全 文 ：Ｒeceived:July 24，2012 Accepted:October 23，2012
Foundation Item:This work was supported by the National Natural Sci-
ence Foundation of China (21072199) ，Natural Science Funding of
Yunnan Province (No． 2009CD112) ，and Foundation of Chinese Acad-
emy of Sciences to Dr． H． P． He，the Yong Academic and Technical
Leader Ｒaising Foundation of Yunnan Province (2010CI047)
* Corresponding author Tel:86-871-5223070;E-mail:haoxj@ mail． kib．
ac． cn;hehongping@ mail． kib． ac． cn
天然产物研究与开发 Nat Prod Ｒes Dev 2013，25:912-915
文章编号:1001-6880(2013)7-0912-04
异叶三宝木叶的化学成分研究
唐贵华1，2，张 于1，何红平1* ，郝小江1*
1中国科学院昆明植物研究所 植物化学与西部植物资源持续利用国家
重点实验室，昆明 650201;2 中国科学院大学，北京 100049
摘 要:从异叶三宝木(Trigonostemon flavidus)叶中分离得到 9 个化合物，经波谱数据分析鉴定为 robustic acid
(1) ，1-［6-hydroxy-2-methoxy-2″，2″-dimethylpyrano-(5″，6″:3，4) ］-2-(4-methoxyphenyl)-1，2-ethanedione (2) ，3β-
ursolic acid (3) ，(6S，7E)-6-hydroxy-4，7-megastigmadien-3，9-dione (4) ，3(-hydroxy-5，6-epoxy-7-megastigmen-9-one
(5) ，(3Ｒ，6Ｒ，7E)-3-hydroxy-4，7-megastigmadien-9-one (6) ，loliolide (7) ，methyl P-coumarate (8) ，和 methyl si-
napate (9)。化合物 1 ～ 7 和 9 为首次从三宝木属(Trigonostemon)植物中分离得到。
关键词:大戟科;异叶三宝木;化学成分;黄酮;降倍半萜
中图分类号:Ｒ284. 1;Q946． 91 文献标识码:A
Chemical Constituents from the Leaves of Trigonostemon flavidus
TANG Gui-hua1，2，ZHANG Yu1，HE Hong-ping1* ，HAO Xiao-jiang1*
1State Key Laboratory of Phytochemistry and Plant Ｒesources in West China，Kunming Institute of Botany，Chinese Academy of Sciences，
Kunming 650201，Yunnan，China;2University of Chinese Academy of Sciences，Beijing 100049，China
Abstract:Nine known compounds were isolated from the leaves of Trigonostemon flavidus． On the basis of spectroscopic
data，their structures were identified as robustic acid (1) ，1-［6-hydroxy-2-methoxy-2″，2″-dimethylpyrano-(5″，6″:3，
4) ］-2-(4-methoxyphenyl)-1，2-ethanedione (2) ，3β-ursolic acid (3) ，(6S，7E)-6-hydroxy-4，7-megastigmadien-3，9-
dione (4) ，3β-hydroxy-5，6-epoxy-7-megastigmen-9-one (5) ，(3Ｒ，6Ｒ，7E)-3-hydroxy-4，7-megastigmadien-9-one (6) ，
loliolide (7) ，methyl P-coumarate (8) ，and methyl sinapate (9)． Compounds 1-7 and 9 were obtained from the genus
Trigonostemon for the first time．
Key words:Euphorbiaceae;Trigonostemon flavidus;chemical constituents;flavonoids;degraded sesquiterpenoids
Introduction
Trigonostemon flavidus Gagnepain，also known as Trigo-
nostemon heterophyllus Merrill，is an evergreen shrub
belonging to the Euphorbiaceae family，and is only dis-
tributed in Sanya city，Hainan Province in China ［1］．
Previous research on this plant have revealed the oc-
currence of modified daphnane diterpenoids ［2］，3，4-
seco-diterpenoids ［2，3］，degraded diterpenoids ［4］，and
phenylpropanoids ［5］． As our ongoing work，we have
carried out a phytochemical investigation on the leaves
