全 文 ：假酸浆中新的醉茄内酯类化合物*
易乾坤1,2, 李摇 波1**, 刘吉开1
(1 中国科学院昆明植物研究所植物化学与西部植物资源持续利用国家重点实验室,
云南 昆明摇 650201; 2 中国科学院研究生院, 北京摇 100049)
摘要: 从假酸浆 (Nicandra physaloides) 全草中分离得到 12 个化合物, 其中两个为新的醉茄内酯类化合
物, 经波谱学方法将其结构鉴定为 nicandrenone methyl ether (1) 和 26S鄄nicandrenone methyl ether (2); 已
知化合物为三个醉茄内酯, nicandrenone (3), Nic鄄7 (4), nicaphysalin E (5), 以及 pinosylvin monomethyl
ether (6), 2S鄄pinocembrin (7), (1S, 2R)鄄1, 2鄄bis (4鄄hydroxy鄄3鄄methoxyphenyl)鄄1, 3鄄propanediol (8), vanil鄄
lin (9), indole鄄3鄄carboxylic acid (10), vanillic acid (11) 和 drummondol (12)。
关键词: 假酸浆; Nicandrenone methyl ether; 26S鄄nicandrenone methyl ether; 醉茄内酯
中图分类号: Q 946摇 摇 摇 摇 摇 摇 摇 文献标识码: A摇 摇 摇 摇 摇 摇 摇 文章编号: 2095-0845(2012)01-101-06
New Withanolides from Nicandra physaloides (Solanaceae)*
YI Qian鄄Kun1,2, LI Bo1**, LIU Ji鄄Kai1
(1 State Key Laboratory of Phytochemistry and Plant Resources in West China, Kunming Institute of Botany, Chinese Academy
of Sciences, Kunming 650201, China; 2 Graduate University of Chinese Academy of Sciences, Beijing 100049, China)
Abstract: Two new withanolides, named nicandrenone methyl ether (1), 26S鄄nicandrenone methyl ether (2), to鄄
gether with ten known compounds were isolated from the whole plants of Nicandra physaloides (Solanaceae). Their
chemical structures were deduced on the basis of spectroscopic analysis. Ten known compounds were identified as
nicandrenone (3), Nic鄄7 (4), nicaphysalin E (5), pinosylvin monomethyl ether (6), 2S鄄pinocembrin (7),
(1S, 2R)鄄1, 2鄄bis (4鄄hydroxy鄄3鄄methoxyphenyl)鄄1, 3鄄propanediol (8), vanillin (9), indole鄄3鄄carboxylic acid
(10), vanillic acid (11) and drummondol (12).
Key words: Nicandra physaloides; Nicandrenone methyl ether; 26S鄄nicandrenone methyl ether; Withanolides
摇 Nicandra physaloides ( Solanaceae) has been
used as folk medicine for sedative, expectorant, fe鄄
ver relieving and detoxification in China (Editorial
Board of National Herbal Compendium, 1975). Its
seed can be utilized to extract edible pectin to make
jelly. The insect antifeedant activities of its leave ex鄄
tract have also been reported (Ascher et al., 1981,
1987). So far, more than twenty 5琢鄄hydroxy鄄6琢,
7琢鄄epoxy鄄1鄄oxo鄄2鄄ene type withanolides have been
obtained from the plant (Anjaneyulu et al., 1997).
In the course of our continuing search for bioactive
natural products from Solanaceae plants, we report
herein the isolation and structural elucidation of two
new withanolides, nicandrenone methyl ether (1),
26S鄄nicandrenone methyl ether (2), together with
three known withanolides, nicandrenone (3), Nic鄄7
(4), nicaphysalin E (5), and other seven known
compounds, pinosylvin monomethyl ether (6), 2S鄄
植 物 分 类 与 资 源 学 报摇 2012, 34 (1): 101 ~ 106
Plant Diversity and Resources摇 摇 摇 摇 摇 摇 摇 摇 摇 摇 摇 摇 摇 摇 摇 摇 DOI: 10. 3724 / SP. J. 1143. 2012. 11086
*
**
Foundation items: The Found of State Key Laboratory of Phytochemistry and Plant Resources in West China (P2008鄄ZZ14), and the Natural
Science Foundation of Yunnan Province (2007C091M)
Author for correspondence; E鄄mail: libo@ mail. kib. ac. cn
Received date: 2011-05-27, Accepted date: 2011-07-25
作者简介: 易乾坤 (1986-) 男, 硕士研究生, 研究方向为天然药物化学。 E鄄mail: yiqiankun@ mail. kib. ac. cn
pinocembrin (7), (1S, 2R)鄄1, 2鄄bis (4鄄hydroxy鄄3鄄
methoxyphenyl )鄄1, 3鄄propanediol ( 8 ), vanillin
(9), indole鄄3鄄carboxylic acid (10), vanillic acid
(11) and drummondol (12). Compounds 6 - 12
were isolated from this plant for the first time.
