全 文 ：Ｒeceived:February 25，2013 Accepted:April 25，2013
Foundation Item:This research project was supported by the Scientific
Foundation of Shanghai Committee of Science and Technology
(12401900501)．
* Corresponding author Tel:86-21-34205989;E-mail:kimhz@ sjtu． edu．
cn;wdzhangy@ hotmail． com
天然产物研究与开发 Nat Prod Ｒes Dev 2014，26:33-37
文章编号:1001-6880(2014)1-0033-05
滇南羊耳菊乙酸乙酯部位化学成分研究
王春辉1，魏攀蕾1，严诗楷1，金慧子1 * ，张卫东1，2 *
1上海交通大学药学院，上海 200240;2 第二军医大学药学院，上海 200433
摘 要:从滇南羊耳菊(Inula wissmanniana)地上部分的乙酸乙酯部位分离得到 16 个化合物，包括 6 个黄酮类，5
个苯丙素类和 5 个其它芳香类化合物，经波谱数据分析鉴定为木犀草素(1) ，3-甲氧基槲皮素(2) ，5 6，4-三羟
基-3，7-二甲氧基黄酮(3) ，洋艾素(4) ，紫杉叶素(5) ，二氢山奈酚(6) ，3 4-二-O-咖啡酰奎宁酸 (7) ，3 5-二-O-
咖啡酰奎宁酸 (8) ，C-veratroylglycol(9) ，2 3-dihydroxy-1-(4-hydroxy-3，5-dimethoxyphenyl)-1-propanone (10) ，咖
啡酸(11) ，邻苯二甲酸二丁酯 (12) ，3 4-二羟基苯甲酸 (13) ，3-羟基-4-甲氧基苯甲酸(14) ，对羟基苯甲酸 (15)
和香兰素 (16)。所有化合物均为首次从该植物中分离得到。
关键词:滇南羊耳菊;旋覆花属;黄酮;苯丙素;芳香化合物
中图分类号:Ｒ284． 1;Q946． 91 文献标识码:A
Chemical Constituents from the Ethyl Acetate Portion of Inula wissmanniana
WANG Chun-hui1，WEI Pan-lei1，YAN Shi-kai1，JIN Hui-zi1 * ，ZHANG Wei-dong1，2 *
1School of Pharmacy，Shanghai Jiao Tong University，Shanghai 200240，China;
2School of Pharmacy，Second Military University，Shanghai 200433，China
Abstract:Sixteen compounds were isolated from the ethyl acetate portion of the aerial part of Inula wissmanniana，inclu-
ding six flavonoids，five phenylpropanoids，and five other aromatic compounds． On the basis of spectral data，their struc-
tures were identified as luteolin (1) ，3-O-methylquercetin (2) ，5 6，4-trihydroxy-3，7-dimethoxyflavone (3) ，artemetin
(4) ，taxifolin (5) ，dihydrokaempferol (6) ，3 4-di-O-caffeoyl quinic acid (7) ，3 5-di-O-caffeoylquinic acid (8) ，C-ve-
ratroylglycol (9) ，2，3-dihydroxy-1-(4-hydroxy-3，5-dimethoxyphenyl)-1-propanone (10) ，caffeic acid (11) ，dibu-
tylphthalate (12) ，3，4-dihydroxybenzoic acid (13) ，3-hydroxy-4-methoxybenzoic acid (14) ，p-hydroxybenzoic acid
(15)and vanillin (16)． All the compounds were isolated from this plant for the first time．
Key words:Inula wissmanniana;Inula;flavonoids;phenylpropanoids;aromatic compounds
Introduction
Inula wissmanniana，a suffrutescent plant belonging to
the Asteraceae family，mainly distributed in the south of
Yunnan province of China，growing at 1200-1650 m a-
bove sea level ［1］． So far，no chemical constituents have
been reported from I． wissmanniana． In this study，we i-
solated and identified sixteen compounds from an ethyl
acetate (EtOAc) extract of the aerial parts of this
plant，including luteolin (1) ，3-O-methylquercetin
