陳效忠，張艷

(黑龍江中醫(yī)藥大學佳木斯學院，黑龍江 佳木斯 154007)

水飛薊中黃酮和木脂素類化學成分研究

陳效忠，張艷*

(黑龍江中醫(yī)藥大學佳木斯學院，黑龍江 佳木斯 154007)

目的：闡述水飛薊種子的化學成分。方法：95%乙醇提取藥材，綜合運用多種色譜技術(shù)(如硅膠柱色譜、葡聚糖凝膠柱色譜、高效液相制備色譜等)分離得到5個化合物，經(jīng)NMR鑒定化合物結(jié)構(gòu)。結(jié)果：從水飛薊種子中分離得到1個黃酮和4個木脂素類化合物。結(jié)論：分離得到的5個化合物為(1R,5R,6R)-6-{4-O-[2-(1-(4-hydroxyphenyl-3-methoxy))glycerol]-3,5-dimethoxyphenyl}-3,7-dioxabicyclo[3.3.0]octan-2-one (1), acutissimalignan B (2), (+)-(7S,8S)-1′,4-dihydroxy-3,3′,5′-trimethoxy-7′,8′,9′-trinor-8,4′-oxyneoligna-7,9-diol (3), (+)-(7S,8S)-4-hydroxy-3,3′,5′-trimethoxy- 8′,9′-dinor-8,4′-oxyneoligna-7,9-diol-7′-oic acid (4), (7′S,8′S)-Bilagrewin (5)，以上化合物均為從該植物中首次發(fā)現(xiàn)。

水飛薊；黃酮；木脂素

水飛薊(SilybummarianumL.Gaertn)又稱水飛雉、乳雉子，是菊科水飛薊屬植物[1]。水飛薊有效成分在果實內(nèi)，水飛薊的干燥果實經(jīng)提取、精制而得到的有效的黃酮類成分稱為水飛薊素[2]。國內(nèi)外學者還對水飛薊植物的其他化學成分進行了研究，發(fā)現(xiàn)了一些非黃酮類成分，如糖、氨基酸、木脂素、三萜、甾醇、有機酸等化學成分[3]。為了進一步研究水飛薊的化學成分, 本文采用多種色譜法從95%乙醇提取物中分離并鑒定了1個黃酮和4個木脂素類化合物。

1 儀器與材料

NMR-600型核磁共振波譜儀;島津公司制備型HPLC;C18反相硅膠柱色譜。

藥材經(jīng)黑龍江中醫(yī)藥大學佳木斯學院陳效忠副教授鑒定為水飛薊(SilybummarianumL.Gaertn)，標本保存于黑龍江中醫(yī)藥大學佳木斯學院標本館。

2 提取與分離

水飛薊種子10 kg壓榨法去油，95%乙醇提取得到浸膏0.8 kg，浸膏經(jīng)硅膠柱色譜，以二氯甲烷-甲醇洗脫，得到Fr.A-Fr.F六個部位，F(xiàn)r.E經(jīng)葡聚糖凝膠Sephadex LH-20柱色譜，甲醇-水(10:1～100:0)洗脫, 得到S1～S10組分，S6用制備型HPLC分離純化得到化合物1 (7 mg), 2 (6 mg)和3 (5 mg), S10用制備型HPLC分離純化得到化合物4(6 mg)和5(8mg)。

3 結(jié)構(gòu)鑒定

化合物1，白色粉末。1H-NMR (CDCl3, 500 MHz): δ 3.50 (1H, m, H-1)，4.40 (1H, d, J=10.0 Hz, H-4a), 4.25 (1H, dd, J=10.0, 3.5 Hz, H-4b), 3.16 (1H, dd, J=10.0, 3.5 Hz, H-5), 4.68 (1H, d, J=7.0 Hz, H-6), 4.54 (1H, dd, J=10.0, 7.0 Hz, H-8a), 4.40 (1H, dd, J=10.0, 1.0 Hz, H-8b), 6.66 (2H, s，H-2′和H-6′)，6.98 (2H, s，H-2″)，6.88 (1H, d，J=8.5, H-5″)，6.77 (1H, d，J=8.5, H-6″)，5.00 (1H, d，J=4.0, H-7″)，4.18 (1H, dd，J=6.5, 3.9, H-8″)，3.90 (1H, m, H-9″a)，3.50 (1H, m, H-9″b)，3.90 (9H, s, OMe);13C-NMR (CDCl3, 125 MHz): δ46.5 (C-1), 177.9 (C-2), 70.5 (C-3), 36.5 (C-4), 49.0 (C-5), 86.2 (C-6), 70.1 (C-8), 135.0 (C-1′), 103.0 (C-2′和C-6′), 153.7 (C-3′和C-5′), 133.7 (C-4′), 131.0 (C-1″), 108.0 (C-2″), 145.0 (C-3″), 146.8 (C-4″), 114.3 (C-5″), 118.6 (C-6″), 72.5 (C-7″), 87.5 (C-8″), 60.2 (C-9″), 56.0 (C-3′和C-5′-OMe), 56.2 (C-3″-OMe)。以上數(shù)據(jù)與文獻[4]報道一致，故鑒定化合物為(1R,5R,6R)-6-{4-O-[2-(1-(4-hydroxyphenyl-3-methoxy))glycerol]-3,5-dimethoxyphenyl}-3,7-dioxabicyclo[3.3.0]octan-2-one (圖1)。

