全 文 ：Flavonoids from Leaves of Heritiera littoralis D.
TIAN Yan , WU Jun , and ZHANG Si＊
(Guangdong Key Laboratory of Marine Materia Medica , South China Sea Institute of Oceanology ,
Chinese Academy of Sciences , Guangzhou 510301 , China)
Key words:Heritiera littoralis D.;Sterculiaceae;Flavonoids
CLC number:R284.1;R284.2 　　　Document code:A　　　Article ID:1003-1057(2004)3-214-03
Introduction
The mangrove plant Heritiera littoralis D.(Sterculi-
aceae)is widely distributed in southeastern Asia and tra-
ditionally used as a fish , arrowhead , and spearhead poi-
son.It has also been used as a folk medicine to treat he-
maturia and diarrhea for a long history in China
[ 1] .Past
investigations on the chemical constituents of this plant
have yielded four triterpenes , five sesquiterpenes , a phe-
nylproanoid-glycerol and four flavonoids[ 2-6] .In the pr-
esent study , eight flavonoids were isolated from the 95%
EtOH extract of the leaves of this plant , and identified as
quercitrin(1), quercetin (2), kaempferol-3-O-(6″-O-
E-p-coumaroyl)-β-D-glucopyranoside (3), kaempferol
(4), kaempferitrin (5), myricetin (6), eriodictyol (7),
and catechin(8)on the basis of their spectral data.
Experimental
General
NMR spectra were recorded in CD3OD , CD3COCD3
and DMSO-d6 using a Bruker ARX-500 spectrometer
(500 MHz for 1H NMR and 125MHz for 13C NMR).1H
and
13
C NMR assignments were supported by HSQC and
HMBC experiments.Silica gel and silica gel GF254 plates
(both from Qingdao Marine Chemical Group Co.)were
used for column chromatography and TLC , respectively.
D101 macroporous adsorptive resin was made by Tianjin
Received date:2004-03-15.
Foundat ion item: National Key Program for Base Research
(2001CCA04700), Know ledge Innovation Pro-
gram of CAS(KZCX3-SW-216)
＊Corresponding author:Tel 86-20-89023105 ,
E-mail zhsimd@scsio.ac.cn
Nankai Chemical Industry.Sephadex LH-20 was pur-
chased from Sigma Chemicals.
Plant material
Heritiera littoralis D.was collected in July 2001
from Wenchang of Hainan Province , south China.The
identification of the plant was performed by Prof.Zhang
Si , Laboratory of Marine Biology , South China Sea Insti-
tute of Oceanology , Chinese Academy of Sciences.
Extraction and isolation
The dried leaves(6.0 kg)of H.littoralis were ex-
tracted with hot 95%EtOH.After removal of the solvent
by evaporation , the residue(800 g)was suspended in wa-
ter and put into the refrigerator at 4 ℃ for several days ,
and after centrifugation at room temperature , the aqueous
layer (200 mL)was subjected to CC in a highly porous co-
polymer of styene and divinylbenzene (D101)and eluted
with H2O , 20% EtOH , 40% EtOH , 60% EtOH and
95%EtOH , successively.The fraction eluted with 40%
EtOH (54 g)was subjected to a column of silica gel with a
CHCl3-MeOH gradient system(1∶0-0∶1), affording eight
fractions.Fraction 2 to 5 were combined(2.5 g)and fur-
ther separated on Sephadex LH-20 with MeOH to provide
compounds 3(250 mg), 1 (50 mg), and 2 (400 mg).
Fraction 6(1.2 g)was further separated on Sephadex LH-
20 with MeOH-H2O(1∶1)to provide compounds 4(200
mg), 5(60 mg), and 6(40 mg).Fraction 7(1.5 g)was
further separated on Sephadex LH-20 with MeOH-H2O(7∶
3)to provide compounds 7(80 mg)and 8(90mg).
Identification
Quercitrin(1)[ 7] 　Yellow needles(methanol), 1H
NMR(DMSO-d6)δ:5.46 (1H , d , J =7.0 Hz , H-
1″), 6.21(1H , d , J =2.0 Hz , H-6), 6.41(1H , d ,
J =2.0Hz , H-8), 6.86(1H , d , J =8.5 Hz , H-5′),
214 Journal of Chinese Pharmaceutical Sciences 2004 , 13(3)
7.58 (1H , dd , J =2.0 Hz , 8.5 Hz , H-6′), 7.62
(1H , d , J =2.0 Hz , H-2′).13C NMR(DMSO-d6)δ:
157.5(s , C-2), 134.7 (s , C-3), 178.8 (s , C-4),
163.6(s , C-5), 100.0 (d , C-6), 165.5 (s , C-7),
94.8(d , C-8), 157.7 (s , C-9), 105.3 (s , C-10),
122.5(s , C-1′), 116.5(d , C-2′), 146.1(s , C-3′),
149.7(s , C-4′), 117.5(d , C-5′), 122.9(d , C-6′),
102.2(d , C-1″), 75.4(d , C-2″), 77.8 (d , C-3″),
71.2(d , C-4″), 78.9(d , C-5″), 62.3(t , C-6″).
