全 文 ：天然产物研究与开发 Nat Prod Ｒes Dev 2015，27:604-608，625
文章编号:1001-6880(2015)4-0604-06
Ｒeceived:September 30，2014;Accepted:March 19，2015
Foundation Item:The Scientific Foundation of Shanghai Committee of
Science and Technology (12401900501)
* Corresponding author Tel:86-21-34205989;E-mail:kimhz@ sjtu． edu．
cn
贡山八角枝叶化学成分研究
叶凤梅，谢阳国，朱 燕，任 杰，王 星，严诗楷，金慧子*
上海交通大学药学院，上海 200240
摘 要:为研究贡山八角枝叶的化学成分，我们利用色谱法对贡山八角( Illicium wardii A． C． Smith)枝叶 95%乙
醇提取物中的化学成分进行分离。利用核磁共振、质谱、红外等方法对分离得到的单体化合物进行结构鉴定，
从贡山八角枝叶中分离得到了 15 个化合物，分别是 β-谷甾醇(1)、二十六烷(2)、红花八角醇(3)、三十四烷醇
(4)、异鼠李素-3-O-β-D-芸香糖苷(5)、acernikol(6)、subamone(7)、苔色酸甲酯(8)、扁柏脂内酯(9)、厚朴酚
(10)、原儿茶酸(11)、异红花八角醇(12)、vitrifol A(13)、右旋二氢去氢双松柏醇(14)、左旋马尾松树脂醇(15)。
其中化合物 2 ～ 15 首次从该植物中分离得到，化合物 7 和 15 为首次从该科植物中分离得到。
关键词:贡山八角;化学成分;八角科;木质素;单萜
中图分类号:Q914． 4 文献标识码:A DOI:10． 16333 / j． 1001-6880． 2015． 04． 009
Chemical Constituents of Branches and Leaves of Illicium wardii A． C． Smith
YE Feng-mei，XIE Yang-guo，ZHU Yan，ＲEN Jie，WANG Xing，YAN Shi-kai，JIN Hui-zi*
School of Pharmacy，Shanghai Jiao Tong University，Shanghai 200240，China
Abstract:To investigate chemical constituents of the branches and leaves of Illicium wardii A． C． Smith． Chemical con-
stituents were isolated using column chromatography from 95% ethanol extracts of the branches and leaves of I． wardii．
Their structures were elucidated by NMＲ，IＲ and MS techniques． Fifteen compounds were obtained and identified as β-
sitosterol (1)，hexacosane (2)，dunnianol (3)，tetratriacontanol (4)，isorhamnetin-3-O-β-D-rutinoside (5)，acernikol
(6)，subamone (7)，methyl-β-orsellinate (8)，hinokinin (9)，magnolol (10)，protocatechuic acid (11)，isodunnianol
(12)，vitrifol A (13)，( + )-dihydrodehydrodiconiferyl alcohol (14) and (-)-massoniresinol (15) ． Compounds 2-15
were obtained from this plant firstly，and compounds 7 and 15 were found from Illiciaceae family firstly．
Key words:Illicium wardii;chemical constituent;Illiciaceae;lignan;monoterpene
Introduction
Illicium wardii A． C． Smith belongs to Illicium genus，
which is the only genus of Illiciaceae family containing
about 50 species globally． There are 28 species and two
variants distributed in the southwest，south and east of
China［1］． Plants from Illicium genus are evergreen trees
or shrubs and some of them are used to treat rheuma-
tism，traumatic injury and stomach cold vomiting in
Traditional Chinese Medicine (TCM)［2］． However，the
phytochemical investigation of I． wardii is seldom re-
ported． Up to now，only fourteen compounds isolated
from the fruits of the plant have been reported by Min
Y，et al ［3］ and Gao YP，et al ［4］． As a continuation of
our phytochemical studies of Illicium genus，we focused
on the isolation and structural identification of chemical
constituents from the branches and leaves of I． wardii
and resulted in the isolation of fifteen compounds，
which were assigned as β-sitosterol (1)，hexacosane
