全 文 ：岷江金丝桃中一个新的间苯三酚类化合物
郭 娜1 , 2 , 陈宣钦1 , 2 , 赵勤实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 650204;
2 中国科学院研究生院 , 北京 100049 )
摘要 : 从岷江金丝桃 ( Hypericumhenryi subsp . uraloides) 中分离得到了一个新的间苯三酚类化合物 (1) , 命
名为 uraloidin A。其结构主要通过 MS , 1D以及 2D NMR 等波谱方法鉴定。同时 , 还得到 7 个已知化合物。
关键词 : 岷江金丝桃 ; 藤黄科 ; 间苯三酚 ; uraloidin A
中图分类号 : Q 946 文献标识码 : A 文章编号 : 0253 - 2700 (2008) 04 - 515 - 04
A New Polyisoprenylated Benzoylphloroglucinol Derivative from
Hypericum henryi subsp . uraloides (Guttiferae)
GUO Na
1 , 2
, CHEN Xuan-Qin
1 , 2
, ZHAO Qin-Shi
1 *
(1 State KeyLaboratory of Phytochemistry and Plant Resources in West China, Kunming Instituteof Botany, Chinese Academy
of Sciences, Kunming 650204 , China; 2 GraduateUviversity of Chinese Academy of Sciences, Beijing 100049 , China)
Abstract: A new polyisoprenylated benzoylphloroglucinol derivative, uraloidin A ( 1) , together with seven known com-
pounds ( 2 - 8) were isolated fromthe aerial parts of the Hypericumhenryi subsp . uraloides . Their structures were estab-
lished on the basis of spectral evidence (MS, IR , 1D- and 2D NMR experiments) .
Key words: Hypericumhenryi subsp . uraloides; Guttiferae; Polyisoprenylated benzoylphloroglucinol ; uraloidin A
The antidepressant activity of the extract of St .
John′s wort ( Hypericum perforatum L .) extracts has
encouraged the investigation of secondary metabolites
from Hypericumspecies, many of which are acylphloro-
glucinol derivatives ( Verotta, 1999; Verotta, 2000 ) .
Hypericumhenryi subsp . uraloides ( Rehd .) N . Rob-
son distributed widely in Yunnan, Sichuan, Guizhou
provinces in China, andmiddleof Burma . Up to now,
there is no report on its chemical constituents . For the
sake of seeking more novel bioactive compounds, we
carriedout extensive chemical studies on the aerial par-
ts of H. henryi subsp . uraloides . In this paper, we
described the isolation and structural elucidation of a
new polyisoprenylated benzoylphloroglucinol derivative .
Seven known compounds were oleanolic acid ( 2 )
(Maillard et al. , 1992) , betulinic acid ( 3) ( Wenkert
et al. , 1978 ) , quercetin (4) ( Wanger et al. , 1976) ,
1 , 5 , 6-trihydroxy-3-methoxyxanthone ( 5 ) ( Terreaux
et al. , 1995) , 1 , 3 , 5 , 6-tetrahydroxyxanthone ( 6)
(J iang et al. , 2003 ) , kielcorin ( 7 ) (Shoer et al. ,
1989) and 1 , 3 , 5 , 6-tetrahydroxy-4-prenylxanthone
(8) (Wu et al. , 1998 ) .
