全 文 :第37卷/第5期/
2013年9月
河北师范大学学报/自然科学版/
JOURNAL OF HEBEI NORMAL UNIVERSITY/Natural Science Edition/
Vol.37 No.5
Sep.2013
收稿日期:2013-04-19;修回日期:2013-05-15
基金项目:国家海洋局908项目(908-02-05-04)
作者简介:冯献起(1983-),男,山东莘县人,硕士,研究方向为天然产物化学.
通信作者:钟惠民(1954-),男,教授,博士,主要从事天然产物化学的研究.E-mail:zhonghuimin@qust.edu.cn.
红树林植物露兜树化学成分研究
冯献起1, 刘艳霞1, 顾明广1, 钟惠民2
(1.燕京理工学院 化工与材料工程学院,河北 廊坊 065201;2.青岛科技大学 化学与分子工程学院,山东 青岛 266042)
摘 要:对红树林植物露兜树的化学成分进行了研究,共分离得到7个化合物.根据化合物的理化性质和波谱
学数据分别鉴定为羽扇豆醇(Lupeol)、(24R)-ergosta-4,7,22-triene-3-one、胆固醇、β-谷甾酮、胡萝卜苷、松柏醛和
邻苯二甲酸二异丁酯.除β-谷甾酮外,其余6种均为首次从该物种提取物中分离得到.
关键词:露兜树;羽扇豆醇;胆固醇;β-谷甾酮;邻苯二甲酸二异丁酯
中图分类号:O 629;Q 949.71+1.2 文献标志码:A 文章编号:1000-5854(2013)05-0492-03
Studies on the Chemical Constituents of Mangrove Plant
Pandanus Tectorius
FENG Xianqi 1, LIU Yanxia1, GU Mingguang1, ZHONG Huimin2
(1.School of Chemical and Materials Engineering,Yanching Institute of Technology,Hebei Langfang 065201,China;
2.Colege of Chemistry and Molecular Engineering,Qingdao University of Science and Technology,Shandong Qingdao 266042,China)
Abstract:Chemical investigation of Pandanus Tectorius led to 7compounds being isolated.The struc-
ture of these compounds was identified by the physico-chemical analysis and MS,NMR spectroscopic meth-
ods.Their structures were determined as lupeol,(24R)-ergosta-4,7,22-triene-3-one,cholesterol,β-sito-
stenone,daucosterol,coniferaldehyde and di-iso-butyl phthalate respectively.In addition to theβ-sito-
stenone,the rest 6compounds were first isolated from this species.
Key words:Pandanus Tectorius;lupeol;cholesterol;β-sitostenone;di-iso-butyl phthalate
露兜树,露兜树科植物,单子叶植物,本科共3属,约800种,广泛分布于热带及亚热带,在我国多产于福
建、台湾、广东、海南等地区[1].在民间有长久的用药历史,作为传统的药物可用来治疗麻风病、风湿病、癫痫
以及咽喉痛等病症[2];其干燥根、根茎及茎具有平肝清热、去湿利尿、发汗解表、行气止痛的功效,可治疗感冒
发热、风湿痹痛、肝火头痛、肝炎、肝硬化腹水、尿路感染、肾炎水肿、眼结膜炎、跌打损伤等病症[3].为寻找具
有新颖结构及良好生物活性的化合物,本文中,笔者对其果实进行了系统的化学成分研究,共分离得到了7
个化合物.根据化合物的理化性质及波谱学数据分别鉴定为①羽扇豆醇、②(24R)-ergosta-4,7,22-triene-3-
one、③胆固醇、④β-谷甾酮、⑤胡萝卜苷、⑥松柏醛、⑦邻苯二甲酸二异丁酯.除④β-谷甾酮外,均为首次从该
物种提取物中分离得到.
DOI:10.13763/j.cnki.jhebnu.nse.2013.05.005
1 实验部分
1.1 仪器和材料
Bruker Avance500核磁共振仪(德国Bruker公司),E-52型旋转蒸发仪、SHB-3循环多用真空泵(上海
亚荣盛华仪器厂);SGW X-4显微熔点仪(上海精密仪器有限公司);Finnigan MAT90质谱仪(美国Bio-Rad
公司);Buchi-C660中压液相色谱仪(瑞士Buchi公司);柱层析硅胶 H(48~75,75~150μm)、硅胶板(青岛
海洋化工厂),溶剂均为分析纯.