(2) ，5 6，4-trihydroxy-3，7-dimethoxyflavone (3) ，ar-
temetin (4) ，taxifolin (5) ，dihydrokaempferol (6) ，3
4-di-O-caffeoyl quinic acid (7 ) ，3，5-di-O-caf-
feoylquinic acid (8) ，C-veratroylglycol (9) ，2，3-di-
hydroxy-1-(4-hydroxy-3，5-dimethoxyphenyl)-1-propa-
none (10) ，caffeic acid (11) ，dibutylphthalate (12) ，
3，4-dihydroxybenzoic acid (13) ，3-hydroxy-4-me-
thoxybenzoic acid (14) ，p-hydroxybenzoic acid (15)
and vanillin (16)． All the compounds were isolated
from this plant for the first time．
Experimental
General procedures
The normal phase silica gel (100-200，200-300 mesh，
Yantai，China) ，MCI gel (CHP20P 75-150 μm，Mit-
subishi Chemical Co．，Japan) ，and Sephadex LH-20
(GE Healthcare Bio-Sciences AB，Sweden)were used
for column chromatography，and precoated silica HS-
GF254 plates were used for TLC (Yantai，China)． HPLC
were performed with SHIMADZU LC 2010AHT，Agilent
Technologies 1200 series，semipreparative HPLC was
obtained on a SHIMADZU LC-6AD series using a Zor-
bax-SB-C18(5 μm，9． 4 × 250 nm)． The ESI-MS were
measured on an Agilent 1100 series mass spectrome-
ter． 1H and 13C NMＲ spectra were measured on a Bruk-
er DＲX-400 spectrometer (400 MHz for 1H NMＲ and
100 MHz for 13C NMＲ)． Chemical shift (δ)were given
in ppm relative to TMS as internal reference and cou-
pling constants (J)in Hz．
Plant material
The aerial parts of I． wissmanniana were collected from
Pingbian county of Yunnan Province，China，in August
2010 and identified by Prof． Zhang Han-Ming，Depart-
ment of Pharmacognosy，School of Pharmacy，Second
Military Medical University． A voucher specimen has
been deposited at School of Pharmacy (NO．
201008DNYEJ)Shanghai Jiao Tong University．
Extraction and isolation
The air-dried and powdered aerial parts of I． wissman-
niana (30． 0 kg)were extracted with 95% EtOH for
three times at room temperature，the extracts were com-
bined and concentrated to yield a residue (631． 4 g)．
The residue was suspended in H2O (6． 0 L)and then
partitioned successively with petroleum ether (12． 0 L
× 5) ，CH2Cl2(12． 0 L × 5) ，EtOAc (12． 0 L × 5)and
n-butanol (12． 0 L × 5) ，giving 133． 2 g，179． 6 g，28．
1 g and 35． 2 g，respectively． The EtOAc fraction was
chromatographed on a silica gel column eluting with
CH2Cl2-MeOH (100 ∶ 1 to 0 ∶ 100)gradient to obtain
six fractions (Fr． 1-Fr． 6)． Six fractions were all ap-
plied to MCI gel column chromatography (MeOH-
H2O，9∶ 1)． Fr． 2 (2． 1 g)was further subjected to a
silica gel column and eluted with CH2Cl2-MeOH (100
∶ 1 to 20 ∶ 1)to give compound 4 (20． 1 mg)． Fr． 3
(3. 1 g)was separated by Sephadex LH-20 (MeOH)
