全 文 ：10) 。以上数据与文献[10 ]报道的 52醛基212异色满
酮一致。
化合物 Ⅸ:白色粉末 ,苦味 ,mp 101～104 ℃(甲
醇) 。UV λMeOHmax nm : 238。 ( + )2APCI2MS m / z :
37514 [ M + H ] + , 37414M + 。1 H2NMR ( C5D5N)δ:
7187 (1H ,s ,H23) ,5191 (1H ,s br , H21) ,5128 (1H ,d ,
J = 716 Hz , H21′) , 5102～ 5120 ( 3H , m , H28 , 10) ,
2196(1H ,d , J = 916 Hz , H29) ,1170～1180 (2H ,m ,
H26) ; 13C2NMR ( C55N)δ: 9716 ( C21) ,15213 ( C23) ,
10917 ( C24) , 6411 ( C25) , 3219 ( C26) , 6415 ( C27) ,
13218 ( C28) , 5018 ( C29) , 12110 ( C210) , 16511 ( C2
11) ,9911 ( C21′) ,7416 ( C22′) ,7814 ( C23′) ,7114 ( C2
4′) ,7910 ( C25′) ,6214 ( C26′) 。以上数据与文献[11 ]
报道的獐牙菜苦苷一致。
化合物 Ⅹ: 白色粉末 , 苦味。UV λMeOHmax nm :
242 ,274。( - )2APCI2MS m / z :35613[ M - ] ,35513
[M - H ] - , 19312 [ M - H - Glc ] - 。其 1 H2NMR、
13C2NMR数据与文献[12 ]报道的龙胆苦苷一致。
化合物 Ⅺ: 白色粉末 , 苦味。UV λMeOHmax nm :
246。( + )2APCI2MS m/ z :35914 [ M + H ] + ,19712
[M + H - Glc ] + 。其 1 H2NMR、13C2NMR数据与文
献[13 ]报道的獐牙菜苷一致。
References :
[ 1 ] 　Northwest Institute of Plateau Biology , The Chinese Academy of
Sciences1 The Tibetan Medicine Glossary (藏药志) [ M ]1 Xin2
ing : Qinghai People’s Press , 19911
[ 2 ] 　Ding J Y , Fan S F , Hu B L , et al1 Isolation and identification
of the xanthone constituents from S wertia f ranchetiana H1
Smith [J ]1 Acta Biol Plat S in (高原生物学集刊) , 1982 , 1 :
26722691
[ 3 ] 　Ding J Y , Fan S F , Hu B L , et al1 On the xanthone glycosides
and flavonoid lucoside from S wertia f ranchetiana H1 Smith
[J ]1 Acta Bot S in (植物学报) , 1988 , 30 (4) : 41424191
[ 4 ] 　Wang J N , Hou C Y1 Studies on chemical constituents of S wer2
tia f ranchetiana H1 Smith [J ]1 Chin Tradit Herb Drugs (中草
药) , 1994 , 25 (8) : 40124031
[ 5 ] 　Kong D Y , Jiang Y , Yao Y , et al1 Glycosides from Seertia
elongata [J ]1 Chin Tradit Herb Drugs (中草药) , 1995 , 26
(1) : 72101
[ 6 ] 　Li Y L , Ding C X , Liu J Q , et al1 Glycosides from S wertia
erythrosticta [J ]1 Chin Tradit Herb Drugs (中草药) , 2002 ,
33 (2) : 10421061
[ 7 ] 　Bian Q Y , Hou C Y , Chen J M1 Chemical constituents from
S wertia calycina Franch [J ]1 Nat Prod Res Dev (天然产物研
究与开发) , 1998 , 10 (1) : 1251
[ 8 ] 　Prakash A , Basumatary P C , Ghosal S , et al1 Chemical con2
stituents of S wertia paniculata [J ]1 Planta Med , 1982 , 45
(1) : 612621
[ 9 ] 　Sun H F , Hu B L , Ding J Y , et al1 Three new glycosides from
Halenia elli ptica [J ]1 Acta Bot S in (植物学报) , 1987 , 29
(4) : 42224281
[ 10 ] 　Xiao H , Yang L , Chen Z N , et al1 New xanthones from S wer2
tia decora [J ]1 J Chin Pharm Sci , 2001 , 10 (4) : 17221741
[ 11 ] 　Luo Y H , Nie R L1 Studies on iridoid glycosides from S wertia
angustif oli n [J ]1 Acta Pharm Sin (药学学报) , 1992 , 27 (2) :
12521291
[ 12 ] 　Zhang Y M , Xu X D , Hou C Y , et al1 Studies on chemical con2
stituents of S wertia pubescens Franch [J ]1 China J Chin M ater
Med (中国中药杂志) , 1996 , 21 (2) : 10321041
[ 13 ] 　He R Y , Nie R L1 Studies on bitter principles from S wertia
mileensis [J ]1 Acta Bot Y unnan (云南植物研究) , 1980 , 2
(4) : 48024821
Lignans in flower buds of Magnolia biondii
GUO Qun , FAN G Hong , SU Wei Ξ
( Hubei Academy of Traditional Chinese Medicine and Pharmacy , Wuhan 430074 , China)
