小蜡树的酚苷及苯乙醇苷类成分

© 1994-2010 China Academic Journal Electronic Publishing House. All rights reserved. http://www.cnki.net

・化学・

小蜡树的酚苷及苯乙醇苷类成分

林生,刘明韬,王素娟,李帅,杨永春,石建功

3

(中国医学科学院北京协和医学院药物研究所中草药物质基础与资源利用

教育部重点实验室,北京100050)

[摘要]　目的:系统研究小蜡树Fraxinux sieboldiana 枝乙醇提取物的化学成分。方法:运用正相和反相硅胶、大孔吸附树

脂、凝胶、反相高效液相等色谱方法进行分离;应用包括一维和二维NMR 等波谱方法鉴定化合物的结构。结果:从小蜡树枝的乙醇提取物水相部位分离得到4个酚苷和12个苯乙醇苷类成分,分别鉴定为:2,62二甲氧基2对苯二酚242O 2β2D 2吡喃葡萄糖苷(1),2,62二甲氧基2对苯二酚212O 2β2D 2吡喃葡萄糖苷(2),42羟基232甲氧基苯基β2D 2吡喃葡萄糖苷(3),42羟基232甲氧基苯基β2D 2吡喃木糖基(1→6)2O 2β2D 2吡喃葡萄糖苷(4),os manthuside H (5),22(42羟基苯基)乙基β2D 2吡喃葡萄糖苷(6),22(3,

42二羟基苯基)乙基β2D 2吡喃葡萄糖苷(7),22羟基242(22羟基乙基)2苯基β2D 2吡喃葡萄糖苷(8),42(22羟基乙基)222甲氧基苯

基β2D 2吡喃葡萄糖苷(9),calceolari oside B (10),calceolari oside A (11),ferruginoside A (12),is olugrandoside (13),类叶升麻苷

(14),chirit ot oside C (15)和p lantasis oside (16)。结论:化合物1～4,9,12,13和16为首次从该属植物中分离得到。

[关键词]　小蜡树;化学成分;酚苷;苯乙醇苷

[收稿日期]　2009212228

[基金项目]　长江学者和创新团队发展计划“PCSI RT ”

(I RT0514);新世纪优秀人才支持计划(NCET )

[通信作者]　3石建功,Tel:(010)831547,Fax:(010)63017757,E 2mail:shijg@i m m.ac .cn

　　小蜡树F raxinux sieboldiana,又称庐山梣,其茎皮在我国江西当地和日本作为中药秦皮使用,具有利尿、止咳平喘、治疗风湿关节炎的作用[1]

。为了从该植物中获得可供新药先导物筛选发现的结构多样性天然产物,作者对采自江西庐山的小蜡树枝化学成分进行了系统的研究。前文对其乙醇提取物中得到的9个新化合物结构以及香豆素类成分及其生物活性进行了详细报道[223]

,本文报道4个酚苷(1～4)和12个苯乙醇苷类成分(5～16)的结构鉴定。其中,化合物1～4,9,12,13和16为首次从该属植物中发现。1　材料I nova 500核磁共振仪,M icr omass Aut os pec 2U lti 2ma ET OF 质谱仪。W aters 600高效液相色谱仪(A ll 2tech 公司Econos phere C 18制备柱,250mm ×22mm ×10μm ,W aters 2478型检测器)。中压液相色谱仪(B úchi Gradient For mer B 2687,Rp C18,43～60μ,Phar macia 公司)。闪式快速分离系统(Sq

16x,combi Flash,Rp C 18,40～60μ,M icr on Silicag Gel,Isco 公司)。Sephadex LH 220为Phar macia 公司

产品。RA 型大孔树脂为北京化工七厂产品。柱色

谱硅胶(2002300目)和薄层色谱硅胶GF254(60型)均为青岛海洋化工厂生产。

小蜡树药材于2004年8月采自江西省庐山,由中国医学科学院药物研究所马林副教授鉴定为小蜡树F .sieboldiana 的枝及枝皮,标本现存于中国医学科学院药物研究所植物标本库,标本号为No .Z H02272。2　提取分离