Results and discussion
Compound 1 was obtained as a white solid. It
was assigned a molecular formula C29H36O6 accord鄄
ing to positive HR鄄ESI鄄MS (m / z 503. 2415 [M +
Na] +, calc. 503. 2409), and the NMR spectral a鄄
nalysis (Table 1). In IR spectrum, strong absorption
at 1 689 cm鄄1 indicated the presence of an 琢, 茁鄄un鄄
saturated ketone group, which was confirmed by sig鄄
nals at 啄C 202. 92 (C鄄1), 140. 18 (C鄄2) and 128. 19
(C鄄3) in the 13C鄄NMR spectrum. The 1H鄄NMR and
13C鄄NMR spectra of 1 showed the presence of 29 car鄄
bons consisting of a carbonyl, four carbon鄄carbon
double bonds, four quaternary carbons including
three oxygen鄄bearing functional groups, seven sp3 me鄄
thines including four oxygen鄄bearing functional
groups, four methylenes and five methyls. In 13C鄄
NMR spectra of 1, oxygen鄄bearing sp3 methines at 啄C
57. 06 and 55. 90 indicated the presence of 6琢, 7琢鄄
epoxy moiety, oxygen鄄bearing quaternary carbons at
啄C 61. 47 and 61. 51 suggested the occurrence of 24琢,
25琢鄄epoxy moiety, oxygen鄄bearing sp3 methines at 啄C
68. 96 and 99. 33 revealed the presence of the 啄鄄lactol
ring in the side chain. The aromatized D鄄ring was
proved by the 13C signals at 啄C 142. 57, 137. 15,
135. 22, 128. 77, 125. 66, 124. 08 and 1H signals at
啄H 7. 35 (d, 7. 8), 7. 06 (d, 7. 8), 7. 0 ( s). The
NMR data mentioned above suggested that it has sim鄄
ilar structure to that of nicandrenone (Gottlieb and
Kirson, 1981). The only difference between them
was that the hydroxyl in nicandrenone is replaced by
methoxyl (啄C 55. 70) in 1. The HMBC spectrum of 1
showed the correlation between the signals at 啄C 99. 23
(C鄄26) and 啄H 3. 15 (OMe), and the correlation be鄄
tween 啄C 55. 70 (OMe) and 啄H 4.55 (H鄄26), which
confirmed the methoxyl group location at C鄄26 (Fig.
1). The configuration at H鄄22 was assigned as 琢鄄ori鄄
entation (0. 5-4. 0 Hz and 9. 0-13. 8 Hz for H鄄22琢,
and 2. 5-7. 0 Hz and 2. 0-5. 0 Hz for H鄄22茁) for ob鄄
served coupling constants of H鄄22 (J=2. 25, 11. 25).
(Minguzzi et al., 2002). In the ROESY spectrum,
the cross鄄peak between H鄄26 and H鄄28, as well as
between OMe and H鄄22 deduced that the methoxyl is
琢鄄orientation (Fig. 1). Thus, compound 1 was iden鄄
tified as nicandrenone methyl ether (Fig. 2).
Fig. 2摇 Structures of compounds 1-5
Compound 2 had the same molecular formula
C29H36O6as that of compound 1, deduced from posi鄄
tive HR鄄ESI鄄MS (m / z 503. 2412 [M+Na] +, calc.