化合物2,白色粉末。1H-NMR (CDCl3, 500 MHz): δ7.56 (1H, d, J=1.8 Hz, H-6), 7.20 (1H, dd, J=8.3, 1.9 Hz, H-6′), 7.05 (1H, d, J=1.9 Hz, H-2′), 7.00 (1H, d, J=8.3 Hz, H-5′), 6.85 (1H, d, J=8.0 Hz, H-5″), 6.75 (1H, dd, J=8.0, 1.9 Hz, H-6″), 6.65 (1H, d, J =1.9 Hz, H-2″), 4.29 (2H, overlap, H-4a, H-4b), 3.93 (3H, s, OMe-3′), 3.85 (3H, s, OMe-3″), 3.82 (1H,m, H-3), 3.08 (1H, dd, J=14.5, 4.3 Hz, H-5a), 2.65 (1H, dd, 14.5, 10.0 Hz, H-5b);13C-NMR (CDCl3, 125 MHz): δ172.3 (C-1), 147.6 (C-4′), 146.9 (C-3′), 146.3 (C-3″), 144.5 (C-4″), 137.6 (C-6), 129.6 (C-1″), 126.5 (C-1′), 125.7 (C-2), 124.0 (C-6′), 121.4 (C-6″), 115.4 (C-5′), 114.3 (C-5″), 112.6 (C-2′), 111.9 (C-2″), 69.3 (C-4), 56.0 (OMe-3′), 55.9 (OMe-3″), 39.7 (C-3), 37.5 (C-5)。以上數(shù)據(jù)與文獻[5]報道一致，故鑒定化合物為acutissimalignan B (圖1)。

圖1 化合物的結(jié)構(gòu)

化合物3，白色粉末。1H-NMR (CDCl3, 500 MHz): δ 7.10 (1H, d, J=2.0, H-2)，6.78 (1H, d, J=8.0, H-5)，6.80 (1H, dd, J=8.0, 2.0, H-6)，5.00 (1H, d, J=7.0, H-7)，3.74 (1H, m, H-8)，3.59 (1H, dd, J=12.0, 3.0, H-9a)，3.22 (1H, d, J=12.0, 3.0, H-9b)，6.20 (1H, brs, H-2′)，6.20 (1H, brs, H-6′), 3.81 (6H, s, OMe), 3.82 (6H, s, OMe);13C-NMR (CDCl3, 125 MHz)：δ 133.9 (C-1), 111.8 (C-2), 147.9 (C-3), 148.3 (C-4), 115.0 (C-5), 120.9 (C-6), 74.0 (C-7), 90.8 (C-8), 61.0 (C-9), 156.0 (C-1′), 94.0 (C-2′), 154.8 (C-3′), 130.0 (C-4′), 154.3 (C-5′), 94.0 (C-6′), 56.0 (C-3和C-5-OMe), 56.4 (C-3′和C-5′-OMe。以上數(shù)據(jù)與文獻[6]報道一致，故鑒定化合物為(+)-(7S,8S)-1′,4-dihydroxy-3,3′,5′-trimethoxy-7′,8′,9′-trinor-8,4′-oxyneoligna-7,9-diol (圖1)。

化合物4，白色粉末。1H-NMR (CDCl3, 500 MHz): δ 7.00 (1H, d, J=2.0, H-2)，6.70 (1H, d, J=8.0, H-5)，6.85 (1H, dd, J=8.0, 2.0, H-6)， 4.95 (1H, d, J=7.0, H-7)，4.06 (1H, m, H-8)，3.78 (1H, dd, J=12.0, 3.0, H-9a)，3.25 (1H, d, J=12.0, 3.0, H-9b)，7.20 (1H, brs, H-2′)，7.20 (1H, brs, H-6′), 3.87 (6H, s, OMe), 3.85 (6H, s, OMe);13C-NMR (CDCl3, 125 MHz)：δ 133.5 (C-1), 111.5 (C-2), 148.9 (C-3), 148.3 (C-4), 115.0 (C-5), 120.9 (C-6), 74.0 (C-7), 90.8 (C-8), 61.0 (C-9), 123.0 (C-1′), 107.0 (C-2′), 153.8 (C-3′), 138.0 (C-4′), 152.3 (C-5′), 108.0 (C-6′), 156.5 (C-7′), 56.0 (C-3和C-5-OMe), 56.4 (C-3′和C-5′-OMe)。以上數(shù)據(jù)與文獻[6]報道一致，故鑒定化合物為(+)-(7S,8S)-4-hydroxy-3,3′,5′-trimethoxy- 8′,9′-dinor-8,4′-oxyneoligna-7,9-diol-7′-oic acid (圖1)。

