全 文 ：Received:March 12，2012;Accepted:May 30，2012
* Corresponding author Tel:86-21-81871245;E-mail:shenyunheng9217018
@ yahoo． com． cn
天然产物研究与开发 Nat Prod Res Dev 2012，24:1743-1746
文章编号:1001-6880(2012)12-1743-04
红波罗花的化学成分研究
陈 红1，2，王 琦1，王贵荣1，范译文1，沈云亨2*
1吉林农业大学中药材学院，长春 130118;2第二军医大学药学院天然药物化学教研室，上海 200433
摘 要:从红波罗花(Incarvillea delavayi)植物的干燥全草乙醇提取物中分离得到 12 个化合物，通过 MS和 NMR
等方法鉴定为 tecomine (1)、epidihydrotecomanine (2)、2，6-二甲基-6-羟基-2-庚烯-4-酮 (3)、marine B (4)、
(3R，5S)-3-methyl-cyclopentyl［1，2-c］pyridine-5-ol (5)、3，4，5-三甲氧基苯甲酸乙酯 (6)、cleroindicin B (7)、
3，4，5-三甲氧基苯甲酸甲酯 (8)、2-(4-乙氧基苯基)-乙醇 (9)、6-羟基苯并二氢呋喃 (10)、β-谷甾酮 (11)、
β-乙酰齐墩果酸 (12)。其中化合物 1 ～ 3、5 ～ 6、8 ～ 12 为首次从角蒿属植物中分离得到，所有化合物均为首次
从该植物中分离得到。
关键词:红波罗花;角蒿属;化学成分
中图分类号:R284. 2 文献标识码:A
Chemical constituents of Incarvillea delavayi
CHEN Hong1，2，WANG Qi1，WANG Gui-rong1，FAN Yi-wen1，SHEN Yun-heng2*
1Department of Pharmacognosy，Jilin Agricultural University，Changchun 130118，China;
2School of Pharmacy，Second Military Medical University，Shanghai 200433，China
Abstract:Twelve known compounds were isolated from the whole plant of Incarvillea delavayi． Based on MS and NMR a-
nalysis，these compounds were determined as tecomine (1) ，epidihydrotecomanine (2) ，2 6-dimethyl-6-hydroxy-2-hep-
tene-4-one (3) ，marine B (4) ，(3R，5S)-3-methyl-cyclopentyl［1，2-c］ pyridine-5-ol (5) ，Ethyl 3，4，5-trimethoxy-
benzoate (6) ，cleroindicin B (7) ，3 4，5-trimethoxy-benzoic acid methyl ester (8) ，2-(4-ethoxy-phenyl)-ethanol (9) ，
2，3-dihydro-benzofuran-6-ol (10) ，β-sitoserone (11)and β-acetyloleanolic acid (12)． Among them，compounds 1-3，5-
6，8-12 were isolated from the genus Incarvillea for the first time，and all compounds were isolated from the species for
the first time．
Key words:Incarvillea delavayi;Incarvillea L．;chemical constituents
Introduction
Incarvillea delavayi Bur． et． Fronch，a member of the
genus Incarvillea (Bignoniace) ，is mainly distributed in
Yunan and Sichuan provinces，China． In Chinese folk
medicine，the roots of this plant are used to treat me-
grim，anemia and to relieve fatigue［1，2］． The presence of
monoterpenoid alkaloids［3，4］，iridoid［5］ and sesquiter-
pene［6］in this plant were previously reported． In this
study，the isolation and structural identification of 12
known compounds from the ethanol extract of the whole
plants of I． delavayi are presented． This is the first re-
port of the isolation of these 12 compounds from the ge-
nus Incarvillea or I． delavayi．
Experimental
Plant materials
The whole plants of I． delavayi were collected in
Eryuan county of Yunnan province，China，in Septem-
ber，2010． It was identified by Prof． Han Ming Zhang，
the Second Military Medical University． The voucher
specimen (No． 201009011)of this herb was kept in
the School of Pharmacy，the Second Military Medical
University．
Instruments
NMR spectral data were recorded on Bruker DRX 400
and 500 MHz NMR spectrometers． Chemical shifts were
recorded as δ values． The ESI-MS data were acquired
on an Agilent-1100-LC /MSD-Trap-XCT mass spec-
trometer (Agilent，USA)．
TLC and Column chromatography
TLC was done on precoated silica gel 254 plates
(Huanghai，0． 15-0． 20 mm thick for TLC analysis，
0. 40-0． 50 mm thick for preparative TLC)． Column
chromatography was performed using silica gel (200-
