全 文 ：天然产物研究与开发 Nat Prod Res Dev 2011，23:1058-1060，1132
文章编号:1001-6880(2011)06-1058-04
Received February 22，2010;Accepted May 11，2010
Foundation Item:This work is financially supported by Program for Ex-
cellent Scientist of Guizhou Province( ［2005］0515) ，Key Science and
Technology Project of Guizhou Province (No． 20076004) ，and the Na-
tional Key Technology R＆D Program (2006BAD07A12)．
* Correspondence author Tel:86-851-8292171;E-mail:jhzx． msm @
gmail． com
华钩藤化学成分研究
刘明川，胡德禹，宋宝安，杨 松* ，金林红
贵州大学精细化工研究开发中心，教育部绿色农药与农业生物工程重点实验室，贵阳 550025
摘 要:从华钩藤(Uncaria sinensis(Oliv．)Havil)的乙醇溶液中分离得到 8 个化合物，经波谱学方法并与已知样
品对照段鉴定为:β-谷甾醇(1)、胡萝卜苷(2)、翅果定碱(3)、乌苏酸(4)、丁香色原酮甙 I(5)、美商陆甙 A(6)、
东莨菪素(7)和乌苏醛(8)。其中化合物 5 和 6 为首次从该植物中分离得到。
关键词:华钩藤;化学成分
中图分类号:R284． 1;Q946． 91 文献标识码:A
Chemical Constituents from Uncaria sinensis (Oliv．)Havil
LIU Ming-chuan，HU De-yu，SONG Bao-an，YANG Song* ，JIN Lin-hong
National-Guizhou Joint Laboratory of Biomass Comprehensive Utilization，Key Laboratory of Green Pesticide and
Agricultural Bioengineering，Ministry of Education，Center for R＆D of Fine Chemicals，Guizhou University，Guiyang 550025，China
Abstract:Eight compounds were isolated from Uncaria sinensis (Oliv．)Havil and their structures were identified by
means of spectroscopic analysis as β-sitosterol (1) ，daucosterol (2) ，pteropodine (3) ，ursolic acid (4) ，eugenoside I
(5) ，phytolaccoside A (6) ，scopoletin (7) ，and ursolic aldehyde (8)． Compounds 5 and 6 were isolated from the U．
sinensis for the first time．
Key words:Uncaria sinensis;chemical constituents
Introduction
Uncaria sinensis (Oliv．)Havil (Gouteng in Chinese)
is widely distributed in southwestern of China，mainly
in Guizhou，Guangxi，and there are 14 species in China
［1-2］，among which 11 species are listed in Table 1．
Table 1 The distribution of the Uncaria Schreb． in China
Plant Distribution in China
U． rhynchophlly (Miq．)Jacks Guizhou，Guangxi．
U． sinensis (Oliv．)Havil， Guizhou，Guangxi，Yunnan
U． lancifolia Hutch． Yunnan．
U． rhyuchophylloides How Guangdong，Guangxi．
U． macrophylla Wall Yunnan．
U． hirsuta Havil． Guangdong，Fujian．
U． sessifructus Roxb． Guizhou
U． scandens(Smith)Hutch Yunnan，Guangxi．
U． yunnanensis K． C． Hsia Yunnan
U． laevigata Wal． ex G． Don Yunnan
U． homomalla Miq Guangxi
The whole plant of U． sinensis has been used for protec-
ting liver，activating blood and antihypertensive for a
long time ［3，4］． Nowadays，more and more researchers
have found that this plants non-alkaloid parts also
could be used as anticancer agents． Yang et al．［5］ re-
ported the triterpene compounds isolated from U． mac-
rophylla Wall show anticancer bioactivity． Ursolic acid，
3β-6β-23-trihydroxyurs-12-en-28-oic acid，showed pro-
liferation inhibitory activity against U2OS with the inhi-
bition rate 43． 8% at the dosage of 25 mg /kg． d，while
that of compound 3β-6β-23-trihydroxyurs-12-en-28-oic
acid was 30． 07% at 25 mg /kg． d． Mitsuo et al．［6］ re-
ported that the methanol extract from U． sinensis showed
a suppressive effect on umu gene expression of the SOS
response in Salmonella typhimurium TA1535 /pSK1002
against the mutagen 3-amino-1，4-dimethyl-5H-pyrido
DOI:10.16333/j.1001-6880.2011.06.013
［4，3b］ indole (Trp-P-1)． Ursolic acid that was isola-
