全 文 ：天然产物研究与开发 Nat Prod Res Dev 2011，23:1002-1005
文章编号:1001-6880(2011)06-1002-04
Received January 20，2010:Accepted April 26，2010
Foundation Item:This work was supported by National Nonprofit Insti-
tute Research Grant of CATAS － ITBB (110301)and the Natural Sci-
ence foundation of Hainan (211020)and Yunnan (2008CD159)．
* Corresponding author Tel:86-898-66989095;E-mail:zhaoyx1011 @
163． com
小金梅草化学成分研究
程忠泉1，3，杨 丹3，马青云2，刘玉清1，周 俊1，赵友兴1，2*
1中国科学院昆明植物研究所植物化学与西部资源持续利用国家重点实验室，昆明 650204;2 中国热带农业
科学院热带生物技术研究所，海口 571101;3 桂林师范高等专科学校，桂林 541001
摘 要:从小金梅草乙醇提取物中分离得到了 12 个化合物，分别为 3-O-β-D-槲皮素葡萄糖苷(1)、3-O-β-D-山柰
酚葡萄糖苷(2)、5-O-β-D-芹菜素葡萄糖苷(3)、α-菠甾醇(4)、2，6-二甲氧基苯甲酸 (5)、3-吲哚甲酸(6)、(2S，
3R，4E，8E)-1-(β-D-吡喃葡萄糖苷)-N-［(R)-2 -羟基-二十碳酰基］-9-甲基-4，8-二烯-1，3-二醇-2-氨基-十八
烷(7)、正三十二烷醇 (8)、14，15-二十碳烯酸(9)、木腊酸(10)、β-谷甾醇(11)、胡萝卜苷(12)。以上化合物均
为首次从该植物中得到。
关键词:小金梅草;黄酮;化学成分
中图分类号:Q946． 91;R284． 1 文献标识码:A
Chemical Constituents from Hypoxis aurea Lour．
CHENG Zhong-quan1，3，YANG Dan3，MA Qing-yun2，LIU Yu-qing1，ZHOU Jun1* ，ZHAO You-xing1，2*
1 State Key Laboratory of Phytochemistry and Plant Resources in West China，Kunming Institute of Botany，the Chinese Academy of
Sciences，Kunming 650204，China;2 Institute of Tropical Bioscience and Biotechnology，Chinese Academy of Tropical
Agricultural Sciences ，Haikou 571101，China;3Guilin Normal College，Guilin 541001，China
Abstract:Twelve compounds were isolated from the ethanol extract of Hypoxis aurea，and their structures were elucidated
by physicochemical properties and spectroscopic analysis as quercetin-3-O-β-D-glucoside(1) ，kaemferol-3-O-β-D-gluco-
side(2) ，apigenin-5-O-β-D-glucopyranoside(3) ，α-spinasterol (4) ，2 6-dimethoxy-benzoic acid (5) ，1H-indole-3-car-
boxylic acid(6) ，(2S，3R，4E，8E)-1-(β-D-glucopyranosyloxy)-3-hydroxy-2［( (R)-2-hydroxyeicosanoly)amino］-9-
methy-4，8-octadecadiene(7) ，n-dotriacontanol(8) ，14，15-eicosenicacid(9) ，lignoceric acid(10) ，β-sitoster-ol (11) ，
daucosterol(12)． All these compounds were found in this plant for the first time．
Key words:Hypoxis aurea;flavonoids;chemical constituents
Introduction
Plants of the family Hypoxidaceae are widely distribu-
ted in Torrid Zone in the world，and previous studies of
the family by our group revealed that it mainly contains
phenolic glycosides and norlignans ［1-3］． Hypoxis aurea
Lour． belongs to the genus Hypoxidaceae，called as xi-
ao jin mei to treat hernia and warm kidney in China［4］
and mainly distributed over the southern part of China，
