全 文 ：天然产物研究与开发 Nat Prod Res Dev 2012，24: 465-468
文章编号: 1001-6880( 2012) 04-0465-04
Received October 12，2010; Accepted March 11，2011
Foundation Item: This project was supported by Innovative Program of
the Chinese Academy of Sciences ( KSCX2-YW-G-06-03 ) ，the West
Light Fund of Chinese Academy of Sciences ( 09C102 ) ，and the Key
Research Projects of Chengdu Bureau of Science and Technology
( 07GGYB214SW) ．
* Corresponding author E-mail: ligy@ cib． ac． cn
四川溲疏的化学成分研究
李昌松1，2，余红伟1，陈晓珍1，吴晓青3，方冬梅1，李国友1*
1中国科学院成都生物研究所，成都 610041; 2 中国科学院研究生院，北京 100049;
3西南交通大学生命科学与工程学院，成都 610031
摘 要:运用多种色谱技术从四川溲疏( Deutzia setchuenensis Franch) 全草的 95%乙醇提取物中首次分离到 9 个
化合物。通过波谱方法和与已知品对照的手段将它们鉴定为: β-谷甾醇( 1) 、白桦酯醇( 2) 、hydrangetin( 3) 、齐墩
果酸( 4) 、肉桂酸( 5) 、齐墩果酸-3-O-β-D-吡喃葡萄糖醛酸苷( 6) 、β-胡萝卜苷( 7) 、齐墩果酸-3-O-( β-D-吡喃葡萄
糖醛酸-6-正丁酯) ( 8) 和齐墩果酸-3-O-β-D-吡喃葡萄糖醛酸-28-O-β-D-吡喃葡萄糖苷( 9) 。
关键词:四川溲疏;甾体;三萜; 香豆素
中图分类号: Q946． 91; R284． 4 文献标识码: A
Chemical Constituents of Deutzia setchuenensis
LI Chang-song1，2，YU Hong-wei1，CHEN Xiao-zhen1，WU Xiao-qing3，FANG Dong-mei1，LI Guo-you1*
1Chengdu Institute of Biology，Chinese Academy of Sciences，Chengdu 610041，China;
2Graduate School of Chinese Academy of Sciences，Beijing 100049，China;
3Faculty of Life Science and Engineering，Southwest Jiaotong University，Chengdu 610031，China
Abstract: Nine compounds were isolated from the 95% ethanol extract of the whole plants of Deutzia setchuenensis
Franch for the first time． On the basis of spectral data or by comparing with authentic samples，they were identified as β-
sitosterol ( 1) ，betulin ( 2) ，hydrangetin ( 3 ) ，oleanolic acid ( 4 ) ，cinnamic acid ( 5 ) ，oleanolic acid 3-O-β-D-glucuro-
nopyranoside ( 6) ，β-daucosterol ( 7) ，oleanolic acid 3-O-( β-D-glucuronopyranoside-6-O-butyl ester) ( 8) and oleanolic
acid 3-O-β-D-glucuronopyranosyl-28-3-O-β-D-glucopyranoside ( 9) ． They were isolated from the plant for the first time．
Key words: Deutzia setchuenensis; steroids; triterpenoids; coumarin
Introduction
Deutzia setchuenensis Franch，a kind of ornamental and
medicinal bush，belonging to the family Hydrangeaceae
widely distributed in Jiangxi，Fujian，Hubei，Hunan，
Guangdong，Guangxi，Guizhou，and Sichuan prov-
ince［1］． Previous studies reported the isolation of iridoid
glucosides［2，3］，saponins［4］，and flavonoids［5］ from this
genus，but the chemical constituent of this plant have
not been studied up to now． In the course of chemical
investigation on this plant，we have obtained nine com-
pounds from the 95% ethanol extract of the whole
plants of D． setchuenensis． The structure of the com-