Quercetin(2)[ 7] 　Yellow needles(methanol), 1H
NMR(DMSO-d6)δ:6.19 (1H , d , J =1.5 Hz , H-
6), 6.40(1H , d , J =1.5 Hz , H-8), 6.90(1H , d , J
=8.7 Hz , H-5′), 7.54 (1H , dd , J =2.0 Hz , 8.7
Hz , H-6′), 7.67 (1H , d , J =2.0 Hz , H-2′).13 C
NMR(DMSO-d6)δ:156.9(s , C-2), 135.9(s , C-3),
175.9(s , C-4), 156.2 (s , C-5), 98.3 (d , C-6),
164.0(s , C-7), 93.5 (d , C-8), 157.3 (s , C-9),
103.1(s , C-10), 122.1(s , C-1′), 115.2(d , C-2′),
145.1(s , C-3′), 147.7(s , C-4′), 115.7(d , C-5′),
121.0(d , C-6′).
Kaempferol-3-O-(6″-O-E-p-coumaroyl)-β-D-glu-
copyranoside (3)[ 8] 　Amorphous yellow powder , 1H
and
13
C NMR(MeOH-d4)specral data:see Tabel 1.
Kaempferol (4)[ 9] 　Yellow needles (methanol),
1
H NMR(DMSO-d6)δ:6.21(1H , d , J =2.0 Hz , H-
6), 6.45(1H , d , J =2.0 Hz , H-8), 6.94(2H , d ,
J =8.6 Hz , H-3′, 5′), 8.05(2H , d , J =8.6 Hz , H-
2′, 6′).13 C NMR(DMSO-d6)δ:156.1 (s , C-2),
135.6(s , C-3), 175.9 (s , C-4), 160.7 (s , C-5),
98.2(d , C-6), 163.9 (s , C-7), 93.4 (d , C-8),
159.2(s , C-9), 105.8(s , C-10), 121.7(s , C-1′),
129.5(d , C-2′), 115.3(d , C-3′), 160.4(s , C-4′),
115.3(d , C-5′), 129.5(d , C-6′).
Kaempferitrin (5)[ 9] 　Yellow needles (metha-
nol), 1H NMR (CD3OD)δ:5.25 (1H , d , J =7.5
Hz , H-1″), 6.21 (1H , d , J =2.0 Hz , H-6), 6.40
(1H , d , J =2.0 Hz , H-8), 6.88 (2H , d , J =8.5
Hz , H-3′, 5′), 8.06(2H , d , J =8.5Hz , H-2′, 6′).
13
C NMR(MeOH-d4)δ:158.5 (s , C-2), 135.5 (s ,
C-3), 179.6(s , C-4), 163.1(s , C-5), 99.8(d , C-
6), 166.0(s , C-7), 94.8(d , C-8), 159.1(s , C-9),
105.8(s , C-10), 122.8(s , C-1′), 132.3(d , C-2′),
116.1(d , C-3′), 161.6(s , C-4′), 116.1(d , C-5′),
132.3(d , C-6′), 104.1(d , C-1″), 75.8(d , C-2″),
78.1 (d , C-3″), 71.4 (d , C-4″), 78.4 (d , C-5″),
62.7(t , C-6″).
Myricetin(6)[ 10] 　Yellow needles(methanol), 1H
NMR(C5D5N)δ:6.27 (1H , d , J =1.5 Hz , H-6),
6.53(1H , d , J =1.5 Hz , H-8), 7.25(2H , br s , H-
2′, 6′).13C NMR(C5D5N)δ:157.3(s , C-2), 135.4
(s , C-3), 177.1(s , C-4), 162.3(s , C-5), 99.1(d ,
C-6), 165.4(s , C-7), 94.2 (d , C-8), 157.3(s , C-
9), 104.3(s , C-10), 120.9(s , C-1′), 116.5(d , C-
2′), 146.8(s , C-3′), 137.7(s , C-4′), 146.8(s , C-
5′), 116.5(d , C-6′).