503. 2409), and the NMR spectral analysis (Table
1). 1H鄄 and 13C鄄NMR spectra of 2 were very similar
to those of 1, which suggested that they have the
same carbon skeleton and substituent. The configu鄄
ration at C鄄22 was also assigned as R for observed
coupling constants of H鄄22 ( J = 3. 20, 11. 51 )
(Minguzzi et al., 2002). The observations of 13C
signal downfield shift for C鄄22 and C鄄26 (驻 2. 83,
1. 72 ppm) and upfield shift for C鄄23 and C鄄27 (驻
-2. 25, -3. 09 ppm) suggested that methoxyl at C鄄
26 of 2 is 茁鄄orientation. In ROESY spectrum of 2,
201摇 摇 摇 摇 摇 摇 摇 摇 摇 摇 摇 摇 摇 摇 摇 摇 摇 植 物 分 类 与 资 源 学 报摇 摇 摇 摇 摇 摇 摇 摇 摇 摇 摇 摇 摇 摇 第 34 卷
the presence of correlation between H鄄26 (啄H 4. 43)
and H鄄22 confirmed the 茁鄄orientation of methoxyl at
C鄄26 (Fig. 1). Thus, compound 2 was identified as
26S鄄nicandrenone methyl ether (Fig. 2).
Compound 4 was identified as Nic鄄7 ( nican鄄
drenone 7) (Begley et al., 1976). Its 1H鄄 and 13C鄄
NMR spectra data were reported for the first time.
The structures of known compounds were identified
by comparison of spectroscopic data with those repor鄄
ted in literatures.
Experimental
General experimental procedures 摇 Optical
rotation was measured on a JASCO P鄄1020 digital
polarimeter. IR spectra were obtained from Bruker
Tensor 27 FT鄄IR spectrometer with KBr pellets. UV
spectra were determined on a Shimadzu UV2401PC
spectrometer. ESIMS and HRESIMS spectra were
recorded on AutoSpec Premier P776 and API QSTAR
Pulsar instrument. NMR spectra were recorded on
Bruker AV鄄400 MHz, DRX鄄500 MHz and AVANCE
III 600 MHz with TCI cryoprobe spectrometers with
TMS as internal standard. Silica gel ( 200 - 300
mesh), Silica gel GF254 (Qingdao Marine Chemical
Co., Ltd), RP鄄18 silica gel (40-63 滋m, Merck,
Germany), MCI gel CHP鄄20P (75 -150 滋m, Mit鄄
subishi Chemical Corporation, Tokyo) and Sephadex
LH鄄20 (Pharmacia) were used for column chroma鄄
tography. Fractions were monitored by TLC and
spots were visualized by heating silica gel plates im鄄
mersed with 10% H2SO4 in ethanol.
Plant material摇 Whole plants of N. physaloides
were collected in Kunming, Yunnan, China, in Oc鄄
tober 2009. A voucher specimen was deposited in
the State Key Laboratory of Phytochemistry and Plant
Resources in West China, Kunming Institute of Bot鄄
any, Chinese Academy of Sciences.
Extraction and isolation 摇 Air鄄dried leaves of
N. physaloides (30 kg) were extracted with methanol
at 70益 for three times. The extracts were concen鄄
trated at 50-70益 to a black residue (1. 8 kg) and
then dissolved in H2 O, fractionated into petroleum
ether (500 g), ethyl acetate (500 g) and n鄄butanol
(300 g). The ethyl acetate extract was subjected to
a silica gel column using CHCl3: MeOH=1颐 0 to 2 颐 1.
Seventeen main fractions (Fr. 1鄄17) were obtained.
By subjected to repeatedly silica gels, Sephadex LH鄄
20, MCI and RP鄄18, Fr. 2 (52 g) afforded com鄄
pounds 1 (30 mg), 2 (250 mg), 3 (10 g), 6 (50
mg), 7 (10 mg) and 9 (100 mg), Fr. 3 (22 g) af鄄
forded compounds 8 (13 mg), 10 (1 mg), 11 (2
mg) and 12 (2 mg), and Fr. 4 (37 g) afforded
compounds 4 (40 mg) and 5 (11 mg).
Nicandrenone methyl ether (1) . White crys鄄
tals, C29 H36 O6; Positive ESI鄄MS m / z: 503 [M +
Na] +; Positive HR鄄ESI鄄MS m/ z: 503. 2415[M+Na] +
(calc. 503. 2409); [ 琢]27. 3D - 13. 9 ( c = 0. 456,
CDCl3); UV (CDCl3) 姿max( log 着): 276 (2. 82),
268 (2. 88), 240 (3. 33) nm; IR 淄max ( cm-1 ):
2924, 2853, 1689, 1632, 1457, 1394, 1379,
1104, 1054; 1H鄄 and 13C鄄NMR: Table 1.