药材的提取和初步分离过程见文献[3]。C 部分经正相硅胶柱色谱分离,氯仿2甲醇(90∶10～0∶100)梯度洗脱,得到5个亚组分(C 1～C 5)。C 1亚组

分经Sephadex LH 220柱色谱纯化(甲醇),再经反相HP LC 制备纯化(甲醇2水25∶75)得到化合物1(1517mg ),2(1212mg ),3(911mg )。C 2亚组分经

反相HP LC 制备纯化(甲醇2水25∶75)得到化合物6(6219mg ),7(4513mg )和8(1612mg )。C 3亚组分

经Sephadex LH 220柱色谱(甲醇2水70∶30)和反相HP LC 制备(甲醇2水20∶80)反复纯化,得到化合物4(20518mg )和5(1115mg )。

30%乙醇洗脱部分用反相中压液相色谱分离,

・

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© 1994-2010 China Academic Journal Electronic Publishing House. All rights reserved. http://www.cnki.net

0～100%甲醇梯度洗脱,一共得到F ～J 5个洗脱部

分。G 部分经正相硅胶柱色谱分离,氯仿2甲醇(100∶0～50∶50)梯度洗脱,得到3个亚组分(G 1～G 3)。G 1亚组分经反相HP LC 制备纯化(甲醇2水30∶70)得到化合物9(1011mg )。G 2亚组分经Seph 2adex LH 220柱色谱反复纯化(甲醇),再经反相HP LC 制备纯化(甲醇2水30∶70)得到化合物10(21518mg ),11(2215mg ),12(1310mg ),13(1110mg ),14(1618mg )和15(1116mg )。I 部分经正相硅胶柱色谱分离,氯仿2甲醇(100∶0～50∶50)梯度洗脱,得到3个亚组分(I 1～I 3)。I 2亚组分经反相HP LC 制备纯化(甲醇2水30∶70)得到化合物16(410mg )。3　结构鉴定

化合物1　白色粉末;ESI 2MS m /z 355[M +

Na ]+,371[M +K ]+;1

H 2NMR (DMS O 2d 6,500MHz )δ:6130(2H,s,H 23,5),4160(1H,d,J =810

Hz,H 21′),3120(1H,dd,J =810,815Hz,H 22′

),3124(1H,dd,J =815,815Hz,H 23′),3109(1H,dd,J =910,815Hz,H 24′),3135(1H,m ,H 25′),3170(1H,dd,J =1115,210Hz,H 26a ′),3139(1H,dd,J =1115,510Hz,H 26b ′),3165(6H,2×OMe ),7176

(1H,s,OH 21)。13

C 2NMR (DMS O 2d 6,125MHz )δ:13014(C 21),14811(C 22,6),9510(C 23,5),15013

(C 24),10116(C 21′),7313(C 22′),7618(C 23′),7011(C 24′),7712(C 25′),6019(C 26′),5518(2×OMe )。以上数据与文献报道2,62二甲氧基2对苯二

酚242O 2β2D 2吡喃葡萄糖苷(2,62di m ethoxy 2p 2hydr o 2

quinone 242O 2β2D 2glucopyranoside )的数据一致

[4]

。

化合物2　白色粉末;ESI 2MS m /z 355[M +Na ]+,371[M +K ]+;1

H 2NMR (DMS O 2d 6,500MHz )δ:6105(2H,s,H 23,5),4163(1H,d,J =715

Hz,H 21′),3119(1H,dd,J =715,815Hz,H 22′

),3116(1H,dd,J =815,815Hz,H 23′),3110(1H,dd,J =910,815Hz,H 24′),3100(1H,m ,H 25′),3159(1H,dd,J =1115,210Hz,H 26a ′),3141(1H,dd,J =1115,510Hz,H 26b ′),3167(6H,2×OMe ),9119