ted from U． sinensis showed strong inhibiting effect and
its ID50 was 0． 17 μmol /mL．
As far as we know，the chemical ingredients of U．
sinensis were not reported yet． In this paper，the chemi-
cal constituents，especially the triterpene natural prod-
ucts from U． sinensis grown in Guizhou，were investiga-
ted．
Experimental
General
Melting point was determined on X4 melting point ap-
paratus and the thermometer was uncorrected． 1H and
13C NMR spectra were recorded on a JOEL-ECX500
NMR instrument． LC-MS spectra were taken on an Agi-
lent 1100 /MSD． IR spectra were obtained on a SHI-
MADZU-IR Prestige-21，(KBr disks)． Silica gel (200-
300 mesh，Qingdao Ocean Chemical Co．，Ltd，China)
were used for column chromatographic separations．
Plant material
The plant of U． sinensis was purchased from Guizhou
Province in August 2007，and identified by Professor
Long Qingde (Guiyang Medical College)． The voucher
specimens were deposited at Guiyang Medical College，
Guiyang，China．
Extraction and isolation
The powdered U． sinensis (15 kg)was extracted with
85% EtOH (3 × 50 L)under reflux，6 h for the fist
time，3h for the second time and 1h for the last time．
After removal of the solvents by evaporation in vacco，
the extract was suspended in water and then extracted
with petroleum ether (10 L × 3 times) ，ethyl acetate
(10 L × 3times)and n-butanol (10 L × 3 times )re-
spectively． The petroleum ether (127 g)was subjected
to silica gel column chromatography with petroleum e-
ther:EtOAc (100∶ 1-1∶ 1)to give 14 fractions，then we
use the silica gel column chromatography to separate
those fractions． Finally we obtained 3 compounds 1(64
mg) ，2(14 mg) ，3(60 mg)． The ethyl acetate extract
(346 g)was subjected to silica gel column chromatog-
raphy with petroleum ether:CH3COCH3(100 ∶ 1-1 ∶ 1)
to give 16 fractions． We used the silica gel column
chromatography to separate those fractions again，and
got five compounds from those fractions:4(120 mg) ，5
(9 mg) ，6(53 mg) ，7(30 mg)and 8(4 mg)．
Structure Identification:
Compound 1 White needles，mp. 132-134 ℃，IR
(KBr)cm-1:3429，2958，1462，1377，1053. The TLC
of compound 1 was the same as β-sitosterol，so it was i-
dentified as β-sitosterol ［4］.
Compound 2 White powder，mp. 298-301 ℃，IR
(KBr)cm-1:3398，2958，1462，1374，1024. The TLC
of compound 2 was the same as daucosterol，so it was i-
dentified as daucosterol ［7］.
Compound 3 White powder，mp. 212-214 ℃，EI-MS
m/z:368［M］+，337，353，223，180，130，69. IR
(KBr)cm-1:3203，2945，1740，1676，1360. 1H NMR
(CDCl3，500 MHz)δ:0. 88，1. 42 (3H，d，J = 10 Hz，
H-22) ，1. 60，1. 71，2. 00，2. 17，2. 47，3. 21，3. 29，
3. 60 (3H，s，H-24) ，4. 34 (1H，m，H-18) ，7. 6. 87-
7. 26 (4H，m，H-9，10，11，12) ，7. 41 (1H，s) ，8. 18
(1H，s). 13 C NMR (CDCl3，125 MHz)δ:18. 6 (C-
22) ，30. 1 (C-14) ，30. 4 (C-15) ，34. 8 (C-20) ，37. 8
(C-6) ，51. 0 (C-21) ，53. 5 (C-24) ，54. 1 (C-5) ，
56. 9 (C-7) ，71. 2 (C-3) ，72. 1 (C-19) ，109. 5 (C-
9) ，109. 8 (C-16) ，122. 5 (C-12) ，124. 5 (C-11) ，
127. 5 (C-10) ，133. 7 (C-8) ，140. 1 (C-13) ，154. 9
(C-17) ，167. 63 (C-23) ，181. 1 (C-2). The IR，1H
NMR，13C NMR and EI-MS data are in agreement with
those of reported data of pteropodine，so we identify it
as pteropodine ［8］.