300 mesh and 100-200 mesh) (Huiyou Silica Gel De-
velopment Co． Ltd，Yantai，P． R． China) ，RP-C18
(GHODS AQ 12S50，Japan) and Sephadex LH-20
(40-70 μm) (Amersham Pharmacia Biotech Ab，Upp-
sala，Sweden)．
Extraction and isolation
The dried whole plants of I． delavayi (18 kg)were ex-
tracted with 90% ethanol for three times． The extract
was combined and evaporated． The concentrated resi-
due was dissolved in 2% HCl (2 L) ，and filtered
through buchner filter (Jiangsu，China)． The filtrate
was extracted with ethyl acetate by liquid-liquid extrac-
tion to yield the ethyl acetate extract． The aqueous layer
was adjusted to pH 10-11 with NH4OH，and then ex-
tracted with CHCl3 to afford a total alkaloid fraction．
The remained aqueous layer was adjusted to pH 7 with
2% HCl，and subsequently extracted with ethyl ace-
tate． The obtained ethyl acetate extract was mixed with
the previous ethyl acetate extract to yield a total ethyl
acetate fraction． The total alkaloid fraction (80 g)was
separated into 5 fractions (A-E)by a neutral alumina
column chromatography eluting with a gradient of pe-
troleum ether (PE)-acetone (100∶ 1-0∶ 1)． Fraction A
was further purified by column chromatography over
neutral alumina，Sephadex LH-20 (CHCl3 ∶ CH3OH 1
∶ 1)and preparative TLC，yielding compounds 1 (23． 6
mg)and 2 (120． 6 mg)． Compound 6 (5． 5 mg)was
obtained from fraction B through similar procedures．
Repeated column chromatography of fraction C over
Sephadex LH-20 (CHCl3 ∶ CH3OH 1 ∶ 1)led to com-
pound 3 (300． 6 mg)． Fraction D was subjected to
neutral alumina column chromatography (PE∶ acetone 7
∶ 1) ，followed by Sephadex LH-20 (CHCl3 ∶ CH3OH 1
∶ 1)and preparative TLC (PE∶ actetone 5∶ 1) ，affording
compound 4 (115． 0 mg)and 7 (259． 8 mg)． Similar-
ly，compound 5 (5． 6 mg)was isolated from fraction
E． Ethyl acetate fraction was separated over silica gel
column eluting with increasing concentrations of ace-
tone in petroleum ether to give three fractions F-H． By
repeated column chromatography over silica gel (PE∶
CHCl3 ∶ CH3OH 25 ∶ 2 ∶ 1) and Sephadex LH-20
(CHCl3 ∶ CH3OH 1 ∶ 1) ，compounds 8 (3． 8 mg)and
11 (7． 2 mg)were isolated from fraction F． Fraction G
was separated over silica gel column chromatography
(PE ∶ acetone 10 ∶ 1) ，and Sephadex LH-20 column
chromatography (CHCl3 ∶ CH3OH 1 ∶ 1)to yield com-
pound 12 (12． 3 mg)． Fraction H was subjected to me-
dium pressure liquid chromatography (MPLC )
(CH3OH∶ H2O 0∶ 100-100∶ 0) ，and further purified by
repeated silica gel column chromatography (PE∶ ethyl
acetate 5∶ 1-3 ∶ 1)to yield compounds 9 (29． 8 mg)
and 10 (102． 3 mg)．
Structural identification
Compound 1 C11 H17 NO，yellow oil;ESI-MS (posi-
tive)m/z 180. 1［M + H］+，202. 0［M + Na］+;1H
NMR (400 MHz，CDCl3-d1)δ:3. 24 (1H，m，H-1a) ，
1. 74 (1H，t，J = 11. 4 Hz，H-1b) ，3. 01 (1H，m，H-
3a) ，1. 74 (1H，t，J = 11. 4 Hz，H-3b) ，2. 72 (1H，
m，H-4) ，5. 83 (1H，s，H-6) ，1. 94 (1H，m，H-8) ，
2. 58 (1H，m，H-9) ，1. 17 (3H，d，J = 6. 0 Hz，H-
10) ，1. 14 (3H，d，J = 5. 2 Hz，H-11) ，2. 32 (3H，s，
NCH3) ;
13C NMR (100 MHz，CDCl3-d1)δ:63. 3 (C-
1) ，62. 1 (C-3) ，35. 2 (C-4) ，183. 6 (C-5) ，124. 4
(C-6) ，210. 6 (C-7) ，45. 2 (C-8) ，49. 7 (C-9) ，15. 1
(C-10) ，15. 0 (C-11) ，45. 6 (C-12). The NMR data
was consistent with the data reported in literature［7］．
Hence，compound 1 was identified as tecomine.