(1H,s,OH 24)。13

C 2NMR (DMS O 2d 6,125MHz )δ:12715(C 21),15311(C 22,6),9318(C 23,5),15318

(C 24),10314(C 21′),7411(C 22′),7614(C 23′),7010(C 24′),7619(C 25′),6110(C 26′),5611(2×OMe )。以上数据与文献报道2,62二甲氧基2对苯二

酚212O 2β2D 2吡喃葡萄糖苷(2,62di m ethoxy 2p 2hydr o 2

quinone 212O 2β2D 2glucopyranoside )的数据一致[5]

。化合物3　白色粉末;ESI 2MS m /z 325[M +

Na ]+;1

H 2NMR (DMS O 2d 6,500MHz )δ:6167(1H,d,J =215Hz,H 22),6163(1H,d,J =910Hz,H 25),6144(1H,dd,J =910,215Hz,H 26),4165(1H,d,

J =715Hz,H 21′

),3119(1H,dd,J =715,815Hz,H 22′),3124(1H,dd,J =815,815Hz,H 23′),3117(1H,dd,J =910,815Hz,H 24′),3123(1H,m ,H 25′),3165(1H,dd,J =1115,210Hz,H 26a ′),3142(1H,dd,J =1115,510Hz,H 26b ′

),3172(3H,OMe ),8150(1H,s,OH 24)。13C 2NMR (DMS O 2d 6,125MHz )δ:15017(C 21),10117(C 22),14718(C 23),14113(C 24),11512(C 25),10719(C 26),10215

(C 21′),7313(C 22′),7711(C 23′),6919(C 24′),7617(C 25′),6018(C 26′

),5515(OMe )。以上数据与文献报道42羟基232甲氧基苯基β2D 2吡喃葡萄糖

苷(42hydr oxy 232methoxyphenyl 2β2D 2glucopyranoside )

的数据一致[6]

。

化合物4　白色粉末;ESI 2MS m /z 457[M +Na ]+,473[M +K ]+;1

H 2NMR (DMS O 2d 6,500MHz )δ:6161(1H,d,J =215Hz,H 22),61(1H,d,J =815Hz,H 25),6149(1H,dd,J =815,215Hz,H 26),

4163(1H,d,J =810Hz,H 21′),4115(1H,d,J =715Hz,H 21″),3172(3H,OMe ),8148(1H,s,OH 24)。

13

C 2NMR (DMS O 2d 6,125MHz )δ:15017(C 21),

10213(C 22),14718(C 23),14113(C 24),11514(C 2

5),10719(C 26),10116(C 21′),7313(C 22′),7615(C 23′),6919(C 24′),7616(C 25′),6816(C 26′),10411(C 21″),7312(C 22″),7517(C 23″),6916(C 24″),6516(C 25″

),5515(OMe )。以上数据与文献报道42羟基232甲氧基苯基β2D 2吡喃木糖基(1→6)2O 2

β2D 2吡喃葡萄糖苷[42hydr oxy 232methoxyphenyl β2D 2

xyl opyranosyl (1→6)2O 2β2D 2glucopyranoside ]的数据

一致[6]

。

化合物5　无色透明胶状物;ESI 2MS m /z 455[M +Na ]+

,471[M +K ]+

,431[M -H ]-;1

H 2NMR (DMS O 2d 6,500MHz )δ:7103(2H,d,J =810Hz,H 22,6),6165(2H,d,J =810Hz,H 23,5),2172(2H,t,

J =710Hz,H 227),3182(1H,m ,H 28a ),3156(1H,

m ,H 28b ),4116(1H,d,J =715Hz,H 21′),2193(1H,dd,J =815,810Hz,H 22′

),3111(1H,dd,J =・

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© 1994-2010 China Academic Journal Electronic Publishing House. All rights reserved. http://www.cnki.net