southeast of Asia and Japan． Chemical investigation of
the rhizomes of H． aurea toward potentially bioactive
secondary metabolites from this genus leaded to the iso-
lation of twelve compounds． These compounds were elu-
cidated as quercetin-3-O-β-D-glucoside (1) ，kaemfer-
ol-3-O-β-D-glucoside (2) ，apigenin-5-O-β-D-glucopyr-
anoside (3) ，α-spinasterol (4) ，2 6-dimethoxy-benzo-
ic acid (5) ，1H-indole-3-carboxylic acid (6) ，(2S，
3R，4E，8E)-1-(β-D-glucopyranosyloxy)-3-hydroxy-2
［( (R)-2-hydroxyeicosanoly)amino］-9-methy-4，8-oc-
tadecadiene (7) ，n-dotriacontanol (8) ，14，15-ei-
cosenic acid (9) ，lignoceric acid (10) ，β-sitosterol
(11)and daucosterol (12)on the basis of spectro-
scopic analysis and comparing spectral data with those
known compounds reported in literatures． All these
compounds were found in this plant for the first time．
Experimental
General
Melting points were measured on a XRC-1 micro-melt-
ing point apparatus and were uncorrected． MS spectra
were obtained on a VG Auto Spec-3000 mass spectrom-
eter． 1H and 13C (DEPT)NMR spectra were recorded
on Bruker AM-400 MHz and DRX-500 MHz spectrom-
eters，with chemical shifts (δ)in ppm relative to TMS
as internal standard and coupling constants in hertz
(Hz)． Silica gel (200-300 mesh)for column chroma-
tography was product of the Qingdao Marine Chemical
Ltd．，Qingdao，P． R． China． Sephadex LH-20 for chro-
matography was purchased from Amersham Biosci-
ences． Reversed-phase chromatography was with RP-18
(LiChroprep，40-63 μm，Merck，Darmstadt，Germa-
ny)．
Plant materials
The whole plant of H． aurea． were collected in Kun-
ming，Yunnan Province，Peoples Republic of China，in
September 2008，and authenticated by professor Peng
Hua． A voucher specimen (KUN 0864822)has been
deposited in the Herbarium of Kunming Institute of
Botany，Chinese Academy of Sciences．
Extraction and Isolation
The air-dried and powdered rhizomes of H． aurea (3． 0
kg)were extracted three times each with 15 L of 95%
EtOH under reflux for 3h． The extracts were evaporated
and the residue was resuspended in 15 L of H2O and
partitioned successively with petroleum ether (3 L ×
3) ，EtOAc (3 L × 3)and n-BuOH (3 L × 3)to yield
petroleum ether extract (49 g) ，EtOAc extract (70 g) ，
n-BuOH extract (210 g) ，respectively． The n-BuOH
(200 g)extract was applied to a silica gel column
chromatography (200-300 mesh)eluted with CHCl3 /
CH3OH /H2O (15∶ 3∶ 0． 5，v /v)to give five fractions．
Fraction 3 (30 g)was purified by column chromatogra-
