全 文 ：大接骨丹的化学成分
吴少华 , 马云保 , 罗晓东 , 吴大刚 , 刘吉开
(中国科学院昆明植物研究所植物化学开放研究实验室 , 云南 昆明　650204)
The Chemical Constituents from Toricellia angulata
WU Shao-Hua , MA Yun-Bao , LUO Xiao-Dong , WU Da-Gang , LIU Ji-Kai＊
(Laboratory of Phytochemistry , Kunming Institute of Botany , The Chinese Academy of Sciences , Kunming 650204)
Keywords:Toricellia angulata;Toricelliaceae;Iridoid glycoside;Phenylpropanoid gly coside;Flavonoid
glycoside;Diterpenoid
关键词:大接骨丹;叨里木科;环烯醚萜甙;苯丙素甙;黄酮甙;二萜
中图分类号:Q 946　　文献标识码:A　　文章编号:0253-2700(2000)02-0214-05
Toricellia angulata Oliv.var.intermedia (Harms.)Hu , belonging to Toricelliaceae , is a single
family and single genus plant.It is distributed in Yunnan , Guizhou , and Sichuan provinces in China
as well as the Himalayas.In Chinese folk medicine , T.angulata is used to treat bone fracture , ton-
sillitis and asthma.It can also be used to expel wind , remove dampness and promote blood circulation
to remove blood stasis (Wu , 1990).During our investigation of the chemical constituents of this
plant , nine compounds have been isolated and identified as two iridoid glycosides , griselinoside (1)
and 10-griselinosidic acid(2), two phenylpropanoid glycosides , syringin(3)and coniferin(4), two
flavonoid glycosides , quercetin-3-O-glucoside (5)and astragalin (6), a diterpenoid , phytol
(7), β-sitosterol , daucosterol , respectively.Among these nine compounds , compounds 2 , 4 , 5 , 6 ,
7 were obtained from this plant for the first time.
EXPERIMENTAL
General procedures　All the maps were obtained on an XRC-1 apparatus and uncorrected.IR
spectrawere recorded on a Bio -Rad FTS -135 Infrared spectrophotometer with KBr pellets.UV
spectra were taken on an UV-210A spectrophotometer.NMR spectra were run on a Brucker AM-
400MHz and a DRX-500 MHz spectrometer with TMS as the internal standard.MS spectra were
measured on Autospec-3000 spectrometer.
Plant material　T .angulata was collected in Lijiang , Yunnan , China in September , 1997
and identified by Mr.Lu Zheng-Wei (Kunming Institute of Botany , Chinese Academy of Sciences ,
云 南 植 物 研 究　 2000 , 22 (2):214～ 218
Acta Botanica Yunnanica　　　　　　　　　　　　　　　　　　　　　　　　　　　
to whom correspondence should be addressed
Received date:1999-07-12, Accepted date:1999-08-20
Kunming , Yunnan , China).
Extraction and Isolation　Dried powder of aerial parts of Toricellia angulata(830 g)were ex-
tracted with methanol three times at room temperature.The extract was concentrated in vacuum to give
a residue (91 g), which was suspended in H2O and then successively partitioned with petroleum ether
(Bp.60 ～ 90℃, chloroform and n-BuOH respectively.The n -BuOH extract (58 g)was chro-
matographed on a silica gel column (1.0 kg , 200 ～ 300 mesh)eluting with CHCl3 by increasing
amount of MeOH to yield eight fractions.Each fraction was further purified by silica gel column chro-
matography repeatedly followed by crystallization and finally afforded compounds:griselinoside (1)
(1.2 g), 10-griselinosidic acid (2)(362 mg), syringin (3)(74 mg), coniferin (4)(15 mg),
quercetin-3-O-glucoside (5)(566 mg), astragalin (6)(11 mg).The petroleum ether extract
(20 g)was chromatographed on a silica gel column(600 g , 200 ～ 300 mesh)eluting with petroleum
ether by increasing amount of Me2CO to give phytol(7)(45mg).