910,815Hz,H 23′),2198(1H,dd,J =910,815Hz,H 24′),3123(1H,m ,H 25′

),3183(1H,dd,J =1115,310Hz,H 26a ′),3140(1H,dd,J =1115,710Hz,H 26b ′),4184(1H,d,J =310Hz,H 21″),3174(1H,d,J =310Hz,H 22″),3183(1H,d,J =915Hz,H 24a ″),3157(1H,d,J =915Hz,H 24b ″),3132(2H,d,J =510Hz,H 25″),9112(1H,s,OH 24),4145～5103(6H,6×OH );13

C 2NMR (DMS O 2d 6,125MHz )δ:12816(C 21),12917(C 22,6),11510(C 23,5),15517(C 24),3418(C 27),6919(C 28),10218(C 21′),7313(C 22′),7616(C 23′),7012(C 24′),7515(C 25′),6717(C 26′),10912(C 21″),7518(C 22″

),7818(C 23″),7312(C 24″),6311(C 25″

)。以上数据与文献报道os manthuside H 的数据一致[7]

。

化合物6　无色透明胶状物;ESI 2MS m /z 323

[M +Na ]+

;NMR 数据与文献报道22(42羟基苯基)乙基β2D 2吡喃葡萄糖苷[22(42hydr oxy phenyl )ethyl

β2D 2glucopyranoside ]的数据一致[8]

。化合物7　棕色胶状物;ESI 2MS m /z 339[M +

Na ]+;1

H 2NMR (DMS O 2d 6,500MHz )δ:6160(1H,br s,H 22),6161(1H,d,J =810Hz,H 25),6146(1H,dd,J =810,215Hz,H 26),2165(2H,t,J =710Hz,H 227),3185(1H,m ,H 28a ),3153(1H,m ,H 2

8b ),4115(1H,d,J =715Hz,H 21′),2195(1H,dd,J =815,810Hz,H 22′),3114(1H,dd,J =815,815Hz,H 23′),3103(1H,dd,J =910,815Hz,H 24′),3107(1H,m ,H 25′

),3165(1H,dd,J =1115,210Hz,H 26a ′),3143(1H,dd,J =1115,610Hz,H 26b ′

);13

C 2NMR (DMS O 2d 6,125MHz )δ:12913(C 21),11515(C 22),14510(C 23),14315(C 24),11613(C 25),11915(C 26),3511(C 27),7010(C 28),10219(C 21′),7315(C 22′),7619(C 23′),7011(C 24′

),7618(C 25′),6111(C 26′)。以上数据与文献报道22(3,42二羟基苯基)乙基β2D 2吡喃葡萄糖苷[22(3,42dihydr oxyphenyl )ethyl β2D 2glucopyranoside ]的数据一

致

[9]

。

化合物8　棕色胶状物;ESI 2MS m /z 339[M +

Na ]+,355[M +K ]+

;NMR (DMS O 2d 6,500MHz )数据与文献报道22羟基242(22羟基乙基)2苯基β2D 2吡喃葡萄糖苷[22hydr oxy 242(22hydr oxyethyl )2phenyl β2

D 2glucopyranoside ]的数据一致[10]

。

化合物9　棕色胶状物;ESI 2MS m /z 355[M +Na ]+;1

H 2NMR (Me OH 2d 4,500MHz )δ:6183(1H,

d,J =210Hz,H 22),7102(1H,d,J =810Hz,H 25),6170(1H,dd,J =810,210Hz,H 26),2171(2H,t,J =710Hz,H 227),3167(2H,J =710Hz,H 228),4176(1H,d,J =710Hz,H 21′),3142(1H,dd,J =815,810Hz,H 22′),3141(1H,dd,J =910,815Hz,H 23′),3129(1H,dd,J =910,815Hz,H 24′