(2)，dunnianol (3)，tetratriacontanol (4)，isorhamne-
tin-3-O-β-D-rutinoside (5)，acernikol (6)，subamone
(7)，methyl-β-orsellinate (8)，hinokinin (9)，magnol-
ol ( 10 )，protocatechuic acid ( 11 )，isodunnianol
(12)，vitrifol A (13)，( + )-dihydrodehydrodiconiferyl
alcohol (14) and (-)-massoniresinol (15)，respec-
tively． Compounds 2-15 were obtained from this plant
firstly，and compounds 7 and 15 were isolated from Illi-
ciaceae family firstly．
Materials and Methods
Plant materials
The plants of I． wardii were collected in Nujiang county
of Yunnan province，China in August 2011 and identi-
fied by Prof． Yuanchuan Zhou，the director of Nujiang
Nationality Medicine Plants Institution．
Experimental apparatus and materials
Melting points were measured by a ＲY-1 micro-melting
point apparatus without correction． Optical rotations
were measured on a Perkin-Elmer 341 digital polarime-
ter． IＲ spectra was obtained on a Bruker FTIＲ Vector
22 spectrometer with KBr pellets． Normal phase silica
gel (200-300 mesh，Yantai)，MCI gel (CHP20P 75-
150 μM，Mitsubishi Chemical Co． ) and Sephadex LH-
20 (GE Healthcare Bio-Sciences AB，Sweden) were
used for column chromatography，and precoated silica
HSGF254(10-40 μm，Yantai) plates were used for TLC
analysis． 1H NMＲ and 13C NMＲ spectra were measured
on a Bruker DＲX-500 spectrometer for 1H NMＲ at 500
MHz and 13C NMＲ，DEPT at 126 MHz． ESI-MS analy-
ses were carried out on Agilent-1100-LC /MSD-Trap
(ESI-MS) and Agilent Micro-Q-Tof in m/z． HPLC and
preparative HPLC analyses were performed with SHI-
MADZU LC-2010AHT，Agilent Technologies 1200 se-
ries and SHIMADZU LPD-20A． Petroleum ether /ethyl
acetate and methylene chloride /methanol ( different
proportions) were used in the chromatographic solvent
system．
Extraction and Isolation
The air-dried branches and leaves of I． wardii (17． 4
kg) were extracted for three times with 95% EtOH by
reflux extraction (2 h / time) ． The extract was further
concentrated under reduced pressure to yield 1． 7 kg
residue． The residue was reconstituted in H2O and liq-
uid-liquid extracted successively with petroleum ether
(PE)，methylene chloride (CH2Cl2) and ethyl acetate
(EtOAc) to yield 300． 0 g，270． 0 g and 100． 0 g，re-
spectively．
PE fraction (100． 0 g) was chromatographed on silica
gel column eluting with PE∶ EtOAc (100∶ 0-0∶ 100，v /
v) to obtain eight subfractions ( a-h) ． Compound 2
(15． 0 mg) was obtained from Fr． a． Compounds 1
(100． 0 mg)，12 (10． 0 mg) and 3 (40． 0 mg) were
obtained from Fr． a，Fr． e and Fr． j，respectively by re-
crystallization．
CH2Cl2 fraction was subjected to silica gel column with
gradient CH2Cl2 ∶ MeOH (100∶ 0-2∶ 1，v /v) as eluents
and eight subfractions ( i-p) were obtained． Fr． i，Fr． l
and Fr． m were applied to MCI gel column chromatog-
raphy ( CH3OH ∶ H2O，9 ∶ 1，v /v) firstly，then some
white powder was obtained from Fr． l，to yield com-
pound 4 (35 mg) by purification． Fr． i was subjected to
