全 文 ：天然产物研究与开发 Nat Prod Res Dev 2012，24:176-178，198
文章编号:1001-6880(2012)02-0176-04
Received August 11，2010;Accepted October 19，2010
Foundation Item:This research project was supported by the Scientific
Foundation of Shanghai Committee of Science and Technology
(09DZ1972200)．
* Corresponding author Tel:86-21-34205989;Email:kimhz@ sjtu． edu．
cn;wdzhangy@ hotmail． com
观光木酚性成分研究
黄 鹰1，常睿洁1，金慧子1* ，张卫东1，2 *
1上海交通大学药学院，上海 200240;2上海第二军医大学药学院，上海 200433
摘 要:从观光木(Tsoongiodendron odorum Chun)茎枝的 80%乙醇提取物中分离得到 11 个酚性化合物，经波谱
鉴定为:对羟基苯甲醛(1)、香草醛(2)、1，3，5-三甲氧基苯(3) ，丁香醛(4)、香草酸(5)、苏式-2，3-二-(4-羟基-3-
甲氧基苯)-3-甲氧基丙醇(6)、赤式-2，3-二-(4-羟基-3-甲氧基苯)-3-甲氧基丙醇(7)、丁香酸(8)、3-羟基-1-(4-羟
基-3，5-二甲氧基苯)-1-丙酮(9)、对羟基苯乙醇(10)和 C-veratroylglycol(11)。其中，化合物 1 ～ 4 和 6 ～ 11 为首
次从该植物中分离得到。
关键词:观光木;木兰科;酚性成分
中图分类号:R284． 1;Q946． 91 文献标识码:A
Phenolic Constituents from Tsoongiodendron odorum Chun
HUANG Ying1，CHANG Rui-jie1，JIN Hui-zi1 * ，ZHANG Wei-dong1，2 *
1School of Pharmacy，Shanghai Jiao Tong University，Shanghai 200240，China;
2School of Pharmacy，Second Military Medical University，Shanghai 200433，China
Abstract:Eleven phenolic constituents were isolated from the 80% ethanol extract of the twigs of Tsoongiodendron odo-
rum Chun． On the basis of spectroscopic methods，their structures were identified as p-hydroxybenzaldehyde (1) ，vanillin
(2) ，1 3，5-trimethoxybenzene (3) ，4-hydroxy-3，5-dimethoxy-benzaldehyde(4) ，vanillic acid (5) ，threo-2，3-bis-(4-
hydroxy-3-methoxyphenyl)-3-methoxy-propanol (6) ，erythro-2，3-bis-(4-hydroxy-3-methoxyphenyl)-3-methoxy-propanol
(7) ，syringic acid (8) ，3-hydroxy-1-(4-hydroxy-3，5-dimethoxyphenyl)-1-propanone (9) ，p-hydroxyl phenethanol
(10) ，and C-veratroylglycol (11)． Compounds 1-4 and 6-11 were isolated from this plant for the first time．
Key words:Tsoongiodendron odorum Chun;Magnoliaceae;phenolic constituents
Introduction
Tsoongiodendron odorum Chun (Magnoliaceae)is an
evergreen tree，mainly distributed in south of China，
such as Jiangxi，Guangdong，Yunnan and so on［1］． The
stem barks and root barks of this plant have been used
to treat cancer by the local people for a long time． Up
to now，only a few chemical constituents have been iso-
lated from this plant［2-4］． In this study on the twigs of
T． odorum，eleven phenolic constituents were isolated
and identified as p-hydroxybenzaldehyde (1) ，vanillin
(2) ，1 3，5-trimethoxybenzene (3) ，4-hydroxy-3，5-di-
methoxy-benzaldehyde (4) ，vanillic acid (5) ，threo-2，
3-bis-(4-hydroxy-3-methoxyphenyl )-3-methoxy-propanol
(6) ，erythro-2，3-bis-(4-hydroxy-3-methoxyphenyl)-3-
methoxy-propanol (7) ，syringic acid (8) ，3-hydroxy-1-
(4-hydroxy-3，5-dimethoxyphenyl)-1-propanone (9) ，
p-hydroxyl phenethanol (10) ，and C-veratroylglycol
(11)． Compounds 1-4 and 6-11 were isolated from this
plant for the first time．
Experimental
General procedures
All melting points were determined on an RY-1 mi-
cromelting point apparatus (uncorrected)． The ESIMS
were measured on an Agilent 1100 series mass spec-