),3130(1H,m ,H 25′),3181(1H,dd,J =1215,215Hz,H 26a ′),3163(1H,dd,J =1215,510Hz,H 26b ′),3180(3H,s,OMe );

13

C 2NMR (Me OH 2d 4,125MHz )δ:13515(C 2

1),11416(C 22),15018(C 23),14614(C 24),11813(C 25),12215(C 26),3918(C 27),13(C 28),10311(C 21′),7510(C 22′),7812(C 23′),7114(C 24′),7719(C 25′),6215(C 26′

),5617(OMe )。以上数据与文献报道42(22羟基乙基)222甲氧基苯基β2D 2吡喃葡萄

糖苷[42(22hydr oxyethyl )222methoxyphenyl β2D 2gluco 2pyranoside ]的数据一致

[11]

。

化合物10　黄色胶状物。ESI 2MS m /z 501

[M +Na ]+;1

H 2NMR (DMS O 2d 6,500MHz )δ:6160(1H,d,J =115Hz,H 22),6157(1H,d,J =810Hz,H 25),6145(1H,dd,J =810,115Hz,H 26),2165(2H,t,J =710Hz,H 227),3179(1H,m ,H 28a ),3158(1H,m ,

H 28b ),4123(1H,d,J =810Hz,H 21′

),2199(1H,dd,J =815,810Hz,H 22′),3113(1H,dd,J =915,910Hz,H 23′),3117(1H,dd,J =910,815Hz,H 24′),3140(1H,m ,H 25′),4139(1H,br d,J =1115Hz,H 26a ′),4115(1H,dd,J =1115,610Hz,H 26b ′

),7104(1H,d,J =115Hz,H 22″),6174(1H,d,J =810Hz,H 25″),6196(1H,dd,J =810,115Hz,H 26″),7146(1H,d,J =1610Hz,H 27″),6127(1H,d,J =1610Hz,H 28″

);13

C 2NMR (DMS O 2d 6,125MHz )δ:12912

(C 21),11518(C 22),14510(C 23),14315(C 24),11613(C 25),11915(C 26),3512(C 27),7012(C 28),10310(C 21′),7314(C 22′),7615(C 23′),7011(C 24′),7318(C 25′),6316(C 26′),12515(C 21″),11318(C 22″),14516(C 23″),14815(C 24″),11515(C 25″),12114(C 26″),14513(C 27″),11419(C 28″

),16616(C 29″

)。以上数据与文献报道calceolari oside B 的数据一致[12]

。

化合物11　黄色胶状物。ESI 2MS m /z 501

[M +Na ]+;1

H 2NMR (DMS O 2d 6,500MHz )δ:6161(1H,br s,H 22),6162(1H,d,J =810Hz,H 25),6148

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(1H,br d,J =810Hz,H 26),2165(2H,t,J =710Hz,H 227),3188(1H,m ,H 28a ),3158(1H,m ,H 28b ),

4127(1H,d,J =810Hz,H 21′),3108(1H,dd,J =815,815Hz,H 22′),3144(1H,dd,J =915,910Hz,H 23′),4163(1H,dd,J =910,915Hz,H 24′),3140(1H,m ,H 25′),3139(1H,br d,J =1115Hz,H 26a ′),3132(1H,dd,J =1115,615Hz,H 26b ′

),7104(1H,br s ,H 22″),6175(1H,d,J =810Hz,H 25″),6199(1H,br d,J =810Hz,H 26″),7146(1H,d,J =1610Hz,H 27″),6123(1H,d,J =1610Hz,H 28″

);13

C 2

NMR (DMS O 2d 6,125MHz )δ:12911(C 21),11518(C 22),14510(C 23),14316(C 24),11613(C 25),

11915(C 26),3511(C 27),7012(C 28),10218(C 21′),7316(C 22′),7417(C 23′),7113(C 24′),7411(C 25′),6019(C 26′),12514(C 21″),11319(C 22″),14518(C 23″),14816(C 24″),11515(C 25″),12113(C 26″),14514(C 27″),11419(C 28″

