硬毛常山中的1个新羽扇豆烷型三萜
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摘要
利用硅胶柱色谱、制备液相色谱、凝胶色谱(Sephadex LH-20)、重结晶等方法从硬毛常山枝叶的甲醇提取物中分离得到9个化合物,采用NMR,MS等方法进行化合物的结构鉴定,分别鉴定为3β,21α-二乙酰基-9,11-烯-7β-羽扇豆醇[3β,21α-O-diacetyl-lup-9(11)-en-7β-ol](1)、Z-对羟基肉桂酸甲酯(2)、顺式香豆酸乙酯(3)、E-对羟基肉桂酸甲酯(4)、反式香豆酸乙酯(5)、4-喹唑酮(6)、7-羟基香豆素(7)、绣球酚(8)、丁香醇C(9)。化合物1为未见报道的新羽扇豆烷型三萜类化合物,化合物1～5,8～9为首次从硬毛常山中分离得到。Nrf2-ARE信号通路活性筛选结果显示,化合物2～5对Nrf2-ARE信号通路具有激活活性。
The chemical constituents from methanol extract of Dichroa hirsuta were separated by silica gel and Sephadex LH-20 column chromatography,high pressure preparative liquid chromatography( HPLC) and recrystallization. Their structures were elucidated by NMR and MS. Nine compounds were obtained and their structures were identified as 3β,21α-O-diacetyl-lup-9( 11)-en-7β-ol( 1),( Z)-methyl p-hydroxycinnamate( 2),cis-p-coumaric acid ethyl ester( 3),( E)-methyl p-hydroxycinnamate( 4),trans-p-coumaric acid ethyl ester( 5),4( 3 H)-quinazolinone( 6),7-hydroxycoumarin( 7),hydrangenol( 8) and thunberginol C( 9). Compound 1 is a new lupane-type triterpenoid,and compounds 1-5,8-9 were firstly isolated from this plant. Dual reporter assay results showed that compounds 2-5 could activate the Nrf2-ARE signaling pathway.
The chemical constituents from methanol extract of Dichroa hirsuta were separated by silica gel and Sephadex LH-20 column chromatography,high pressure preparative liquid chromatography( HPLC) and recrystallization. Their structures were elucidated by NMR and MS. Nine compounds were obtained and their structures were identified as 3β,21α-O-diacetyl-lup-9( 11)-en-7β-ol( 1),( Z)-methyl p-hydroxycinnamate( 2),cis-p-coumaric acid ethyl ester( 3),( E)-methyl p-hydroxycinnamate( 4),trans-p-coumaric acid ethyl ester( 5),4( 3 H)-quinazolinone( 6),7-hydroxycoumarin( 7),hydrangenol( 8) and thunberginol C( 9). Compound 1 is a new lupane-type triterpenoid,and compounds 1-5,8-9 were firstly isolated from this plant. Dual reporter assay results showed that compounds 2-5 could activate the Nrf2-ARE signaling pathway.
引文
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[2]张雅,李春,雷国莲.常山化学成分研究[J].中国实验方剂学杂志,2010,16(5):40.
[3]李燕,刘明川,金林红,等.常山化学成分及生物活性研究进展[J].广州化工,2010,39(9):7.
[4]Jang C S,Fu F Y,Wang C Y,et al. An alkaloid with high activity from Dichroa febrifuga[J]. Science,1946,103:59.
[5]Chou T Q,Fu F Y,Kao Y S. Antimalarial constituents of Chinese drug,Chang Shan,Dichvoa febvifuga Lour[J]. J Am Chem Soc,1948,70(5):1765.
[6]John A,Brockman J R,Mead J F,et al. Alkaloids of Dichroa febrifuga isolation and degradative studies[J]. J Am Chem Soc,1949,71(3):1048.
[7]Murata K,Takano F,Fushiya S,et al. Potentiation by febrifugine of host defense in mice against Plasmodium berghei NK65[J]. Biochem Pharmacol,1999,58:1593.
[8]张覃沐,吕富华.几种抗疟药(常山碱乙,氯胍和环氯胍)及黄芩素等的抗阿米巴作用[J].武汉医学院学报,1985(l):11.
[9]程友斌,杨成俊,胡玉涛,等.海州常山的化学成分与药理作用研究[J].中国实验方剂学杂志,2012,18(20):325.
[10]Vermel E M,Kruglyak-Syrkina S A. Anticancer activity of the alkaloid febrifugine in animal experiments[J]. Voprosy Onkologii,1960,6(7):56.
[11]Choi B T,Lee J H,Shin K W,et al. Anti-inflammatory effects of aqueous extract from Dichroa febrifuga root in rat liver[J].Acta Pharmacol Sin,2003,24(2):127.
[12]刘向前,邹亲朋,陆昌洙.天然产物中羽扇豆烷型三萜波谱特征[J].湖南中医药大学学报,2013,33(9):10.
[13]崔俣,马海英,孔力.Nrf2/ARE通路与机体抗氧化机制的研究进展[J].吉林大学学报,2011,37(1):187.
[14]Giovanni E M,Watson A,Gao L,et al. Nrf2/ARE regulated antioxidant gene expression in endothelial and smooth muscle cell in oxidative stress:implications for atherosclerosis and preeclampsia[J]. Acta Physiol Sin,2007,59(2):117.
[15]董渠龙,王华,侯海燕,等.Nrf2-ARE信号通路功能的研究进展[J].国际妇产科学杂志,2015,42(4):425.
[16]谭亲友,张靖.Nrf2-ARE信号通路功能与临床疾病及相关药物的研究新进[J].中国医院药学杂志,2016,36(15):1331.
[17]Siddiqui S,Siddiqui B S,Naeed A. Pentacyclic tritrpenoids from the leaves of Plumeria obtuse[J]. Phytochemistry,1989,28(11):3143.
[18]Wang G,Zhu L J,Zhao Y Q,et al. A natural product from Cannabis sativa subsp. sativa inhibits homeodomain-interacting protein kinase 2(HIPK2),attenuating MPP+-induced apoptosis in human neuroblastoma SH-SY5Y cells[J]. Bioorg Chem,2017,72:64.
[19]Michael D,Andreas D,Thomas H. Sensomics analysis of key bitter compounds in the hard resin of hops(Humulus lupulus L.)and their contribution to the bitter profile of pilsner-type beer[J]. J Agric Food Chem,2015,63(13):3402.
[20]Li J,Shen Q,Bao C H,et al. A new dicoumarinyl ether from the roots of Stellera chamaejasme L[J]. Molecules,2014,19(2):1603.
[21]Zhang W,Shen Y,Liu R,et al. Coumarins from the bark of Daphne marginata[J]. Chem Nat Compd,2007,43(3):317.
[22]Ebihara T,Kawai T,Kuroyanagi M,et al. Studies on the anticomplementary activity of Jozann. anticomplementary activity of steroid derivatives[J]. Yakugaku Zasshi,1991,111(6):299.
[23]Yoshikawa M,Matsuda H,Shimoda H,et al. Development of bioactive functions in Hydrangeae Dulcis Folium. V. on the antiallergic and antimicrobiapl principles of Hydrangeae Dulcis Folium.(2).thunberginols C,D,and E,thunberginol G 3'-O-glucoside,(-)-hydrangenol 6'-O-glucoside,and(+)-hydran[J].Chem Pharm Bull,1996,44(8):1440.