广西山豆根化学成分的研究
云南大学学报(自然科学版),2011,33(1):72 76
Journal of Yunnan University CN 53-1045/NISSN 0258-7971http ://www.yndxxb.ynu.edu.cn
广西山豆根化学成分的研究
1,2隆金桥,林1,311华,羊晓东,赵静峰,李*良1
(1.云南大学教育部自然资源药物化学重点实验室,云南昆明650091;
2.百色学院化学与生命科学系,广西百色533000;3.安顺学院化学与生物农学系,贵州安顺561000)
摘要:对产于广西靖西的山豆根化学成分进行研究,采用硅胶柱层析、重结晶等分离手段从中分离纯化得
通过现代波谱技术和理化常数测定鉴定了它们的结构,分别为:高丽槐素(maackiain 1),红车到10个化合物,
7,4' -二羟基黄酮(7,4' -dihydroxy -flavone 4),轴草苷(trifolirhizin 2),苷草素(liquiritigenin 3),豆甾醇
(stigmasterol 5),羽扇豆醇(lupeol 6),十五烷酸(pentadecanoic acid 7),苯甲酸(benzoic acid 8),β-谷甾醇(β
-sitosterol 9),4,6,7,8为首次从该植物中分离得到.胡萝卜苷(daucosterol 10),其中化合物3,
关键词:山豆根;豆科;化学成分;黄酮
中图分类号:R 284.1;Q 949.751.9;Q 946文献标识码:A 文章编号:0258-7971(2011)01-0072-05
山豆根为豆科(Leguminosae )槐属(Sophora L.)植物越南槐(Sophora tonkinensis Gapnep.)的干燥根及根茎,主产于广西、贵州、云南、广东、江西等地,其味苦、性寒、有毒,具有清热解毒、消肿利咽的功效,主治
[1]火毒蕴结、咽喉肿痛、齿龈肿痛等症.前人对从上海、湖南等地的山豆根化学成分进行了研究,迄今为
[2-6].为了深入了解山豆根已报道山豆根的化学成分主要有生物碱、多糖、酚性成分、黄酮类等化合物止,
我们对尚未见报道的产于广西靖西的山豆根化学的药用活性成分以及地域差异对植物活性成分的影响,
成分进行了深入研究,从中分离得到10个化合物,并用波谱学方法确定了它们的化学结构,分别为:高丽
7,4' -二羟基黄酮(7,4' -di-红车轴草苷(trifolirhizin 2),苷草素(liquiritigenin 3),槐素(maackiain 1),
hydroxy -flavone 4),豆甾醇(stigmasterol 5),羽扇豆醇(lupeol 6),十五烷酸(pentadecanoic acid 7),苯甲
4,6,7,8为首次β-谷甾醇(β-sitosterol 9),胡萝卜苷(daucosterol 10),其中化合物3,酸(benzoic acid 8),
从该植物中分离得到.
1
1.1实验部分仪器及材料实验所用硅胶是青岛海洋化工厂生产的0.15 0.074nm 或0.074 0.48nm 硅胶.TLC 亦采用该厂生产的GF 254高效硅胶板,其他试剂均为化学纯或分析纯.熔点用XT -4显微熔点测定仪测定(温度计未校正);紫外和红外分别用岛津UV -210A 和IR -450光谱仪测定;质谱用VG Auto Spec -3000质谱仪及LCMS -QP1000色质联用仪测定;NMR 用Bruker AV -300Hz 核磁共振仪测定(TMS 作内标).
1.2
1.3山豆根(Sophora tonkinensis Gapnep.)于2009年8月采于广西省靖西县.样品经百色学院苏仕林副教授鉴定,现存放于云南大学教育部植物资源药物化学重点实验室.植物样品提取与分离12.5kg 山豆根粗粉用95%的工业乙醇冷浸提取(4ˑ 30L ),合并提取液后,减压蒸馏回收提取液,得粗提物.将粗提物悬浮于水中,分别以石油醚、乙酸乙酯、正丁醇萃取,得石油醚部分76g ,*收稿日期:2010-07-27
基金项目:国家自然科学基金资助项目(21062025);云南省教育厅科学研究基金项目(06Z018A ).