Griselinoside(1):C18H24O12 , as a white foam;FAB-MS (negative ion mode)m/ z(%):
431 [M-H] - (19), 269 [ M-C6H11O5] - (28);UVλmax (MeOH)nm (logε):238 (4.12);
IRνmax (KBr)cm-1:3418 , 2957 , 1750 , 1635 , 1441 , 1306 , 1164 , 1076 , 946 , 770;1H NMR
(400 MHz , C5D5N):δ5.43(1H , d , J1 ,9=8.9Hz , H-1), 7.66 (1H , s , H-3), 3.86 (1H , d ,
J5 ,9=7.7Hz , H-5), 2.81 (2H , t , J=4.3Hz , H-7), 3.76 (1H , m , H-8), 3.01 (1H , dt ,
J=8.4 , 1.4Hz , H -9), 3.63 (3H , s , OCH3), 3.55 (3H , s , OCH3), 5.29 (1H , d , J=
7.8Hz , Hglu-1), 4.13 (1H , t , J =8.1Hz , Hg lu -2), 4.27 (1H , t , J=7.6Hz , Hglu-3),
4.25 (1H , t , J=7.6Hz , Hglu-4), 4.01 (1H , m , Hg lu-5), 4.52 (1H , dd , J=11.8 , 2.0Hz ,
Hg lu-6a), 4.34 (1H , d , J=11.8Hz , Hg lu -6b).13C NMR data see Table 1.(Jensen et al ,
1980).
10-Griselinosidic acid (2):C17H22O12 , amorphous white powder;mp 194.5 ～ 196℃;EI-
MS(70eV)m/ z(%):256 [ M -C6H10O5] + (31), 162 [ C6H10O5] + (30), 139 (67), 127
(40), 95 (43), 73 (100), 60 (99);UVλmax (MeOH)nm(logε):238 (3.97);IRνmax (KBr)
cm
-1:3521 , 3371 , 2927 , 1742 , 1683 , 1623 , 1443 , 1326 , 1191 , 1079 , 985;1H NMR (400
MHz , C5D5N):δ5.52(1H , d , J1 ,9=8.8Hz , H-1), 7.68 (1H , s , H-3), 3.99 (1H , d , J5 , 9
=7.9Hz , H-5), 3.03 (1H , dd , J=19.5 , 2.8Hz , H-7), 2.84 (1H , dd , J=19.6 , 9.7Hz ,
H-7′), 3.87 (1H , dt , J=9.3 , 2.5Hz , H-8), 3.21 (1H , dt , J=7.6 , 1.4Hz , H-9), 3.64
(3H , s , OCH3), 5.32 (1H , d , J=7.8Hz , Hglu-1), 4.13 (1H , t , J=8.2Hz , Hglu-2), 4.27
(1H , t , J=8.8Hz , Hglu-3), 4.25 (1H , t , J=8.8Hz , Hglu-4), 4.02 (1H , m , Hglu-5),
4.52 (1H , dd , J=11.8 , 2.2Hz , Hg lu-6a), 4.34 (1H , d , J=11.8Hz , Hglu-6b).13C NMR da-
ta see Table 1.(Foderaro et al , 1992).