to give 4 subfractions． The subfraction 2 was submitted
to preparative HPLC (ＲP18，210 nm，CH3CN-H2O-
HCOOH，17 ∶ 83 ∶ 0． 1) ，yielding compounds 9 (3． 8
mg，tＲ = 13． 4 min) ，10 (1． 6 mg，tＲ = 14． 3 min) ，14
(50． 8 mg，tＲ = 25． 4 min)and 15 (23． 0 mg，tＲ =
35. 5 min)． The subfraction 4 was submitted to prepar-
ative HPLC (ＲP18，210 nm，MeOH-H2O，80 ∶ 20) to
obtain 12 (9． 0 mg，tＲ = 24． 0 min)． Fr． 4 (3． 7 g)was
subjected to Sephadex LH-20 (MeOH)to give 5 sub-
fractions． The subfraction 3 was separated by prepara-
tive HPLC (ＲP18，210 nm，CH3CN-H2O-HCOOH，17
∶ 83∶ 0． 1)to give compounds 3 (11． 1 mg，tＲ = 72． 1
min) ，11 (29． 0 mg，tＲ = 19． 3 min) ，13 (17． 1 mg，tＲ
= 12． 5 min)and 16 (21． 6 mg，tＲ = 41． 8 min) ，the
subfraction 4 was separated by preparative HPLC
(ＲP18，210 nm，CH3CN-H2O，20 ∶ 80)to yield com-
pounds 1 (102． 2 mg，tＲ = 51． 3 min) ，2 (5． 0 mg，tＲ
= 97． 2 min) ，5 (58． 4 mg，tＲ = 27． 0 min)and 6
(13． 3 mg，tＲ = 35． 2 min)． Compounds 7 (37． 7 mg，tＲ
= 60． 5 min)and 8 (25． 8 mg，tＲ = 78． 6 min)were
obtained after the purification of Fr． 6 (5． 2 g)by
Sephadex LH-20 (MeOH) and preparative HPLC
(ＲP18，210 nm，CH3CN-H2O-HCOOH，20∶ 80∶ 0． 1)．
Structure identification
Luteolin (1) C15 H10 O6，yellow amorphous powder，
ESI-MS (positive)m/z 309 ［M + Na］+，ESI-MS
(negative)m/z 285 ［M-H］-;1 H NMＲ (400 MHz，
DMSO-d6)δ:12. 94 (1H，s，5-OH) ，7. 40 (1H，brs，
H-6) ，7. 38 (1H，s，H-2) ，6. 87 (1H，d，J = 8. 1
Hz，H-5) ，6. 64 (1H，s，H-3) ，6. 43 (1H，d，J = 1. 4
Hz，H-8) ，6. 17 (1H，d，J = 1. 4 Hz，H-6) ;13 C NMＲ
(100 MHz，DMSO-d6)δ:181. 7 (C-4) ，164. 1 (C-
7) ，163. 9 (C-2) ，161. 5 (C-9) ，157. 3 (C-5) ，149. 7
(C-4) ，145. 8 (C-3) ，121. 5 (C-1) ，119. 0 (C-
6) ，116. 1 (C-5)113. 4 (C-2) ，103. 7 (C-10) ，
102. 9 (C-3) ，98. 9 (C-6) ，93. 9 (C-8). The NMＲ
and MS data were in accordance with those reported in
the literature ［2］，and identified 1 as luteolin.
3-O-Methylquercetin (2) C16 H12 O7，yellow amor-
phous powder，ESI-MS (positive)m/z 339 ［M +
Na］+，ESI-MS (negative)m/z 315［M-H］-;1H NMＲ
(400 MHz，CD3OD) δ:7. 61 (1H，s，H-2) ，7. 52
(1H，d，J = 8. 5 Hz，H-6) ，6. 89 (1H，d，J = 8. 5
Hz，H-5) ，6. 39 (1H，s，H-8) ，6. 19 (1H，brs，H-6) ，
3. 77 (3H，s，3-OCH3) ;
13C NMＲ (100 MHz，CD3OD)
δ:180. 0 (C-4) ，166. 0 (C-7) ，163. 1 (C-5) ，158. 4
(C-9) ，158. 0 (C-2) ，150. 0 (C-4) ，146. 5 (C-3) ，
139. 5 (C-3) ，122. 9 (C-1) ，122. 3 (C-6) ，116. 5
43 Nat Prod Ｒes Dev Vol. 26
(C-2) ，116. 4 (C-5) ，105. 9 (C-10) ，99. 8 (C-6) ，
94. 6 (C-8) ，60. 5 (3-OCH3). The NMＲ and MS data
were in accordance with those reported in the literature
［3］，and identified 2 as 3-O-methylquercetin.