pounds were identified as β-sitosterol ( 1 ) ，betulin
( 2) ，hydrangetin ( 3 ) ，oleanolic acid ( 4 ) ，cinnamic
acid ( 5 ) ，oleanolic acid 3-O-β-D-glucuronopyranoside
( 6) ，β-daucosterol ( 7 ) ，oleanolic acid 3-O-( β-D-glu-
curonopyranoside-6-O-butyl ester) ( 8 ) ，and oleanolic
acid 3-O-β-D-glucuronopyranosyl-28-3-O-β-D-glucopy-
ranoside ( 9 ) ． Here，we describe the isolation and
structure elucidation of these compounds．
Experimental
General
Melting point data: X-6 precise melting point apparatus
( Beijing Fukai Science and Technology Development
Company Limited) ; Optical rotations: Perkin-Elmer 341
polarimeter; FT-IR spectra: Perkin-Elmer spectrum one
FT-IR spectrometer; NMR spectra: Bruker Advance 600
spectrometer ( 1H: 600 MHz; 13C: 150 MHz) ，with TMS
internal standard; ESI-MS spectra: Finnigan LCQDECA
ion trap mass spectrometer; HR-ESI-MS spectra Bruker
BioTOF-Q mass spectrometer ( Bruker Daltonics，Bil-
lerica，MA，USA) ． Silica gel ( 200 － 300 mesh，Qingd-
ao Haiyang Chemical Co． Ltd． ) ，RP-C18 ( 40 － 63 μm，
Merck KGaA，Darmstadt，Germany ) ，MCI gel ( CHP
20P，75 － 150 μm; Mitsubishi Chemical Industries，To-
kyo，Japan ) ． D101 macrosporous resin ( Shanghai
Moshu Scientific Instruments Co． Ltd． ) ．
Plant material
The whole plants of Deutzia setchuenensis were collected
in Yanbian County of Sichuan Province，China，in July
2008． A voucher specimen ( A171-3 ) was authentica-
ted by Prof． Hu Fa-ding at Chengdu Institute of Biolo-
gy，Chinese Academy of Sciences ( CAS) ，and deposi-
ted in the Herbarium of the Chengdu Institute of Biolo-
gy，Chinese Academy of Sciences，CAS．
Extraction and Isolation
The air-dried，powdered whole plants of D． setchuenen-
sis ( 4 kg) was exhaustively extracted with 95% EtOH
( 3 times，rt) ． The extract was concentrated in vacuum
to yield a residue ( 300 g) ． The crude extract was sus-
pended in H2O and then partitioned successively with
petroleum ether，EtOAc，and n-BuOH to obtain petrole-
um ether ( A，40 g) ，EtOAc ( B，35 g) ，and n-BuOH
( C，100g) fractions． Fraction B was subjected to silica
gel column chromatography to yield B1 and B2． Frac-
tion B1 was further chromatographied to give B11，
B12，and B13 ( petroleum ether /acetone，10 ∶ 1，v /v )
on a silica gel． Crystallization of B12 ( 2 g) from ace-
tone gave compound 1( 1 g) ． Fraction B13 was chroma-
tographied on a silica gel column eluted with CHCl3 to
give successively 2 ( 30 mg) and 3 ( 10 mg) ． Fraction
B2 ( 20 g) was further separated over silica gel column
( CHCl3 /MeOH，100 ∶ 1，v /v ) to get B21，B22，and