a series of chromatographic columns，such as silica gel
column，Sephadex LH-20，to obtain three subfractions
Fr． i-1-Fr． i-3． And Fr． i-1 and Fr． i-3 were subjected to
preparative HPLC (ＲP18，210 nm)，yielded compound
7 (17． 0 mg，30% CH3CN as eluents) from Fr． i-1，
and compounds 8 (7． 0 mg，75% MeOH)，9 (3． 0 mg，
75% MeOH) and 10 (3． 0 mg，85% MeOH) were ob-
tained from Fr． i-3． Fr． m was subjected to preparative
HPLC (ＲP18，210 nm，45% MeOH)，and to yield 5
(30． 0 mg) and 6 (25． 0 mg) ．
EtOAc fraction (100 g) was subjected to silica gel col-
umn with the gradient CH2Cl2 ∶ MeOH (100∶ 0-2∶ 1，v /
v) as eluents and 9 subfractions (q-y) were obtained．
Fr． s was subjected to a series of chromatographic col-
umns，such as silica gel column，Sephadex LH-20 and
preparative HPLC (ＲP18，210 nm) to yield compounds
11 (50． 0 mg，20% MeOH) and 13 (16． 0 mg，20%
MeOH)，14 (120． 0 mg，40% MeOH) and 15 (35． 0
mg，40% MeOH) ．
Structural identification
Compound 1 Colorless needle crystal (MeOH)，mp
136-138 ℃ ． Compound 1 exhibited the same Ｒf value
with the standard β-sitosterol by TLC detection in three
different eluents，and the melting point of the mixture
didnt vary;It became purple under 105 ℃ by vanillin-
sulfuric acid color reaction;Meanwhile，the result of
Liebermann-Berchard reaction was positive． IＲ ( υKBr
max，cm-1) ∶ 3445 (OH)，2978 (CH3)，2868 (CH2)，
1650 (C = C)，1465 (CH3 + CH2)，1380，1165 ( iso-
propyl)，1060 (C-O-) ． The above data was in accord-
ance with those reported in the literature［5］，hence
compound 1 was identified as β-sitosterol．
506Vol. 27 YE Feng-mei，et al:Chemical Constituents of Branches and Leaves of Illicium wardii A． C． Smith
Compound 2 White power (CH2Cl2)，C26 H54，ESI-
MS (positive):m/z 389 ［M + Na］+，ESI-MS (nega-
tive):m/z 365［M-H］-;1H NMＲ (500 MHz，CDCl3)
δ:1． 26 (54H，m，H-2 ～ 25)，0． 88 (6H，t，J = 7． 0
Hz，H-1，26);13 C NMＲ (126 MHz，CDCl3 ) δ:14． 1
(C-1，6)，22． 7 (C-2，25)，29． 4 (C-4，23)，29． 7 (C-
5，22)，29． 7 (C-6 ～ C-21)，31． 9 (C-3，4) ． The NMＲ
data was in accordance with those reported in the liter-
ature［6］，hence compound 2 was identified as hexaco-
sane.
Compound 3 White crystal (MeOH)，C27 H26 O3，
ESI-MS ( positive): m/z 421 ［M + Na］+，ESI-MS
(negative):m/z 397 ［M-H］-;1H NMＲ (500 MHz，
CD3OD) δ:7. 09 (2H，d，J = 1. 9 Hz，H-3，3″)，
7. 07 (2H，brs，H-3，5)，7. 02 (2H，dd，J = 8. 2，2. 2
Hz，H-5，5″)，6. 87 (2H，d，J = 8. 2 Hz，H-6，6″)，
6. 03 ～ 5. 90 (3H，m，H-8，8，8″)，5. 11 ～ 4. 97 (6H，
m，H-9，9，9″)，3. 39 (2H，d，J = 6. 7 Hz，H-7)，
3. 34 (4H，J = 6. 6 Hz，H-7，7″);13 C NMＲ (126
MHz，CD3OD) δ: 39. 1 ( C-7，7″)，39. 1 ( C-7 )，
114. 4 ( C-9，9″)，114. 6 ( C-9 )，115. 8 ( C-6″)，
126. 2 (C-2，2″)，127. 6 (C-2，6)，128. 6 (C-5，5″)，
130. 8 (C-3，5)，131. 6 (C-3，3″)，131. 7 (C-4，4″)，
132. 3 (C-4)，137. 9 (C-8)，138. 0 (C-8，8″)，149. 1
(C-1)，151. 9 (C-1，1″) . The NMＲ data was in ac-
cordance with those reported in the literature［7］，hence
compound 3 was identified as dunnianol.