Abstract : Object 　To investigate the chemical constituents in flower buds of M agnolia biondii in order to
seek reference materials for making the quality standard of Flos M agnoliae , and also get further knowledge
about its effective components1 Methods 　Compounds were isolated by column chromatography with silica gel1
Their st ructures were identified by spectral analysis ( IR , MS , 1 H2NMR , 13C2NMR) 1 Results 　Four lignams
and a neolignan were obtained and identified1 They are veraguensin ( Ⅰ) , pinoresinol dimethyl ether ( Ⅱ) ,
magnolin ( Ⅲ) , lirioresinol2B dimethyl ether ( Ⅳ) , and denudatone ( Ⅴ) 1 Conclusion 　Compound Ⅰand Ⅴ
are found in this plant for the first time1
Key words : M agnolia biondii Pamp1 ; Fols M agnoliae ; lignan ; neolignan ; veraguensin ; denudatone
·948·中草药 　Chinese Traditional and Herbal Drugs 　第 35 卷第 8 期 2004 年 8 月
Ξ 收稿日期 :2003210205
基金项目 :“九五”国家科技攻关项目 (962903202204)
作者简介 :郭　群 ,女 ,硕士 ,主任药师 ,从事中草药研究。　Tel : (027) 87439959 　E2mail :guoqun @public1wh1hb1cn
望春花中的木脂素类化学成分研究
郭 　群 ,方 　红 ,苏 　玮
(湖北省中医药研究院 ,湖北 武汉 　430074)
摘 　要 :目的 　研究望春花 M agnolia biondii 花蕾的木脂素类化学成分 ,为制定辛夷的质量标准寻找标准物质 ,也
为了进一步了解其有效成分。方法 　硅胶柱色谱分离 ,波谱分析 (UV、IR、MS、1 H2NMR、13C2NMR) 鉴定结构。结
果
分离并鉴定了 4 个木脂素 ( Ⅰ～ Ⅳ) 和 1 个新木脂素 ( Ⅴ) 类化合物 : veraguensin ( Ⅰ) 、松脂素二甲醚 (pinoresinol
dimethyl ether , Ⅱ) 、木兰脂素 ( magnolin , Ⅲ) 、里立脂素 B 二甲醚 (lirioresinol2B dimethyl ether , Ⅳ) 和 denudatone
( Ⅴ) 。结论 　化合物 Ⅰ和 Ⅴ系首次从该植物中分离得到。
关键词 :望春花 ;辛夷 ;木脂素 ;新木脂素 ;veraguensin ; denudatone
中图分类号 :R28411 　　　文献标识码 :A 　　　文章编号 :0253 2670 (2004) 08 0849 04
　　The dried flower buds of M agnolia biondii
Pamp1 are used as a Chinese crude drug Flos M agno2
l iae (“Xin2Yi”) for the treatment of nasal congestion
with headache1 Previous reports[1 , 2 ] on chemical in2
vestigations of this plant showed that lignans and ne2
olignans are the major constituents apart f rom volatile
oil1 In order to establish the quality standard of Flos
M agnoliae some researches on the anti2inflammatory ,
antiallergic , and anti2bacterial activities of extracts
and volatile oil of M 1 biondii were made1 EtOH ex2
t ract and volatile oil were found to have obvious ef2
fects on antibacteria[3 ] , and CH2Cl2 extract have sig2
nificant effects on anti2inflammation and antiallergy[4 ]1 The chemical constituents of the CH2Cl2 extract of
M 1 biondii were further reinvestigated1 Four lignans
and a neolignan were isolated1 A lignan ( ver2
aguensin , Ⅰ) and a neolignan ( denudatone , Ⅴ)
were found from this plant for the first time1 The
other three known lignans are pinoresinol dimethyl
ether ( Ⅱ) , magnolin ( Ⅲ) , lirioresinol2B dimethyl
ether ( Ⅳ) 1 The isolation of these compounds and i2
dentification of their st ructure are hereby reported1
Experimental section
General experimental procedures : Mps were de2
termined on a microscopic thermal and were uncor2
rected1 UV spectra were measured on Hitachi U3210
spectrometer in MeOH solution1 IR spectra were
recorded using a Nicolet Impact 400 spectrometer in
KBr pellet1 1 H2NMR and 13C2NMR spectra were