Eriodictyol(7)[ 10] 　Yellow needles (methanol),
1
H NMR(DMSO-d6)δ:2.65(1H , dd , J =3.5 , 16.5
Hz , H-3a), 3.46 (1H , dd , J =12.5 , 16.5 Hz , H-
3b), 5.36 (1H , dd , J =3.5 , 12.5 Hz , H-2), 5.80
(1H , s , H-6), 5.98 (1H , s , H-8), 6.80 (1H , d ,
J =8.0Hz , H-5′), 6.98(1H , d , J =8.0Hz , H-6′),
7.22(1H , s , H-2′).13 C NMR (DMSO-d6)δ:78.4
(d , C-2), 42.0(t , C-3), 197.0(s , C-4), 163.0(s ,
C-5), 95.8(d , C-6), 167.0(s , C-7), 94.8(d , C-
8), 162.8(s , C-9), 103.2(s , C-10), 127.9(s , C-
1′), 115.8(d , C-2′), 146.2(s , C-3′), 147.5(s , C-
4′), 115.2(d , C-5′), 122.5(d , C-6′).
Catechin(8)[ 11] 　White needles (methanol), 1H
NMR(CD3COCD3)δ:2.50 (1H , dd , J =8.2 , 16.0
Hz , H-4b), 2.88(1H , dd , J =5.2 , 16.2 Hz , H-4a),
3.95(1H , m , H-3), 4.52(1H , d , J =7.6 Hz , H-2),
5.85(1H , s , H-8), 6.00(1H , s , H-6), 6.71(1H , d ,
J =8.0 Hz , H-5′), 6.75(1H , d , J =8.0 Hz , H-6′),
6.83(1H , s , H-2′).13C NMR(CD3COCD3)δ:82.7
(d , C-2), 68.4(t , C-3), 28.8(t , C-4), 157.2(s , C-
5), 96.2(d , C-6), 157.7 (s , C-7), 95.5 (d , C-8),
156.9 (s , C-9), 100.6 (s , C-10), 132.2 (s , C-1′),
115.2(d , C-2′), 145.6(s , C-3′), 145.7 (s , C-4′),
115.7(d , C-5′), 120.0(d , C-6′).
Figure 1　Selected HMBC correlations of compound 3
215Journal of Chinese Pharmaceutical Sciences 2004 , 13(3)
Table 1　1H and 13C NMR data in MeOH-d4 for compound 3
Position 　δH(J in Hz) δc　
2 159.4s
3 135.2s
4 179.4s
5 163.0s
6 6.08 d(J =2.0) 100.1d
7 166.1s
8 6.26 d(J =2.0) 94.9d
9 158.5s
10 105.6s
1′ 122.8s
2′and 6′ 7.95 d(J =8.8) 132.2d
3′and 5′ 6.78 d(J =8.8) 116.1d
4′ 161.5s
1″ 104.0s
2″ 75.7d
3″ 78.1d
4″ 71.8d
5″ 75.8d
6″ 4.26 d(J =11.8) 64.3d
4.15 dd(J =6.6 ,11.8)
1 127.1s
2 and 6 7.26 d(J =8.6) 131.2d
3 and 5 6.75 d(J =8.6) 116.8d
4 161.8s
7 7.36 d(J =16.0) 146.5d
8 6.03 d(J =16.0) 114.8d
9 168.8s
Acknowledgements
The authors are grateful to Huang Jian-she and Xiao
Zhi-hui(Laboratory of NMR Analysis and Measurement ,
South China Sea Institute of Oceanology , CAS) for
recording the NMR spectra.
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银叶树树叶中的黄酮类化合物
田　艳 , 吴　军 , 张　
(中国科学院南海海洋所 广东省海洋药物重点实验室 , 广州 510301)
摘要:目的　研究银叶树 Heritiera littoralis D.的化学成分。方法　利用硅胶柱层析进行分离和纯化, 并通过波谱分析鉴定结
构。结果　从银叶树的叶子中分离鉴定了8个黄酮类化合物 , 分别为栎皮苷(quercitrin 1), 槲皮素(quercetin 2),山柰酚-3-O-(6″-O-E-
p-香豆酰基)-β-D-吡喃葡萄糖(kaempferol-3-O-(6″-O-E-p-coumaroyl)-β-D-gluco-pyranoside 3), 山柰酚(kaempferol 4), 山柰苷(kaempferitrin
5), 杨梅黄酮(myricetin 6), 圣草酚(eriodictyol 7)和儿茶素(catechin 8)。结论　化合物2-8首次从该植物中分离得到。
关键词:银叶树;梧桐科;黄酮
216 Journal of Chinese Pharmaceutical Sciences 2004 , 13(3)