26S鄄nicandrenone methyl ether (2) . White
solid, C29 H36 O6; Positive ESI鄄MS m / z: 503 [M+
Na] +; Positive HR鄄ESI鄄MS m/ z: 503. 2412 [M +
Na] +(calc. 503. 2409); [琢]27. 3D +37. 2 ( c = 4. 44,
CDCl3); UV (CDCl3) 姿max ( log 着): 277 (2. 62),
268 (2. 69), 240 (3. 14) nm; IR 淄max(cm-1): 2972,
2932, 2907, 2835, 1689, 1460, 1424, 1379, 1110,
1083, 1057, 920; 1H鄄 and 13C鄄NMR: Table 1.
Nicandrenone (3) . Colorless crystal, C28H34
O6; Positive ESI鄄MS m / z: 489 [M+Na] +; 1H鄄NMR
(CDCl3, 500 MHz): 啄H 7. 31 (1H, d, J = 8. 1 Hz,
H鄄15), 7. 01 (1H, br. d, J =8. 1 Hz, H鄄16), 6. 94
(1H, s, H鄄18), 6. 58 (1H, ddd, J = 10. 1, 5. 0,
2. 0 Hz, H鄄3), 5. 83 (1H, dd, J=10. 1, 2. 4 Hz, H鄄
2), 4. 94 (3H, s, H鄄26), 3. 98 (1H, br. s, H鄄7),
3. 86 (1H, m, H鄄22), 3. 20 (1H, d, J = 3. 9 Hz,
H鄄6), 3. 02 (1H, d, J = 11. 6 Hz, H鄄8), 2. 92
(1H, m, H鄄12), 2. 82 (1H, m, H鄄11), 2. 79 (1H,
m, H鄄12), 2. 72 (1H, m, H鄄20), 2. 69 (1H, m,
H鄄4), 2. 55 (1H, dd, J = 18. 9, 5. 0 Hz, H鄄4),
1. 88 (1H, td, J=11. 6, 3. 51 Hz, H鄄9), 1. 81
(1H, dd, J= 14. 0, 2. 2 Hz, H鄄23), 1. 56 (1H,
m, H鄄23), 1. 51 (1H, m, H鄄11), 1. 33 (3H, s,
3011 期摇 摇 摇 摇 摇 摇 摇 YI Qian鄄Kun et al. : New Withanolides from Nicandra physaloides (Solanaceae) 摇 摇 摇 摇 摇 摇 摇 摇 摇
Table 1摇 1H鄄 and 13C鄄NMR data of 1 and 2 in CDCl3(啄 in ppm, J in Hz)
Position
1a
啄C 摇 啄H
2a
啄C 摇 啄H
1 202. 92 s 202. 33 s
2 128. 97 d 5. 90 (d, 9. 9) 128. 29 d 5. 78 (d, 8. 0)
3 140. 18 d 6. 65 (dd, 9. 9, 4. 7) 139. 84 d 6. 54 (m)
4 37. 11 t 2. 77 (d, 19. 0), 2. 63 (dd, 19. 0, 4. 7) 36. 44 t 2. 66 (d, 14. 8) , 2. 50 (dd, 14. 8, 4. 0)
5 73. 03 s 72. 74 s
6 57. 06 d 3. 26 (d, 3. 6) 56. 34 d 3. 15 (d, 2. 8)
7 55. 90 d 4. 06 (br. s) 55. 76 d 3. 94 (br. s)
8 38. 77 d 3. 09 (d, 11. 0) 38. 10 d 2. 98 (d, 9. 2)
9 32. 06 d 1. 90 ( td, 11. 0, 2. 1) 31. 28 d 1. 84 (m)
10 51. 94 s 51. 19 s
11 24. 62 t 2. 85 (m), 1. 58 (m) 23. 95 t 2. 78 (m), 1. 49 (m)
12 29. 57 t 2. 97 (m), 2. 85 (m) 28. 95 t 2. 87 (m), 2. 77 (m)
13 137. 15 s 136. 24 s
14 135. 22 s 134. 75 s
15 124. 08 d 7. 35 (d, 7. 8) 123. 60 d 7. 28 (d, 6. 4)
16 125. 66 d 7. 06 (d, 7. 8) 124. 71 d 6. 98 (d, 6. 4)
17 142. 57 s 141. 37 s
18 128. 77 d 7. 00 ( s) 128. 10 d 6. 91 ( s)
19 14. 31 q 1. 26 ( s) 13. 64 q 1. 16 ( s)
20 43. 94 d 2. 67 (m) 43. 50 d 2. 69 (m)
21 18. 40 q 1. 23 (d, 8. 80) 16. 31 q 1. 17 (d, 6. 20)
22 68. 96 d 3. 93 (ddd, 11. 25, 7. 64, 2. 25) 71. 79 d 3. 65 (ddd, 11. 51, 7. 01, 3. 20)