Compound 2 C11 H19 NO，yellow oil;ESI-MS (posi-
tive)m/z 182. 1［M + H］+，204. 0［M + Na］+;1H
NMR (400 MHz，CDCl3-d1)δ:2. 88 (1H，m，H-1a) ，
2. 10 (1H，m，H-1b) ，2. 70 (1H，m，H-3a) ，1. 57
(1H，t，J = 11. 2 Hz，H-3b) ，1. 44 (1H，m，H-4) ，
1. 63 (1H，m，H-5) ，2. 27 (2H，m，H-6) ，2. 45 (1H，
m，H-8) ，1. 81 (1H，m，H-9) ，0. 81 (3H，d，J = 6. 4
Hz，H-10) ，1. 01 (3H，d，J = 6. 8 Hz，H-11) ，2. 21
(1H，s，NCH3) ;
13 C NMR (100 MHz，CDCl3- d1)δ:
55. 6 (C-1) ，62. 9 (C-3) ，32. 6 (C-4) ，39. 2 (C-5) ，
43. 2 (C-6) ，221. 3 (C-7) ，43. 7 (C-8) ，44. 8 (C-
4471 Nat Prod Res Dev Vol. 24
9) ，12. 8 (C-10) ，17. 7 (C-11) ，46. 6 (NCH3). The
NMR data was consistent with the data reported in lit-
erature［8］. Hence，compound 2 was identified as epidi-
hydrotecomanine.
Compound 3 C9H16O2，yellow oil;ESI-MS (positive)
m/ z 179. 1［M + Na］+，1H NMR (400 MHz，CDCl3)
δ:1. 81 (3H，s，H-1) ，2. 07 (3H，s，2-CH3) ，5. 95
(1H，s，H-3) ，2. 49 (2H，s，H-5) ，1. 15 (6H，s，6-
CH3，H-7) ，4. 19 (1H，s，6-OH) ;
13 C NMR (100
MHz，CDCl3)δ:21. 0 (C-1) ，157. 2 (C-2) ，27. 9 (2-
CH3) ，124. 7 (C-3) ，202. 3 (C-4) ，54. 2 (C-5) ，70. 0
(C-6) ，29. 5 (2C，C-7，6-CH3). The NMR data was
consistent with the data reported in literature［9］
. Hence，compound 3 was identified as 2，6-dimethyl-6-
hydroxy-2-heptene-4-one.
Compound 4 C11 H21 NO，yellow oil;ESI-MS (posi-
tive)m/z 184. 2［M + H］+，206. 3［M + Na］+;1H
NMR (400 MHz，CDCl3-d1)δ:2. 52 (1H，m，H-1a) ，
1. 59 (1H，m，H-1b) ，2. 45 (1H，m，H-3a) ，1. 63
(1H，m，H-3b) ，2. 03 (1H，m，H-4) ，1. 87 (1H，m，H-
5) ，1. 39 (2H，m，H-6) ，1. 78 (1H，m，H-7a) ，1. 08
(1H，m，H-7b) ，1. 66 (1H，m，H-8) ，2. 03 (1H，m，H-
9) ，0. 79 (3H，d，J = 8. 0 Hz，H-10) ，3. 31 (2H，d，J
= 4. 0 Hz，H-11) ，2. 16 (3H，s，NCH3) ;
13 C NMR
(100 MHz，CDCl3-d1)δ:57. 4 (C-1) ，58. 0 (C-3) ，
30. 7 (C-4) ，41. 2 (C-5) ，22. 1 (C-6 ) ，26. 0 (C-7) ，
45. 1 (C-8) ，40. 8 (C-9) ，17. 6 (C-10) ，66. 3 (C-
11) ，46. 2 (NCH3). The NMR data was consistent with
the data reported in literature［10］. Hence，compound 4
was identified as marine B.