5，6，4-Trihydroxy-3，7-dimethoxyflavone (3) C17
H14O7，yellow needle crystals，ESI-MS (positive)m/z
353［M + Na］+，ESI-MS (negative)m/z 329 ［M-
H］－;1H NMＲ (400 MHz，DMSO-d6)δ:12. 38 (1H，
brs，5-OH) ，7. 96 (2H，d，J = 8. 6 Hz，H-2，6) ，6. 94
(2H，d，J = 8. 6 Hz，H-3，5) ，6. 85 (1H，s，H-8) ，
3. 90 (3H，s，7-OCH3) ，3. 79 (3H，s，3-OCH3) ;
13 C
NMＲ (100 MHz，DMSO-d6)δ:178. 1 (C-4) ，160. 3
(C-4) ，155. 7 (C-2) ，154. 5 (C-7) ，148. 9 (C-9) ，
145. 7 (C-5) ，137. 5 (C-3) ，130. 0 (C-2，6) ，129. 6
(C-6) ，120. 7 (C-1) ，115. 7 (C-3，5) ，105. 6 (C-
10) ，90. 9 (C-8) ，59. 7 (3-OCH3) ，56. 3 (7-OCH3)
. The NMＲ and MS data were in accordance with those
reported in the literature ［4］，and identified 3 as 5，6，
4-trihydroxy-3，7-dimethoxyflavone.
Artemetin (4) C20 H20 O8，yellow amorphous pow-
der，ESI-MS (positive)m/z 411 ［M + Na］+，ESI-MS
(negative)m/z 387 ［M-H］-;1H NMＲ (400 MHz，
DMSO-d6)δ:12. 6 (1H，brs，5-OH) ，7. 74 (1H，dd，J
= 8. 6，1. 8 Hz，H-6) ，7. 67 (1H，d，J = 1. 8 Hz，H-
2) ，7. 16 (1H，d，J = 8. 6 Hz，H-5) ，6. 94 (1H，s，
H-8) ，3. 94，3. 83，3. 70 (each 3H，s，3 × -OCH3) ，
3. 87 (6H，s，2 × -OCH3) ;
13 C NMＲ (400 MHz，DM-
SO-d6)δ:178. 3 (C-4) ，158. 7 (C-7) ，155. 5 (C-
9) ，151. 8 (C-2) ，151. 6 (C-5) ，151. 3 (C-4) ，148. 5
(C-3) ，138. 1 (C-3) ，131. 6 (C-6) ，122. 1 (C-1) ，
122. 0 (C-6) ，111. 6 (C-5) ，111. 3 (C-2) ，105. 6
(C-10) ，91. 5 (C-8) ，60. 0，59. 8，56. 5，55. 7，55. 6
(6 × -OCH3). The NMＲ and MS data were in accord-
ance with those reported in the literature ［5］，and iden-
tified 4 as artemetin.
Taxifolin (5) C15H12O7，yellow amorphous powder，
ESI-MS (positive)m/z 327 ［M + Na］+，ESI-MS
(negative)m/z 303 ［M-H］-;1H NMＲ (400 MHz，
CD3OD)δ:6. 97 (1H，s，H-2) ，6. 84 (1H，d，J =
8. 0 Hz，H-5) ，6. 79 (1H，d，J = 8. 0 Hz，H-6) ，5. 91
(1H，s，H-8) ，5. 87 (1H，s，H-6) ，4. 89 (1H，d，J =
11. 4 Hz，H-2) ，4. 49 (1H，d，J = 11. 4 Hz，H-3) ;13 C
NMＲ (100 MHz，CD3OD) δ:198. 2 (C-4) ，168. 6
(C-7) ，164. 4 (C-5) ，164. 3 (C-9) ，147. 0 (C-4) ，
146. 2 (C-3) ，129. 8 (C-1) ，120. 9 (C-6) ，116. 1
(C-2) ，115. 9 (C-5) ，101. 8 (C-10) ，97. 3 (C-6) ，
96. 3 (C-8) ，84. 9 (C-2) ，73. 5 (C-3). The NMＲ and
MS data were in accordance with those reported in the
literature ［6］，and identified 5 as toxifolin.