B23 based on TLC analysis． Fraction B21 was subjec-
ted to chromatography over MCI gel ( MeOH /H2O，95
∶ 5，v /v) and crystallize in CHCl3 to give 4 ( 50 mg) ．
Fraction B22 was separated over silica gel column
( CHCl3 /MeOH，250 ∶ 1，v /v ) to yield 5 ( 400 mg ) ，
Fraction B23 was separated over RP-C18 silica gel col-
umn ( MeOH /H2O，2 ∶ 1，v /v ) to give 6 ( 100 mg ) ．
Fraction C was separated over macroporous resin D101
column ( H2O /MeOH，100 ∶ 0，80 ∶ 20，60 ∶ 40，20 ∶ 80，
0∶ 100，v /v) to get C1，C2 and C3． Compounds 7 ( 15
mg) and 8( 80 mg) were obtained from Fraction C3 by
silica gel column ( CHCl3 /MeOH，15 ∶ 1，v /v ) ． 9 ( 50
mg) was isolated from Fraction C2 by silica gel column
eluted with n-BuOH saturated by water．
Identification
Compounds 1，4，and 7 were identified successively as
β-sitosterol，oleanolic acid，and β-daucosterol by com-
paring them with authentic samples on TLC and co-
melting point．
Betulin ( 2) C30H50O2 ． white powder，mp． 236 － 238
℃. ESI-MS m/z: 465 ［M + Na］+ ; 1H NMR ( CDCl3，
600 MHz) δ: 4. 68 ( 1H，s，H-29 ) ，4. 58 ( 1H，s，H-
29) ，3. 79 ( 1H，d，J = 10. 5 Hz，H-28) ，3. 33 ( 1H，d，
J = 10. 5 Hz，H-28) ，3. 18 ( 1H，m，H-3) ，1. 68 ( 3H，
s，H-30) ，1. 02 ( 3H，s，H-26 ) ，0. 98 ( 3H，s，H-27 ) ，
0. 96 ( 3H，s，H-23) ，0. 82 ( 3H，s，H-25) ，0. 76 ( 3H，
s，H-24) . 13C NMR ( CDCl3，150 MHz) δ: 38. 7 ( t，C-
1) ，27. 4 ( t，C-2 ) ，78. 9 ( d，C-3 ) ，38. 8 ( s，C-4 ) ，
55. 3 ( d，C-5 ) ，18. 3 ( t，C-6 ) ，34. 2 ( t，C-7 ) ，40. 9
( s，C-8) ，50. 4 ( d，C-9) ，37. 2 ( s，C-10) ，20. 8 ( t，C-
11) ，25. 2 ( t，C-12 ) ，37. 3 ( d，C-13 ) ，42. 7 ( s，C-
14) ，27. 1 ( t，C-15 ) ，29. 2 ( t，C-16 ) ，47. 8 ( s，C-
17) ，48. 8 ( d，C-18 ) ，47. 8 ( d，C-19 ) ，150. 5 ( s，C-
20) ，29. 8 ( t，C-21 ) ，33. 9 ( t，C-22 ) ，27. 9 ( s，C-
23) ，15. 3 ( s，sC-24 ) ，16. 1 ( s，C-25 ) ，15. 9 ( s，C-
26 ) 14. 7 ( s，C-27 ) ，60. 5 ( t，C-28 ) ，109. 6 ( t，C-
29) ，19. 1 ( s，C-30 ) . It was identified by comparison
of the physical and spectral data with those repor-
ted［6］．
Hydrangetin ( 3) C10H8O4. colorless flakes( CHCl3 ) ．
mp 153-155 ℃ . ESI-MS m/z: 191［M-H］-. 1H NMR
( CDCl3，600 MHz ) δ: 7. 63 ( 1H，d，J = 9. 5 Hz，H-
4) ，6. 24 ( 1H，d，J = 9. 5 Hz，H-3) ，7. 11 ( 1H，d，J =
8. 5 Hz，H-5 ) ，6. 90 ( 1H，d，J = 8. 5 Hz，H-6 ) ，4. 11
( 3H，s，8-OCH3 ) ，6. 47 ( 1H，s，OH ) .
13 C NMR
( CDCl3，150 MHz) δ: 61. 8 ( q，8-OCH3 ) ，112. 2 ( d，
C-6) ，112. 6 ( d，C-3) ，113. 2 ( s，C-4a) ，123. 3 ( d，C-
5 ) ，133. 7 ( s，C-8 ) ，144. 3 ( d，C-4 ) ，147. 2 ( s，C-
8a) ，152. 1 ( s，C-7 ) ，160. 4 ( s，C-2 ) . The physical
664 Nat Prod Res Dev Vol. 24
and spectral data are in accordance with those repor-
ted［7］.