Results and Discussion
Compound 1 was isolated as a colorless viscous
oil , themolecular formulaof 1 wasdetermined to beC38
H50 O5 by negative-ion HR-ESI-MS at m?z 585 .3590
( calcd . 585 .3580) . The IR spectrumshowed hydroxyl
and double bond absorption bands at 3441 and 1629
cm- 1 , respectively . The13 C NMR spectrum ( Table 1)
云 南 植 物 研 究 2008 , 30 (4) : 515～518
Acta Botanica Yunnanica DOI : 10 .3724?SP. J . 1143 .2008.08094
? ?Author for correspondence; E-mail : qinshizhaosp@yahoo. com; Tel : + 86 - 871 - 5223058
Received date: 2008 - 05 - 14 , Accepted date: 2008 - 05 - 25
作者简介 : 郭娜 ( 1981 - ) 女 , 在读硕士研究生 , 主要从事天然产物的分离和结构修饰。
Table 1 NMR Data ( acetone- d6 ) for 1 (δ in ppm, J in Hz)
No . δH δC No . δH δC
1 n- 206 ?. 2 ( s) 22 5 .09 ( d, 8 . 4) 123 .4 (d)
2 n- 80 ?. 2 (s) 23 - 133 .8 ( s)
3 n- 50 ?. 1 (s) 24 1 .68 ( s) 26 .0 ( q)
4 n1 ?. 90 ( m) 43 .8 ( d) 25 1 .61 ( s) 18 .0 ( q)
5 n1 ?. 79 (m) , 2 . 29 ( d, 3 3. 96 ) 39 ?. 4 ( t) 26 2 .97 ( dd , 7 . 3 , 13 .9 ) , 3 . 10 ( dd, 7 . 5 , 13 .9) 22 .8 ( t)
6 n- 60 ?. 9 (s) 27 5 .16 ( t, 7 . 4) 122 .1 (d)
7 n- 174 ?. 3 ( s) 28 - 132 .5 ( s)
8 n- 116 ?. 0 ( s) 29 1 .62 ( s) 25 ~. 82 (q)
9 n- 193 ?. 8 ( s) 30 1 .61 ( s) 17 .9 ( q)
10 ?- 194 ?. 9 ( s) 31 1 .97 (dd, 6 . 0 , 13 .1) , 2 . 71 ( dd, 10 @. 2 , 13 .0) 30 .0 ( t)
14 ?1 .17 (s) 14 .7 ( q) 32 4 .80 ( dd , 6 ?. 0 , 10 .2 ) 91 .6 ( d)
15 ?1 .54 ( m) , 2 . 14 ( m) 37 ?. 3 ( t) 33 - 70 .7 (s)
16 ?2 .04 ( m) , 2 . 22 ( m) 25 . 79 ( t) 34 1 .35 ( s) 26 .2 ( q)
17 ?5 .06 ( d, 7 . 0) 125 ?. 7 ( d) 35 1 .22 ( s) 25 .7 ( q)
18 ?- 131 ?. 4 ( s) 1 w′ - 138 .0 ( s)
19 ?1 .64 (s) 25 .9 ( q) 2 5′, 6′ 7 .48 ( d, 7 . 4) 128 .9 (d)
20 ?1 .64 (s) 17 .8 ( q) 3 5′, 5′ 7 .25 ( t, 7 . 8) 128 .6 (d)
21 ?1 .92 ( t, 3 . 1 ) , 2 . 26 ( m) 27 ?. 9 ( t) 4 w′ 7 .43 ( t, 7 . 4) 132 .7 (d)
Fig . 1 The structures of 1 and furohyperforin
showed 38 carbon signals including three carbonyl
groups (δC 206 .2 , 194 .9 , 193 .8 ) , a benzene ring
(δC 138.0 , 128 .6 × 2 , 128 .9 × 2 , 132.7 ) , nine
methyls, six methylenes, five methines, one of which
bore an oxygen atom (δC 91.6 ) , and nine quaternary
carbones ( including four saturated and oneoxygened) .
In Addition, it isnoteworthy that C - 7 (δC 174 .3) was
an quaternary carbon of enol connected to the oxygen
atom . The
1
H NMR spectrum also exhibited the pres-
ence of nine singlet methyls, a mono-substituated
benzene ring [ (δH 7 .48 ( d, J = 7 .4 Hz) , 7 . 25 ( t, J
= 7 .8 Hz) , 7 . 43 ( t, J = 7 .4 Hz) ] and three tri-sub-
stituted double bonds at 5 .06 ( d, J = 7 .0 Hz) , 5 . 09
( d, J = 8 .4 Hz) and 5 .16 ( t, J = 7 .4 Hz) . Further
analysis of 2D NMR spectra using HSQC and HMBC
techniques enabled the assignment of
1
H and
13
C NMR
signals .