recorded on Bluker ARX - 500 or Varian Mercury -
VX300 , CDCl3 , TMS as i nt1 standard1 EI2MS was
performed on HP5988 or Finnigan Trace GC2MS , di2
rect insertion1 Silica gel ( f rom Qingdao Marine
Chemical Group Co1 , Qingdao , Shandong Province ,
China) was used for column chromatography1
Plant material1 Dired flower buds of M agnolia
biondii Pamp. were collected in Hubei Province ,
China , in February 1999 , and identified by Professor
Wang Ke2qin , f rom Department of Pharmacognosy ,
Hubei Academy of Traditional Chinese Medicine and
Pharmacy1 The voucher specimen have been deposit2
ed at Department of Pharmacognosy , Hubei Academy
of Traditional Chinese Medicine and Pharmacy
(Wuhan , China) 1
Extraction and isolation : The CH2Cl2 extract of
air2dried flower buds ( 115 kg) of M 1 biondii was
concentrated (60 g) , and then chromato2graphed on
silica gel eluting with a solvent gradient of petroleum
ether2EtOAc from 9∶1 to 7∶31 The first f raction was
repeatedly recrystallized from MeOH to give ver2
aguensin (30 mg) 1 The second fraction was isolated
by column chromatography with silica gel again , and
successively gave pinoresinol dimethyl ether ( 70
mg ) , magnolin ( 105 mg ) , and lirioresinol2B
dimethyl ether (50 mg) 1 The third f raction was re2
crystallized to give denudatone (36 mg) 1
Identif ication
Veraguensin ( Ⅰ) 1 C22 H28O5 , colorless crystals ,
mp 12810 - 12912 ℃1 UV λMeOHmax nm : 20418 ,
23114 , 278171 IR νKBrmax ( cm - 1 ) : 2 949 , 1 590 ,
1 518 , 1 326 , 1 235 , 1 130 , 1 025 , 870 , 815 ,
7601 EI2MS m/ z :372 [ M ] + (67) , 287 (16) , 235
(19) , 207 (58) , 206 (100) , 191 (91) , 175 (97) ,
165 (71) , 160 (66) , 151 ( 62) , 138 [ Ar ] ( 70) ,
131 (35) , 107 (44) , 91 (56) , 77 (54) , 55 (20) 1
1 H2NMR (300 MHz , CDCl3) :δ0166 (3H , d , J =
·058· 中草药 　Chinese Traditional and Herbal Drugs 　第 35 卷第 8 期 2004 年 8 月
710 Hz , 32Me) , 1107 (3H , d , J = 710 Hz , 42Me) ,
1179 (1H , m , H23) , 2126 (1H , m , H24) , 3186 ,
3188 , 3189 , 3191 (each 3H , s , OMe) , 4143 (1H ,
d , J = 9 Hz , H25) , 5114 (1H , d , J = 8 Hz , H22) ,
6186 (2H , m , H26′/ H26″) , 6188 (2H , s , H22′/ H2
2″) , 7105 ( 2H , d , J = 11 Hz , H25′/ H25″) 1
13C2NMR ( 75 MHz , CDCl3 ) : δ 15125 and 15132
(32Me/ 42Me) , 46128 and 48122 (C23/ C24) , 56113
(OMe) , 83130 and 87152 ( C22/ C25) , 110128 and
110171 ( C22′/ C22″) , 110198 and 111134 ( C25′/ C2
5″) , 118191 and 119148 ( C26′/ C26″) , 133176 and
134107 ( C21′/ C21″) , 148132 and 148185 ( C23′/ C2
3″) , 148185 and 149125 (C24′/ C24″) 1 According to
the analysis of 13C2NMR , DEPT , 1 H2NMR , MS ,
IR spectra , the st ructure of 2 , 52bis ( 3′, 4′2
dimethoxyphenyl)23 , 42dimethyl tet rahydrofuran can
be deduced1 The deduced structure and the data of
Mp and 1 H2NMR are excellently coincident with
those of veraguensin[5 ]1
Pinoresinol dimethyl ether ( Ⅱ) [1 ,6 ]1 C22 H26O6 ,
colorless crystals , mp 98 - 99 ℃. UV λMeOHmax nm :
20210 , 23010 , 27810. IR νKBrmax ( cm - 1 ) : 1 605 ,
1 591 , 1 517 , 1 465 , 1 448 , 1 426 , 1 343 , 1 327 ,
1 267 , 1 234 , 1 184 , 1 154 , 1 144 , 1 131 , 1 109.