Syringin(3):C17H24O9 , colorless needles(acetone);mp 188.5 ～ 190.0℃;FAB-MS(nega-
tive ion mode)m/ z(%):371 [M -H] - (22), 209 [M-C6H11O5] - (9), 357 [ M-CH3] -
(12);UVλmax (MeOH)nm (logε):221 (4.56), 266 (4.26), 300 (3.35);IRνmax (KBr)
cm-1:3565 , 3433 , 3391 , 2901 , 1589 , 1511 , 1421 , 1241 , 1133 , 1093 , 1029 , 966;1H NMR
2152 期　　　 　　　　　　　　　　　吴少华等:大接骨丹的化学成分　　　　　 　　　　　　　　
(400MHz , C5D5N):δ6.87 (2H , s , H-3 , 5), 6.88 (1H , d , J=15.8Hz , H-7), 6.62 (1H ,
dt , J=15.8 , 5.0Hz , H-8), 4.58 (2H , dd , J=5.0 , 1.3Hz , H-9), 3.74 (6H , s , H-10 ,
11), 5.82 (1H , d , J=6.9Hz , Hg lu-1), 4.32 (3H , m , overlap , Hglu-2 , 3 , 4), 3.94 (1H ,
m , Hg lu-5), 4.31 (1H , d , J=11.7Hz , Hg lu -6a), 4.40 (1H , dd , J=11.7 , 2.6Hz , Hg lu -
6b).13C NMR data see Table 1.(Jensen et al , 1980).
Coniferin(4):C16H22O8 , amorphous white powder;mp 183 ～ 185℃;FAB-MS(negative ion
mode)m/ z(%):341 [M-H] - (13), 327 [M-CH3] - (4);UV λmax (MeOH)nm (logε):
213 (4.42), 260 (4.29), 293 (3.79), 306 (3.60);IRνmax (KBr) cm-1:3400 , 2910 , 1589 ,
1516 , 1419 , 1258 , 1229 , 1082 , 1025 , 968;1H NMR(400 MHz , C5D5N):δ7.18 (1H , d , J=
1.8Hz , H-3), 7.03 (1H , dd , J=8.4 , 1.8Hz , H -5), 7.53 (1H , d , J=8.4Hz , H-6),
6.85 (1H , d , J=15.9Hz , H-7), 6.56 (1H , dt , J=15.9 , 5.2Hz , H-8), 4.56 (2H , dd , J
=5.2 , 1.5Hz , H-9), 3.73 (3H , s , H-10), 5.68 (1H , d , J=6.8Hz , Hg lu-1), 4.38 (1H ,
t , J=7.1Hz , Hglu-2), 4.35 (2H , m , overlap , Hglu-3 , 4), 4.12 (1H , m , Hglu-5), 4.33
(1H , d , J=11.9Hz , Hglu-6a), 4.52 (1H , dd , J=11.9 , 2.2Hz , Hglu-6b).13C NMR data see
Table 1.(Falshaw et al , 1969).
Quercetin-3-O-glucoside (5):C21H20O12 , yellow powder;mp 223 ～ 225℃;FAB-MS
(negative ion mode)m/ z(%):463 [M-H] - (100), 300 [M -H-C6H11O5] - (5);UVλmax
216　　　　　　 　　　　　　　　　云　南　植　物　研　究　　　　　 　　　　　　　　　22卷
(MeOH)nm (logε):207 (4.57), 257 (4.35), 263 (4.31), 291 (3.96), 361 (4.27);IRνmax
(KBr)cm-1:3354 , 2905 , 1658 , 1607 , 1503 , 1365 , 1307 , 1205 , 1088 , 998;1H NMR(400
MHz , C5D5N):δ6.68 (1H , d , J=2.0Hz , H-6), 6.62 (1H , d , J=2.0Hz , H -8), 8.45
(1H , d , J=2.0Hz , H -2′), 7.24 (1H , d , J=8.4Hz , H -5′), 8.10 (1H , dd , J=8.4 ,
2.0Hz , H-6′), 6.08 (1H , d , J=7.8Hz , Hglu-1), 4.16 (1H , t , J=6.1Hz , Hglu-2), 4.32
(1H , t , J=6.2Hz , Hglu -3), 4.28 (1H , t , J=6.2Hz , Hglu-4), 4.42 (1H , dd , J=10.9 ,
6.3Hz , Hglu-5), 4.60 (1H , d , J=3.1Hz , Hglu-6a), 4.81 (1H , t , J=9.2Hz , Hglu-6b).
13C NMR data see Table 2.(龚运淮 , 1986).