Dihydrokaempferol (6) C15 H12 O6，yellow needle
crystals，ESI-MS (positive)m/z 311［M + Na］+，ESI-
MS (negative) m/z 287 ［M-H］-;1H NMＲ (400
MHz，CD3OD)δ:7. 34 (2H，d，J = 8. 6 Hz，H-2，
6) ，6. 83 (2H，d，J = 8. 6 Hz，H-3，5) ，5. 92 (1H，
s，H-8) ，5. 88 (1H，s，H-6) ，4. 97 (1H，d，J = 11. 4
Hz，H-2) ，4. 53 (1H，d，J = 11. 4 Hz，H-3) ;13C NMＲ
(100 MHz，CD3OD)δ:198. 5 (C-4) ，168. 8 (C-5) ，
164. 6 (C-9) ，159. 2 (C-4) ，130. 4 (C-2，6) ，
129. 3 (C-1) ，116. 2 (C-3，5) ，101. 9 (C-10) ，
97. 4 (C-6) ，96. 3 (C-8) ，85. 0 (C-2) ，73. 7 (C-3)．
The NMＲ and MS data were in accordance with those
reported in the literature ［7］，and identified 6 as di-
hydrokaempferol.
3，4-di-O-Caffeoyl quinic acid (7) C25 H24 O12，
yellow amorphous powder，ESI-MS (negative)m/z 515
［M-H］-;1H NMＲ (400 MHz，CD3OD)δ:7. 62 (1H，
d，J = 15. 0 Hz，H-7) ，7. 53 (1H，d，J = 15. 0 Hz，H-
7″) ，7. 03 (2H，s，H-2，2″) ，6. 91 (2H，d，J = 7. 0
Hz，H-6，6″) ，6. 77 (2H，d，J = 8. 1 Hz，H-5，5″) ，
6. 30 (1H，d，J = 14. 0 Hz，H-8″) ，6. 21 (1H，d，J =
14. 0 Hz，H-8) ，5. 67 (1H，m，H-3) ，4. 32 (1H，m，
H-5) ，3. 73 (1H，m，H-4) ，2. 00?2. 31 (4H，m，H-2，
6) ;13C NMＲ (100 MHz，CD3OD)δ:168. 5 (C-9) ，
168. 3 (C-9″) ，149. 5 (C-4，4″) ，147. 7 (C-7，7″) ，
147. 5 (C-3″) ，146. 6 (C-3) ，127. 7 (C-1″) ，127. 6
(C-1) ，123. 1 (C-6，6″) ，116. 4 (C-5，5″) ，115. 2
(C-8，8″) ，114. 6 (C-2，2″) ，75. 9 (C-4) ，69. 6 (C-
3) ，69. 1(C-5) ，39. 5 (C-6) ，38. 3 (C-2). The NMＲ
and MS data were in accordance with those reported in
the literature ［8］，and identified 7 as 3，4-di-O-caffeoyl
quinic acid.
3，5-di-O-Caffeoyl quinic acid (8) C25 H24 O12，
yellow amorphous powder，ESI-MS (negative)m/z 515
［M-H］-;1H NMＲ (400 MHz，CD3OD)δ:7. 63 (1H，
d，J = 15. 6 Hz，H-7″) ，7. 57 (1H，t，J = 15. 6 Hz，H-
53Vol. 26 WANG Chun-hui，et al:Chemical Constituents from the Ethyl Acetate Portion of Inula wissmanniana
7) ，7. 06 (2H，brs，H-2，2″) ，6. 96 (2H，d，J = 8. 0
Hz，H-6，6″) ，6. 77 (2H，d，J = 8. 0 Hz，H-5，5″) ，
6. 35 (1H，d，J = 15. 8 Hz，H-8″) ，6. 26 (1H，d，J =
15. 8 Hz，H-8) ，5. 42 (2H，brs，H-3，5) ，3. 96 (1H，
brs，H-4) ，2. 02-2. 23 (4H，m，H-2，6) ;13 C NMＲ
(100 MHz，CD3OD)δ:168. 9 (C-9″) ，168. 4 (C-9) ，
149. 6 (C-4″) ，149. 5 (C-4) ，147. 9 (C-3″) ，147. 1
(C-7″) ，146. 8 (C-3，7) ，127. 9 (C-1″) ，127. 8 (C-
1) ，123. 1 (C-6″) ，123. 0 (C-6) ，116. 5 (C-5″，8″) ，
115. 6 (C-5) ，115. 3 (C-2″) ，115. 2 (C-2) ，115. 1
(C-8) ，74. 7 (C-1) ，72. 5 (C-3) ，72. 1 (C-5) ，70. 6
(C-4) ，38. 2 (C-2) ，36. 3 (C-6). The NMＲ and MS
data were in accordance with those reported in the lit-
erature ［9］，and identified 8 as 3，5-di-O-caffeoyl quinic
acid.