of T． flavidus collected in Hainan Province． Herein，we
report the identification of nine known compounds
(Fig． 1) ，including two flavonoids，robustic acid (1)
and 1-［6-hydroxy-2-methoxy-2″，2″-dimethylpyrano-
(5″，6″:3，4) ］-2-(4-methoxyphenyl)-1，2-ethanedi-
one (2) ，one triterpene，3β-ursolic acid (3) ，four de-
graded sesquiterpenoids，(6S，7E)-6-hydroxy-4，7-me-
gastigmadien-3，9-dione (4) ，3β-hydroxy-5，6-epoxy-7-
megastigmen-9-one (5) ，(3Ｒ，6Ｒ，7E)-3-hydroxy-4，7-
megastigmadien-9-one (6)and loliolide (7) ，and two
phenylpropanoids，methyl P-coumarate (8)and methyl
sinapate (9)． Compounds 1-7 and 9 were obtained
from Trigonostemon for the first time．
Experimental section
Experimental instruments
1H and 13C NMＲ spectra were recorded on Bruker AM-
DOI:10.16333/j.1001-6880.2013.07.002
400 and Bruker DＲX-500 spectrometers using TMS as
an internal standard． ESI-MS analyses were carried out
on an API Qstar Pulsar 1 instrument． Silica gel (80-
100 and 300-400 mesh，Qingdao Makall Group Co．，
Ltd．) ，MCI gel CHP 20P (75-150 μm，Mitsubishi
Chemical Corporation，Tokyo) ，C8 silica gel (20-45
μm，Fuji Silysia Chemical Ltd．) ，and SephadexLH-20
(GE Healthcare Bio-Xciences AB)were used for col-
umn chromatography，and silica gel GF254(Qingdao)
was used for preparative TLC in the form of precoated
plates． TLC spots were visualized under UV light and
by dipping into 5% H2SO4 in EtOH followed by heating．
Plant material
The leaves of T． flavidus were collected from Sanya cit-
y，Hainan Province，the People’s Ｒepublic of China，in
December 2010． The plant was identified by one of the
authors (Gui-hua Tang) ，and a voucher specimen
(H20101201)was deposited at State Key Laboratory
of Phytochemistry and Plant Ｒesources in West China，
Kunming Institute of Botany．
Extraction and isolation
The air-dried leaves of T． flavidus (13． 0 kg)were
powdered and extracted with MeOH for three times (4，
3，and 3 h，respectively)under reflux． After evapora-
ting the solution under reduced pressure，the crude res-
idue was suspended in water and then partitioned suc-
cessively with petroleum ether (PE)and EtOAc to give
two corresponding portions． The PE extract (340． 0 g)
was subjected to column chromatography (CC)over
silica gel (80-100 mesh)using PE-Me2CO (100∶ 1→0
∶ 1)to yield five fractions (A-E)． Fr． B (36． 5 g)was
subjected to CC over MCI gel CHP 20P (80% -90%
MeOH)and then over C8 silica gel eluting with a gra-
dient of increasing MeOH in H2O (35% -95%)to gain
seven fractions (B1-B7)． Subsequently，Fr． B1 was
chromatographed on a Sephadex LH-20 column
(MeOH)and a silica gel column (300-400 mesh，PE-
Me2CO，10∶ 1)followed by a Sephadex LH-20 column
(Me2CO)to obtain 4 (48． 4 mg)． After recrystalliza-