Astragalin(6):C21H20O11 , yellow powder;mp 233 ～ 235.5℃;FAB -MS (negative ion
mode)m/ z(%):447 [M-H] - (100), 284 [M-H-C6H11O5] - (9);UVλmax (MeOH)nm
(logε):207 (4.48), 266 (4.35), 298 (4.11), 342 (4.26);IRνmax (KBr)cm-1:3424 , 3186 ,
2826 , 1658 , 1609 , 1507 , 1364 , 1268 , 1182 , 1090 , 1018 , 846;1H NMR(400 MHz , C5D5N):
δ6.69 (2H , s , H-6 , 8), 8.49 (2H , dd , J=9.6 , 2.8Hz , H-2′, 6′), 7.16 (2H , dd , J=
9.6 , 2.8Hz , H-3′, 5′), 6.22 (1H , d , J=8.0Hz , Hglu-1), 4.16 (1H , t , J=6.0Hz , Hglu-
2), 4.30 (2H , m , overlap , Hglu-3 , 4), 4.41 (1H , m , Hg lu -5), 4.61 (1H , d , J=3.2Hz ,
Hg lu-6a), 4.81 (1H , t , J=9.2Hz , Hg lu-6b).13C NMR data see Table 2.(龚运淮 , 1986).
Table 1　13C NMR spectral data of compounds1-4(Pyridine-d5)
C 1 2 3 4 C 1 2 3 4
1 97.47 97.74 134.06 147.60 11 166.77 166.97 56.67
2 153.96 147.60 COOCH3 51.37 51.43
3 153.16 153.21 105.43 111.12 52.28
4 104.73 104.93 131.22 132.48 Glu-1 102.14 102.05 105.08 102.42
5 44.18 44.33 105.43 119.94 2 74.63 74.69 76.12 74.95
6 211.30 212.20 153.96 116.79 3 78.43 78.46 78.72 78.58
7 37.06 37.56 129.48 129.43 4 71.59 71.67 71.76 71.38
8 39.42 40.07 131.22 130.04 5 78.79 78.83 78.43 78.88
9 40.64 41.09 62.83 62.97 6 62.71 62.78 62.83 62.49
10 174.27 176.44 56.67 56.05
Table 2　13C NMR spectral data of compounds 5 , 6(Pyridine-d5)
C 5 6 C 5 6
2 157.96 157.65 3′ 146.71 116.09
3 135.55 135.78 4′ 150.74 131.99
4 178.88 178.91 5′ 117.91 116.09
5 162.75 162.85 6′ 122.81 131.99
6 99.84 99.89 Glu-1″ 105.59 104.99
7 165.96 165.98 2″ 73.40 73.36
8 94.59 94.64 3″ 75.46 75.39
9 157.62 157.65 4″ 69.83 69.83
10 105.22 105.31 5″ 77.64 77.60
1′ 122.38 122.06 6″ 62.00 61.98
2′ 116.27 131.99
2172 期　　　 　　　　　　　　　　　吴少华等:大接骨丹的化学成分　　　　　 　　　　　　　　
Phytol(7):C20H40O , colorless oil;EI-MS (70eV)m/ z (%):296 [M] + , 278 [M -
H2O] + , 71 (100);IRνmaxcm-1:3340(O-H), 1668(C=C);1H NMR(400 MHz , CDCl3):δ
5.39(1H , t , J=7.0Hz , =CH-CH2-OH), 4.14 (2H , d , J=7.0Hz , =CH-CH2-OH),
1.98 (2H , t , J=7.0Hz , (CH2-CH2 -C=), 1.66 (3H , s , (CH =C -CH3);　13C NMR
(100 MHz , CDCl3):δ140.2(-C=CH-), 123.1 (-C=CH-), 59.4 (-C=CH-CH2OH),
39.9 (-CH2-C=CH-), 16.1 (CH3-C=CH-).(Aoki et al , 1982).
Acknowledgements　We are grateful to the Analytical G roup of the Department of Phytochemistry Kunming Institute of
Botany for measurements of all spectra.
References
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