The above-mentioned data disclosed that 1 was a
polyisoprenyland benzoylphloroglucinol derivative . The
13 C NMR of 1 was very similar to thoseof furohyperfor-
in (Verotta et al. , 1999) . Correlations between H - 15
(δH 1 .54 and 2 .14) and C - 2 (δC 80 .2 ) , C - 3 (δC
50 .1) , C - 4 (δC 43 .8 ) and C - 14 (δC 14 .7) , H - 21
(δH 1 .92 and 2 .26) and C - 4 (δC 43 .8 ) , C - 5 (δC
39 .4) , H - 26 (δH 2 .97 , 3 .10 ) and C - 7 (δC
174 .3 ) , C - 9 (δC 193 .8 ) , H - 31 (δH 1 .97 and
615 云 南 植 物 研 究 30 卷
2 .71) and C - 5 (δC 39.4 ) , C - 6 (δC 60 .9) in HMBC
spectrum ( Fig . 2 ) also confirmed the similarity of 1
and furohyperforin . The only difference between them
emerged at C - 10 , in which the substituent group was
abenzene ring in 1 , replaced the isopropyl group in fu-
rohyperforin . Correlations between H - 2′and 6′(δH
7 .48) and C - 10 (δC 194 .9) in HMBC spectrumsug-
gested that the benzene ring was attached to C - 10 .
Fig . 2 Key HMBC correlations for 1
ROESY correlationbetween H - 32 (δH 4 .80) and
H - 5a (δH 2 .29 ) , incombination with biogenetic con-
siderations, indicated that the configurationof 1 was the
same as that in furohyperforin . Thus the structure of 1
was assigned as shown in Fig . 1, named uraloidin A .
Experimental
General Optical rotationsweremeasuredon a HoribaSE-
PA-300 automatic digital polarimeter . IR spectra were conducted
on aBio-Rad FTS-135 spectrometer withKBr pellets . UV spectra
were obtained on a UV 2401 PC spectrometer . 1 H , 13 C NMR
and 2D NMR spectra were recorded on a DRX-500 NMR spec-
trometer with TMS as internal standard . MS data were obtained
on a VG Autospec-3000 spectrometer . HPLC separations were
performed on a HP 1100 apparatus equipped with a diode array
UV detector and ZORBAX SB-C18 ( 9 .4× 250 mm) column .
Column chromatographywere performed on silica gel ( 200 - 300
mesh, Qingdao Marine Chemical Inc . China) , Lichroprep RP-
18 gel (40 - 63μm, Merck, Dramstadt, Germany) and Sephadex
LH-20 (25 - 100μm, Amersham Biosciences, Sweden) . Thin-
layer chromatograph (TLC) was carried out on silica gel 60 F254
on glass plates (Merck) using various solvent systems .
Plant material The aerial parts of H. henryi subsp .
uraloideswerecollected fromJinpin, Yunnan Province, China in
July 2007 and identified by Associate Prof . Yu Shaowen at Kun-
ming Institute of Botany, Chinese Academy of Sciences .
Extraction and Isolation The dried and powdered aerial
parts of 4 .0 kgof H. henryi subsp . uraloideswereextracted with
MeOH for three times under roomtemperature and then concen-
trated under reduced pressure . The concentrated MeOH extract
(810 g) was dissolved in water and extracted with petroleum
ether and ethyl acetate step by step, obtained 110 g petroleum
ether extract and 45 g ethyl acetate extract . The petroleum ether
extractwas subjectedto silicagel column chromatograph withpe-
troleum ether-AcOEt (1∶0 to 5∶5 , then acetone) and obtained
fractions 1 - 7 . Each fraction was further purified by repeated CC
(silica gel , Rp-18 , Sephadex LH-20) then HPLC to give com-
pounds: 1 (16 .45 mg) , 2 (11 .5 mg) , 3 (120 mg) . The petro-
leumether extract was subjected to silica gel column chromato-
graph with petroleum ether-AcOEt (1∶1 to 4∶6 , then acetone)
and obtained fractions 1 - 4 . Eachfraction was further purifiedby
repeatedCC ( silica gel and Sephadex LH-20 ) to afford com-
pounds: 4 ( 160 mg) , 5 ( 9 .72 mg) , 6 (81 .6 mg) , 7 ( 62 .9
mg) , 8 (238.6 mg) .