EI2MS m/ z : 386 [ M + ] ( 80 ) , 355 ( 10 ) , 219
(26) , 177 (92) , 166 (88) , 165 (100) , 151 (98) ,
138 (66) , 77 (72) . 1 H2NMR (300 MHz , CDCl3) :
δ3111 (2H , m , H21/ H25) , 3186 , 3189 , (each 6H ,
s , OMe) , 3188 , 4125 (each 2H , m , H24/ H28) ,
4175 ( 2H , m , H22/ H26) , 6182 - 6190 ( 6H , m ,
Ar2H) 1
Magnolin ( Ⅲ) [1 ,7 ] 1 C23 H28O7 , colorless crys2
tals , mp 9114 - 9219 ℃, UV λMeOHmax nm : 20410 ,
22910 , 27810. IRνKBrmax (cm - 1) : 1 587 , 1 519 ,
1 505 , 1 464 , 1 414 , 1 360 , 1 331 , 1 299 , 1 287 ,
1 267 , 1 253 , 1 210 , 1 186 , 1 164 , 1 153 , 1 123 ,
1 093 , 1 080 , 1 063 , 1 038 , 1 003. EI2MS m / z :
416 [ M + ] (100) , 385 (8) , 219 (11) , 207 (29) ,
195 ( 42) , 181 ( 56) , 177 ( 64) , 165 ( 96) , 151
(93) , 138 (40) , 77 ( 32) 1 1 H2NMR ( 300 MHz ,
CDCl3) :δ 3111 (2H , m , H21/ H25) , 3182 , 3186 ,
3189 (each , 3H , s , OMe) , 3186 (6H , s , OMe) ,
3192 , 4127 (each 2H , m , H24/ H28) ; 4174 ( 2H ,
m , H22/ H26) , 6156 (2H , s , Ar2H) ; 6183 - 6190
(3H , m , Ar2H) 1 13C2NMR (75 MHz , CDCl3 ) ;δ
54132 ( C21) , 54165 ( C25) , 56118 (OMe) , 56140
(OMe) , 61112 (OMe) , 72100 ( C24) , 72118 ( C2
8) , 85195 ( C22) , 86127 ( C26) , 102189 ( C22″/ C2
6″) , 109130 ( C22′) , 111113 ( C25′) , 118147 ( C2
6′) , 133157 ( C21′) , 137104 ( C21″) , 137170 ( C2
4″) , 148181 (C23′) , 149136 (C24′) , 153162 (C23″/
C25″) 1
Lirioresinol2B dimethyl ether ( Ⅳ ) [1 ,6 ] 1
C24 H30O8 , colorless crystals , mp 12215 - 125 ℃,
UV λMeOHmax nm : 20710 , 23010 ( shoulder peak ) ,
270101 IRνKBrmax (cm - 1) : 1 591 , 1 510 , 1 461 ,
1 442 , 1 372 , 1 328 , 1 239 , 1 180 , 1 130 , 1 109 ,
1 060 , 1 040 , 1 0101 EI2MS m / z : 446 [ M + ]
(96) , 224 (10) , 207 (41) , 196 (39) , 195 (56) ,
181 ( 95 ) , 125 ( 42 ) , 77 ( 52 ) 1 1 H2NMR ( 300
MHz , CDCl3 ) :δ 3109 (2H , m , H21/ H25) , 3183
(6H , s , OMe) , 3186 (12H , s , OMe) , 3193 and
4130 (each 2H , m H24/ H28) , 4174 (2H , m , H22/
H26) , 6156 (4H , s , Ar2H) 1
Denudatone ( Ⅴ) 1 C22 H26O6 , colorless crystals ,
mp 23510 - 23915 ℃1 UV λMeOHmax nm : 20512 ,
258141 IRνKBrmax (cm - 1 ) : 1 666 , 1 612 , 1 5901 EI2
MS m/ z : 386 [ M + ] (95) , 233 (20) , 223 (38) ,
222 (100) , 210 (87) , 209 (94) , 196 (90) , 195