C-Veratroylglycol (9) C10 H12 O5，brown amorphous
powder，ESI-MS (positive)m/z 235［M + Na］+，ESI-
MS (negative) m/z 211 ［M-H］-;1H NMＲ (400
MHz，CD3OD)δ:7. 59 (1H，s，H-2) ，7. 57 (1H，d，J
= 8. 5 Hz，H-6) ，6. 87 (1H，d，J = 8. 5 Hz，H-5) ，
5. 11 (1H，t，J = 4. 8 Hz，H-8) ，3. 88 (3H，s，3-
OCH3) ，3. 86 (1H，m，H-9α) ，3. 72 (1H，m，H-
9β) ;13C NMＲ (100 MHz，CD3OD)δ:199. 7 (C-7) ，
153. 9 (C-4) ，149. 3 (C-3) ，128. 0 (C-1) ，125. 1 (C-
6) ，115. 9 (C-5) ，112. 5 (C-2) ，75. 5 (C-8) ，66. 2
(C-9) ，56. 5 (3-OCH3). The NMＲ and MS data were
in accordance with those reported in the literature ［10］，
and identified 9 as C-veratroylglycol.
2，3-Dihydroxy-1-(4-hydroxy-3，5-dimethoxyphe-
nyl)-1-propanone (10) C11H14O6，white amorphous
powder，ESI-MS (positive)m/z 265［M + Na］+，ES-
IMS (negative)m/z 241 ［M-H］-;1 H NMＲ (400
MHz，CD3OD)δ:7. 34 (2H，s，H-2，6) ，5. 11 (1H，
dd，J = 5. 0，4. 0 Hz，H-2) ，3. 90 (6H，s，3，5-
OCH3) ，3. 85 (1H，dd，J = 11. 6，4. 0 Hz，H-3α) ，
3. 73 (1H，dd，J = 11. 6，5. 0 Hz，H-3β) ;13 C NMＲ
(100 MHz，CD3OD)δ:199. 6 (C-1) ，149. 5 (C-3，
5) ，107. 9 (C-2，6) ，75. 6 (C-2) ，66. 3 (C-3) ，
57. 0 (3，5-OCH3). The NMＲ and MS data were in
accordance with those reported in the literature ［11］，
and identified 10 as 2，3-dihydroxy-1-(4-hydroxy-3，5-
dimethoxyphenyl)-1-propanone.
Caffeic acid (11) C9H8O4，brown amorphous pow-
der，ESI-MS (positive)m/z 203 ［M + Na］+，ESI-MS
(negative)m/z 179 ［M-H］-;1H NMＲ (400 MHz，
CD3OD)δ:7. 52 (1H，d，J = 15. 6 Hz，H-1) ，7. 03
(1H，s，H-2) ，6. 91 (1H，d，J = 8. 1 Hz，H-6) ，6. 76
(1H，d，J = 8. 1 Hz，H-5) ，6. 21 (1H，d，J = 15. 6
Hz，H-2) ;13 C NMＲ (100 MHz，CD3OD)δ:171. 4
(C-3) ，149. 4 (C-4) ，147. 0 (C-3) ，146. 7 (C-2) ，
127. 8 (C-1) ，122. 8 (C-5) ，116. 5 (C-6) ，115. 7 (C-
1) ，115. 1 (C-2). The NMＲ and MS data were in ac-
cordance with those reported in the literature ［12］，and
identified 11 as caffeic acid.