Compound 4 White powder，mp. 257-260 ℃ . IR
(KBr)cm-1:3450，2926，1695 (C = O) ，1456，1028，
997. 1H NMR: (500 MHz，CD3OH) δ:0. 78 (s，
CH3) ，0. 82 (s，CH3) ，0. 89 (d，J = 5 Hz，CH3) ，1. 16
(s，CH3) ，3. 2 (1H，q，J = 5. 3 Hz，H-3) ，5. 2 (1H，t，
J = 1. 5 Hz，H-12). 13 C NMR (CDCl3，125 MHz)δ:
14. 6 (C-29) ，14. 7 (C-30) ，16. 2 (C-23) ，16. 5 (C-
24) ，18. 1 (C-26) ，20. 1 (C-25) ，22. 7 (C-11) ，23. 0
(C-3) ，24. 0 (C-21) ，26. 6 (C-15) ，27. 4 (C-7) ，
27. 9 (C-16) ，30. 4 (C-6) ，33. 0 (C-22) ，36. 7 (C-
12) ，36. 8 (C-5) ，38. 5 (C-13) ，38. 7 (C-20) ，39. 0
(C-9) ，39. 1 (C-19) ，39. 5 (C-14) ，41. 9 (C-10) ，
53. 1 (C-18) ，55. 4 (C-9) ，78. 4 (C-8) ，125. 6 (C-
2) ，138. 3 (C-1) ，180. 1 (C-28). The TLC of com-
pound 4 was the same as ursolic acid，and IR，1H
9501Vol. 23 LIU Ming-chuan，et al:Chemical Constituents from Uncaria sinensis (Oliv．)Havil
NMR，13C NMR data are in agreement with those of re-
ported data of ursolic acid ［9］.
Compound 5 White powder，mp. 245-248 ℃，EI-MS
m/z:354［M］+，192，164，69，IR (KBr)cm-1:3429 (-
OH) ，2926，1669 (C = O) ，1442，1091，677. 1H NMR
(CD3OD，500 MHz)δ:3. 39 ～ 3. 41 (3H，m，H-2，
6) ，3. 49 ～ 3. 52 (1H，m，H-5) ，3. 8 ～ 3. 9 (2H，m，
H-3，4) ，4. 6 ～ 5. 01 (4H，m，glc-OH) ，5. 05 (1H，
d，J = 10 Hz，H-1) ，2. 3 (3H，s，H-9) ，6. 1 (2H，s，H-
5，6) ，6. 4 (1H，s，H-7) ，6. 6 (1H，s，H-2). 13 C NMR
(CD3OD，125 MHz)δ:19. 0 (C-9) ，61. 0(C-6) ，
69. 8(C-4) ，73. 3(C-2) ，76. 4(C-3) ，77. 0 (C-
5) ，94. 5 (C-1) ，107. 9 (C-7) ，100. 2 (C-8a) ，
105. 4 (C-2) ，99. 6 (C-5) ，158. 0 (C-4a) ，161. 6 (C-
6) ，163. 4 (C-8) ，168. 6 (C-3) ，182. 8 (C-1). The
IR，1H NMR，13 C NMR and EI-MS data are in agree-
ment with those of reported data of eugenoside I ［10，11］.