Compound 4 White amorphous powder (CH2Cl2 )，
C34H70 O，ESI-MS ( positive):m/z 517 ［M + Na］
+，
ESI-MS (negative):m/z 493［M-H］-;1H NMＲ (500
MHz，CDCl3) δ:3. 64 (2H，t，J = 6. 7 Hz，H-1)，
1. 25 (29H，brs，H-2 ～ H-33)，0. 88 (3H，t，J = 6. 3
Hz，H-34);13 C NMＲ (126 MHz，CDCl3 ):14. 1 (C-
34)，22. 7 (C-33)，25. 7 (C-3)，29. 4 (C-31)，29. 6
(C-4 ～ C-30)，31. 9 (C-32)，32. 8 (C-2)，63. 1 (C-
1). The NMＲ data was in accordance with those repor-
ted in the literature［8］，hence compound 4 was identi-
fied as tetratriacontanol.
Compound 5 Yellow needle crystal (MeOH)，C28
H32O16，ESI-MS (positive):m/z 647［M + Na］
+，ESI-
MS (negative):m/z 623 ［M-H］-;Molish reation and
HCl-Mg reation showed positive result. The aglycone is
isorhamnetin by hydrolysis，and the glycosyl is com-
posed of glucose and rhamnose by paper chromatogra-
phy detection. 1H NMＲ ( 500 Hz CD3OD) δ: 7. 94
(1H，d，J = 1. 9 Hz，H-2)，7. 62 (1H，dd，J = 2. 0
Hz，8. 5 Hz，H-6)，6. 91 (1H，d，J = 8. 5 Hz，H-
5)，6. 19 (1H，d，J = 2. 0 Hz，H-6)，6. 44 (1H，d，J
= 2. 0 Hz，H-8)，5. 20 (1H，d，J = 7. 4 Hz，H-1″)，
4. 52 (1H，d，J = 1. 3 Hz，H-1″)，3. 94 (3H，s，
CH3O-3)，3. 81 (1H，dd，J = 11. 1，0. 5 Hz，Ha-6″)，
3. 61 ～ 3. 25 (11H，m，H-1″ ～ 5″，H-6″，H-1″ ～ 5″)，
1. 10 (3H，d，J = 6. 3 Hz，H-6″);13 C NMＲ (101
MHz，CD3OD) δ:16. 6 ( C-6″)，55. 3 ( CH3O-3)，
67. 1 (C-6″)，68. 4 (C-5″)，70. 2 (C-2″)，70. 6 (C-
3″)，70. 8 (C-4″)，72. 4 (C-4″)，74. 5 (C-2″)，75. 9
(C-5″)，76. 8 (C-3″)，101. 0 (C-1″)，101. 1 (C-8)，
103. 1 (C-6)，103. 8 (C-1″)，103. 9 (C-10)，113. 1
( C-2)，114. 7 ( C-5)，121. 6 ( C-6)，122. 6 ( C-
1)，134. 0 ( C-3 )，146. 9 ( C-4)，149. 5 ( C-3)，
157. 1 (C-2)，157. 3 (C-9)，161. 4 (C-5)，166. 2 (C-
7)，177. 7 (C-4) . The NMＲ data was in accordance
with those reported in the literature［9］，hence com-
pound 5 was identified as isorhamnetin-3-O-β-D-rutino-
side.