phy silica gel with CHCl3 /CH3OH /H2(7 ∶ 3 ∶ 0． 5，v /
v) ，to yield four sub-fractions based on TLC analysis．
Sub-fraction 2，were purified on RP-18 with 20% to
100% aqueous CH3OH，and on Sephadex LH-20 with
CH3OH /CH3Cl (1∶ 1，v /v)to afford compounds 1 (12
mg) ，2 (8 mg)and 3 (5 mg)． EtOAc extract (60 g)
was subjected to column chromatography on silica gel
(200-300 mesh)column eluted with petroleum ether /
acetone (10∶ 1，v /v)to give five fractions． Sub-fraction
3(35 g)was repeatedly purified over silica gel (200-
300 mesh)eluted with CHCl3 /MeOH (from 20∶ 1 to 5
∶ 1，v /v) ，and then on Sephadex LH-20 eluted with
MeOH/CHCl3(1 ∶ 1，v /v)to yield compounds 4 (14
mg) ，5 (10 mg) ，6 (5 mg) ，7 (15mg) ，10 (18 mg) ，
11 (146 mg)and 12 (76 mg)． Sub-fraction 1 (19 g)
was chromatographyed on silica gel (200-300 mesh)
using petroleum ether /acetone (20∶ 1，v /v)as an elu-
ant to give the compounds 8 (258 mg)and 9 (35
mg)．
Results and Discussion
Quercetin-3-O-β-D-glucoside (1) Yellow powder，
C21H20 O12，mp. 242-245 ℃，FABMS (-)m/z:463 ［
M-H］-，1H NMR (CD3OD，400 MHz)δ:12. 62 (1H，
s，OH) ，7. 66 (1H，t，J = 8. 4，2. 1 Hz，H-6) ，7. 50
(1H，d，J = 2. 1 Hz，H-2) ，6. 80 (1H，d，J = 8. 4 Hz，
H-5) ，6. 39 (1H，d，J = 2. 0 Hz，H-6) ，6. 18 (1H，d，
J = 2. 0 Hz，H-8) ，5. 36 (1H，d，J = 7. 7 Hz，H-1) ，
3. 15 ～ 3. 63 (11H，m，H-2 ～ 6). 13 C NMR
(CD3OD，100 MHz)δ:156. 3 (C-2) ，133. 4 (C-3) ，
177. 5 (C-4) ，161. 3 (C-5) ，98. 7 (C-6) ，164. 2 (C-
7) ，93. 6 (C-8) ，156. 3 (C-9) ，103. 9 (C-10) ，121. 1
(C-1) ，122. 4 (C-2) ，156. 2 (C-3) ，148. 4 (C-
4) ，115. 9 (C-5) ，122. 0 (C-6) ，101. 3 (C-1) ，
71. 2 (C-2) ，75. 9 (C-3) ，67. 9 (C-4) ，73. 2 (C-
5) ，60. 2 (C-6). The MS and NMR data were iden-
tical to those of literature ［5］.
Kaemferol-3-O-β-D-glucoside (2) Yellow powder，
C21H20O11，mp. 178-179 ℃，FABMS (-)m/z:447［M-
H］-，1H NMR (CD3OD，500 MHz)δ:8. 07 (2H，d，J
= 8. 9 Hz，H-2，6) ，6. 9 (2H，d，J = 8. 9 Hz，H-3，
5) ，6. 32 (1H，d，J = 1. 8 Hz，H-8) ，6. 14 (1H，d，J =
1. 8 Hz，H-6) ，5. 08 (1H，d，J = 7. 7 Hz，H-1) ，3. 81
～ 3. 30 (11H，m，H-2 ～ 6). 13 C NMR (CD3OD，
125 MHz)δ:158. 7 (C-2) ，132. 3 (C-3) ，179. 3 (C-
4) ，161. 6 (C-5) ，95. 3 (C-6) ，168. 6 (C-7) ，93. 3
(C-8) ，158. 3 (C-9) ，105. 4 (C-10) ，122. 8 (C-1) ，
135. 5 (C-2) ，116. 1 (C-3) ，158. 7 (C-4) ，116. 1
(C-5) ，132. 3 (C-6) ，105. 2 (C-1) ，73. 1 (C-
3001Vol. 23 CHENG Zhong-quan，et al:Chemical Constituents from Hypoxis aurea Lour．
2) ，77. 1 (C-3) ，70. 0 (C-4) ，75. 1 (C-5) ，
62. 0 (C-6). The MS and NMR data were identical to
those of literature ［5］.