),16519(C 29″

)。以上数据与文献报道calceolari oside A 的数据一致

[12]

。

化合物12　棕色胶状物。ESI 2MS m /z 663

[M +Na ]+;1

H 2NMR (DMS O 2d 6,500MHz )δ:6154(1H,br s,H 22),6153(1H,br d,J =810Hz,H 25),6140(1H,br d,J =810Hz,H 26),2156(2H,t,J =710Hz,H 227),3179(1H,m ,H 28a ),3154(1H,m ,H 28b ),4147(1H,d,J =810Hz,H 21′),4123(1H,d,J =715Hz,H 21″),7106(1H,br d ,H 22

),6176(1H,d,J =810Hz,H 25

),7100(1H,br d,J =810Hz,H 26 ),7147(1H,d,J =1610Hz,H 27 ),6126(1H,d,J =1610Hz,H 28 );13C 2NMR (DMS O 2d 6,125MHz )δ:12912(C 21),11518(C 22),14419(C 23),14315(C 24),11613(C 25),11916(C 26),3510(C 27),6918(C 28),10011(C 21′),7412(C 22′),7517(C 23′),7011(C 24′),7314(C 25′

),6813(C 26′),10314(C 21″),7315(C 22″),7619(C 23″),7010(C 24″),7617(C 25″),6110(C 26″),12516(C 21 ),11412(C 22 ),14516(C 23 ),14814(C 24 ),11514(C 25 ),12113(C 26 ),14511(C 27 ),11419(C 28 ),16517(C 29 )。以上数据与文献报道ferrugino 2side A 的数据一致

[13]

。

化合物13　棕色胶状物。ESI 2MS m /z 663

[M +Na ]+;1

H 2NMR (DMS O 2d 6,500MHz )δ:6162(1H,br s,H 22),6161(1H,br d,J =810Hz,H 25),

6148(1H,br d,J =810Hz,H 26),2167(2H,t,J =710Hz,H 227),3186(1H,m ,H 28a ),3154(1H,m ,

H 28b ),4133(1H,d,J =810Hz,H 21′),4122(1H,d,J =715Hz,H 21″),7104(1H,br d ,H 22

),6174(1H,d,J =810Hz,H 25 ),6199(1H,br d,J =810Hz,H 26 ),7145(1H,d,J =1610Hz,H 27 ),6125(1H,d,J =1610Hz,H 28 );13C 2NMR (DMS O 2d 6,125MHz )δ:12912(C 21),11518(C 22),14418(C 23),14316(C 24),11614(C 25),11915(C 26),3510(C 27),7011(C 28),10215(C 21′),7114(C 22′),7715(C 23′),6719(C 24′),7513(C 25′),6811(C 26′),10314(C 21″),7315(C 22″),7619(C 23″),7010(C 24″),7617(C 25″),6110(C 26″),12515(C 21 ),11416(C 22 ),14517(C 23 ),14815(C 24 ),11515(C 25 ),12111(C 26 ),14510(C 27 ),11418(C 28 ),16611(C 29 )。以上数据与文献报道is olug 2randoside 的数据一致

[14]

。

化合物14　棕色胶状物。ESI 2MS m /z 663

[M +Na ]+

;NMR (DMS O 2d 6)数据与文献报道类叶

升麻苷(acteoside )的数据一致[15]

。

化合物15　黄色胶状物。ESI 2MS m /z 663

[M +Na ]+,679[M +K ]+

;NMR (DMS O 2d 6)数据与文献报道chirit ot oside C 的数据一致[12]