Compound 5 C9H11 NO，yellow oil;ESI-MS (posi-
tive)m/z 172. 2［M + Na］+;1H NMR (400 MHz，
C5D5N-d5)δ:7. 56 (1H，d，J = 5. 6 Hz，H-2) ，7. 16
(1H，d，J = 5. 6 Hz，H-5) ，8. 72 (1H，t，J = 5. 6
Hz，H-6) ，3. 46 (1H，m，H-7) ，2. 43 (1H，m，H-8a) ，
2. 03 (1H，m，H-8b) ，5. 53 (1H，d，J = 5. 9 Hz，H-
9) ，1. 17 (3H，d，J = 7. 2 Hz，H-10) ;13C NMR (100
MHz，C5D5N-d5) δ:148. 8 (C-2) ，144. 4 (C-3) ，
155. 3 (C-4) ，120. 5 (C-5) ，146. 9 (C-6) ，36. 1 (C-
7) ，45. 2 (C-8) ，74. 2 (C-9) ，21. 0 (C-10). The
NMR data was consistent with the data reported in lit-
erature［11］. Hence，compound 5 was identified as (3R，
5S)-3-methyl-cyclopentyl［1，2-c］pyridine-5-ol.
Compound 6 C12 H16 O5，yellow oil;ESI-MS (posi-
tive) m/z 263. 1 ［M + Na］+，503. 1 ［2M +
Na］+;1H NMR (400 MHz，CDCl3-d1)δ:7. 28 (2H，
s，H-2，H-6) ，4. 35 (2H，q，J = 7. 1 Hz，-
OCH2CH3) ，1. 38 (3H，t，J = 7. 1 Hz，-OCH2CH3) ，
3. 89 (9H，d，J = 3. 5 Hz，-OCH3 × 3) ;
13 C NMR
(100 MHz，CDCl3-d1)δ:125. 7 (C-1) ，106. 9 (C-2，
C-6) ，153. 1 (C-3，C-5) ，142. 3 (C-4) ，166. 5 (C-
7) ，61. 4 (-OCH2CH3) ，14. 6 (-OCH2CH3) ，56. 4 (3-
OCH3，5-OCH3) ，61. 1 (4-OCH3). The NMR data was
consistent with the data reported in literature［12］．
Hence，compound 6 was identified as Ethyl 3，4，5-tri-
methoxybenzoate.
Compound 7 C8H14 O3，yellow oil;ESI-MS (nega-
tive)m/z 157. 1 ［M - H］-;1H NMR (400 MHz，
CDCl3-d1)δ:2. 05 (2H，m，H-2a，H-6a) ，1. 68 (2H，
m，H-2b，H-6b) ，2. 67 (2H，m，H-3a，H-5a) ，2. 17
(2H，m，H-3b，H-5b) ，1. 75 (2H，t，J = 5. 8 Hz，H-
7) ，3. 88 (2H，t，J = 5. 8 Hz，H-8) ;13 C NMR (100
MHz，CDCl3-d1)δ:70. 6 (C-1) ，36. 9 (C-2，C-6) ，
37. 1 (C-3，C-5) ，213. 3 (C-4) ，41. 8 (C-7) ，59. 5
(C-8). The NMR data was consistent with the data re-
ported in literature［13］. Hence，compound 7 was identi-
fied as cleroindicin B.
Compound 8 C11 H14 O5，yellow oil;ESI-MS (posi-
tive) m/z 249. 2 ［M + Na］+，475. 1 ［2M +
Na］+;1H NMR (500 MHz，CDCl3-d1)δ:7. 28 (2H，
s，H-2，H-6) ，3. 88 (3H，s，-COOCH3) ，3. 89 (9H，s，-
OCH3 × 3) ;
13C NMR (125 MHz，CDCl3-d1)δ:125. 4
(C-1) ，107. 0 (C-2，C-6) ，153. 1 (C-3，C-5) ，142. 3
(C-4) ，167. 0 (C-7) ，52. 5 (-COOCH3) ，56. 4 (3-
OCH3，5-OCH3) ，61. 1 (4-OCH3). The NMR data was
consistent with the data reported in literature［14］．
Hence，compound 8 was identified as 3，4，5-trime-
thoxy-benzoic acid methyl ester.
