全 文 ：Two novel compounds from Ardisia punctata L ind.l
LI Chun
1* , YUE Dang-kun2 , BU Peng-b in1 , SUN You-fu1
(1. Institu te of Ch ineseMa teriaM edica, Ch ina Academ y of ChineseM edicine Sciences, B eijing 100700 , Ch ina;
2. X ian-Janssen Pharmaceutica l Ltd. , Beijing 100027 , China)
Abstract:To study the chem ical constituents o f Ard isia puncta ta , compounds w ere iso lated w ith a
combination of multi-chromatog raphy. Their structu res w ere dete rm ined on the basis of spectra l ana lysis
and comparison to those o f the known compounds. A 1, 4-benzoquinone derivative and a a lky lphenol we re
iso lated from the pe troleum e ther extract o f the roo ts o fArdisia punctata. Their struc tures w ere e lucidated
as 2-tridecy l-3-[ (2-tridecy l-4-acetoxy-6-me thoxy)-phenoxy l ] -6-methoxy-1, 4-benzoquinone (1) and
2-methoxy-4-hydroxy-6-tridecy l-pheny l acetate (2). The tw o compounds are bo th new.
Key words:Ardisia punctata;1, 4-benzoquinone;alky lphenol;belamcandaquinone F;ard isipheno l
D
CLC num ber:R284. 2　　　D ocum ent code:A　　　Artic le ID:0513 - 4870(2007)09 -0959 - 05
Received 2007-03-25.
* Correspond ing au thor　Tel:86 -10 - 84047332,
E-m ail:w enyeli@yahoo. com. cn
血党中两个新化合物的结构鉴定
李　春 1* , 岳党昆2 , 卜鹏滨 1 , 孙有富1
(1. 中国中医科学院 中药研究所 , 北京 100700;2. 西安杨森制药有限公司 , 北京 100027)
摘要:为了系统研究广西草药血党的化学成分。本文采用多种色谱技术和光谱技术对血党根部进行了分离提
取和结构鉴定。从石油醚提取部位分离得到两个新化合物 , 经鉴定其结构分别为 2-十三烷基-3-[ (2-十三烷基-4-乙
酰氧基-6-甲氧基)-苯氧基 ] -6-甲氧基-1, 4-苯醌(1)和 2-甲氧基-4-羟基-6-十三烷基-乙酸苯酯(2)。化合物 1, 2均为
新化合物。
关键词:血党;1, 4-苯醌;烷基酚;be lam candaqu inone F;ardisipheno lD
Introduction
Ardisia puncta ta Lind.l (Myrsinaceae) has been
used in Chinese traditiona lmed icine to treat menstrual
disorders, injuries from falls and rheum atic pa ins[ 1] .
In prev ious study
[ 2] , we have iso la ted th ree new
1, 4-benzoquinones deriva tives from the ch lo ro form
ex tract o f the roots of Ard isia puncta ta. F rom the
petroleum ether extrac t o f the roo ts, we isola ted
add itional new 1, 4-benzoqu inone de rivatives 1 and new
alky lphenol 2, designa ted as be lamcandaquinones F
and ardisipheno l D respective ly a long w ith the known
be lam candaqu inone s C -E
[ 3]
and ardisipheno lA -C.
R esults and d iscussion
Be lam candaquinone F (1) amorphous powde r.
Positive ES I-MS o f 1 show ed an ion peak [M +H ] + a t
m /z 683.7, TOF-MS of 1 show ed an ion peak
[M +Na] + a tm /z 705.7. The mo lecular fo rmula o f
1 was determ ined as C42H66O7 by the HR-FAB-MS a t
705.468 8 [ M +N a ] + (Calcd:705.470 6). The
1
H NMR spectrum of 1 exhibited signa ls for tw o
aliphatic chains [ δ2.43(2H , t, J =8.0 H z), 2.39
(2H , t, J =8.0 H z), 1.48(2H , td, J =7.5 H z),
1.40(2H , td, J =7.5 H z), 1.21 - 1.31(40H , m),
0.88 (6H , t, J =7.0 H z)] , two me thoxy l groups
[ δ3.71 and 3.79 ] , and three arom atic protons
[ δ5.74(1H , s), 6.25(1H , d, J =3 Hz), and 6.45
(1H , d , J =3H z)] . The 13C NMR spec trum revealed
the presence o f tw o methy l groups (δ14.1), tw o
959 药学学报 Ac ta Pharm aceu tica S in ica 2007, 42(9):959 - 963
me thoxyl groups (δ56.1 and 56.9), at least 24
me thy lenes(δ22.7 - 31.9), and 12 aromatic carbons
signa ls (δ100 - 190 ) be long ing to one 1 , 4-
benzoquinone ring and one benzene ring. S ignals of
one ace toxy l g roup w ere also obse rved atδ2.32(3H ,
s), 20.5(OCOCH3) and 169.0(OCOCH 3).