Dibutylphthalate (12) C16 H22 O4，pink oil，ESI-MS
(positive)m/z 301 ［M + Na］+;1H NMＲ (CD3OD，
400 MHz)δ:7. 71 (2H，dd，J = 5. 7，3. 3 Hz，H-3，
6) ，7. 60 (2H，dd，J = 5. 7，3. 3 Hz，H-4，5) ，4. 28
(4H，t，J = 6. 6 Hz，H-8，8) ，1. 73 (4H，m，J = 6. 6
Hz，H-9，9) ，1. 44 (4H，m，J = 7. 6 Hz，H-10，10) ，
0. 97 (6H，t，J = 7. 6 Hz，H-11，11) ;13 C NMＲ
(CD3OD，100 MHz)δ:169. 3 (C-7，7) ，133. 6 (C-1，
2) ，132. 3 (C-4，5) ，129. 9 (C-3，6) ，66. 7 (C-8，
8) ，31. 7 (C-9，9) ，20. 2 (C-10，10) ，14. 0 (C-11，
11). The NMＲ and MS data were in accordance with
those reported in the literature ［13］，and identified 12 as
dibutylphthalate.
3，4-Dihydroxybenzoic acid (13) C7H6O4，white
needle crystals，ESI-MS (positive)m/z 177 ［M +
Na］+，ESI-MS (negative)m/z 153［M-H］-;1H NMＲ
(400 MHz，CD3OD) δ:7. 43 (1H，s，H-2) ，7. 41
(1H，d，J = 10. 0 Hz，H-6) ，6. 78 (1H，d，J = 10. 0
Hz，H-5) ;13C NMＲ (100 MHz，CD3OD)δ:170. 2 (C
= O) ，151. 5 (C-4) ，146. 0 (C-3) ，123. 9 (C-2) ，
117. 7 (C-6) ，115. 8 (C-5). The NMＲ and MS data
were in accordance with those reported in the literature
［14］，and identified 13 as 3，4-dihydroxybenzoic acid.
3-Hydroxy-4-methoxybenzoic acid (14) C8H8O4，
white needle crystals，ESI-MS (positive)m/z 191［M
+ Na］+，ESI-MS (negative)m/z 167 ［M-H］-;1H
NMＲ (400 MHz，CD3OD)δ:7. 56 (1H，brs，H-2，) ，
7. 55 (1H，brs，H-6) ，6. 83 (1H，d，J = 8. 3 Hz，H-
5) ，3. 89 (3H，s，4-OCH3) ;
13 C NMＲ (100 MHz，
CD3OD)δ:152. 5 (C-4) ，148. 7 (C-3) ，125. 3 (C-
6) ，115. 8 (C-2) ，113. 9 (C-5) ，56. 4 (4-OCH3). The
63 Nat Prod Ｒes Dev Vol. 26
NMＲ and MS data were in accordance with those re-
ported in the literature ［15］，and identified 14 as 3-hy-
droxy-4-methoxybenzoic acid.
p-Hydroxybenzoic acid (15) C7H6O3，white amor-
phous powder，ESI-MS (negative) m/z 137 ［M-
H］-;1H NMＲ (400 MHz，CD3OD)δ:7. 86 (2H，d，J
= 8. 0 Hz，H-2，6) ，6. 80 (2H，d，J = 8. 0 Hz，H-3，
5) ;13 C NMＲ (100 MHz，CD3OD) δ:170. 8 (1-
COOH) ，163. 6 (C-4) ，133. 3 (C-2，6) ，123. 5 (C-
1) ，116. 3 (C-3，5). The NMＲ and MS data were in
accordance with those reported in the literature ［16］，
and identified 15 as p-hydroxybenzoic acid.
Vanillin (16) C8H8O3，white needle crystal，ESI-MS
(negative)m/z 151 ［M-H］-;1H NMＲ (CD3OD，400
MHz)δ:9. 63 (1H，s，1-CHO) ，7. 38 (2H，brs，H-2，
6) ，6. 83 (1H，d，J = 8. 0 Hz，H-5) ，3. 87 (3H，s，3-
OCH3) ;
13 C NMＲ (CD3OD，400 MHz)δ:190. 7 (1-
CHO) ，151. 7 (C-4) ，147. 2 (C-3) ，129. 9 (C-1) ，
127. 3 (C-6) ，114. 4 (C-5) ，108. 9 (C-2) ，56. 1 (3-
OCH3). The NMＲ and MS data were in accordance
with those reported in the literature ［17］，and identified
16 as vanillin.
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