Compound 6 White amorphous powder (MeOH)，
C31H38 O11，ESI-MS(positive):m/z 609 ［M + Na］
+，
ESI-MS (negative):m/z 585［M-H］-;1H NMＲ (400
MHz，CD3OD) δ:6. 96 (1H，s，H-2″)，6. 76 (1H，d，J
= 8. 0 Hz，H-6″)，6. 74 (2H，s，H-2，5″)，6. 70 (1H，
s，H-6)，6. 70 (2H，s，H-2，6)，5. 54 (1H，m，H-
7)，4. 90 (1H，d，J = 5. 2 Hz，H-7″)，4. 24 (1H，m，
H-8″)，3. 86 (3H，s，CH3O-3)，3. 81 (3H，s，CH3O-
3″)，3. 78 (6H，s，CH3O-3，5)，3. 75 (2H ，m，H-
9)，3. 59 (2H，m，H-9″)，3. 57 (2H，m，H-9)，3. 46
(1H，m，H-8)，2. 62 (2H，t，J = 7. 8 Hz，H-7)，1. 81
(2H，m，H-8);13C NMＲ (101 MHz，CD3OD) δ:32. 9
(C-7)，35. 8 (C-8)，55. 7 (C-8)，56. 4 (CH3O-3″)，
56. 7 (CH3O-5，3)，56. 9 (CH3O-3)，61. 7 (C-9″)，
62. 3 (C-9)，65. 1 (C-9)，74. 1 (C-7″)，87. 4 (C-
8″)，88. 7 ( C-7)，103. 9 ( C-2)，104. 0 ( C-6)，
111. 4 ( C-2″)，114. 2 ( C-2 )，115. 8 ( C-5″)，118. 0
(C-6)，120. 7 (C-6″)，129. 5 (C-5)，133. 7 (C-1″)，
136. 3 ( C-4)，137. 2 ( C-1)，145. 3 ( C-3)，147. 0
(C-4″)，147. 5 (C-4)，148. 7 (C-3″)，154. 6 (C-3，
606 Nat Prod Ｒes Dev Vol. 27
5);The NMＲ data was in accordance with those re-
ported in the literature［10］，hence compound 6 was i-
dentified as acernikol.
Compound 7 Colorless oil (MeOH)，C10H16O2，ESI-
MS (positive):m/z 191 ［M + Na］+，ESI-MS (nega-
tive):m/z 167［M-H］-;1H NMＲ (500 MHz，CD3OD)
δ:6. 74 (1H，s，H-2)，4. 31 (1H，d，J = 9. 6 Hz，H-
7)，2. 39 (1H，dd，J = 16. 0，3. 6 Hz，H-5b)，2. 20
(1H，m，H-4，5a)，1. 91 (1H，m，H-6)，1. 76 (3H，s，
CH3-3)，0. 98 (3H，d，J = 6. 8 Hz，CH3-6)，0. 92
(3H，d，J = 6. 8 Hz，CH3-4);
13 C NMＲ (126 MHz，
CD3OD) δ:15. 36 (CH3-3)，16. 76 (CH3-4)，20. 88
(CH3-6)，27. 33 (C-4)，37. 27 (C-5)，51. 24 (C-6)，
69. 47 (C-7)，135. 44 (C-2)，151. 91 (C-3)，202. 39
(C-1) . The NMＲ data was in accordance with those
reported in the literature［11］，hence compound 7 was i-
dentified as subamone.
Compound 8 Colorless crystal (MeOH)，C10H12O4，
ESI-MS ( positive): m/z 219 ［M + Na］+，ESI-MS
(negative):m/z 195 ［M-H］-;1 H NMＲ (500 MHz，
CD3OD) δ: 6. 21 ( 1H，s，H-5 )，3. 89 ( 3H，s，
CH3O-)，2. 41 (3H，s，CH3-6)，1. 99 (3H，s，CH3-
3);13 C NMＲ (126 MHz，CD3OD) δ:6. 6 (CH3-3)，
22. 9 (CH3-6)，50. 6 (CH3O-)，103. 5 (C-1)，108. 5
(C-3)，110. 2 (C-5)，139. 5 (C-6)，160. 3 (C-2)，
162. 8 (C-4)，172. 6 (C = O);The NMＲ data was in
accordance with those reported in the literature［12］，hence
compound 8 was identified as methyl-β-orsellinate.