23 35. 52 t 1. 97 (dd, 14. 21, 2. 25)1. 55 (dd, 14. 21, 11. 25) 33. 27 t
1. 81 (m)
1. 72 (dd, 14. 18, 11. 51)
24 61. 47 s 61. 91 s
25 61. 51 s 60. 88 s
26 99. 33 d 4. 55 ( s) 101. 05 d 4. 43 ( s)
27 17. 21 q 1. 35 ( s) 14. 12 q 1. 21 ( s)
28 18. 60 q 1. 35 ( s) 18. 54 q 1. 24 ( s)
OCH3 55. 70 q 3. 15 ( s) 55. 06 q 3. 29 ( s)
a At 500 / 125 MHz
H鄄27), 1. 32 (3H, s, H鄄28), 1. 20 (1H, s, H鄄
19), 1. 20 (3H, d, J = 7. 0 Hz, H鄄19); 13C鄄NMR
(CDCl3, 125 MHz): 啄C 202. 66 (s, C鄄1), 128. 54 (d,
C鄄2), 140. 02 (d, C鄄3), 36. 54 (t, C鄄4), 72. 55 (s,
C鄄5), 56. 54 (d, C鄄6), 55. 28 (d, C鄄7), 38. 24 (d,
C鄄8), 31. 38 (d, C鄄9), 51. 33 (s, C鄄10), 24. 06 (t,
C鄄11), 29. 05 (t, C鄄12), 136. 61 (s, C鄄13), 134. 90
(s, C鄄14), 123. 78 (d, C鄄15), 125. 04 (d, C鄄16),
141. 15 (s, C鄄17), 128. 26 (d, C鄄18), 13. 79 (q, C鄄
19), 42. 74 (d, C鄄20), 17. 03 (q, C鄄21), 67. 19 (d,
C鄄22), 33. 43 (t, C鄄23), 64. 14 (s, C鄄24), 63. 16
(s, C鄄25), 91. 29 (d, C鄄26), 16. 30 ( q, C鄄27),
18. 40 (q, C鄄28). (Gottlieb and Kirson, 1981)
Nicandrenone 7 (4) . White crystals, C28H38
O7; Positive ESI鄄MS m / z: 509 [M+Na] +; 1H鄄NMR
(CDCl3, 500 MHz): 啄H 5. 86 (1H, d, J=11. 5 Hz,
H鄄2), 6. 62 (1H, dd, J = 11. 5, 4. 0 Hz, H鄄3),
5. 00 (1H, s, H鄄26), 3. 74 (1H, br. d, J = 13. 0
Hz, H鄄22), 3. 48 (1H, dd, J = 15. 1, 4. 0 Hz, H鄄
11), 3. 40 (1H, br. s, H鄄7), 3. 09 (1H, d, J=4. 0
Hz, H鄄6), 2. 70 (1H, d, J=16. 0 Hz, H鄄4), 2. 58
(1H, dd, J=16. 0, 4. 0 Hz, H鄄4), 2. 52 (1H, d, J
=15. 1 Hz, H鄄11), 2. 20 (1H, br. t, J = 13. 5 Hz,
H鄄8), 2. 03 (1H, m, H鄄17), 1. 98 (1H, m, H鄄9),
1. 95 (1H, m, H鄄15), 1. 91 (1H, m, H鄄23), 1. 81
(1H, m, H鄄16), 1. 77 (1H, m, H鄄23), 1. 63 (1H,
m, H鄄14), 1. 60 (1H, m, H鄄15), 1. 60 (1H, m,
H鄄20), 1. 47 (1H, m, H鄄16), 1. 43 (3H, s, H鄄
27), 1. 43 (3H, s, H鄄28), 1. 24 (3H, s, H鄄18),
1. 08 (3H, s, H鄄19), 0. 87 (3H, d, J=8. 0 Hz, H鄄
21); 13C鄄NMR (CDCl3, 125 MHz): 啄C 201. 42 (s,
C鄄1), 128. 76 (d, C鄄2), 139. 87 (d, C鄄3), 36. 54
(t, C鄄4), 73. 15 (s, C鄄5), 56. 09 (d, C鄄6), 56. 93
(d, C鄄7), 35. 48 (d, C鄄8), 37. 47 (d, C鄄9), 51. 39
( s, C鄄10), 38. 26 (t, C鄄11), 212. 48 (s, C鄄12),
57. 62 ( s, C鄄13), 52. 70 (d, C鄄14), 23. 58 ( t,
401摇 摇 摇 摇 摇 摇 摇 摇 摇 摇 摇 摇 摇 摇 摇 摇 摇 植 物 分 类 与 资 源 学 报摇 摇 摇 摇 摇 摇 摇 摇 摇 摇 摇 摇 摇 摇 第 34 卷
C鄄15), 26. 83 (t, C鄄16), 42. 96 (d, C鄄17), 14. 69
(q, C鄄18), 11. 43 (q, C鄄19), 39. 66 (d, C鄄20),
12. 85 (q, C鄄21), 65. 05 (d, C鄄22), 29. 48 ( t,
C鄄23), 65. 44 (s, C鄄24), 63. 90 (s, C鄄25), 91. 72
(d, C鄄26), 16. 54 (q, C鄄27), 18. 97 (q, C鄄28).