trometer． NMR spectra were measured on a Bruker
DRX-500 spectrometer，operating at 500 MHz for1H
and 125 MHz for13 C NMR． Chemical shift (δ)were
given in ppm relative to TMS as internal standard and
coupling constants in Hz． Silica gel (200-300 mesh，
DOI:10.16333/j.1001-6880.2012.02.009
Yantai，China)was used for column chromatography，
and precoated silica GF254 plates were used for TLC
(Qingdao Haiyang Chemical Co．，Ltd．，China)． Semi-
preparative HPLC was obtained on a Shimadzu LC-6AD
series equipped with an SPD-20 spectrophotometer u-
sing a Zorbax-SB-C18 5 μm (9． 4 × 250 nm，ID)．
Plant material
The twigs of T． odorum were collected from Jiangxi
Province of China in July，2008 and identified by Prof．
Huang Bao-kang，Department of Pharmacognosy，School
of Pharmacy，Second Military Medical University． A
voucher specimen was deposited at School of Pharma-
cy，Shanghai Jiao Tong University．
Extraction and Isolation
The air-dried and powdered twigs of T． odorum (10． 0
kg)were extracted with 80% EtOH for three times at
room temperature． The solvents were concentrated un-
der vacuum to yield a residue (525． 0 g)． The residue
was dissolved in water (5． 0 L)and extracted succes-
sively with petroleum ether (5． 0 L × 10) ，ethyl acetate
(5． 0 L × 10)and n-butanol (5． 0 L × 10)to give cor-
responding fractions A (38． 5 g) ，B (83． 6 g) ，and C
(185． 5 g)． Fraction B was subjected to silica gel col-
umn chromatography with a step gradient of CH2Cl2-
MeOH (100∶ 1-0∶ 100)to give 12 fractions B1—B12．
Fraction B2 was separated on silica gel column eluted
by CH2Cl2-MeOH (20 ∶ 1-1 ∶ 1) to give 8 fractions
B21—B28． Fraction B21 was subjected repeatedly to
silica gel column chromatography and further purified
successively through semi-HPLC to yield compounds 1
(7． 0 mg) ，2 (10． 0 mg) ，3 (60． 0 mg) ，and 4 (32． 5
mg)． Similarly，fraction B22—B24 were purified in the
same manner to yield compounds 5 (30． 0 mg) ，6 (1．
5 mg) ，7 (1． 5 mg) ，8 (4． 5 mg) ，9 (6． 2 mg) (5-9
from B22) ，10 (12． 0 mg，from B23) ，and 11 (7． 5
mg，from B24)．
Results and Discussion
p-Hydroxybenzaldehyde (1) C7H6O2，white needle
crystal (CH3OH) ，mp. 110 ～ 112 ℃;ESI-MS m/z:121
［M – H］–;1H NMR (CD3OD)δ:9. 76 (1H，s，
CHO-1) ，7. 77 (2H，d，J = 8. 5 Hz，H-2，6) ，6. 91
(2H，d，J = 8. 5 Hz，H-3，5) ;13 C NMR (CD3OD)δ:
192. 8 (CHO-1) ，165. 2 (C-4) ，133. 4 (C-2，6) ，
130. 3 (C-1) ，116. 9 (C-3，5). The NMR and MS data
were in accordance with those reported in the litera-
ture［5］，and compound 1 was identified as p-hydroxy-
benzaldehyde.
Vanillin (2 ) C8H8O3，white needle crystal
(CH3OH) ，mp. 68 ～ 71 ℃;ESI-MS m/z:151［M –
H］–;1H NMR (CDCl3)δ:9. 83 (1H，s，CHO-1) ，
7. 43 (2H，br s，H-2，6) ，7. 04 (1H，d，J = 7. 0 Hz，H-
5) ，3. 97 (3H，s，CH3O-3) ;
13 C NMR (CDCl3)δ:
190. 7 (CHO-1) ，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 (CH3O-3). The NMR and MS data were in ac-
cordance with those reported in the literature［6］，and
compound 2 was identified as vanillin.