化合物5，黃色粉末, HCl-Mg 反應(yīng)陽性, FeCl3反應(yīng)陽性。1H-NMR (CDCl3, 500 MHz): 6.67 (2H, s, H-2′ 和 H-6′), 3.96 (6H, s, OMe-3′ 和 OMe-5′), 4.95 (1H, d, J=8.0 Hz, H-7′), 4.08 (1H, dt, J=8.0, 3.0 Hz, H-8′), 3.60 (1H, m, H-9′a), 3.92 (1H, m, H-9′b), 6.92 (1H, d, J=2.0 Hz, H-2), 3.93 (3H, s, OMe-5), 6.75 (1H, d, J=2.0 Hz, H-6), 7.35 (1H, d, J=16.0 Hz, H-7), 6.62 (1H, dd, J=16.0, 7.5 Hz, H-8), 9.68 (1H, d, J=7.6 Hz, CHO);13C-NMR (CDCl3, 125 MHz):δ126.9 (C-1′), 104.8 (C-2′), 147.8 (C-3′), 135.6 (C-4′), 147.3 (C-5′), 104.5 (C-6′), 76.8 (C-7′), 79.3 (C-8′), 61.5 (C-9′), 127.0 (C-1), 111.8 (C-2), 144.5 (C-3), 136.5 (C-4), 149.6 (C-5), 104.5 (C-6), 152.3 (C-7), 127.8 (C-8), 193.6 (C-9) 56.7 (OMe-3′), 56.6 (OMe-5), 56.7 (OMe-5′)。以上數(shù)據(jù)與文獻[7]報道一致，故鑒定化合物為(7′S,8′S)-Bilagrewin (圖1)。

[1] 陳毓荃,王春梅.水飛薊綜合利用基礎(chǔ)研究[J].西北農(nóng)業(yè)學報,1997,6(4):91-93.

[2] 柯銘清.中草藥有效成分理化與藥理特性[M].長沙:湖南科學技術(shù)出版社,1982:266.

[3] 石玉生，吳鵬程，張艷.水飛薊賓對UVA致人表皮角質(zhì)形成細胞光老化保護作用的研究[J].中醫(yī)藥信息,2014,31(3):20-21.

[4] Xian-Wen Yang, Pei-Ji Zhao, Yan-Lin Ma,et al.Mixed Lignan-Neolignans from Tarenna attenuate[J].J. Nat. Prod,2007,70(4):521-525.

[5] Patoomratana Tuchinda, Jittra Kornsakulkarn, Manat Pohmakotr, et al.Dichapetalin-Type Triterpenoids and Lignans from the Aerial Parts of Phyllanthus acutissima[J].J. Nat. Prod,2008,71,655-663.

[6] Liang Xiong, Cheng-geng Zhu, Yan-ru Li, et al. Lignans and Neolignans from Sinocalamus affinis and Their Absolute Configurations[J].J. Nat. Prod,2011,74,1188-1200.

[7] Jih-Jung Chen, Tzu-Ying Wang, Tsong-Long Hwang. Neolignans, a Coumarinolignan, Lignan Derivatives, and a Chromene: Anti-inflammatory Constituents fromZanthoxylum a Wicennae[J].J. Nat. Prod, 2008,71(2):212-217.

Flavonoid and Lignins fromSilybummarianumL.Gaertn

CHEN Xiao-zhong, ZHANG Yan

(JiamusiCollegeofHeilongjiangUniversityofChineseMedicine,Jiamusi154007,China)

Objective:To investigate the chemical constituents from the seeds ofSilybummarianumL.Gaertn. Methods:The seeds ofSilybummarianumL.Gaertn were extracted with 95% ethanol. Five compounds were extracted from the plant by various isolation methods (including silica gel column chromatography, sephadex-LH20, and HPLC), and compound structures were determined by NMR spectra. Results:Five compounds were separated fromSilybummarianumL.Gaertn for the first time, including one flavonoid and four lignins, which were (1R,5R,6R)-6-{4-O-[2-(1-(4-hydroxyphenyl-3-methoxy))glycerol]-3,5-dimethoxyphenyl}-3,7-dioxabicyclo[3.3.0]octan-2-one(1), acutissimalignan B(2), (+)-(7S,8S)-1′,4-dihydroxy-3,3′,5′-trimethoxy-7′,8′,9′-trinor-8,4′-oxyneoligna-7,9-diol(3), (+)-(7S,8S)-4-hydroxy-3,3′,5′-trimethoxy- 8′,9′-dinor-8,4′-oxyneoligna-7,9-diol-7′-oic acid(4), and (7′S,8′S)-Bilagrewin(5).

SilybummarianumL.Gaertn; Flavonoid; Lignins

2016-08-26

2016-09-15

黑龍江中醫(yī)藥大學佳木斯學院自主課題

陳效忠(1962-)，男，副教授，主要從事常用中草藥藥效物質(zhì)基礎(chǔ)研究。

*通訊作者：張艷(1982-)，女，碩士，講師，主要從事常用中草藥微量活性成分研究。

R284.1

A

1002-2392(2017)04-0064-03