Apigenin-5-O-β-D-glucopyranoside (3) Yellow
powder，C21 H20 O10，mp. 240-242 ℃，FABMS (-) ，m/
z:431［M-H］-. 1H NMR (CD3OD，400 MHz)δ:8. 10
(2H，d，J = 8. 8 Hz，H-2，6) ，7. 9 (1H，s，H-3) ，6. 9
(2H，d，J = 8. 8 Hz，H-3，5) ，6. 41 (1H，d，J = 1. 9
Hz，H-8) ，6. 21 (1H，d，J = 1. 9 Hz，H-6) ，5. 15 (1H，
d，J = 7. 8 Hz，H-1) ，3. 31 ～ 3. 82 (m)protons of
glucose;13C NMR (CD3OD，100 MHz)δ:162. 5 (C-
2) ，105. 8 (C-3) ，179. 7 (C-4) ，158. 5 (C-5) ，104. 9
(C-6) ，161. 6 (C-7) ，99. 9 (C-8) ，158. 3 (C-9) ，
108. 5 (C-10) ，122. 7 (1) ，128. 1 (C-2) ，116. 1
(C-3) ，160. 9 (C-4) ，116. 1 (C-5) ，128. 5 (C-
6) ，104. 9 (C-1) ，73. 0 (C-2) ，77. 1 (C-3) ，
67. 0 (C-4) ，75. 0 (C-5) ，61. 9 (C-6). The MS
and NMR data were identical to those of literature ［6］.
α-Spinasterol (4) Colorless powder，C29 H52 O3，
mp. 250-252 ℃，EIMS m/z :448 ［M］+，430，412，
397;1H NMR (CDCl3，400 MHz)δ:0. 82 (3 H，s，19-
CH3) ，0. 83 (3 H，d，J = 8. 6 Hz) ，0. 84 (3 H，d，J =
6. 3 Hz) ，0. 86 (3 H，d，J = 7. 5 Hz) ，0. 92 (3H，d，J
= 6. 6 Hz) ，1. 19 (3H，s，18-CH3) ，4. 07 (1H，m，H-
3) ，3. 52 (1H，br s，H-6) ;13 C NMR (CDCl3，100
MHz)δ:31. 2 (C-1) ，32. 7 (C-2) ，67. 8 (C-3) ，41. 1
(C-4) ，76. 3 (C-5) ，76. 4 (C-6) ，34. 3 (C-7) ，28. 4
(C-8) ，46. 2 (C-9) ，38. 7 (C-10) ，21. 4 (C-11) ，
40. 3 (C-12) ，43. 1 (C-13) ，56. 6 (C-14) ，24. 4 (C-
15) ，26. 8 (C-16) ，56. 3 (C-17) ，12. 1 (C-18) ，17. 0
(C-19) ，36. 4 (C-20) ，19. 3 (C-21) ，34. 9 (C-22) ，
26. 8 (C-23) ，46. 3 (C-24) ，29. 7 (C-25) ，18. 9 (C-
26) ，19. 9 (C-27) ，23. 5 (C-28) ，12. 3 (C-29). The
1H and 13C NMR data were identical to those of litera-
ture ［7］.
2，6-Dimethoxy-benzoic acid (5) Colourless pow-
der，C9H10O4，mp. 164-165 ℃，FABMS (+)m/z:183
［M +1］+，165 (M + -OH) ，150 (165-CH3) ，137 (M
+ -COOH) ，151 (M + -OCH3) ;
1H NMR (CD3OD，
500 MHz)δ:3. 80 (6H，s，2OCH3) ，6. 64 (2H，d，J =
8. 4 Hz，H-3，H-5) ，7. 22 (1H，d，J = 8. 4 Hz，H-4) ;
13C NMR (CD3OD，125 MHz)δ:157. 7 (C-2，C-6) ，
130. 2 (C-4) ，115. 3 (C-1) ，105. 2 (C-3，C-5) ，56. 3
(2，6-OMe). The MS and NMR spectral data were in
consistent with those reported ［8］.
1H-indole-3-carboxylic acid (6) Yellow powder，
C9H7O2N，mp. 210-215 ℃，EIMS m/z:161 ［ M ］
+
(100) ，144 (98) ，116 (26) ，89 (16). 1H NMR
(CD3OD，400 MHz)δ:13. 0 (1H，br s，N-H) ，8. 88
(1H，d，J = 7. 8 Hz，H-7) ，8. 53 (1H，d，J = 2. 7 Hz，
H-2) ，7. 61 (1H，d，J = 8. 0 Hz，H-4) ，7. 40 (1H，t，J
= 7. 8 Hz，H-6) ，7. 32 (1H，t，J = 7. 8 Hz，H-5). 13 C
NMR (CD3OD，100 MHz) δ:133. 0 (C-2) ，108. 7
(C-3) ，122. 0 (C-4) ，123. 6 (C-5) ，122. 4 (C-6) ，
112. 9 (C-7) ，138. 2 (C-8) ，127. 5 (C-9) ，169. 3
(COOH). The MS and NMR data were identical to
those of literature ［9］.