1，3，5-Trimethoxybenzene (3) C9H12 O3，yellow
needle crystal (CH2Cl2) ，mp. 53 ～ 55 ℃;ESI-MS m/
z:191［M + Na］+;1H NMR (CDCl3)δ:5. 85 (3H，s，
H-2，4，6) ，3. 81 (9H，s，CH3O-1，3，5) ;
13 C NMR
(CDCl3)δ:157. 3 (C-1，3，5) ，107. 4 (C-2，4，6) ，
56. 4 (CH3O-1，3，5). The NMR and MS data of 3 were in
accordance with those reported in the literature［7］.
4-Hydroxy-3，5-dimethoxy-benzaldehyde (4)
C9H10O4，light yellow solid，mp. 110 ～ 113 ℃;ESI-MS
m/z:181［M – H］–;1H NMR (CDCl3) δ:9. 81
(1H，s，CHO-1) ，7. 15 (2H，s，H-2，6) ，3. 96 (6H，s，
CH3O-3，5) ;
13C NMR (CDCl3)δ:190. 7 (CHO-1) ，
147. 4 (C-3，5) ，140. 9 (C-4) ，128. 3 (C-1) ，106. 7
(C-2，6) ，56. 4 (CH3O-3，5). The NMR and MS data
were consistent with those reported in the literature［8］.
Vanillic acid (5) C8H8O4，white needle crystal
(CH3OH) ，mp. 159-161 ℃;ESI-MS m/z:167［M –
H］–;1H NMR (CD3OD)δ:7. 55 (2H，m，H-2，6) ，
6. 84 (1H，d，J = 8. 5 Hz，H-5) ，3. 89 (3H，s，CH3O-
3) ;13 C NMR (CD3OD)δ:170. 0 (COOH-1) ，152. 7
(C-4) ，148. 7 (C-3) ，125. 3 (C-6) ，123. 1 (C-1) ，
115. 8 (C-5) ，113. 8 (C-2) ，56. 4 (CH3O-3). The
NMR and MS data were in accordance with those re-
ported in the literature［9］，and compound 5 was identi-
fied as vinillic acid.
threo-2，3-Bis-(4-hydroxy-3-methoxyphenyl)-3-me-
thoxy-propanol (6) C18 H22 O6，white oil;ESI-MS
771Vol. 24 HUANG Ying，et al:Phenolic Constituents from Tsoongiodendron odorum Chun
m/z:333［M – H］–;1H NMR (CD3OD)δ:6. 46-
6. 72 (6H，m，ArH) ，4. 30 (1H，d，J = 8. 5 Hz，H-7) ，
4. 06 (1H，m，H-9a) ，3. 87 (1H，m，H-9b) ，3. 75，
3. 67 (each 3H，s，CH3O-3，3) ，3. 21 (3H，s，CH3O-
7) ，3. 00 (1H，m，H-8) ;13 C NMR (CD3OD) δ:
148. 6，148. 3 (C-3，3) ，146. 9，146. 2 (C-4，4) ，
133. 2，132. 6 (C-1，1) ，123. 2，121. 5 (C-6，6) ，
115. 7，115. 5，114. 7，112. 4 (C-2，2，5，5) ，87. 4
(C-7) ，64. 9 (C-9) ，57. 0，56. 5，56. 3 (CH3O-3，3，
7) ，56. 1 (C-8). The NMR and MS data were consist-
ent with those reported in the literature［10］.
erythro-2，3-Bis-(4-hydroxy-3-methoxyphenyl)-3-
methoxy-propanol (7) C18H22O6，white oil;ESI-MS
m/z:333［M – H］–;1H NMR (CD3OD)δ:6. 46-
6. 72 (6H，m，ArH) ，4. 47 (1H，d，J = 5. 5 Hz，H-7) ，
3. 89 (2H，m，H-9) ，3. 68，3. 65 (each 3H，s，CH3O-
3，3) ，3. 15 (3H，s，CH3O-7) ，2. 85 (1H，m，H-8) ;
13
C NMR (CD3OD)δ:148. 5，148. 3 (C-3，3)，146. 8，
146. 0 (C-4，4)，132. 6，132. 3 (C-1，1)，122. 6，121. 3
(C-6，6)，115. 6，115. 5，114. 4，118. 8 (C-2，2，5，5)，
84. 9 (C-7)，64. 4 (C-9)，56. 8，56. 4，56. 2 (CH3O-3，3，
7)，56. 0 (C-8). The NMR and MS data of 7 were in ac-
cordance with those reported in the literature［11］.