Compound 9 Colorless oil (MeOH)，C20H18O6，ESI-
MS(positive):m/z 377 ［M + Na］+，ESI-MS ( nega-
tive):m/z 353［M-H］-;1H NMＲ (500 MHz，CD3OD)
δ:6. 71 (1H，brd，J = 8. 1 Hz，H-5)，6. 68 (1H，d，J
= 8. 3 Hz，H-5)，6. 61 (2H，s，H-2，2)，6. 52 (2H，
m，H-6，6)，5. 90 (4H，td，J = 5. 2，1. 2 Hz，-O-
CH2-O-)，4. 16 (1H，dd，J = 9. 0，7. 5 Hz，Ha-9)，
3. 93 (1H，dd，J = 9. 1，7. 7 Hz，Hb-9)，2. 91 (1H，
dd，J = 13. 7，5. 2 Hz，Ha-7)，2. 79 (1H，dd，J =
13. 7，5. 2 Hz，Hb-7)，2. 64 (1H，m，H-8)，2. 54 (1H，
d，J = 2. 7 Hz，Ha-7)，2. 52 (1H，s，H-8)，2. 49
(1H，m，Hb-7);
13 C NMＲ (126 MHz，CD3OD) δ:
34. 2 (C-7)，37. 6 (C-7)，41. 2 (C-8)，46. 3 (C-
8)，71. 4 (C-9)，100. 8 (-O-CH2-O-)，100. 9 (-O-
CH2-O-)，107. 6 ( C-5)，107. 7 ( C-5)，108. 5 ( C-
2)，109. 0 ( C-2 )，121. 3 ( C-6 )，122. 1 ( C-6)，
131. 6 ( C-1)，132. 2 ( C-1)，146. 3 ( C-4)，146. 4
(C-4)，147. 8 (C-3)，147. 8 (C-3)，179. 9 (C-9)
. The NMＲ data was in accordance with those reported
in the literature［13］，hence compound 9 was identified
as hinokinin.
Compound 10 White amorphous powder (MeOH)，
C18H18 O2，ESI-MS( positive):m/z 289 ［M + Na］
+，
ESI-MS (negative):m/z 265［M-H］-;1H NMＲ (500
MHz，CD3OD) δ:7. 22 (1H，d，J = 1. 9 Hz，H-2)，
7. 20 (1H，dd，J = 8. 2，2. 2 Hz，H-6)，6. 98 (1H，d，
J = 2. 1 Hz，H-2)，6. 90 (1H，dd，J = 8. 2，2. 2 Hz，
H-6)，6. 78 (2H，m，H-5，3)，5. 91 ～ 6. 06 (2H，m，
H-8，8)，4. 98 ～ 5. 08 (4H，m，H-9，9)，3. 38 (2H，
d，J = 6. 6 Hz，H-7，7);13 C NMＲ ( 126 MHz，
CD3OD) δ:33. 9 (C-7)，39. 1 (C-7)，113. 9 (C-5)，
114. 0 (C-5)，114. 1 (C-9)，115. 4 (C-9)，125. 9
(C-6)，127. 3 (C-6)，127. 7 (C-1)，128. 6 (C-3)，
130. 1 ( C-2)，130. 5 ( C-2)，131. 1 ( C-1)，137. 1
(C-8)，138. 2 (C-8)，151. 9 (C-4)，153. 8 (C-4);
The NMＲ data was in accordance with those reported
in the literature［14］，hence compound 10 was identified
as magnolol.
Compound 11 Colorless crystal (MeOH)，C7H6O4，
ESI-MS( positive ): m/z 177 ［M + Na］+，ESI-MS
(negative):m/z 153 ［M-H］-;1 H NMＲ (500 MHz，
CD3OD) δ:7. 45 (1H，d，J = 1. 9 Hz，H-2)，7. 43
(1H，dd，J = 8. 2，1. 9 Hz，H-6)，6. 81 (1H，d，J =
8. 2 Hz，H-5);13C NMＲ (126 MHz，CD3OD) δ:114. 6
(C-5)，116. 6 (C-2)，122. 1 (C-6)，122. 7 (C-1)，
144. 6 ( C-3)，150. 1 ( C-4)，169. 0 ( C = O)，The
NMＲ data was in accordance with those reported in the
literature［15］，hence compond 11 was identified as pro-
tocatechuic acid.