Compound 6 White flake，mp. 230-234 ℃，IR
(KBr)cm-1:3400 (-OH) ，2972，1683 (C = O) ，
1047. 1H NMR (CD3OD，500 MHz)δ:3. 80 (2H，d，J
=10 Hz，H-2) ，3. 26 ～ 3. 35 (2H，m，H-3，4) ，3. 61
(1H，q，J = 5 Hz，H-5) ，4. 32 (1H，d，J = 5 Hz，H-
6) ，5. 57 (1H，t，J = 5 Hz，H-2) ，4. 1 (3H，s，H-31) ，
4. 3 (2H，d，J = 5 Hz，H-24) ，2. 27 ～ 0. 72 is the hy-
drogen on the six-member rings. 13 C NMR (CD3OD，
125 MHz)δ:177. 8 (C-28) ，175. 8 (C-29) ，132. 7
(C-1) ，128. 9 (C-2) ，105. 6 (C-1) ，88. 4 (C-8) ，
77. 3 (C-3) ，76. 4 (C-2) ，74. 6 (C-4) ，71. 0 (C-
5) ，62. 3 (C-24) ，55. 6 (C-31) ，55. 8 (C-17) ，55. 6
(C-10) ，54. 2 (C-4) ，47. 8 (C-9) ，46. 7 (C-14) ，
39. 5 (C-18) ，39. 0 (C-19) ，38. 7 (C-20) ，38. 5 (C-
5) ，37. 0 (C-13) ，36. 7 (C-12) ，36. 5 (C-6) ，36. 2
(C-21) ，30. 0 (C-15) ，29. 7 (C-22) ，27. 5 (C-16) ，
26. 0 (C-3) ，24. 5 (C-7) ，22. 6 (C-30) ，20. 63 (C-
27) ，18. 1 (C-25) ，17. 1 (C-11) ，16. 1 (C-26) ，15. 9
(C-23). The IR，1H NMR，13C NMR data are in agreement
with those of reported data of phytolaccoside A ［12］.
Compound 7 Yellow needles，mp. 202-204 ℃，1H
NMR (CD3COCD3，500 MHz)δ:8. 75 (1H，s，OH) ，
7. 82 (1H，d，J = 10 Hz，H-4) ，7. 16 (1H，s，H-5) ，
6. 76 (1H，s，H-8) ，6. 15 (1H，d，J = 10 Hz，H-3) ，
3. 87 (3H，s，OCH3).
13 C NMR (CD3COCD3，125
MHz)δ:160. 4 (C-2) ，150. 9 (C-9) ，150. 3 (C-7) ，
145. 1 (C-4) ，143. 8 (C-6) ，112. 5 (C-10) ，111. 2
(C-3) ，109. 1 (C-5) ，102. 8 (C-8) ，55. 8 (OCH3)
. The IR，1H NMR，13 C NMR data are in agreement
with those of reported data of scopoletin ［13］.
Compound 8 White powder，mp. 236-238 ℃，IR
(KBr)cm-1:2926，1730. 1H NMR (CDCl3，500 MHz)
δ:0. 77 (s，CH3) ，0. 85 (s，CH3) ，0. 87 (d，J = 6. 5
Hz，CH3) ，1. 08 (s. CH3) ，3. 2 (s，br. 3-H) ，5. 2
(1H，t，J = 1. 6 Hz，12-H). 13 C NMR (CDCl3，125
MHz)δ:15. 5 (C-29) ，15. 6 (C-30) ，17. 0 (C-23) ，
17. 1 (C-24) ，18. 3 (C-26) ，21. 2 (C-25) ，23. 3 (C-
11) ，23. 6 (C-3) ，24. 2 (C-21) ，27. 3 (C-15) ，28. 0
(C-7) ，28. 2 (C-16) ，29. 7 (C-6) ，31. 0 (C-22) ，
36. 7 (C-12) ，37. 0 (C-5) ，38. 6 (C-13) ，38. 8 (C-
20) ，38. 9 (C-9) ，39. 1 (C-19)，39. 5 (C-14)，41. 9 (C-
10)，47. 9 (C-17)，47. 6 (C-4)，52. 7 (C-18)，〗55. 3 (C-
9)，79. 1 (C-8)，125. 9 (C-2)，138. 0 (C-1)，207. 1 (C-
28). The IR，1H and 13C NMR data are in agreement with
those of reported data of ursolic aldehyde ［14］.
Acknowledgment This work is financially supported
by Program for Excellent Scientist of Guizhou Province
( ［2005］0515) ，Key Science and Technology Project
of Guizhou Province (No. 20076004) ，and the National
Key Technology R＆D Program (2006BAD07A12).
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