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滇南羊耳菊乙酸乙酯部位化学成分研究(英文)



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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