The substitution pattern of the tw o aliphatic
chains, tw ome thoxy l groups and one acetoxy l g roup on
the 1, 4-benzoqu inone ring as w ell as the benzene ring
w as furthe r revea led by HMBC corre lations as shown in
Figure 1.
F igure 1　HMBC co rrela tions fo r the benzoqu inone
ring and benzene ring of 1
By the above analysis, it w as deduced that the
1, 4-benzoquinone ring and the benzene ring w ere
linked togethe r by the C-3 and C-1′. How ever,
comparing to that o f be lam candaquinone D , the
chem ical sh ifts o f the carbons on 1 all changed.
Particu larly, the chem ica l shifts of C-3, C-6 and C-1′
had a downfie ld shifts δ12.8, 21.2, and 6.8,
respective ly, and the chem ical shifts of C-1, C-2,
C-4, C-5 and C-2′had an upfield shiftsδ1.9, 13.7,
9.0, 5.9 and 6.4, respectively. The sim ilar changes
w ere observed from ard isianone A to ard isianone B
[ 4]
and from belamcando l B to be lamcando l A
[ 5]
. These
sugge sted the presence of an oxygen atom between C-3
and C-1′, which w as supported by the de tection o f
characteristic fragment ion peaks a tm /z 364, 322 in
the GCT-MS as shown in Figure 2.
Thus, taking the molecula r formu la and the
biogenesis into consideration, each a liphatic chain on
the compound 1was a C13 chain, wh ich w as confirmed
by the fragmen t ion peaks atm /z 499 in theMALDI-
TOF-MS as shown in Figure 2. Thereby, the struc ture
o f 1 was de term ined as 2-tridecy l-3-[ (2-tridecy l-4-
ace toxy-6-me thoxy)-phenoxy l] -6-me thoxy-1, 4-benzo-
quinone (Figure 3).
Ardisiphenol D (2 ) needles from M eOH.
Positive ESI-MS of 2 show ed an ion peak [M +NH4 ] +
atm /z 382.4 and an ion peak [M +H ] + a tm /z
365.3. Themo lecu lar formula of 2 was determ ined as
C22H36O4 by theM S and
13
C NMR spectrum analysis.
The
1
H NMR spec trum of 2 show ed signals o f twometa
coup led arom atic pro tons at δ6.24(1H , d, J =2.7
Hz) and 6.18 (1H , d, J =2.7 Hz), signal o f a
methoxy l g roup atδ3.71(3H , s), and signals due to a
long a lky l chain atδ0.86(3H , t, J =6.9 H z), 1.23
-1.49(18H , m), 2.38(2H , t, J =7.2H z). The 13C
NMR spectrum o f 2 show ed signals for a tetra-
substituted benzene atδ131.6, 153.8, 98.1, 151.7,
107.5 , and 136.5, and signals for an alkyl side
chain. S igna ls o f an acetoxy l g roup w ere a lso obse rved
at δ2.29 (3H , s), 20.5 (OCOCH3 ) and 169.8
(OCOCH3). The position o f the substituents on the
benzene ring w as de term ined by diffe rence NOE
experiments as show n in Figure 4. These results
established that 2 is 2-me thoxy-4-hydroxy-6-tridecy l-
pheny l aceta te (Figure 5).
F igure 3　Structures of be lamcandaqu inone D and be lam candaqu inone F (1)
960 药学学报 Ac ta Pharm aceu tica S in ica 2007, 42(9):959 - 963
F igure 2　Key fragmenta tions of 1 inMALD I-TOF-MS
F igure 4　NOEs observed for 2 F igure 5　S tructure of ardisipheno lD (2)
Expermi ental
M elting poin ts w ere de term ined on a PHMK
apparatus and are unco rrected.
1
H NMR (500MHz),
13
C NMR (125 MH z), 1H-1H COSY , HMQC and
HMBC spec tra w e re recorded on a Bruke r DRX-500
digita l NMR spectrome ter, using solvent peaks as a
reference standard. ES I-MS spectra we re taken on a
M S-2010 spectrome ter. GCT-MS spec traw e re taken on
aGCT spectrometer. MALD I-TOF spectra w ere taken
on a BIFLEX 3 spec tromete r. Co lumn chroma tog raphy
w as performed on silica gel(100 - 200 mesh) and on
C18 silica ge l(40 - 75 mesh) (Merck).
961 L I Chun, et a l:Two novel com pounds from Ardisia punctata L ind.l
The roots o fArdisia punctata Lind.l (10 kg)were
co llec ted from Dayao M ountain, Guangxi prov ince,
China, in O ctober 2001. The identification of the p lant
w as made by Professor D ai B in, Institute o f Fo lk
M edicines of Guangx i province, Nanning, China.