作者简介:隆金桥(1970-),男,广西人,副教授,主要从事天然药物化学研究.
E -mail :liliang5758@hotmail.com.通讯作者:李良(1965-),男,云南人,教授,主要从事天然药物化学研究,
第1期隆金桥等:广西山豆根化学成分的研究73
6乙酸乙酯部分158g ,正丁醇部分33g.其中石油醚部分反复通过硅胶柱层析,分别得到化合物5(1.1g )、
(185mg )和9(280mg );乙酸乙酯部分反复通过硅胶柱层析,2(31mg )、3分别得到化合物1(103mg )、
(1.27g )、4(15mg )、7(231mg )、8(200mg )和10(150mg ),经各种波谱数据以及与标准品对照的方法鉴定其结构
.
图1山豆根中的化合物1 6的结构
Fig.1The structures of compounds 1—6from Sophora tonkinensis
2
2.1结构鉴定化合物120m.p.177 179ħ .[CH 3OH ).白色针晶(CHCl 3),分子式:C 16H 12O 5,α]D -265(0.254,
IR (KBr )νmax :3433,2919,1623,1508,1476,1341,1182,1148,1034cm -1.ESI -MS (m /z):284[M ]+.1H NMR (300MHz ,CDCl 3)δ:7.36(1H ,d ,J =8.0Hz ,H -5),6.72(1H ,s ,H -2' ),6.54(1H ,dd ,J =8.0,2.0Hz ,H -6),6.44(1H ,s ,H -5' ),6.41(1H ,d ,J =2.4Hz ,H -8),5.91(2H ,dd ,J =11.6,1.6Hz ,-O -CH 2-O -),5.47(1H ,d ,J =7.2Hz ,H -4а),4.22(1H ,dd ,J =10.8,4.8Hz ,H -3а),3.64(1H ,t ,J =10.8Hz ,H -2b ),3.48(1H ,m ,H -2a ).13C NMR (75MHz ,CDCl 3)δ:66.5(C -2),40.1(C -3),78.5(C -4),132.1(C -5),109.8(C -6),157.0(C -7),103.7(C -8),156.7(C -9),112.7(C -10),117.9(C -1' ),104.7(C -2' ),141.7(C -3' ),148.1(C -4' ),93.8(C -5' ),156.6(C -6' ),101.3(-O -CH 2-O -).以上波谱数据与高丽槐素[7]一致,故确定该化合物为高丽槐素(maackiain ).
2.2化合物220m.p.144 145ħ .[CH 3OH ).白色针晶(CH 3OH ),分子式:C 22H 22O 10,α]D -153(0.107,IR (KBr )νmax :3400,1621,1504,1475,1459,1385,1165,1074cm -1.ESI -MS (m /z):446[M ]+.1H NMR (300MHz ,DMSO -d 6)δ:7.38(1H ,d ,J =8.0Hz ,H -5),6.98(1H ,s ,H -2' ),6.74(1H ,dd ,J =8.8,2.4Hz ,H -6),6.52(1H ,s ,H -5' ),6.55(1H ,d ,J =2.4Hz ,H -8),5.92(2H ,d ,J =14.8Hz ,-O -CH -O -),5.58(1H ,d ,J =7.6Hz ,H -1ᵡ ),5.57(1H ,d ,J =7.2Hz ,H -4),4.27(1H ,dd ,J =10.4,4.0Hz ,H -
3),3.62(1H ,m ,H -2b ),3.45(1H ,m ,H -2a ).13C NMR (75MHz ,DMSO -d 6)δ:65.8(C -2),48.5(C -
3),77.5(C -4),131.8(C -5),110.3(C -6),158.4(C -7),104.1(C -8),156.1(C -9),114.1(C -
10),118.1(C -1' ),105.2(C -2' ),141.0(C -3' ),147.4(C -4' ),93.1(C -5' ),156.1(C -6' ),100.8(-O -CH 2-O -),100.3(C -1ᵡ ),73.1(C -2ᵡ ),76.5(C -3ᵡ ),69.6(C -4ᵡ ),77.0(C -5ᵡ ),60.6(C -6ᵡ ).以上波谱数据与红车轴草苷[8]一致,故确定该化合物为红车轴草苷(trifolirhizin ).