(Gottlieb and Kirson, 1981)
Nicaphysalin E (5) . White crystals, C28H34
O6; Positive ESI鄄MS m / z: 489 [M+Na] +; 1H鄄NMR
(CDCl3, 500 MHz): 啄H 5. 82 (1H, d, J=10. 0 Hz,
H鄄2), 7. 93 (1H, s, H鄄CHO), 7. 29 (1H, d, J=
7. 30 Hz, H鄄15), 7. 00 (1H, d, J = 7. 30 Hz, H鄄
16), 6. 92 (3H, s, H鄄18), 6. 75 (1H, dd, J =
10. 0, 5. 0 Hz, H鄄3), 5. 07 (1H, m, H鄄22), 3. 98
(1H, br. s, H鄄7), 3. 19 (1H, d, J=3. 0 Hz, H鄄6),
3. 06 (1H, d, J = 11. 0 Hz, H鄄8), 2. 90 (1H, m,
H鄄12), 2. 85 (1H, m, H鄄20), 2. 80 (1H, m, H鄄
11), 2. 80 (1H, m, H鄄12), 2. 70 (1H, d, J=19. 0
Hz, H鄄4), 2. 55 (1H, dd, J=19. 0, 5. 0 Hz, H鄄4),
2. 05 (3H, s, H鄄26), 1. 99 (1H, m, H鄄23), 1. 85
(1H, br. t, J = 11. 0 Hz, H鄄9), 1. 52 (1H, m, H鄄
11), 1. 31 (1H, m, H鄄23), 1. 20 (3H, d, J =6. 5
Hz, H鄄21), 1. 19 (3H, s, H鄄19), 1. 00 (3H, d, J
=6. 0 Hz, H鄄28); 13C鄄NMR (CDCl3, 125 MHz): 啄C
202. 66 (s, C鄄1), 128. 57 (d, C鄄2), 140. 10 (d, C鄄
3), 36. 82 (t, C鄄4), 72. 75 (s, C鄄5), 56. 78 (d,
C鄄6), 55. 48 (d, C鄄7), 38. 50 (d, C鄄8), 31. 64
(d, C鄄9), 51. 60 (s, C鄄10), 24. 26 (t, C鄄11), 29. 26
(t, C鄄12), 137. 08 (s, C鄄13), 135. 61 (s, C鄄14),
124. 14 (d, C鄄15), 125. 17 (d, C鄄16), 140. 24 (s, C鄄
17), 128. 70 (d, C鄄18), 13. 99 (q, C鄄19), 43. 35
(d, C鄄20), 17. 59 (q, C鄄21), 75. 69 (d, C鄄22),
34. 84 (t, C鄄23), 42. 97 (d, C鄄24), 211. 52 (s,
C鄄25), 28. 56 ( q, C鄄26), 17. 70 ( q, C鄄28 ),
160. 84 (d, CHO). (Shingu et al., 1994)
Pinosylvin monomethyl ether ( 6 ) . White
powder, C15H14O2; 1H鄄NMR (CDCl3, 500 MHz):
啄H 7. 48 (2H, d, J = 7. 41 Hz, H鄄2忆, 6忆), 7. 35
(2H, t, J=7. 41 Hz, H鄄3忆, 5忆), 7. 27 (1H, t, J =
7. 41 Hz, H鄄4忆), 7. 04 (1H, d, J = 16. 23 Hz, H鄄
8), 6. 98 (1H, d, J=16. 23 Hz, H鄄7), 6. 68 (1H,
s, H鄄6), 6. 64 (1H, s, H鄄2), 6. 40 (1H, s, H鄄4),
3. 79 ( 3H, s, OMe ); 13C鄄NMR ( CDCl3, 125
MHz): 啄C 160. 99 ( s, C鄄3), 156. 87 ( s, C鄄5),
139. 83 (s, C鄄1), 137. 06 (s, C鄄1忆), 129. 49 (d,
C鄄8), 128. 77 (d, C鄄3忆, 5忆), 128. 30 (d, C鄄7),
127. 88 (d, C鄄4忆), 126. 71 (d, C鄄2忆, 6忆), 106. 26
(d, C鄄2), 105. 10 (d, C鄄6), 101. 17 (d, C鄄4),
55. 49 (d, OMe). (Luk et al., 1983).