Cinnamic acid ( 5 ) C9H8O2. white powder，mp 131
－ 133℃ . ESI-MS m/z: 187［M + K］+ . 1H NMR
( CDCl3，600 MHz) δ: 7. 81 ( 1H，d，J = 16. 0 Hz，H-
2) ，7. 57 ( 2H，m，H-5，9 ) ，7. 42 ( 3H，m，H-6，H-7
and H-8) ，6. 48 ( 1H，d，J = 16. 0 Hz，H-3) . 13 C NMR
( CDCl3，150 MHz) δ: 172. 1 ( s，C-1 ) ，147. 1 ( s，C-
4) ，134. 1 ( d，C-2 ) ，130. 7 ( d，C-3 ) ，129. 0 ( d，C-
9) ，129. 0 ( d，C-5 ) ，128. 4 ( d，C-6 ) ，128. 4 ( d，C-
8) ，117. 3 ( d，C-7) . The physical and spectral data are
identical to those reported［8］.
Oleanolic acid 3-O-β-D-glucuronopyranoside ( 6)
C36 H56 O9. white powder. ESI-MS m/z: 631 ［M －
H］－ ． 1H NMR ( C5D5N，600 MHz) δ: 5. 45 ( 1H，brs，
H-12) ，4. 91 ( 1H，d，J = 7. 9 Hz，GlcA-H-1 ) ，4. 52-
4. 03 ( 4H，GlcA-H-2，GlcA-H-3，GlcA-H-4 and GlcA-
H-5) ，3. 33 ( 1H，dd，J = 11. 8，4. 3 Hz，H-3 ) ，3. 28
( 1H，dd，J = 13. 6，3. 9 Hz，H-18 ) ，1. 32 ( 3H，s ) ，
1. 29 ( 3H，s ) ，1. 01 ( 3H，s ) ，0. 98 ( 3H，s ) ，0. 97
( 3H，s ) ，0. 96 ( 6H，s ) ，0. 83 ( 3H，s ) . 13 C NMR
( C5D5N，150 MHz) δ: 89. 9 ( d，C-3) ，39. 5 ( s，C-4) ，
56. 7 ( d，C-5 ) ，123. 5 ( d，C-12 ) ，145. 7 ( s，C-13 ) ，
27. 1 ( s，C-23 ) ，17. 9 ( s，C-24 ) ，179. 9 ( s，C-28 ) ，
107. 1 ( d，GlcA-C-1) ，76. 3 ( d，GlcA-C-2) ，79. 0 ( d，
GlcA-C-3 and GlcA-C-5 ) ，72. 8 ( d，GlcA-C-4 ) ，no
signal ( GlcA-C-6) . The physical and spectral data are
equal to those reported［9］.
Oleanolic acid 3-O-( β-D-glucuronopyranoside-6-O-
butyl ester ) ( 8 ) C40 H64 O9. white powder. ESI-MS
m/z: 711 ［M + Na］+，727［M + K］+ . 1H NMR
( C5D5N，600 MHz ) δ: 5. 48 ( 1H，brs，H-12 ) ，5. 00
( 1H，d，J = 7. 9 Hz，GlcA-H-1 ) ，4. 62-4. 10 ( 4H，Gl-
cA-H-2，GlcA-H-3，GlcA-H-4 and GlcA-H-5 ) ，3. 7
( 2H，brs，Butyl-H-1 ) ，3. 37 ( 1H，dd，J = 11. 8，4. 3
Hz，H-3 ) ，3. 30 ( 1H，dd，J = 13. 6，3. 9 Hz，H-18 ) ，
1. 32 ( 3H，s ) ，1. 30 ( 3H，s ) ，1. 01 ( 3H，s ) ，0. 98
( 3H，s) ，0. 97 ( 3H，s) ，0. 96 ( 6H，s) ，0. 83 ( 3H，s) ，
0. 78 ( 3H，t，J = 7. 4 Hz，Butyl-H-4 ) . 13 C NMR
( C5D5N，150 MHz) δ: 88. 8 ( d，C-3) ，38. 4 ( s，C-4) ，
55. 5 ( d，C-5 ) ，122. 3 ( d，C-12 ) ，144. 6 ( s，C-13 ) ，
27. 1 ( s，C-23 ) ，16. 7 ( s，C-24 ) ，179. 9 ( s，C-28 ) ，
107. 1 ( d，GlcA-C-1) ，75. 2 ( d，GlcA-C-2) ，77. 7 ( d，
GlcA-C-3) ，72. 8 ( d，GlcA-C-4 ) ，77. 1 ( d，GlcA-C-
5) ，170. 1 ( s，GlcA-C-6) ，64. 7 ( t，Butyl-C-1) ，30. 63
( t，Butyl-C-2) ，19. 00 ( t，Butyl-C-3 ) ，13. 49 ( q，Bu-
tyl-C-4) . The physical and spectral data are in consist-
ent with those reported［9］.
