd,= 13.2, 1.5 Hz, H-6α), 1.83 (1H, overlapped, H-7), 1.83 (1H, overlapped, H-8), 2.55 (1H, dd,= 13.5, 7.3 Hz, H-9β), 2.43 (1H, dd,= 13.5, 1.8 Hz, H-9α), 6.48 (1H, s, H-11), 0.73 (3H, dd,= 7.1 Hz, H-17), 0.99 (3H, d,= 7.1 Hz, H-18), 3.54 (3H, s, 1-OCH3), 3.88 (3H, s, 2-OCH3), 3.89 (3H, s, 3-OCH3), 5.95 (1H, d,= 1.4 Hz, 12, 13-OCH2O), 5.94 (1H, d,= 1.4 Hz, 12, 13-OCH2O), 3.83 (3H, s, 14-OCH3)；13C-NMR (100 MHz, CDCl3): 151.5 (C-1), 139.8 (C-2), 152.9 (C-3), 107.5 (C-4), 139.5 (C-5), 35.5 (C-6), 40.8 (C-7), 33.9 (C-8), 38.9 (C-9), 132.6 (C-10), 106.0 (C-11), 147.7 (C-12), 134.9 (C-13), 141.3 (C-14), 122.3 (C-15), 122.5 (C-16), 12.5 (C-17), 22.1 (C-18), 60.7 (1-OCH3), 61.1 (2-OCH3), 55.9 (3-OCH3), 100.8 (12, 13-OCH2O), 59.7 (14-OCH3)。以上數(shù)據(jù)與文獻(xiàn)報(bào)道對比基本一致[24]，鑒定化合物21為γ-schisandrin。

化合物22：白色固體（甲醇）；[α]20 D?8.7°(0.072，MeOH)；C22H24O6；ESI-MS/: 385.32 [M＋H]+。1H-NMR (400 MHz, CDCl3): 6.48 (1H, s, H-4), 2.54 (1H, dd,= 13.6, 7.2 Hz, H-6β), 2.44 (1H, dd,= 13.6, 1.9 Hz, H-6α), 1.82 (1H, m, H-7), 1.82 (1H, m, H-8), 2.24 (1H, dd,= 13.2 , 9.5 Hz, H-9β), 2.00 (1H, d,= 13.2 Hz, H-9α), 6.48 (1H, s, H-11), 0.96 (3H, d,= 7.2 Hz, H-17), 0.73 (3H, d,= 7.2 Hz, H-18), 3.82 (3H, s, 1-OCH3), 5.94 (2H, overlapped, 2, 3-OCH2O), 5.94 (2H, overlapped, 12, 13-OCH2O), 3.83 (3H, s, 14-OCH3)；13C-NMR (100 MHz, CDCl3): 141.4 (C-1), 134.8 (C-2), 147.7 (C-3), 106.2 (C-4), 132.9 (C-5), 38.9 (C-6), 33.7 (C-7), 40.8 (C-8), 35.4 (C-9), 138.3 (C-10), 103.3 (C-11), 148.8 (C-12), 134.5 (C-13), 141.1 (C-14), 121.1 (C-15), 122.3 (C-16), 21.9 (C-17), 12.7 (C-18), 59.8 (1-OCH3), 100.8 (2, 3-OCH2O), 100.8 (12, 13-OCH2O), 59.8 (14-OCH3)。以上數(shù)據(jù)與文獻(xiàn)報(bào)道對比基本一致[30]，故鑒定化合物22為schisandrin C。

化合物23：白色晶體（甲醇）；[α]20 D?150.0°(0.056，MeOH)；C28H34O9；ESI-MS/: 537.28 [M＋Na]+。1H-NMR (400 MHz, CDCl3): 6.76 (1H, s, H-4), 5.67 (1H, s, H-6), 1.95 (1H, m, H-8), 2.30 (1H, dd,= 14.0, 9.7 Hz, H-9β), 2.15 (1H, d,= 14.0 Hz, H-9α), 6.50 (1H, s, H-11), 1.13 (3H, d,= 7.0 Hz, H-17), 1.30 (3H, s, H-18), 6.01 (1H, m, H-3), 1.67 (3H, d,= 7.0 Hz, H-4), 1.56 (3H, s, H-5), 3.55 (3H, s, 1-OCH3), 3.86 (3H, s, 2-OCH3), 3.88 (3H, s, 3-OCH3), 5.92 (1H, d,= 1.4 Hz, 12, 13-OCH2O), 5.86 (1H, d,= 1.4 Hz, 12, 13-OCH2O), 3.68 (3H, s, 14-OCH3)；13C-NMR (100 MHz, CDCl3): 152.0 (C-1), 141.8 (C-2), 152.2 (C-3), 110.1 (C-4), 130.9 (C-5), 84.3 (C-6), 72.3 (C-7), 42.5 (C-8), 36.5 (C-9), 137.6 (C-10), 102.7 (C-11), 148.7 (C-12), 134.4 (C-13), 140.7 (C-14), 121.5 (C-15), 122.2 (C-16), 19.0 (C-17), 28.2 (C-18), 166.3 (C-1), 127.7 (C-2), 135.4 (C-3), 14.4 (C-4), 11.6 (C-5), 60.8 (1-OCH3), 61.0 (2-OCH3), 56.0 (3-OCH3), 100.6 (12, 13-OCH2O), 59.1 (14-OCH3)。以上數(shù)據(jù)與文獻(xiàn)報(bào)道對比基本一致[31]，鑒定化合物23為schisantherin C。