植物样品由中国海洋大学提供,该样品于2006年11月采自海南省三亚梅山东锣西鼓岛,种属由南海研
究所周仁林研究员鉴定.样品洗净、风干后粉碎待用.
1.2 提取与分离
4kg粉碎后的样品用5L质量分数为95%乙醇回流提取3次,每次4h,合并减压浓缩后得到浸膏
430g.用蒸馏水溶解后,分别用石油醚、乙酸乙酯、正丁醇各萃取3次,浓缩后得石油醚浸膏30g,乙酸乙酯
浸膏23g及正丁醇浸膏25g.经反复硅胶柱色谱、中压柱色谱分离,结晶及重结晶方法纯化,得到化合物①
108.1mg,②12.0mg,③22.7mg,④56.7mg,⑤87.6mg,⑥23.5mg,⑦14.3mg.
2 结构鉴定
化合物① 无色针状结晶(甲醇),5%硫酸-乙醇(体积分数,下同)显红色,熔点215~216℃,Lieber-
mann-Burchard反应呈阳性(终色为紫色),说明该化合物为三萜类化合物.1 HNMR(500MHz,CDCl3),δ:
0.76(3H,s),0.79(3H,s),0.83(3H,s),0.94(3H,s),0.97(3H,s),1.03(3H,s),1.68(3H,s),3.19(1H,
dd,J=11.2,6.4Hz),4.57(1H,s),4.69(1H,s);13 CNMR(125MHz,CDCl3),δ:38.72(C-1),27.41(C-2),
79.03(C-3),38.96(C-4),55.42(C-5),18.30(C-6),34.39(C-7),40.91(C-8),50.57(C-9),37.23(C-10),
21.08(C-11),25.35(C-12),38.22(C-13),42.91(C-14),27.50(C-15),35.67(C-16),43.04(C-17),48.45
(C-18),48.03(C-19),150.08(C-20),29.90(C-21),40.03(C-22),28.19(C-23),15.28(C-24),16.09(C-
25),14.46(C-26),14.49(C-27),18.07(C-28),109.32(C-29),19.31(C-30).以上数据与文献[4]报道一致,
因此确定其为羽扇豆醇.
化合物② 白色粉末,5%硫酸-乙醇显红色,Liebermann-Burchard反应呈阳性(终色为绿色),说明该
化合物为甾醇类化合物.1 HNMR(CDCl3,500MHz),δ:5.85(1H,s),5.21(1H,m),5.16(1H,m),4.73
(1H,m),1.23(3H,s),1.01(3H,d,J=7.0Hz),0.89(3H,d,J=7.0Hz,28-Me),0.81(6H,d,J=6.5Hz,
26,27-Me),0.58(3H,s);13CNMR(CDCl3,125MHz),δ:32.57(C-1),33.35(C-2),199.33(C-3),120.54
(C-4),169.72(C-5),37.60(C-6),116.91(C-7),140.58(C-8),45.56(C-9),38.54(C-10),21.92(C-11),
38.62(C-12),43.21(C-13),54.74(C-14),21.96(C-15),27.82(C-16),55.08(C-17),12.04(C-18),22.53
(C-19),40.08(C-20),20.73(C-21),135.06(C-22),131.89(C-23),42.43(C-24),32.72(C-25),19.36(C-
26),19.68(C-27),17.12(C-28).以上数据与文献[5]报道吻合,确定其为(24R)-ergosta-4,7,22-triene-3-one.