tion of 1 (85． 8 mg)from Fr． B2，the stock was chro-
matographed on a Sephadex LH-20 column (MeOH)
and a silica gel column (300-400 mesh，PE-Me2CO，6
∶ 1)to afford 3 (16． 5 mg)． Fr． B3 was subjected to CC
over Sephadex LH-20 column (CHCl3-MeOH，1∶ 1)to
gain two subfractions (B31-B32)． Subfraction B31 was
purified by a silica gel column (300-400 mesh，PE-
Me2CO，12 ∶ 1) and a Sephadex LH-20 column
(MeOH)to get 7 (8． 8 mg)． Subfraction B32 was sub-
jected to CC over a silica gel column (300-400 mesh，
PE-Me2CO，12 ∶ 1) and a Sephadex LH-20 column
(Me2CO)to obtain 5 (9． 7 mg)． Fr． B4 was chromato-
graphed on a Sephadex LH-20 column (MeOH)and a
silica gel column (PE-Me2CO，6∶ 1)to yield 6 (10． 1
mg) ，purified by preparative TLC (CHCl3-Me2CO，3∶
1)． Fr． B5 was purified by a silica gel column (300-400
mesh，PE-EtOAc，6∶ 1)to get 8 (7． 5 mg)and 9 (6． 0
mg)． Fr． B6 was subjected to CC over a Sephadex LH-
20 column (MeOH)followed by a silica gel column
(300-400 mesh，PE-Me2CO，10 ∶ 1)to obtain 2 (5． 4
mg)．
Structure identification
Fig. 1 The chemical structures of compounds 1-9
Ｒobustic acid (1) White crystal;C22H20 O6 ESI-MS
(positive)m/z 403 ［M + Na］+;1H NMＲ (CDCl3，
400 MHz)δ:7. 47 (2H，d，J = 8. 8 Hz，H-2，6) ，
6. 96 (2H，d，J = 8. 8 Hz，H-3，5) ，6. 64 (1H，s，H-
8) ，6. 51 (1H，d，J = 10. 0 Hz，H-4″) ，5. 78 (1H，d，
J = 10. 0 Hz，H-3″) ，3. 98 (3H，s，5-OCH3) ，3. 83
(3H，s，4(-OCH3) ，1. 49 (6H，s，2″-CH3 × 2) ;
13 C
NMＲ (CDCl3，100 MHz)δ:162. 6 (s，C-4) ，160. 2
(s，C-2) ，158. 9 (s，C-7) ，157. 1 (s，C-4) ，153. 7
(d，C-5) ，152. 1 (s，C-9) ，131. 7 (d，C-2，6) ，131. 4
(d，C-3″) ，123. 3 (s，C-1) ，115. 0 (d，C-4″) ，113. 5
(d，C-3，5) ，110. 7 (s，C-6) ，103. 8 (s，C-3) ，101. 8
(s，C-10) ，101. 7 (d，C-8) ，77. 6 (s，C-2″) ，64. 4 (q，
319Vol. 25 TANG Gui-hua，et al:Chemical Constituents from the Leaves of Trigonostemon flavidus
5-OCH3) ，55. 2 (q，4-OCH3) ，28. 0 (q，2″-CH3 ×
2)． Its NMＲ and MS data were identical with those re-
ported in the literature ［6，7］.
1-［6-Hydroxy-2-methoxy-2″，2″-dimethylpyrano-(5″，
6″:3，4)］-2-(4-methoxyphenyl)-1，2-ethanedione
(2) Yellow oil;C21 H20 O6 ESI-MS (positive)m/z
391 ［M + Na］+;1H NMＲ (CDCl3，400 MHz)δ:
7. 87 (2H，d，J = 8. 7 Hz，H-2，6) ，6. 97 (2H，d，J
= 8. 7 Hz，H-3，5) ，6. 31 (1H，d，J = 10. 0 Hz，H-
4″) ，6. 24 (1H，s，H-5) ，5. 58 (1H，d，J = 10. 0 Hz，
H-3″) ，3. 88 (3H，s，4-OCH3) ，3. 52 (3H，s，2-
OCH3) ，1. 44 (6H，s，2″-CH3 × 2) ;
13C NMＲ (CDCl3，
100 MHz)δ:197. 9 (s，C-7) ，189. 4 (s，C-8) ，166. 2
(s，C-6) ，164. 2 (s，C-4) ，163. 3 (s，C-4) ，159. 2
(s，C-2) ，131. 5 (d，C-2，6) ，128. 2 (d，C-3″) ，
125. 9 (s，C-1) ，116. 1 (d，C-4″) ，114. 2 (d，C-3，
5) ，107. 2 (s，C-1) ，106. 4 (s，C-3) ，100. 9 (d，C-
5) ，78. 0 (s，C-2″) ，55. 5 (q，4(-OCH3) ，63. 0 (q，2-
OCH3) ，28. 1 (q，2″-CH3 × 2). The NMＲ and MS data
were in consistent with those reported in the literature
［7］.