。

化合物16　黄色胶状物。ESI 2MS m /z 475

[M -H ]-;1

H 2N MR (Me OH 2d 4,500MHz )δ:6185(1H,d,J =210Hz,H 22),6173(1H,d,J =810Hz,H 25),6170(1H,dd,J =810,210Hz,H 26),4156(1H,dd,J =1110,310Hz,H 27),3195(1H,dd,J =1315,310Hz,H 28a ),31(1H,dd,J =1315,1110Hz,H 28b ),

4146(1H,d,J =810Hz,H 21′),3120(1H,dd,J =1010,810Hz,H 22′),3162(1H,dd,J =1010,1010Hz,H 23′),3146(1H,dd,J =1010,1010Hz,H 24′

),3173(1H,m,H 25′

),4155(1H,dd,J =1210,210Hz,H 26a ′),4134(1H,dd,J =1210,610Hz,H 26b ′),7105(1H,d,J =210Hz,H 22″),6178(1H,d,J =810Hz,H 25″),6195(1H,dd,J =810,210Hz,H 26″),7158(1H,d,J =1610Hz,H 27″),6130(1H,d,J =1610Hz,H 28″);13C 2N MR (Me OH 2d 4,125MHz )δ:12919(C 21),11417(C 22),14615(C 23),14613(C 24),11615(C 25),11914(C 26),7818(C 27),7218(C 28),9915(C 21′),8019(C 22′),7510(C 23′),7210(C 24′),7712(C 25′),15(C 26′),12717(C 21″),11510(C 22″

),14618・

599・第35卷第8期

2010年4月

Vol 135,Issue 　8Ap ril,2010

© 1994-2010 China Academic Journal Electronic Publishing House. All rights reserved. http://www.cnki.net

(C 23″),14916(C 24″),11611(C 25″),12311(C 26″),14713(C 27″),11510(C 28″),16910(C 29″

)。以上数据与文献报道p lantasis oside 的数据一致,并通过DEPT,HS QC 和H MBC 谱对其数据进行了准确的归属[16]

。

[参考文献]

[1]　邬家林1梣属植物化学分类与资源利用的研究[J ]1川药校

刊,1985(4):181

[2]　L in S,W ang S J,L iu M T,et al 1Glycosides fr om the stem bark

of Fraxinus sieboldiana [J ]1J Nat Pr od,2007,70:8171

[3]　林生,刘明韬,王素娟,等1小蜡树的香豆素成分及其抗氧

化活性[J ]1中国中药杂志12008,33(14):17081

[4]　Chung M I,LaiM H,Yen M H,et al 1Phenolics fr om Hyperi 2

cum ge m iniflorum [J ]1Phyt oche m istry,1997,44:9431

[5]　O tsuka H,Takeuchi M,I noshiri S,et al 1Phenolic compounds

fr om Coix lachrym al 2jobi var 1Ma 2yuen [J ]1Phyt oche m istry,19,28(3):8831

[6]　Kitaji m a J,Ka moshita A,Ishika wa T,et al 1Glycosides of A trac 2

tyl odes japonica[J ]1Che m Phar m Bull,2003,51:1521

[7]　Sugiyama,M,Kikuchi M 1Phenylethanoid glycosides fr om O s 2

m anthus asiaticus [J ]1Phyt ochem istry,1993,32:15531

[8]　Tanahashi T,W atanabe H,It oh A,et al 1Five secoiridoid gluco 2

sides fr om Fraxinus for m osana [J ]1Phyt oche m istry,1993,32:1331

[9]　Lee T H,Kuo Y C,W ang G J,et al 1Five ne w phenolics fr om

the r oots of Ficus beecheyana [J ]1J Nat Pr od,2002,65:14971

[10]　Sugiyama M ,kikuchi M 1Studies on the constituents of O s m an 2

thus Species 1X 1Structures of phenolic glucosides fr om the leaves

of O s m anthus asiatius Nakai[J ]1Che m Phar m Bull,1992,40:3251

[11]　Kuo Y H,Shue M Z 1Ne w esters,22(42hydr oxy 232methoxyphe 2

nyl )ethyl hexa 2and octacosanoates fr om the leaves of C innam o 2

m um reticulatum Hay[J ]1J Chin Chem Soc,1991,38:651

[12]　Da m t oft S,Jensen S R 1Three phenylethanoid glucosides of unu 2

sual structure fr om Chirita sinensis (Gesneriaceae )[J ]1Phyt o 2che m istry,1994,37:4411