Syringic acid (8) C9H10 O5，white solid，mp. 187 ～
190 ℃;ESI-MS m/z:197［M – H］–;1H NMR
(CD3OD)δ:7. 33 (2H，s，H-2，6) ，3. 88 (6H，s，
CH3O-3，5) ;
13 C NMR (CD3OD)δ:170. 0 (COOH-
1) ，148. 7 (C-3，5) ，141. 0 (C-4) ，123. 9 (C-1) ，
108. 3 (C-2，6) ，56. 8 (CH3O-3，5). The NMR and
MS data were in accordance with those reported in the
literature［12］.
3-Hydroxy-1-(4-hydroxy-3，5-dimethoxyphenyl)-1-
propanone (9) C11H14 O5，light yellow solid，mp. 78
～ 81 ℃;ESI-MS m/z:225［M – H］–;1H NMR
(CD3OD)δ:7. 30 (2H，s，H-2，6) ，3. 94 (2H，t，J =
6. 0 Hz，H-9) ，3. 87 (6H，s，CH3O-3，5) ，3. 15 (2H，
t，J = 6. 0 Hz，H-8) ;13C NMR (CD3OD)δ:199. 6 (C-
7) ，149. 7 (C-3，5) ，138. 0 (C-4) ，127. 0 (C-1) ，
107. 6 (C-2，6) ，59. 2 (C-9) ，56. 8 (CH3O-3，5) ，
41. 5 (C-8). The NMR and MS data were consistent
with those reported in the literature［13］.
p-Hydroxyl phenethanol (10) C8H10 O2，light
yellow oil;ESI-MS m/z:137［M – H］–;1H NMR
(CD3OD)δ:6. 95 (2H，d，J = 8. 0 Hz，H-2，6) ，6. 62
(2H，d，J = 8. 0 Hz，H-3，5) ，3. 60 (2H，t，J = 7. 0 Hz，
H-8) ，2. 64 (2H，t，J = 7. 0 Hz，H-7) ;13 C NMR
(CD3OD)δ:156. 9 (C-4) ，131. 2 (C-1) ，131. 0 (C-
2，6) ，116. 3 (C-3，5) ，64. 7 (C-8) ，39. 5 (C-7). The
NMR and MS data were in accordance with those re-
ported in the literature［14］.
C-veratroylglycol (11) C10 H12 O5，light yellow oil;
ESI-MS m/z:211［M – H］–;1H NMR (CD3OD)δ:
7. 50 (2H，m，H-2，6) ，6. 80 (1H，d，J = 8. 0 Hz，H-
5) ，5. 04 (1H，m，H-8) ，3. 83 (3H，s，CH3O-3) ，3. 80
(1H，m，H-9a) ，3. 66 (1H，m，H-9b) ;13 C NMR
(CD3OD)δ:199. 7 (C-7) ，152. 3 (C-4) ，149. 4 (C-
3) ，127. 3 (C-1) ，125. 3 (C-6) ，116. 1 (C-2) ，112. 6
(C-5) ，75. 7 (C-8) ，66. 4 (C-9) ，56. 5 (CH3O-3)．
The NMR and MS data were in accordance with those
reported in the literature［15］.
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(下转第 198 页)
871 Nat Prod Res Dev Vol. 24
临界 CO2 萃取技术对含有挥发性成分的中药来说，
是一种有效的新型分离技术，整个操作过程耗时短，
效率高，操作温度低，可大量保存药材的有效成分，
可广泛地运用于中药的有效成分的提取。北细辛超
临界 CO2 萃取物得率高于水蒸汽蒸馏挥发油近 1
倍，且颜色较浅，说明其成分未受高温发生明显的氧
化变色。
3 结论
采用超临界 CO2 萃取法所得北细辛 SFE 萃取
物主要成分甲基丁香酚(约占 44． 62%)略高于水蒸
汽蒸馏法(43． 02%) ，与文献报道北细辛甲基丁香
酚的含量较高相一致［1］。但化学组成上北细辛 SFE
萃取物与北细辛挥发油有明显差异。其主要差别在
于前者保留时间 10 min以前成分消失，而保留时间
31 min左右的低挥发性的脂溶性成分含量较高，提
示二者化学成分与药效不能等同，其相关性有必要
做进一步研究。
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891 天然产物研究与开发 Vol. 24