(77) , 181 (84) , 164 (76) , 147 (71) , 135 (80) ,
121 (43) , 107 (73) , 91 (70) , 77 (58) , 69 (63) , 65
(38) , 53 (21) , 44 (35) 1 1 H2NMR (300 MHz , CD2
Cl3) :δ0158 (3H , d , J = 6 Hz , H29) , 1174 (1H ,
dd , J = 13 , 12 Hz , H29′) , 2107 ( 1H , m , H28) ,
2122 (1H , d , J = 12 Hz , H27′) , 2134 (2H , m , H2
7′/ H29′) , 2154 (1H , m , H27) , 3165 (3H , s , 5′2
OMe) , 3179 (3H , s , 42OMe) , 3183 (6H , s , 3/ 52
OMe) , 5104 (1H , t , J = 5 Hz , H28′) , 5148 (1H ,
s , H26′) , 5177 (1H , s , H23′) , 6136 (2H , s , H22/
H26) 1 13C2NMR ( 75 MHz , CDCl3 ) :δ 14187 ( C2
9) , 38104 ( C29′) , 43186 ( C27′) , 45149 ( C28) ,
47114 ( C27 ) , 50159 ( C21′) , 55154 ( 5′2OMe ) ,
56138 (3/ 52OMe) , 61110 (42OMe) , 82116 (C28′) ,
101161 (C23′) , 104170 (C22/ C26) , 109126 (C26′) ,
136185 ( C21 ) , 139134 ( C24 ) , 153148 ( C25′) ,
153152 (C23/ C25) , 180142 (C22′) , 183140 (C24′) 1
·158·中草药 　Chinese Traditional and Herbal Drugs 　第 35 卷第 8 期 2004 年 8 月
It is identified by comparison with reference data[8 ]1
References :
[ 1 ] 　Ma Y L , Han G Q1 Studies on the lignans from M agnolia
biondii [J ]1 China J Chin M ater Med (中国中药杂志 ) ,
1995 , 20 (2) : 10221041
[ 2 ] 　Ma Y L , Huang Q L , Han G Q1 A neolignan and lignans from
M agnolia biondii [J ]1 Phytochemist ry , 1996 , 41 ( 1) : 2872
2891
[ 3 ] 　Guo Q , Su W1 Experimental study on antibacteria of M agnolia
biondii [J ]1 Chin J Tradit Med Sci Tech (中国中医药科技) ,
1999 , 6 (1) : 181
[ 4 ] 　Zhang Y Z , Li X L1 Studies on effects of anti2inflammation and antiallergy of CH2Cl2 extract from M agnolia biondii [J ]1 ChinTradit Herb Drugs (中草药) , 2001 , 32 (9) : 81128131[ 5 ] 　Barata L E S , Baker P M , Gottlieb O R , et al1 Neolignans ofV irola surinamensis [J ]1 Phytochemist ry , 1978 , 17 : 78327861[ 6 ] 　Kakisawa H , Chen Y P , Hsu H Y1 Lignans in flower buds ofM agnolia f argesii [J ]1 Phytochemist ry , 1972 , 11 : 2289222931[ 7 ] 　Miyazawa M , Kasahara H , Kameoka H1 Phenolic lignans fromflower buds of M agnolia f argesii [J ]1 Phytochemist ry , 1992 ,31 (10) : 3666236681[ 8 ] 　Iida T , Tchino K , Ito K1 Neolignans from M agnolia denudata[J ]1 Phytochemist ry , 1982 , 21 (12) : 2939229411
人工种植高山红景天中抑制脯酰肽内切酶的化学成分
李 　俊1 ,范文哲2 ,门田重利2 ,义祥辉1 Ξ