Oleanolic acid 3-O-β-D-glucuronopyranosyl-28-3-
O-β-D-glucopyranoside ( 9) C42H66O14 . white pow-
der. ESI-MS m/z: 817［M + Na］+，793［M － H］－ . 1H
NMR ( C5D5N，600 MHz) δ: 6. 3 ( 1H，d，J = 8. 0 Hz，
Glc-H-1 ) ，5. 42 ( 1H，brs，H-12 ) ，4. 75 ( 1H，d，J =
7. 9 Hz，GlcA-H-1 ) ，4. 45-3. 91 ( 10H，m，sugars ) ，
3. 27 ( 1H，dd，J = 11. 8，4. 3 Hz，H-3 ) ，3. 18 ( 1H，
dd，J = 13. 6，3. 9 Hz，H-18 ) ，1. 28 ( 3H，s ) ，1. 28
( 3H，s) ，1. 26 ( 3H，s) ，1. 09 ( 3H，s) ，0. 95 ( 3H，s) ，
0. 94 ( 3H，s) ，0. 90 ( 3H，s) ，0. 82 ( 3H，s) . 13C NMR
( C5D5N，150 MHz) δ: 88. 7 ( d，C-3) ，38. 4 ( s，C-4) ，
55. 5 ( d，C-5 ) ，121. 4 ( d，C-12 ) ，143. 8 ( s，C-13 ) ，
28. 1 ( s，C-23 ) ，16. 8 ( s，C-24 ) ，176. 2 ( s，C-28 ) ，
106. 3 ( d，GlcA-C-1) ，75. 0 ( d，GlcA-C-2) ，78. 6 ( d，
GlcA-C-3) ，73. 4 ( d，GlcA-C-4 ) ，77. 8 ( d，GlcA-C-
5) ，95. 5 ( d，Glc-C-1) ，73. 9 ( d，Glc-C-2) ，78. 6 ( d，
Glc-C-3) ，70. 9 ( d，Glc-C-4 ) ，79. 1 ( d，Glc-C-5 ) ，
62. 0 ( d，Glc-C-6) ，no signal ( GlcA-C-6) . The physi-
cal and spectral data are in accordance with those re-
ported［9］.
Acid Hydrolysis of Compounds 6，8 and 9.
Each sample ( 5 mg) was refluxed with 10% HCl ( 4
mL) for 4 h. The reaction mixture was evaporated to
dry and then partitioned with EtOAc and H2O. The
EtOAc extract was purified by chromatography on
Sephadex LH-20 ( 2. 5 × 100 cm，50 g) . The aglycone
of 6，8 and 9 was determined to be oleanolic acid by
TLC comparison with authentic sample. The rest of the
aqueous layer was neutralized ( 10%，N，N-dioctylm-
ethylamine in CHCl3 ) and concentrated under reduced
pressure. Glucose and glucuronic acid were identified
by TLC comparison with authentic samples.
Alkaline Hydrolysis of Compounds 8 and 9.
The saponin ( 2 mg) in KOH 10% ( 2 mL) was heated
at 100 ℃ in a sealed tube for 75 min. After acidifica-
tion with HCl ( pH 5 ) ，the monodesmosides were ex-
tacted with n-BuOH. The hydrolysates of compounds 8
and 9 were identified to be compound 6. The aqueous
764Vol. 24 LI Chang-song，et al: Chemical Constituents of Deutzia setchuenensis
solution of compound 9 contained glucose，identified by
TLC comparison with an authentic sample.
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864 Nat Prod Res Dev Vol. 24