[13]　Calis I,Tasde m ir D,Sticher O,et al 1Phenlethanoid glycosides

fr om D igitalis ferruginea subs p 1ferruginea (D 1aurea L indley,Scr ophulariaceae )[J ]1Che m Phar m Bull,1999,47:13051

[14]　I ossifova T,Vogler B,Klaiber I,et al 1Caffeic acid esters of

phenylethanoid glycosides fr om Fraxinus ornus bark [J ]1Phyt o 2che m istry,1999,50:2971

[15]　M iyase T,Koizum i A,Ueno A,et al 1Studies on the acyl gly 2

cos odes fr om Leucoseptrum j aponicum (M iq 1)Kita mura etMurata [J ]1Che m Phar m Bull,1982,30:27321

[16]　N ishibe S,Ta maya ma Y,Sasahara M,et al 1A phenylethanoid

glycoside fr om P lantago asiatica [J ]1Phyt oche m istry,1995,38:7411

Phenoli c and phenylethano i da l glycosi des fro m branch

of Frax i n us si ebold i a na

L I N Sheng,L I U M ingtao,WANG Sujuan,L I Shuai,Y ANG Yongchun,SH I J iangong

3

(Key L aboratory of B ioactive Substances and R esources U tilization of Chinese Herbal M edicine,M inistry of Education,Institute of M ateria M edica,Chinese A cade m y of M edical Sciences and Peking U nion M edical College,B eijing 100050,China )

　　[Abstract]　O bjecti ve:To investigate che m ical constituents fr om an ethanolic extract of the branch of Fraxinus sieboldiana

(O leaceaue ).M ethod:The constituents were is olated and purified by a combinati on of vari ous chr omat ographic techniques including

silica gel,macr opor ous ads orbent resin,Sephadex LH 220,and p reparative HP LC .Structures of the is olates were elucidated by s pectr o 2scop ic methods including 1D and 2D NMR and MS techniques .Result:Four phenolic and t w elve phenylethanoidal glycosides were ob 2

tained and their structures were identified as 2,62di m ethoxy 2p 2hydr oquinone 242O 2β2D 2glucopyranoside (1),2,62di m ethoxy 2p 2hydr o 2quinone 212O 2β2D 2glucopyranoside (2),42hydr oxy 232methoxyphenyl β2D 2glucopyranoside (3),42hydr oxy 232methoxyphenyl β2D 2xy 2l opyranosyl (1→6)2O 2β2D 2glucopyranoside (4),os manthuside H (5),22(42hydr oxyphenyl )ethyl β2D 2glucopyranoside (6),22(3,

42dihydr oxyphenyl )ethyl β2D 2glucopyranoside (7),22hydr oxy 242(22hydr oxyethyl )2phenyl β2D 2glucopyranoside (8),42(22hydr oxy 2ethyl )222methoxyphenyl β2D 2glucopyranoside (9),calceolari oside B (10),calceolari oside A (11),ferruginoside A (12),is olugran 2doside (13),acteoside (14),chirit ot oside C (15),and p lantasis oside (16).Conclusi on:Compounds 124,9,12,13and 16were obtained fr om the genus Fraxinus f or the first ti m e .

[Key words]　Fraxinus sieboldiana ;che m ical constituents;phenolic glycosides;phenylethanoid glycosides

do i:10.4268/cjc mm 20100811

[责任编辑　王亚君]

・

699・第35卷第8期

2010年4月

Vol 135,Issue 　8Ap ril,2010