2S鄄pincembrin (7) . White powder, C15 H14
O4; [琢] 18. 2D -16. 2 ( c = 0. 11, MeOH); 1H鄄NMR
(CDCl3, 500 MHz): 啄H 7. 44 (2H, m, H鄄2忆, 6忆),
7. 41 (2H, m, H鄄3忆, 5忆), 7. 37 (1H, m, H鄄4忆),
5. 97 (2H, d, J = 0. 86 Hz, H鄄7, 9), 5. 38 (1H,
dd, J=3. 05, 13. 05 Hz, H鄄3), 3. 06 (1H, dd, J =
13. 05, 17. 16 Hz, H鄄4), 2. 77 (1H, dd, J =3. 05,
17. 16 Hz, H鄄4); 13C鄄NMR (CDCl3, 125 MHz): 啄C
195. 63 (s, C鄄4), 166. 70 (s, C鄄8), 163. 83 (s, C鄄
6), 163. 09 (s, C鄄10), 138. 42 (s, C鄄1忆), 128. 84
(d, C鄄3忆, 4忆, 5忆), 126. 16 (d, C鄄2忆, 6忆), 102. 46
(s, C鄄5), 96. 55 (d, C鄄7), 95. 67 (d, C鄄9), 79. 11
(d, C鄄2), 43. 27 (d, C鄄3). (Yuan et al., 2008)
(1S,2R) 鄄1,2鄄bis(4鄄hydroxy鄄3鄄methoxyphe鄄
nyl) 鄄1,3鄄propanediol (8) . White powder, C17H20
O6; [琢] 12. 3D +0. 27 ( c = 1. 95, MeOH); 1H鄄NMR
(CD3OD, 500 MHz): 啄H 6. 71 (1H, d, J = 3. 22
Hz, H鄄2忆), 6. 69 (1H, d, J=3. 28 Hz, H鄄2义), 6. 64
(4H, m, H鄄5忆, 5义, 6忆, 6义), 4. 92 (1H, d, J=6. 54
Hz, H鄄1), 3. 83 (1H, dd, J =6. 54, 10. 70 Hz, H鄄
3), 3. 76 (3H, s, H鄄OMe(3义)), 3. 69 (3H, s, H鄄
OMe(3忆)), 3. 68 (1H, m, H鄄3), 2. 91 (1H, q, J
=6. 54 Hz, H鄄2); 13C鄄NMR (CD3OD, 125 MHz):
啄C 75. 62 (d, C鄄1), 56. 90 (d, C鄄2), 64. 57 (t, C鄄
3), 136. 59 (s, C鄄1忆), 111. 60 (d, C鄄2忆), 148. 59
(s, C鄄3忆), 146. 69 (s, C鄄4忆), 115. 76 (d, C鄄5忆),
120. 43 (d, C鄄6忆), 132. 39 (s, C鄄1义), 114. 57 (d,
C鄄2义), 148. 49 ( s, C鄄3义), 146. 27 ( s, C鄄4义),
115. 55 (d, C鄄5义), 123. 24 (d, C鄄6义), 56. 26 (q,
C鄄3忆), 56. 38 (q, C鄄3义). (Kazuko et al., 1998)
Vanillin (9) . White powder, C8 H8 O3; 1H鄄
NMR (CDCl3, 500 MHz): 啄H 9. 82 (1H, s, H鄄7),
7. 45 (2H, m, H鄄2, 6), 7. 06 (1H, d, J =8. 41 Hz,
H鄄5), 3. 93 (3H, s, H鄄OMe(3)); 13C鄄NMR (CDCl3,
125 MHz): 啄C 129. 58 (s, C鄄1), 109. 06 (d, C鄄2),
147. 39 (s, C鄄3), 152. 09 (s, C鄄4), 114. 65 (d, C鄄
5011 期摇 摇 摇 摇 摇 摇 摇 YI Qian鄄Kun et al. : New Withanolides from Nicandra physaloides (Solanaceae) 摇 摇 摇 摇 摇 摇 摇 摇 摇
5), 127. 62 (d, C鄄6), 191. 34 ( d, C鄄7), 56. 03