(2S，3R，4E，8E)-1-(β-D-Glucopyranosyloxy)-3-
hydroxy-2［(R)-2-hydroxyeicosanoly)amino ］-9-
methy-4，8-octadecadiene (7) Colorless powder，
C45H85NO9，mp. 190-192 ℃ FABMS (m/z) (%)784
［M + H ］+ (15) ，516 (6) ，280 (11). 1H NMR
(C5D5N，500 MHz) δ:8. 36 (1H，d，J = 9. 4 Hz，
NH) ，4. 95-4. 19 (protons of glucose) ，0. 85 (3H，t，J
= 6. 9 Hz，H-18 or 21). 13 C NMR (C5D5N，125
MHz) δ:71. 5 (C-1) ，54. 6 (C-2) ，72. 3 (C-3) ，
132. 1 (C-4) ，132. 2 (C-5) ，130. 2 (C-8) ，131. 1 (C-
9) ，32. 9 (C-10) ，29. 6-30. 1 (CH2) ，14. 3 (C-18) ，
175. 7 (C-1) ，72. 5 (C-2) ，14. 3 (C-5) ，105. 7 (C-
1) ，75. 2 (C-2) ，78. 5 (C-3) ，71. 5 (C-4) ，
78. 6 (C-5) ，62. 6 (C-6). The NMR data were i-
dentical to those of literature ［10］.
1-Dotriacontanol (8) White powder，C32 H66 O，
mp. 88-89 ℃，EIMS m/z:448［M-H2O］
+，420 (6) ，
392 (10) ，139 (13). 1H NMR (CDCl3，500 MHZ)δ:
0. 88 (3H，t，J = 6. 5 Hz) ，1. 26 ～ 1. 30 (58H，br m) ，
1. 60 (2H，m) ，3. 64 (2H，t，J = 7. 0 Hz，CH2OH) ;
13C NMR (CDCl3，125 MHZ)δ:64. 4 (C-1) ，34. 4
(C-2) ，31. 9 ～ 22. 7 (C-3 ～ 31) ，14. 1 (C-32). The
MS and NMR data were identical to those of literature
［11］.
14，15-Eicosenic acid (9) White solid，C20 H36 O2，
mp. 158-159 ℃，EIMS m/z:308 ［M ］+，290 ［M-
H2O］
+，266 (6) ，239 (10). 1H NMR (CDCl3，400
MHZ)δ:0. 88(3H，t，J = 6. 5 Hz) ，1. 26 ～ 4. 30
4001 Nat Prod Res Dev Vol. 23
(30H，br m) ，5. 24 (2H，m). The MS and 1H NMR
data were identical to those of literature ［12］.
Lignoceric acid (10) White solid，C24 H48 O2，
mp. 72-73 ℃，EIMS m/z:368 ［ M ］+ . 1H NMR
(CDCl3，400 MHZ)δ:0. 87(3H，t，J = 6. 7 Hz) ，1. 27-
1. 31 (40H，br m) ，1. 60 (2H，m) ，2. 44 (2H，t，J =
7. 0，CH2OH). The MS and NMR data were identical to
those of literature ［13］. Compounds 11 and 12 were de-
termined to be β-sitosterol and daucostero respectively
by comparing their TLC behaviors with standard sam-
ples.
Acknowledgements This research was supported by
the fund (P2008-ZZ22) of State Key Laboratory of
Phytochemistry and Plant Resources in West China. We
appreciate the analytical group of the State Key Labora-
tory of Phytochemistry and Plant Resources in West
China，Kunming Institute of Botany，Chinese Academy
of Sciences for all spectra tests.
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5001Vol. 23 CHENG Zhong-quan，et al:Chemical Constituents from Hypoxis aurea Lour．