化合物24：白色晶體（甲醇）；[α]20 D?13.5°(0.052，MeOH)；C22H26O6；ESI-MS/: 387.26 [M＋H]+。1H-NMR (400 MHz, CDCl3): 6.63 (1H, s, H-4), 2.25 (1H, dd,= 13.2, 9.4 Hz, H-6β), 2.00 (1H, d,= 13.2 Hz, H-6α), 1.83 (1H, overlapped, H-7), 1.83 (1H, overlapped, H-8), 2.55 (1H, dd,= 13.6, 7.3 Hz, H-9β), 2.44 (1H, dd,= 13.6, 1.8 Hz, H-9α), 6.49 (1H, s, H-11), 0.73 (3H, d,= 7.1 Hz, H-17), 0.97 (3H, d,= 7.1 Hz, H-18), 3.50 (3H, s, 1-OCH3), 3.93 (3H, s, 2-OCH3), 5.70 (1H, s, 3-OH), 5.96 (2H, d,= 1.4 Hz, 12, 13-OCH2O), 3.78 (3H, s, 14-OCH3)；13C-NMR (100 MHz, CDCl3): 150.4 (C-1), 137.5 (C-2), 148.8 (C-3), 110.3 (C-4), 140.4 (C-5), 35.2 (C-6), 41.0 (C-7), 33.9 (C-8), 39.1 (C-9), 132.8 (C-10), 106.3 (C-11), 147.8 (C-12), 135.2 (C-13), 141.4 (C-14), 121.6 (C-15), 122.6 (C-16), 12.5 (C-17), 22.0 (C-18), 60.3 (1-OCH3), 61.2 (2-OCH3), 100.9 (12, 13-OCH2O), 59.8 (14-OCH3)。以上數(shù)據(jù)與文獻(xiàn)報(bào)道對比基本一致[32]，鑒定化合物24為neglschisandrin E。

化合物25：黃色粉末（甲醇）；[α]20 D＋117.9°(0.056，MeOH)；C24H30O6；ESI-MS/: 415.30 [M＋H]+。1H-NMR (400 MHz, CDCl3): 6.65 (1H, s, H-4), 3.00 (1H, d,= 12.3 Hz, H-6β), 2.93 (1H, d,= 12.3 Hz, H-6α), 2.70 (1H, m, H-8), 2.54 (2H, m, H-9), 6.55 (1H, s, H-11), 1.01 (3H, d,= 7.2 Hz, H-17), 4.86 (1H, d,= 2.0 Hz, H-18a), 4.72 (1H, d,= 2.0 Hz, H-18b), 3.60 (3H, s, 1-OCH3), 3.86 (3H, s, 2-OCH3), 3.90 (3H, s, 3-OCH3), 3.89 (3H, s, 12-OCH3), 3.89 (3H, s, 13-OCH3), 3.62 (3H, s, 14-OCH3)；13C-NMR (100 MHz, CDCl3): 151.4 (C-1), 140.3 (C-2), 153.1 (C-3), 107.1 (C-4), 136.6 (C-5), 37.2 (C-6), 154.0 (C-7), 38.7 (C-8), 37.9 (C-9), 133.3 (C-10), 110.5 (C-11), 152.0 (C-12), 140.5 (C-13), 151.6 (C-14), 123.8 (C-15), 122.6 (C-16), 20.7 (C-17), 111.0 (C-18), 60.7 (1-OCH3), 61.1 (2-OCH3), 56.0 (3-OCH3), 56.1 (12-OCH3), 61.1 (13-OCH3), 60.7 (14-OCH3)。以上數(shù)據(jù)與文獻(xiàn)報(bào)道對比基本一致[33]，鑒定化合物25為7(18)-dehydroschisandro A。