2.3化合物3m.p.200 201ħ .ESI -MS (m /z):257[M +无色针晶(CHCl 3),分子式:C 15H 12O 4,
1]+.1H NMR (300MHz ,DMSO -d 6)δ:10.56(br s ,7-OH ),9.57(br s ,4-OH ),7.64(1H ,d ,J =8.6Hz ,H -5),7.32(2H ,d ,J =8.5Hz ,H -2,H -6),6.79(2H ,d ,J =8.5Hz ,H -3,H -5),6.50(1H ,dd ,J =8.6,2.1Hz ,H -6),6.33(1H ,d ,J =2.1Hz ,H -8),5.44(1H ,dd ,J =12.8,2.8Hz ,H -2),3.11(1H ,dd ,J =16.8,12.8Hz ,H -3),2.62(1H ,dd ,J =16.8,2.8Hz ,H -3);13C NMR (75MHz ,DMSO -d 6)δ:79.1(C -2),43.0(C -3),190.1(C -4),128.4(C -5),110.4(C -6),164.6(C -7),102.5(C -8),
74云南大学学报(自然科学版)第33卷163.2(C -9),113.5(C -10),129.3(C -1' ),128.2(C -2' ,C -6' ),115.1(C -3' ,C -5' ),157.6(C -4' ).以上波谱数据与苷草素[9]一致,故确定该化合物为苷草素(liquiritigenin ).
2.4化合物4M +黄白色粉末(CH 3OH ),分子式:C 16H 10O 4.m.p.314 316ħ .ESI -MS (m /z):255[
DMSO -d 6)δ:7.90(2H ,d ,J =9.0Hz ,H -2' ,6' ),7.84(1H ,d ,J =9.0Hz ,H -1]+.1H NMR (300MHz ,
5),6.95(1H ,d ,J =2.0Hz ,H -8),6.92(2H ,d ,J =9.0Hz ,H -3' ,5' ),6.88(1H ,dd ,J =9.0,2.0Hz ,H -
6.70(1H ,s ,H -3);13C NMR (75MHz ,DMSO -d 6)δ:162.3(C -2),104.4(C -3),176.2(C -4),6),
126.4(C -5),114.7(C -6),163.1(C -7),102.4(C -8),157.3(C -9),116.1(C -10),121.7(C -1' ),128.1(C -2' ,6' ),115.8(C -3' ,5' ),160.7(C -4' ).以上波谱数据与7,4' -二羟基黄酮[10]一致,故
4' -二羟基黄酮(7,4' -dihydroxy -flavone ).确定该化合物为7,
2.5化合物5m.p.149 151ħ .ESI -MS (m /z):412白色针晶(CH 3COOCH 2CH 5),分子式:C 29H 48O ,
[M ]+.1H NMR (300MHz ,CDCl 3)δ:5.32(1H ,d ,J =5.0Hz ,H -6),5.12(1H ,dd ,J =15.2,7.8Hz ,H -
22),5.02(1H ,dd ,J =15.2,7.8Hz ,H -23),3.50(1H ,t ,J =5.2Hz ,H -3),0.95(3H ,d ,J =6.8Hz ,21-
0.88(3H ,t ,J =7.2Hz ,29-CH 3),0.86(3H ,d ,J =7.0Hz ,26-CH 3),0.83(3H ,d ,J =7.0Hz ,27-CH 3),
CH 3),0.81(3Hs ,19-CH 3),0.68(3H ,s ,18-CH 3).13C NMR (75MHz ,CDCl 3)δ:31.5(C -1),31.9(C -
2),71.7(C -3),39.6(C -4),140.2(C -5),121.6(C -6),31.5(C -7),31.9(C -8),50.2(C -9),36.5(C -10),21.5(C -11),39.7(C -12),42.3(C -13),55.9(C -14),24.6(C -15),29.1(C -16),56.8(C -17),12.2(C -18),19.4(C -19),40.5(C -20),21.0(C -21),138.2(C -22),129.2(C -23),51.2(C -24),31.9(C -25),18.6(C -26),21.2(C -27),25.4(C -28),12.2(C -29).以上波谱数据与豆甾醇