Compound 12 Colorless oil (MeOH)，C27 H26 O3，
ESI-MS( positive ): m/z 421 ［M + Na］+，ESI-MS
(negative):m/z 397 ［M-H］-;1 H NMＲ (400 MHz，
CD3OD) δ:7. 30 (1H，brs，H-3″)，7. 26 (2H，d，J =
8. 2 Hz，H-2，6)，7. 15 (2H，d，J = 8. 2 Hz，H-3，
5)，7. 03 (1H，d，J = 8. 2 Hz，H-5″)，6. 85 (1H，d，J
= 8. 2 Hz，H-6″)，5. 99 (3H，m，H-8，8，8″)，5. 12 ～
5. 00 (6H，m，H-9，9，9″)，3. 36 (6H，d，J = 6. 5
706Vol. 27 YE Feng-mei，et al:Chemical Constituents of Branches and Leaves of Illicium wardii A． C． Smith
Hz，H-7，7，7″);13 C NMＲ (101 MHz，CD3OD) δ:
40. 4 ( C-7，7″)，40. 5 ( C-7 )，115. 6 ( C-9，9″)，
115. 8 ( C-9)，117. 0 ( C-3)，117. 1 ( C-6″)，121. 6
(C-2，6)，125. 1 (C-6)，125. 4 (C-5)，127. 6 (C-
2″)，129. 1 (C-3，5)，129. 9 (C-3″)，132. 1 (C-3″)，
132. 9 (C-4，4″)，133. 7 (C-4)，139. 3 (C-8)，139. 5
(C-8，8″)，141. 5 (C-1)，147. 8 (C-2)，152. 4 (C-
1″)，154. 0 (C-1) . The NMＲ data was in accordance
with those reported in the literature［6］，hence copound
12 was identified as isodunnianol.
Compound 13 Yellow oil (MeOH)，C30 H34 O9，ESI-
MS (positive):m/z 561 ［M + Na］+，ESI-MS (nega-
tive):m/z 537［M-H］-;1H NMＲ (500 MHz，CD3OD)
δ:6. 93 (1H，brs，H-2)，6. 93 (1H，brs，H-2)，6. 92
(1H，brs，H-6″)，6. 81 (1H，dd，J = 8. 2，1. 7 Hz，H-
6)，6. 76 (1H，d，J = 8. 1 Hz，H-5)，6. 73 (2H，brs，
H-2″，6)，5. 52 (2H，d，J = 6. 2 Hz，H-7，7)，3. 85
(3H，s，CH3O-3)，3. 83 ( 3H，s，CH3O-3 )，3. 81
(3H，s，CH3O-3″)，3. 76 (2H，m，H-9)，3. 59 ～ 3. 55
(2H，m，H-9″)，3. 51 (2H，m，H-9)，2. 62 (2H，J =
7. 7 Hz，H-7″)，1. 82 (2H，m，H-8″);13 C NMＲ(126
MHz，CD3OD) δ:31. 5 ( C-8″)，34. 4 ( C-7″)，53. 8
(C-8 )，54. 1 ( C-8)，54. 97 ( CH3O-3 )，55. 34
(CH3O-3″)，55. 37 (CH3O-3)，60. 82 (C-9″)，63. 35
(C-9 )，63. 6 ( C-9)，87. 9 ( C-7 )，87. 8 ( C-7)，
109. 2 (C-2)，110. 4 (C-2)，112. 7 (C-2″)，114. 4
(C-5)，114. 8 (C-6)，116. 5 (C-6″)，118. 3 (C-6)，
128. 4 (C-5″)，128. 9 (C-5)，132. 9 (C-1)，135. 4
( C-1)，135. 6 ( C-1″)，143. 8 ( C-3)，144. 0 ( C-
3″)，146. 0 ( C-4 )，146. 4 ( C-4″)，147. 8 ( C-3 )，
147. 8 (C-4) . The NMＲ data was in accordance with
those reported in the literature［16］，hence compound 13
was identified as vitrifol A.