化合物③ 白色针状晶体(丙酮),熔点148~150℃.5%硫酸-乙醇显红色.1 HNMR(500MHz,
CDCl3),δ:5.35(1H,d,J=5.5Hz),3.50(1H,m),1.01(3H,s),0.90(3H,d,J=6.0Hz),0.87(6H,d,J=
6.0Hz),0.70(3H,s);13 CNMR(125MHz,CDCl3),δ:37.28(C-1),31.65(C-2),71.75(C-3),42.30(C-4),
140.77(C-5),121.67(C-6),31.91(C-7),31.91(C-8),50.17(C-9),36.51(C-10),21.09(C-11),39.70(C-
12),42.30(C-13),56.79(C-14),24.30(C-15),28.01(C-16),56.19(C-17),12.05(C-18),19.40(C-19),35.
79(C-20),18.73(C-21),36.21(C-22),23.86(C-23),39.81(C-24),28.01(C-25),22.81(C-26),22.57(C-
27).以上数据与文献[6]报道一致,确定其结构为胆固醇.
化合物④ 白色粉末状固体,易溶于丙酮及氯仿,5%硫酸-乙醇显红色.1 HNMR(500MHz,CDCl3),δ:
0.72(3H,s,18-Me),0.80(3H,d,J=8.0Hz,26-Me),0.82(3H,b,27-Me),0.85(3H,t,J=7.5Hz,29-
Me),0.92(3H,d,J=6.5Hz,21-Me),1.17(3H,s,19-Me),5.74(1H,s).13 CNMR(125MHz,CDCl3),δ:
199.71(C-3),171.76(C-5),123.74(C-4),56.00(C-14),55.88(C-17),53.82(C-9),45.83(C-19),42.39(C-
13),39.62(C-12),38.61(C-10),36.12(C-20),35.64(C-1),35.60(C-8),33.99(C-22),33.90(C-2),32.96
(C-6),32.86(C-7),29.15(C-25),28.20(C-16),25.9(C-23),24.20(C-15),23.81(C-28),21.03(C-11),
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19.02(C-26),18.92(C-27),18.65(C-21),17.37(C-19),11.96(C-29),11.96(C-18).以上数据与文献[7]报
道一致,确定其为β-谷甾酮.
化合物⑤ 白色粉末状固体,熔点297~300℃.5%硫酸-乙醇显红色,推测为甾醇类化合物,但不溶于
多种有机试剂.在多种体系中检测与胡萝卜苷的Rf值一致,并且与标准品混合后,熔点不下降,故推测化合
物为胡萝卜苷.
化合物⑥ 白色粉末,5%硫酸-乙醇显绿色.EI-MS m/z:178.1[M]+.1 HNMR(500MHz,CDCl3),δ:
9.66(1H,d,J=8.0Hz),7.40(1H,d,J=15.5Hz),7.13(1H,d,J=8.0Hz),7.08(1H,s),6.97(1H,d,
J=8.5Hz),6.60(1H,dd,J=8.5,15.5Hz),5.98(1H,s),3.96(3H,s);13 CNMR(125MHz,CDCl3),δ:
191.21(d,C-9),152.97(d,C-7),148.64(s,C-1),146.45(s,C-2),126.87(d,C-4),124.02(s,C-8),121.56
(d,C-5),114.70(d,C-6),109.16(d,C-3),53.56(q,OCH3).经与文献[8]波谱数据对照,基本一致,故可鉴
定化合物为松柏醛.
化合物⑦ 无色油状物,5%乙醇-硫酸显红色.综合碳谱、氢谱信息可知分子中存在一个苯环,且所给
出的信号相对简单,因此推断化合物分子具有对称结构.EI-MS m/z:278.4[M]+.1 HNMR(500MHz,
CDCl3),δ:7.72(1H,d,J=6.5Hz),7.52(1H,dd,J=6.0,3.0Hz),4.08(2H,t,J=6.5Hz),2.03(1H,
m),0.96(6H,d,J=7.0Hz);13CNMR(125MHz,CDCl3),δ:167.70(s,C-7和C-7′),132.38(s,C-1和C-
2),130.92(d,C-4和C-5),128.85(d,C-3和C-6),71.80(t,C-8和C-8′),27.72(d,C-9和C-9′),19.16
(q,C-10,C-10′,C-11和C-11′).与文献[9]波谱数据基本一致,故鉴定化合物是邻苯二甲酸二异丁酯.
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(责任编辑 邱 丽)
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