2.6[11]一致,故确定该化合物为豆甾醇(stigmasterol ).M ]+.1H NMR (CDCl 3,300MHz )δ:4.66白色粉末,分子式:C 30H 50O.ESI -MS (m /z):426[化合物6
(1H ,d ,H -29),4.54(1H ,d ,H -29),3.18(2H ,dd ,J =10.4,4.8Hz ),1.68(3H ,s ,H -30),0.76,0.79,0.83,0.94,0.97,1.03(18H ,s ,6ˑ CH 3).13C NMR (CDCl 3,75Hz )δ:38.7(C -1),27.4(C -2),79.0(C -
3),38.8(C -4),55.3(C -5),18.3(C -6),34.3(C -7),40.8(C -8),50.4(C -9),37.2(C -10),20.9(C -11),25.2(C -12),38.1(C -13),42.3(C -14),27.4(C -15),35.6(C -16),42.8(C -17),48.3(C -18),48.0(C -19),150.9(C -20),29.8(C -21),40.0(C -22),27.9(C -23),15.3(C -24),16.1(C -25),15.9(C -26),14.5(C -27),17.9(C -28),109.3(C -29),19.3(C -30).以上数据与羽扇豆醇[12]一致,故确定该化合物为羽扇豆醇(lupeol ).
化合物7m.p.50 52ħ .通用试剂不显色,白色粉末(CH 3OH ),分子式:C 15H 12,碘蒸气显黄色斑2.7
M -1]+.1H NMR (300MHz ,CDCl 3)δ:7.26(1H ,提示其可能是脂肪族类化合物.ESI -MS (m /z):241[点,
s ),2.35(2H ,t )为连接羧基的CH 2,1.63(2H ,m ),1.30(22H ,m )示为12ˑ CH 2,0.88(3H ,t )为末端CH 3.故确定该化合物为正十五烷酸.
2.8化合物8m.p.121 123ħ .IR (KBr )νmax :3465,白色针晶(CH 3CH 2COOC 2H 5),分子式:C 7H 6O 2,
1685,1596,1448,1423.ESI -MS (m /z):122[M ]+.1H NMR (300MHz ,CDCl 3)δ:7.41(2H ,dd ,J =7.8,
6.3Hz ,H -3,5),7.55(1H ,dd ,J =7.8,1.2Hz ,H -4),8.05(2H ,dd ,J =6.3,1.2Hz ,H -2,6);13C NMR (300MHz ,CDCl 3)δ:130.1(C -1),131.3(C -2),129.4(C -3),133.8(C -4),129.4(C -5),131.3(C -
6),167.8(C -7).以上数据与苯甲酸[13]一致,故确定该化合物为苯甲酸(benzoic acid ).
2.9化合物9m.p.136.5 137ħ ,无色针状晶体,分子式:C 29H 50O ,与β-谷甾醇标准品进行对照,混合
R f 值一致,熔点不下降;在多种溶剂系统中进行薄层层析(TLC )检测,且显色相同,故确定为β-谷甾醇(β
-sitosterol ).
2.10化合物10白色粉末,分子式:C 35H 60O 6,与胡萝卜苷标准品进行对照,在多种溶剂系统中进行薄层
R f 值一致,层析(TLC )检测,且显色相同,故确定为胡萝卜苷(daucosterol ).
第1期隆金桥等:广西山豆根化学成分的研究753结果与讨论
4,6,7,8为首次从该植物中分离本文从产于广西靖西的山豆根中分离出10个化合物,其中化合物3,
得到.文献报道,山豆根醇提取物对Fenton 反应所产生的羟自由基具有一定的清除能力;对超氧阴离子也
[14][15]具有清除能力;其水提取物对急性炎症、免疫性炎症均有显著的抗炎作用.山豆根中黄酮类化合物
[16-17];该植物中其它黄酮类化合物如槲皮素等如高丽槐素(1)、红车轴草苷(2)等具有良好的生理活性
[18-19].具有较好的抗肿瘤活性
本研究从广西靖西山豆根的乙醇浸膏的石油醚和乙酸乙酯萃取部分中没有分离得到生物碱成分,可
20]能由于生物碱成分极性较大,存在于正丁醇部分中,我们将做进一步的研究.另外,文献[报道了广西
不同产地山豆根的生物碱的指纹图谱比较,结果显示产于广西百色(包含靖西)的山豆根中生物碱含量最低,这也是本文研究中目前暂没有分离得到生物碱成分的原因之一.