3β-Ursolic acid (3) White amorphous powder;C30
H48O3 ESI-MS (positive)m/z 479 ［M + Na］
+;1H
NMＲ (C5D5N，500 MHz)δ:5． 49(1H，br． s，H-12) ，
3. 45 (1H，dd，J = 10. 0 and 6. 1 Hz，H-3) ，1. 24
(3H，s，H-23) ，1. 22 (3H，s，H-27) ，1. 05 (3H，s，H-
26) ，1. 02 (3H，s，H-24) ，0. 99 (3H，d，J = 6. 3 Hz，
H-29) ，0. 94 (3H，d，J = 6. 1 Hz，H-30) ，0. 88 (3H，
s，H-25) ;13C NMＲ (C5D5N，100 MHz)δ:180. 0 (s，
C-28) ，139. 3 (s，C-13) ，125. 7 (d，C-12) ，78. 2 (d，
C-3) ，55. 9 (d，C-5) ，53. 6 (d，C-18) ，48. 1 (d，C-
9) ，48. 1 (s，C-17) ，42. 6 (s，C-14) ，40. 0 (s，C-8) ，
39. 54 (s，C-4) ，39. 45 (d，C-19，20) ，39. 4 (t，C-1) ，
37. 5 (s，C-10) ，37. 3 (t，C-22) ，33. 6 (t，C-7) ，31. 2
(t，C-21) ，28. 9 (q，C-23) ，28. 7 (t，C-15) ，28. 2 (t，
C-2) ，25. 0 (t，C-16) ，24. 0 (q，C-27) ，23. 7 (t，C-
11) ，21. 5 (q，C-30) ，18. 8 (t，C-6) ，17. 6 (q，C-
29) ，17. 5 (q，C-26) ，16. 6 (q，C-24) ，15. 7 (q，C-
25). Its NMＲ and MS data were in accordance with
those reported in the literature ［8］.
(6S，7E)-6-Hydroxy-4，7-megastigmadien-3，9-di-
one (4) Colorless oil;C13 H18 O3 ESI-MS (positive)
m/z 245［M + Na］+;1H NMＲ (CDCl3，400 MHz)
δ:6. 83 (1H，d，J = 15. 7 Hz，H-7) ，6. 45 (1H，d，J
= 15. 7 Hz，H-8) ，5. 94 (1H，s，H-4) ，2. 58 (1H，d，J
= 17. 0 Hz，H-2a) ，2. 32 (1H，d，J = 17. 0 Hz，H-
2b) ，2. 29 (3H，s，H-10) ，1. 88 (3H，s，H-13) ，1. 09
(3H，s，H-11) ，1. 01 (3H，s，H-12) ;13 C NMＲ
(CDCl3，100 MHz)δ:197. 7 (s，C-9) ，197. 3 (s，C-
3) ，160. 9 (s，C-5) ，145. 3 (d，C-7) ，130. 3 (d，C-
8) ，127. 6 (d，C-4) ，79. 2 (s，C-6) ，49. 5 (t，C-2) ，
41. 5 (s，C-1) ，28. 3 (q，C-10) ，24. 3 (q，C-12) ，
22. 9 (q，C-11) ，18. 7 (q，C-13). Its NMＲ and MS da-
ta were in consistent with those reported in the literature
［9］.
3(-Hydroxy-5，6-epoxy-7-megastigmen-9-one (5)
Colorless oil;C13 H20 O3 ESI-MS (positive)m/z 247
［M + Na］+;1H NMＲ (CDCl3，400 MHz)δ:7. 00
(1H，d，J = 15. 6 Hz，H-7) ，6. 27 (1H，d，J = 15. 6
Hz，H-8) ，3. 88 (1H，m，H-3) ，2. 37 (1H，dd，J =
14. 4 and 4. 9 Hz，H-4a) ，2. 27 (3H，s，H-10) ，1. 75
(1H，dd，J = 14. 4 and 4. 4 Hz，H-2a) ，1. 63 (1H，
dd，J = 14. 4 and 8. 8 Hz，H-4b) ，1. 25 (1H，dd，J =
14. 4 and 9. 0 Hz，H-2b) ，1. 18 (6H，s，H-12，13) ，
0. 96 (3H，s，H-11) ;13C NMＲ (CDCl3，100 MHz)δ:
197. 5 (s，C-9) ，142. 5 (d，C-7) ，132. 5 (d，C-8) ，
69. 4 (s，C-6) ，67. 3 (s，C-5) ，63. 9 (d，C-3) ，46. 6
(t，C-2) ，40. 5 (d，C-4) ，35. 1 (s，C-1) ，29. 3 (q，C-
12) ，28. 2 (q，C-10) ，24. 9 (q，C-11) ，19. 8 (q，C-
13). Its NMＲ and MS data were identical with those
reported in the literature ［10］.