(d, C鄄OMe(3)). (Hu and Zheng, 2005)
Indole鄄3鄄carboxylic acid (10) . White pow鄄
der, C9 H7 NO2; Positive ESI鄄MS m / z: 184 [M +
Na] +; 1H鄄NMR ( CDCl3 ( CD3OD added ), 500
MHz): 啄H 8. 16 (1H, dd, J = 3. 05, 5. 87 Hz, H鄄
5), 7. 95 (1H, s, H鄄2), 7. 45 (1H, dd, J =3. 11,
5. 92 Hz, H鄄8), 7. 25 (2H, m, H鄄6, 7); 13C鄄NMR
(CDCl3(CD3OD added), 125 MHz): 啄C 132. 41 (d,
C鄄2), 107. 74 (s, C鄄3), 136. 58 (s, C鄄4), 121. 20
(d, C鄄5), 122. 68 (d, C鄄6), 121. 62 (d, C鄄7),
111. 88 (d, C鄄8), 126. 18 (s, C鄄9), 168. 27 (s, C鄄
10). (Shaheen et al., 1987)
Vanillic acid (11) . White powder, C8H8O4;
Positive ESI鄄MS m/ z: 191 [ M + Na] +; 1H鄄NMR
(CD3OD, 500 MHz): 啄H 7. 57 (1H, d, J=8. 64 Hz,
H鄄6), 7. 56 (1H, s, H鄄2), 6. 84 (1H, d, J=8. 64
Hz, H鄄5), 3. 89 (3H, s, H鄄8); 13C鄄NMR (CD3
OD, 125 MHz): 啄C 123. 12 (s, C鄄1), 115. 77 (d,
C鄄2), 148. 57 (s, C鄄3), 152. 55 (s, C鄄4), 113. 74
(d, C鄄5), 125. 22 (d, C鄄6), 170. 14 ( s, C鄄7),
56. 33 (s, C鄄8). (Zou and Yang, 2005)
Drummondol (12) . White powder, C13 H20
O4; 1H鄄NMR (CDCl3, 500 MHz): 啄H 6. 16 (1H,
dd, J=6. 37, 15. 25 Hz, H鄄2忆), 5. 85 (1H, dd, J=
1. 16, 15. 25 Hz, H鄄1忆), 4. 39 (1H, p, J=6. 37 Hz,
H鄄3忆), 3. 84 (1H, dd, J = 2. 93, 8. 22 Hz, H鄄7),
3. 70 (1H, d, J=8. 22 Hz, H鄄7), 2. 55 (2H, br. s,
H鄄4), 2. 51 (1H, dd, J = 2. 84, 18. 41 Hz, H鄄2),
2. 37 (1H, d, J=18. 41 Hz, H鄄2), 1. 27 (3H, d, J
=6. 37 Hz, H鄄Me(3忆)), 1. 13 (3H, s, H鄄Me(5)),
0. 94 (3H, s, H鄄Me(1)); 13C鄄NMR (CDCl3, 125
MHz): 啄C 47. 84 (s, C鄄1), 52. 61 (t, C鄄2), 208. 68
(s, C鄄3), 52. 77 (t, C鄄4), 81. 86 (s, C鄄5), 77. 23
(t, C鄄7), 85. 68 ( s, C鄄8), 123. 77 (d, C鄄1忆),
139. 98 (d, C鄄2忆), 68. 34 (d, C鄄3忆), 15. 80 (q,
C鄄Me(1)), 24. 23 ( q, C鄄Me(3忆)), 18. 87 ( q,
C鄄Me(5)). (Powell and Smith, 1981)
Acknowledgements: The authors are grateful to the members
of analytical group for the spectral measurements in Kunming
Institute of Botany, Chinese Academy of Sciences.
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