化合物26：棕色油狀物（甲醇）；[α]20 D+11.5°(0.096，MeOH)；C20H24O4；ESI-MS/: 329.20 [M＋H]+。1H-NMR (400 MHz, CDCl3): 6.62 (1H, d,= 1.9 Hz, H-2), 6.83 (1H, d,= 7.9 Hz, H-5), 6.63 (1H, dd,= 7.9, 1.9 Hz, H-6), 2.74 (1H, dd,= 13.6, 6.0 Hz, H-7a), 2.24 (1H, dd,= 13.6, 9.1 Hz, H-7b), 1.73 (1H, overlapped, H-8), 0.84 (3H, d,= 6.8 Hz, H-9), 3.87 (3H, s, 3-OCH3), 5.45 (1H, s, 4-OH), 6.65 (1H, d,= 1.7 Hz, H-2), 6.73 (1H, d,= 7.9 Hz, H-5), 6.60 (1H, dd,= 7.9, 1.7 Hz, H-6), 2.70 (1H, dd,= 13.2, 6.4 Hz, H-7a), 2.29 (1H, dd,= 13.2, 9.1 Hz, H-7b), 1.73 (1H, overlapped, H-8), 0.82 (3H, d,= 6.8 Hz, H-9), 5.92 (2H, s, 3, 4-OCH2O)；13C-NMR (100 MHz, CDCl3): 133.9 (C-1), 111.5 (C-2), 146.4 (C-3), 143.7 (C-4), 114.1 (C-5), 121.8 (C-6), 39.0 (C-7), 39.4 (C-8), 16.4 (C-9), 56.0 (3-OCH3), 135.8(C-1), 109.5 (C-2), 147.6 (C-3), 145.6 (C-4), 108.1 (C-5), 121.8 (C-6), 39.2 (C-7), 39.5 (C-8), 16.3 (C-9), 100.9 (3, 4-OCH2O)。以上數(shù)據(jù)與文獻(xiàn)報(bào)道對比基本一致[34]，鑒定化合物26為anwulignan。

4 討論

近年來課題組對蘇黃止咳膠囊改善氣道重塑[35]、痰阻塞[36]、抑制炎癥反應(yīng)[37]、以及治療CVA[38-39]和PIC[40]等方面的藥理機(jī)制進(jìn)行了闡釋，其功效成分及機(jī)制正在研究中。本研究作為該項(xiàng)目的一部分，進(jìn)一步豐富了其臣藥五味子化學(xué)成分的多樣性，為后續(xù)開展蘇黃止咳膠囊的藥效物質(zhì)基礎(chǔ)研究及其質(zhì)量控制奠定了基礎(chǔ)。

利益沖突 所有作者均聲明不存在利益沖突

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A new dibenzocyclooctadiene lignan from

DI Tong-lian1, LIU Xiao-qing2, WU Nan1, CHEN Xiao-yuan1, FAN Jun-ting3, TAN Ning-hua1

1. School of Traditional Chinese Pharmacy, China Pharmaceutical University, Nanjing 211198, China 2. Beijing Haiyan Pharmaceutical Co., Ltd., Yangtze River Pharmaceutical Group, Beijing 102206, China 3. School of Pharmacy, Nanjing Medical University, Nanjing 211116, China

To study the lignans in.The petroleum ether extract mainly contained lignans ofwas isolated and purified by silica gel column chromatography, medium pressure reversed phase column chromatography, semi-prepared and prepared liquid chromatography. The structures of compounds were identified by spectral data.Twenty-six compounds were obtained, in which 24 were dibenzocyclooctadiene lignans. They were identified as schiviridin B (1), sphaerandrin A (2), sieverlignan E (3), arisanschinin G (4), widdaranal F (5), gomisin A (6), gomisin B (7), gomisin D (8), gomisin G (9), (?)-gomisin K1(10), (＋)-gomisin K2(11), (?)-gomisin L1(12), (＋)-gomisin M1(13), gomisin N (14), angeloylgomisin H (15), angeloylgomisin O (16), angeloylgomisin Q (17), benzoylgomisin Q (18), schisandrin (19), schisandrin A (20), γ-schisandrin (21), schisandrin C (22), schisantherin C (23), neglschisandrin E (24), 7(18)-dehydroschisandro A (25), and anwulignan (26).Compound 1 is new and compounds 2—5 are isolated from this plant for the first time.

(Turcz.) Baill.; schiviridin B; dibenzocyclooctadiene lignans; sphaerandrin A; sieverlignan E; arisanschinin G; widdaranal F; schisandrin

R284.1

A

0253 - 2670(2023)12 - 3759 - 12

10.7501/j.issn.0253-2670.2023.12.002

2023-04-02

國家自然科學(xué)基金項(xiàng)目（32070356）

邸同蓮，女，碩士研究生，研究方向?yàn)橹兴幬镔|(zhì)基礎(chǔ)和質(zhì)量控制研究。E-mail: 1282046265@qq.com

通信作者：譚寧華，教授，博士生導(dǎo)師，主要從事含環(huán)肽中藥和止咳中藥系統(tǒng)研究。E-mail: nhtan@cpu.edu.cn

范君婷，副教授，主要從事天然藥物化學(xué)與作用機(jī)制研究。E-mail: juntingfan@njmu.edu.cn

[責(zé)任編輯 王文倩]