Compound 14 White amorphous powder (MeOH)，
C20H24 O6，ESI-MS( positive):m/z 383 ［M + Na］
+，
ESI-MS ( negative ): m/z 359 ［M-H］-;1 H NMＲ
(400Hz CD3OD) δ:6. 95 (1H，brs，H-2)，6. 82 (d，J
= 8. 2 Hz，H-6)，6. 76 (1H，d，J = 8. 2 Hz，H-5)，
6. 71 (2H，brs，H-2，6)，5. 48(1H，d，J = 6. 3 Hz，H-
7)，3. 85 (3H，s，CH3O-3)，3. 79 (3H，s，CH3O-3)，
3. 75 (2H，m，H-9)，3. 56 (2H，t，J = 6. 4 Hz，H-
9)，3. 47 (1H，m，H-8)，2. 61(2H，t，J = 7. 6 Hz，H-
7)，1. 81 ( 2H，m，H-8 );13 C NMＲ ( 101 MHz，
CD3OD) δ:33. 0 (C-7)，35. 8 (C-8)，55. 4 (C-8)，
56. 4 (CH3O-3)，56. 8 (CH3O-3)，62. 3 (C-9)，65. 0
(C-9)，89. 0 (C-7)，110. 6 (C-2)，114. 1 (C-2)，
116. 2 ( C-5)，118. 1 ( C-6 )，119. 8 ( C-6)，130. 1
(C-5)，134. 81 (C-1)，137. 1 (C-1)，145. 2 (C-3)，
147. 5 ( C-4 )，147. 5 ( C-4)，149. 1 ( C-3) . The
NMＲ data was in accordance with those reported in the
literature［17］，hence compound 14 was identified as
( + )-dihydrodehydrodiconiferyl alcohol.
Compound 15 Colorless crystal (MeOH)，C20 H24
O8，ESI-MS(positive):m/z 415 ［M + Na］
+，ESI-MS
(negative):m/z 391 ［M-H］-;1 H NMＲ (500 MHz，
CD3OD) δ:7. 02 (1H，d，J = 1. 7 Hz，H-2)，6. 94
(1H，d，J = 2. 1 Hz，H-2)，6. 79 (1H，dd，J = 8. 2，
1. 8 Hz，H-6)，6. 76 (1H，m，H-6)，6. 74 (2H，m，H-
5，5)，5. 00 (1H，s，H-7)，3. 87 (1H，d，J = 9. 0 Hz，
Hb-9)，3. 85 (3H，s，CH3O-3)，3. 84 (3H，s，CH3O-
3)，3. 80 (1H，d，J = 11. 5 Hz，Ha-9)，3. 69 (1H，d，
J = 11. 5 Hz，Ha-9)，3. 68 (1H，d，J = 8. 9 Hz，Hb-
9)，2. 97 (1H，d，J = 13. 9 Hz，Ha-7)，2. 90 (1H，
d，J = 13. 9 Hz，Hb-7);
13 C NMＲ ( 126 MHz，
CD3OD) δ:38. 7 ( C-7)，55. 0 × 2 ( CH3O-3，3)，
63. 0 (C-9)，73. 4 (C-9)，80. 7 (C-8)，81. 0 (C-
8)，84. 8 (C-7)，111. 5 (C-2)，114. 0 (C-2)，114. 0
(C-5)，114. 3 (C-5)，120. 3 (C-6)，122. 7 (C-6)，
128. 8 ( C-1)，129. 8 ( C-1)，144. 7 ( C-4)，145. 7
(C-4)，147. 1 (C-3)，147. 2 (C-3) . The NMＲ data
was in accordance with those reported in the litera-
ture［18］，hence compond 15 was identified as (-)-mas-
soniresinol.
Ｒeference
1 Editorial board of Flora of China. Flora of China. Beijing:Sci-
ence Press，2004，30:199-202.
2 Wang GW. Chemical Constituents of the stems and leaves of
Illicium lanceolatum A. C. Smith. Shanghai: Second Military
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(下转第 625 页)
806 Nat Prod Ｒes Dev Vol. 27
些制备工艺工程都可能会对黄酮类成分的提取造成
影响［8，9］。故本研究采用乙酸乙酯为提取溶剂，与
参考文献［4］采用 30%乙醇为提取溶剂，所得到的黄
酮类成分及杂质含量亦有所差异，复方的提取工艺
对原药材的黄酮类成分会造成影响。
由此可知，战骨的黄酮类成分，在组成复方后，
在复方提取及制剂制备的工艺过程中，加热会影响
黄酮类成分的组成及含量。我们的后续研究会重点
对这部分内容进行探讨。有针对性的优化战骨复方
制剂的制备工艺，完善含有战骨药材的中成药的质
量标准，确保用药的安全和有效。
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526Vol. 27 江志霞等:战骨药材及其复方制剂的指纹图谱分析及牡荆素含量测定