Compound 9 C10 H14 O2，yellow oil;ESI-MS (posi-
tive)m/z 189. 2［M + Na］+;1H NMR (400 MHz，
C5D5N-d5)δ:7. 33 (2H，d，J = 8. 6 Hz，H-2，H-6) ，
6. 99 (2H，d，J = 8. 6 Hz，H-3，H-5) ，3. 03 (2H，t，J
= 7. 0 Hz，H-7) ，3. 92 (2H，q，J = 7. 0 Hz，H-8) ，
4. 09 (2H，t，J = 7. 0 Hz，-OCH2CH3) ，1. 28 (3H，t，
5471Vol. 24 CHEN Hong，et al:Chemical constituents of Incarvillea delavayi
J = 7. 0 Hz，-OCH2CH3) ;
13 C NMR (C5D5N，100
MHz)δ:132. 6 (C-1) ，130. 8 (C-2，C-6) ，115. 1 (C-
3，C-5) ，158. 2 (C-4) ，39. 9 (C-7) ，63. 8 (C-8) ，
64. 1 (-OCH2CH3) ，15. 3 (-OCH2CH3). By the above
NMR data，the structure of compound 9 can beidenti-
fied as 2-(4-ethoxy-phenyl)-ethanol，a known simple
compound［15］. However，no NMR data of this compound
are available in published literatures，although we
searched a lot of literatures and databases. Herein，we
reported the NMR data of 9 for the first time.
Compound 10 C8H8O2，yellow oil;ESI-MS (nega-
tive)m/z 135. 2 ［M - H］-;1H NMR (400 MHz，
MeOD-d4) δ:4. 44 (2H，t，J = 8. 6，H-2) ，3. 10
(2H，t，J = 8. 6 Hz，H-3) ，6. 51 (1H，s，H-5) ，6. 66
(1H，dd，J = 7. 8 Hz，H-7) ，6. 50 (1H，d，J = 7. 8
Hz，H-8) ;13C NMR (100 MHz，CD3OD)δ:72. 2 (C-
2) ，31. 2 (C-3) ，129. 3 (C-4) ，114. 9 (C-5) ，152. 3
(C-6) ，113. 2 (C-7) ，110. 0 (C-8) ，154. 7 (C-9)．
The NMR data was consistent with the data reported in
literature［16］. Hence，compound 10 was identified as 2，
3-dihydro-benzofuran-6-ol.
Compound 11 C29 H48 O，white needle crystal
(CHCl3) ;EI-MS m/z 412［M］
+;TLC behavior was i-
dentical to that of authentic β-sitosterone.
Compound 12 C32 H50 O4， white needle crystal
(CHCl3) ;ESI-MS m/z 521. 6［M + Na］
+;1H NMR
(500 MHz，CDCl3)δ:4. 47 (1H，t，J = 7. 8 Hz，H-
3) ，5. 24 (1H，s，H-12) ，0. 82，0. 83，0. 87，0. 90，
0. 91，1. 10，1. 22 (7 × 3H，s，7 × -CH3) ，2. 02 (3H，
s，-COCH3) ;13 C NMR (125 MHz，CDCl3) δ:37. 9
(C-1) ，28. 2 (C-2) ，81. 1 (C-3) ，38. 2 (C-4) ，55. 5
(C-5) ，18. 4 (C-6) ，32. 7 (C-7) ，39. 5 (C-8) ，47. 7
(C-9) ，37. 2 (C-10) ，23. 0 (C-11) ，122. 7 (C-12) ，
143. 8 (C-13) ，41. 7 (C-14) ，27. 8 (C-15) ，23. 6 (C-
16) ，46. 7 (C-17) ，41. 1 (C-18) ，46. 0 (C-19) ，30. 7
(C-20) ，34. 0 (C-21) ，32. 6 (C-22) ，29. 9 (C-23) ，
15. 3 (C-24) ，16. 9 (C-25) ，17. 3 (C-26) ，26. 0 (C-
27) ，183. 1 (C-28) ，33. 3 (C-29) ，23. 7 (C-30) ，
171. 3 (-COCH3) ，21. 5 (-COCH3). The NMR data
was consistent with the data reported in literature［17］．
Hence，compound 12 was identified as 3β-acetyl-olean-
olic acid.
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