(11 广西师范大学 资源与环境学系 ,广西 桂林 　541004 ; 　21 日本富山医科药科大学和汉药研究所 ,日本 富山 　2630)
摘 　要 :目的 　研究人工种植高山红景天中具有较强的脯酰肽内切酶 (prolyl endopeptidase , PEP) 抑制活性的化学
成分。方法 　人工种植高山红景天用甲醇提取 ,不同极性溶剂分级萃取 ,分别用硅胶和 Sephadex L H220 柱色谱分
离 ,测定化合物的理化常数和波谱数据 ,鉴定化合物结构。结果 　从人工种植高山红景天甲醇提取物的醋酸乙酯
萃取部分分离得到 8 个单体化合物 :没食子酸 ( Ⅰ) 、红景天苷 ( Ⅱ) 、72 O2β2D2葡萄糖23 ,4′,5 ,82四羟基黄酮 ( Ⅲ) 、红
景天黄酮苷 ( Ⅳ) 、表儿茶素 ( Ⅴ) 、表儿茶素没食子酸 ( Ⅵ) 、红景天氰苷 A ( Ⅶ) 、β2D2葡萄糖23 ,72二甲基242羟基22 ,62
辛二烯 ( Ⅷ) 。结论 　首次从人工种植红景天分离出显示较强的 PEP 抑制活性组份中分离出 8 个单体化合物。
关键词 :高山红景天 ;脯酰肽内切酶 ;红景天苷
中图分类号 :R28411 　　　文献标识码 :A 　　　文章编号 :0253 2670 (2004) 08 0852 03
Chemical constituent as inhibitor to prolyl endopeptidase from underground part
of cultivated Rhodiola sachalinensis
L I J un1 , FAN Wen2zhe2 , KADO TA Shigetoshi2 , YI Xiang2hui1
(11 Department of Resources and Environmental Science of Guangxi Normal University , Guilin 541004 , China ;
21 Research Institute for Wakan2Yaku ( Traditional Sino2Japanese Medicines) , Toyama Medical
and Pharmaceutical University , Toyama , 2630 Japan)
Abstract : Object 　To study the chemical constituents as inhibitors to prolyl endopeptidase f rom the under2
ground part of cultivated Rhodiola sachali nensis A. Bor. Methods 　The compounds were isolated on silica gel
column and purified by Sephadex L H220 , and identified by spectral data and physicochemical properties1 Results
　Eight compounds were obtained from EtOAc extract and identified as gallic acid ( Ⅰ) , salidroside ( Ⅱ) , 3 ,
4′2t rihydroxyflavone272O2β2D2glucopyranoside ( Ⅲ) , rhodioflavonoside ( Ⅳ) , epigallocatechin ( Ⅴ) , epigallo2
catechin gallate ( Ⅵ) , rhodiocyanoside A ( Ⅶ) , 3 , 72dimethy242hydroxy22 , 62octadien2O2β2D2glucoside ( Ⅷ) 1
Conclusion 　The compounds are first isolated as inhibitors to prolyl endopeptidase f rom the underground part of
cultivated R . sachali nensis1
Key words : Rhodiola sacnali nensis A1 Bor1 ; prolyl endopeptidase ( PEP) ; salidroside
　　高山红景天 Rhodiola sachali nensis A1 Bor1 为 红景天科多年生草本植物 ,具有很高的药用价值。
·258· 中草药 　Chinese Traditional and Herbal Drugs 　第 35 卷第 8 期 2004 年 8 月
Ξ 收稿日期 :2003210215
基金项目 :教育部重点基金资助项目 (0194) ;广西省自然科学基金资助项目 (桂科基 0144025)
作者简介 :李　俊 (1964 - ) ,男 ,广西浦北人 ,广西师范大学资源与环境学系高级工程师 ,硕士生导师 ,主要从事天然产物的化学成分及
其生物活性研究。　Tel : (0773) 5846201 　E2mail :lijun9593 @tom1com