报道了购于上海的山豆根的主要成分为黄酮及酚性成分;
[5][6]陈耀祖等报道了购于甘肃的山豆根的主要成分为多糖成分;窦金辉等报道了购于北京的山豆根的主
2、3和4为黄酮类化合物,6为三要成分为生物碱成分.本文从广西靖西的山豆根中分离得到的化合物1、
萜类化合物,我们将进一步对其进行生物活性研究,从而为该药用植物的充分利用提供科学依据.前人报道的文献中,谭桂山和果德安等[2-4]参考文献:
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76云南大学学报(自然科学版)第33卷
Study on the chemical constituents of Sophora tonkinensisi from Guangxi
2LONG Jin-qiao 1,,LIN Hua 3,YANG Xiang-dong 1,ZHAO Jing-feng 1,LI Liang 1
(1.Key Laboratory of Medicinal Chemistry for Natural Resources (Yunnan University ),Ministry of Education ,
School of Chemical Science and Technology ,Yunnan University ,Kunming 650091,China ;
2.The Faculty of Chemistry and Life Sciences ,Baise College ,Baise 533000,China ;
3.The Faculty of Chemistry and Bio -Agriculture ,Anshun College ,Anshun 561000,China )
Abstract :The chemical constituents of Sophora tonkinensis Gapnep.were studied and ten compounds were i-solated by silica column chromatography and recrystallization.The structures of the compounds were elucidated as maackiain (1),trifolirhizin (2),liquiritigenin (3),7,4' -dihydroxy -flavone (4),stigmasterol (5),lupeol
(6),pentadecanoic acid (7),benzoic acid (8),β-sitosterol (9)and daucosterol (10)by spectral analysis.Compounds 3,4,6,7and 8were isolated from this plant for the first time.
Key words :Sophora tonkinensis ;Leguminosae ;chemical constituents ;flavone
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[10]赵声蓉.多模式温度集成预报[J ].应用气象学报,
2006,17(1):52-58.
[11]周兵,赵翠光,赵声蓉.多模式集合预报技术及其分
J ].应用气象学报,2006,17(增刊):104-析与检验[
109.
[12]黄嘉佑.气象统计分析与预报方法[M ].北京:气象2000:38-50,60-74.出版社,[13]朱乾根,林锦瑞,寿绍文,等.天气学原理和方法[M ].北京:气象出版社,1992:843-850.[14]李勇.2007年6 8月T213与ECMWF 及日本模式J ].气象,2007,33(11):93-100.中期预报性能检验[
Multi -model compositive MOS method application of fine temperature forecast
2ZHANG Xiu-nian 1,,CAO Jie 1,YANG Shu-yu 2,QI Ming-hui 2
(1.Department of Atmosphere ,Yunnan University ,Kunming 650091,China ;
2.Yunnan Meteorological Observatory ,Kunming 650034,China )
Abstract :By using T213and ECMWF model products ,the multi -model compositive MOS method has been researched and tested in temperature forecasting.And it has been compared to the single -model MOS method al-so.It has been found that multi -model method overmatch the single -model method in forecasting obviously.The multi -model MOS method can use useful information and advantages of multiple models'products and make better forecast.In system designing ,the identification of factors has been drawn into to solve the problem of multi -model data complexity.During the test ,it has been found there are some obvious differences of temperature forecasting in each season.Especially the summer's level is higher than the other three seasons.The main reason is that the daily minimum and maximum temperature changed less in summer then in the others.It makes the forecast to be more easily.But the MOS method still devotes great contributions.
Key words :compositive MOS ;Multi -model ;temperature forecast ;numerical model application