Dried and powdered roo ts (10 kg)were extrac ted
th ree times w ith methanol and concentrated to afford
1.1 kg of residue. Theme thano l ex tractw as sub jec ted
to a co lumn chromatog raphy over silica ge l(100 -200
mesh) using pe tro leum ethe r, chlo rofo rm , e thy l
acetate and me thano l to obta in four fractions. The
petroleum ether extrac t (96 g) was sub jected to a
co lumn ch roma tography over silica ge l (100 - 200
mesh) e lu ting w ith pe troleum ether-E tOA c(10∶0 ～ 5∶
5) and E tOAc. The 180 co llected fractions(500mL)
were combined in to fou r fractions (F1 -F4) based on
TLC. Frac tion F4 [ pe tro leum e ther-E tOA c (8.5 ∶
1.5)] was column ch roma tographed over silica gel
(100 - 200 mesh) using pe tro leum ethe r-E tOA c (9.5
∶0.5 -8∶2) to ob tain three fractions (F4 -1 - F4 -3).
F4 - 1 [ pe troleum e ther-E tOA c ( 9 ∶ 1 )] was
chromatographed on silica gelw ith CHC l3-MeOH (10∶
0 - 9∶1) to give two frac tions. F4 - 1 - 2 [ CHC l3-MeOH(9.8 ∶0.2)] was subjected to ODS co lumn using
M eOH to obtain be lam candaquinone F (421 mg) and
ardisipheno lD (924mg).
Indentification
Be lam candaquinone F (1):Ye llow powder, mp
83 - 85 ℃;ESI-MS (m /z):683.7 [M +H ] +;
MALDI-TOF-MS (m /z) (%):705.7 [ M +N a] +
(100 ), 647.9 (15.8), 642.7 ( 63.3), 619.8
(13.3), 551.0(31.7), 541.6(10), 523.0(11.7),
498.6(16.7);GCT-MS (m /z) (%):365(3.1),
364(12.5), 323(22.5), 322(100), 320(18.8),
193(2.5), 179(3.1), 166(3.1), 154(21.9), 153
(17.5), 139(3.1), 138(6.9), 125(2.5);1H NMR
and
13
C NMR see Table 1.
ArdisiphenolD (2):Colou less need le, mp 57 -
59 ℃;ESI-MS (m /z):382.4[M +NH 4 ] +, 365.3
[M +H] + , 364.3[M ] +;E I-MS (m /z):365, 364,
324, 323, 322(100%), 154, 138, 124 , 69;1H NMR
δ:0.86(3H , t, J =6.9 Hz, H-13′), 1.23(20H , br s,
H-3′-H-12′), 1.49(2H , br s, H-2′), 2.29(3H , s,
-OCOCH3), 2.38(2H , t, J =7.2 H z, H-1′), 3.71
(3H , s, -OCH 3), 6.18(1H , d, J =2.7 Hz, H-5),
6.24(1H , d , J =2.7 H z, H-3);13 C NMR δ:14. 1
Table 1　1H NMR (500H z) and 13C NMR (125 Hz) data fo r be lamcandaqu inone s D and F in CDC l3
No.
Be lam candaqu inone D [ 2]
δH δC
Belam candaqu inone F
δH δC
1 182. 2 180. 3
2 146. 9 133. 2
3 140. 9 153. 5
4 187. 8 178. 5
5 5. 99(1H , s) 107. 4 5. 74(1H , s) 101. 6
6 158. 9 165. 6
7 2. 18(1H , m), 2. 32(1H , m) 28. 1 2. 39(2H , t, J=8H z) 23. 7
8 1. 29(2H , m) 29. 6 1. 40(2H , td, J=7.5 H z) 28. 4
1′ 112. 3 133. 7
2′ 143. 2 136. 9
3′ 6. 28(1H , d, J =1. 5 H z) 108. 2 6. 25(1H , d, J =3H z) 106. 9
4′ 156. 6 154. 9
5′ 6. 15(1H , d, J =1. 5 H z) 100. 8 6. 45(1H , d, J =3H z) 98. 3
6′ 153. 6 152. 1
7′ 2. 18(2H , m) 33. 4 2. 43(2H , t, J=8H z) 30. 3
8′ 1. 41(2H , b r s) 29. 6 1. 48(2H , td, J=7.5 H z) 29. 9
9 - 16(9′- 16′) 1. 14 -1. 29(16H , m) 28. 2 - 29. 9 1. 21 - 1.31(16H , m) 29. 3 - 29. 7
17(17′) 1. 29(2H , m) 31. 9 1. 24(2H , m) 31. 9
18(18′) 1. 24(2H , m) 22. 7 1. 24(2H , m) 22. 7
19(19′) 0. 87(3H , t, J =6.5 H z) 14. 1 0. 88(3H , t, J=7H z) 14. 1
6-OCH3 3. 85(3H , s) 56. 3 3. 71(3H , s) 56. 9
6′-OCH 3 3. 79(3H , s) 56. 1
4′-OCOCH3 2. 32(3H , s) 20. 5
4′-OCOCH3 169. 0
962 药学学报 Ac ta Pharm aceu tica S in ica 2007, 42(9):959 - 963
(C-13′), 22.7(C-12′), 20.5 (-OCOCH3 ), 31.9
(C-11′), 29.3-30.1(C-1′-C-10′), 55.8(-OCH 3),
98.1(C-3), 107.5(C-5), 131.6(C-1), 136.5(C-6),
151.7(C-4), 153.8(C-2), 169.8(-OCOCH 3).