(3Ｒ，6Ｒ，7E)-3-Hydroxy-4，7-megastigmadien-9-
one (6) Colorless oil;C13 H20 O2 ESI-MS (positive)
m/z 231［M + Na］+;1H NMＲ (CD3OD，400 MHz)
δ:6. 67 (1H，dd，J = 15. 8 and 10. 3 Hz，H-7) ，6. 13
(1H，d，J = 15. 8 Hz，H-8) ，5. 60 (1H，br. s，H-4) ，
4. 22 (1H，br. s，H-3) ，2. 58 (1H，d，J = 10. 3 Hz，H-
6) ，2. 27 (3H，s，H-10) ，1. 79 (1H，dd，J = 13. 2 and
5. 4 Hz，H-2a) ，1. 62 (3H，s，H-13) ，1. 39 (1H，dd，J
= 13. 2 and 7. 1 Hz，H-2b) ，1. 01 (3H，s，H-11) ，
0. 90 (3H，s，H-12) ;13 C NMＲ (CD3OD，100 MHz)
δ:200. 8 (s，C-9) ，149. 8 (d，C-7) ，135. 9 (s，C-5) ，
134. 7 (d，C-8) ，127. 3 (d，C-4) ，65. 9 (d，C-3) ，
55. 5 (d，C-6) ，45. 0 (t，C-2) ，35. 0 (s，C-1) ，29. 8
(q，C-11) ，27. 1 (q，C-10) ，24. 5 (q，C-12) ，22. 8
(q，C-13). Its NMＲ and MS data were in accordance
419 Nat Prod Ｒes Dev Vol. 25
with those reported in the literature ［11］.
Loliolide (7) Colorless oil;C11H16O3 ESI-MS (posi-
tive)m/z 219 ［M + Na］+;1H NMＲ (CDCl3，400
MHz)δ:5. 68 (1H，s，H-7) ，4，32 (1H，br. s，H-3) ，
2. 47 (1H，dd，J = 14. 0 and 2. 2 Hz，H-4a) ，1. 97
(1H，dd，J = 14. 0 and 2. 5 Hz，H-2a) ，1. 74 (1H，
dd，J = 14. 5 and 3. 6 Hz，H-4b) ，1. 51 (1H，dd，J =
14. 5 and 3. 6 Hz，H-2b) ，1. 77 (3H，s，H-11) ，1. 46
(3H，s，H-9) ，1. 26 (3H，s，H-10) ;13C NMＲ (CDCl3，
100 MHz)δ:182. 7 (s，C-6) ，172. 9 (d，C-8) ，112. 8
(d，C-7) ，86. 8 (s，C-5) ，66. 7 (d，C-3) ，47. 2 (t，C-
2) ，45. 5 (t，C-4) ，35. 0 (s，C-1) ，30. 6 (q，C-9) ，
26. 9 (q，C-11) ，26. 4 (q，C-10). Its NMＲ and MS da-
ta were identical with those reported in the literature
［12］.
Methyl P-coumarate (8) White amorphous pow-
der;C10 H10 O3 ESI-MS (positive)m/z 201 ［M +
Na］+;1H NMＲ (CD3OD，400 MHz)δ:7. 59 (1H，d，
J = 16. 0 Hz，H-7) ，7. 45 (2H，d，J = 8. 6 Hz，H-2，
6) ，6. 79 (2H，d，J = 8. 6 Hz，H-3，5) ，6. 32 (1H，d，
J = 16. 0 Hz，H-8) ，3. 75 (3H，s，9-OCH3). The
NMＲ and MS data were in accordance with those re-
ported in the literature ［13］.
Methyl sinapate (9) White amorphous powder;C12
H14O5 ESI-MS (positive)m/z 261 ［M + Na］
+;1H
NMＲ (CD3OD，400 MHz)δ:7. 59 (1H，d，J = 15. 9
Hz，H-7) ，6. 89 (2H，s，H-2，6) ，6. 38 (1H，d，J =
15. 9 Hz，H-8) ，3. 87 (6H，s，3，5-OCH3) ，3. 76 (3H，
s，9-OCH3) ;
13 C NMＲ (CD3OD，100 MHz)δ:169. 6
(s，C-9) ，149. 4 (s，C-3，5) ，147. 0 (d，C-7) ，139. 6
(s，C-4) ，126. 6 (s，C-1) ，115. 6 (d，C-8) ，106. 8
(d，C-2，6) ，56. 8 (q，3，5-OCH3) ，52. 0 (q，9-OCH3)
. The NMＲ and MS data were in accordance with those
reported in the literature ［14］.