Acknow ledgem ents　The autho rs thank the P rofessor Dai
Bin of the Institute o f Fo lk M ed ic ines o f Guangx i p rovince, for
the co llec tion and identifica tion o f the p lant ma teria.l The
autho rs are also grate fu l to D r. Tu Guang zhong andM r. X iong
Shaoxiang, Beijing M icro chem istry Institute and Institu te o f
Chem istry, Chinese Academ y o f Science s, fo r obta in ing the
NMR andMS m easurements respec tively.
References
[ 1] Jiang su New M ed ica l Co llege. D ictionary o f Ch inese
T raditiona lM edicine Shanghai(中药大辞典) [M ] . 1st
ed. Shanghai: Shangha i Science and Techno logy
Publishe r, 1977:254.
[ 2] M egum i S, Toshika zu S, N ijsiri R, et a.l A rdisiphenols
A-C, nove l an tiox idants from the fruits ofArdisia colora ta
[ J] . Chem Pharm Bu ll, 2001, 49:1664 - 1665.
[ 3] Li C, Yue DK, Bu PB, e t a.l Three new
be lam candaqu inones from Ardisia puncta ta Lind.l [ J] .
A cta Pha rm a S in (药学学报), 2006, 41:830 - 834.
[ 4] Fukuyam a Y, K iriyam a Y, Okino J. Na turally occurring
5-lipoxygena se inhibito r. II. 1) structu res and syn theses
of a rdisianones A and B, and m aesanin, a lkeny l-1, 4-
benzoquinones from the rh izom e o fArdisia japonica [ J] .
Chem Pha rm Bull, 1993, 41:561 - 565.
[ 5] Fukuyam a Y, Okino J, Kodam a M. S tructure s of
be lam cando ls A and B iso lated fo rm the seed of
B elam canda ch inensis [ J] . Chem Pha rm Bu ll, 1991, 39:
1877 - 1879.
欢迎订阅 2008年《药学学报》
《药学学报》(CN:11 - 2163 /R, ISSN:0513 - 4870)是由中国药学会主办 、中国医学科学院中国协和医科大学
药物研究所承办 、国内外公开发行的药学综合性学术期刊。辟有栏目:述评和综述 、研究论文 、研究简报 、学术动
态。本刊自 1953年创刊以来 , 一直报道药学领域原始性 、创新性科研成果 , 旨在促进国内外学术交流。刊登论文
内容包括药理学 、合成药物化学 、天然药物化学 、药物分析学 、药剂学 、生药学等。
《药学学报》为我国自然科学核心期刊 ,据中国科学引文数据库的数据统计 , 在中国科技核心期刊排行表中 ,
《药学学报》名列前茅 , 在药学类期刊中居首位;本刊已被世界主要检索系统收录 , 为我国药学界高水平的学术刊
物 , 在国际上享有一定知名度。本刊 1999年荣获首届 “国家期刊奖” , 2001年入选中国期刊方阵 “双高” (高知名
度 、高学术水平)期刊;2002年被评为第二届 “国家期刊奖百种重点科技期刊 ”, 并荣获第三届 “中国科技优秀期刊
奖”二等奖;2002 ～ 2005年连续 5届荣获 “百种中国杰出学术期刊”称号。
本刊为 96页 ,月刊 , 大 16开本。每期定价 15元 , 全年定价 180元。国内邮发代码:2 - 233, 国外代码:M105。
欢迎广大作者踊跃投稿 ,欢迎广大读者订阅。可采用的订阅方式如下:
通过当地邮局;
通过 E-m ail(yxxb@ imm. ac. cn)或从网上(www. yxxb. com. cn)下载订阅单 , 填好后寄至编辑部;
通过本刊编辑部 , 联系人:李淑芬 、张晓晔
电话:86 -10 - 63165208, 传真:86 - 10 -63026192
编辑部地址:北京市先农坛街 1号《药学学报》编辑部
邮编:100050
963 L I Chun, et a l:Two novel com pounds from Ardisia punctata L ind.l