Acknowledgment We are grateful to all members of
the analytical group for recording spectra in the State
Key Laboratory of Phytochemistry and Plant Ｒesources
in West China，Kunming Institute of Botany，CAS. This
work was supported by the National Natural Science
Foundation of China (21072199) ，the Natural Science
Funding of Yunnan Province (2009CD112) ，and Foun-
dation of Chinese Academy of Sciences to
Dr. H. P. He，the Yong Academic and Technical Leader
Ｒaising Foundation of Yunnan Province (2010CI047).
Ｒeferences
1 Li PT，Zhuang XY，Huang JX，et al． Notes on Trigonostemon
(Euphorbiacea)for the Flora of China． Harvard Papers in
Botany，2006，11:117-120．
2 Dong SH，Liu HB，Xu CH，et al． Constituents of Trigonoste-
mon heterophyllus． J Nat Prod，2011，74:2576-2581．
3 Li YX，Mei WL，Zuo WJ，et al． Two new compounds from
Trigonostemon heterophyllus． Phytochem Lett，2012，5:41-44．
4 Tang GH，Zhang Y，Gu YC，et al． Trigoflavidols A-C，degrad-
ed diterpenoids with antimicrobial activity，from Trigonoste-
mon flavidus． J Nat Prod，2012，75:996-1000．
5 Li YX(李奕星) ，Zuo WJ(左文健) ，Wang H(王辉) ，et al．
Chemical constituents from the twigs of Trigonostemon hetero-
phyllus． Chin J Me Chem(中国药物化学杂志) ，2012，22:
120-123．
6 Donnelly DMX，Molloy DJ，Ｒeilly JP，et al． Aryllead-mediated
synthesis of linear 3-arylpyranocoumarins:synthesis of robustin
and robustic acid． J Chem Soc，Perk Trans，1995，1:2531-2534．
7 Magalhaes AF，Tozzi AMGA，Magalhaes EG，et al． New prenylat-
ed metabolites of Deguelia longeracemosa and evaluation of their
antimicrobial potential． Planta Med，2006，72:358-363．
8 Alves JS，de Castro JCM，Freire MO，et al． Complete assign-
ment of the 1H and 13C NMＲ spectra of four triterpenes of
the ursane，artane，lupane and friedelane groups． Magn Ｒeson
Chem，2000，38:201-206．
9 Knapp H，Weigand C，Gloser J，et al． 2-Hydroxy-2，6，10，10-
tetramethyl-1-oxaspiro［4． 5］dec-6-en-8-one:precursor of 8，
9-dehydrotheaspirone in white-fleshed nectarines． J Agric
Food Chem，1997，45:1309-1313．
10 Choi S，Yang M，Lee K，et al． Lignan and terpene constituents
from the aerial parts of Saussurea pulchella． Arch Pharm Ｒes，
2007，30:1067-1074．
11 Machida K，Kikuchi M． Norisoprenoids from Viburnum dilata-
tum． Phytochemistry，1996，41:1333-1336．
12 Yan L(严岚) ，Jin HZ(金慧子) ，Nie LY(聂利月) ，et al．
Chemical constituents from Inula nervosa Wall． Nat Prod Ｒes
Dev(天然产物研究与开发) ，2011，23:258-261．
13 El-Batta A，Jiang C，Zhao W，et al． Wittig reactions in water
media employing stabilized ylides with aldehydes． Synthesis
of α，β-unsaturated esters from mixing aldehydes，α-bromoes-
ters，and Ph3P in aqueous NaHCO3 ． J Org Chem，2007，72:
5244-5259．
14 Chand S，Banwell MG． Biomimetic preparation of the racemic
modifications of the stilbenolignan aiphanol and three conge-
ners． Aust J Chem，2007，60:243-250．
519Vol. 25 TANG Gui-hua，et al:Chemical Constituents from the Leaves of Trigonostemon flavidus