uraloidin A (1) : C38 H50 O5 , colorless oil ; [α] 28D - 55 .0 ( c
0 .10 , CH3 OH) ; UV ( CH3 OH ) λmax ( logε) 204 ( 4.6 ) nm;
IR (KBr) νmax 3441 , 3074 , 2923 , 1638 , 1629 , 1510 , 1499 ,
1449 , 1408 cm- 1 ; 1 H and 13 C NMR data see Table 1; HRES-
IMS m?z 585 .3590 ( calcd for [M-H] - , 585 .3580) .
oleanolic ( 2) : C30 H50 O3 , white powder; 13 C NMR ( 100
MHz, CD3 Cl) : δC 38 .4 (t, C - 1) , 26 .9 (t, C - 2) , 78.9 ( d, C
- 3) , 39 .2 (s, C - 4) , 55 .2 (d, C - 5) , 18.2 ( t, C - 6 ) , 32.6
(t, C - 7) , 38.6 (s, C - 8) , 47 .6 ( d, C - 9) , 37 .0 (s, C - 10) ,
22.9 (t, C - 11 ) , 122 .3 ( d, C - 12) , 143 .7 (s, C - 13) , 41.1
(s, C - 14) , 27.6 (t, C - 15) , 23 .3 (t, C - 16) , 46 .3 (s, C -
17) , 41.6 ( d, C - 18) , 45 .9 (t, C - 19 ) , 30 .6 (s, C - 20) ,
33.8 (t, C - 21) , 32.4 (t, C - 22) , 28.0 (q, C - 23) , 15.5 ( q,
C- 24) , 15.2 (q, C - 25) , 16 .8 ( q, C - 26) , 25 .8 (q, C - 27) ,
181 .2 (s, C - 28) , 33.0 ( q, C - 29) , 23.5 (q, C- 30) .
betulinic acid ( 3 ) : C30 H48 O3 , white powder; 13 C NMR
(100MHz, CD3 Cl ) : δC 38 .7 (t, C - 1) , 27 .3 ( t, C - 2) , 78 .9
(d, C - 3) , 38 .8 (s, C - 4) , 55 .3 (s, C - 5) , 18 .2 (t, C -
6) , 34 .3 (t, C - 7) , 40.6 (s, C - 8) , 50 .5 (d, C - 9 ) , 37 .1
(s, C - 10) , 20 .8 ( t, C - 11) , 25 .4 (t, C - 12) , 38 .3 ( d, C
- 13) , 42 .4 (s, C - 14) , 29 .6 (t, C - 15) , 32 .1 ( t, C - 16 ) ,
56 .2 (s, C - 17) , 49 .2 ( d, C - 18) , 46.8 ( d, C - 19 ) , 150 .3
(s, C - 20) , 30 .5 ( t, C - 21) , 37 .0 (t, C - 22) , 27 .9 ( q, C
- 23) , 15 .3 (q, C - 24 ) , 16 .1 ( q, C - 25) , 16 .0 (q, C - 26) ,
14 .6 ( q, C - 27) , 179 .2 (s, C - 28) , 109 .6 ( t, C - 29) , 19 .3
(q, C - 30) .
quercetin (4) : C15 H10 O7 , yellow powder; 1 H NMR ( 400
MHz, acetone- d6 ) : δH 6 .25 ( 1H, d, J = 1 .5 Hz, H - 6 ) ,
7154 期 GUO Na et al . : A New Polyisoprenylated Benzoylphloroglucinol Derivative from Hypericumhenryi . . .
6 .51 (1H, d, J = 1.5 Hz, H - 8) , 7 . 82 (1H, d, J = 1.7 Hz,
H - 2′) , 6 . 98 ( 1H , d, J = 6 .8 Hz, H - 5′) , 7. 69 (1H, dd, J
= 1 .7 , 6 .8 Hz, H - 6′) ; 13 C NMR (100 MHz, acetone- d6 ) :
δC 146.9 (s, C - 2) , 136 .7 (s, C - 3 ) , 176 .5 ( s, C - 4 ) ,
157 .7 (s, C - 5) , 99 .1 ( d, C - 6 ) , 164 .9 ( s, C - 7) , 94 .4
(d, C - 8) , 162 .3 (s, C - 9) , 104 .1 (s, C - 10) , 121.4 (s, C
- 1′) , 115 .7 ( d, C - 2′) , 145.8 (s, C - 3′) , 148 .3 (s, C -
4′) , 116 .2 ( d, C - 5′) , 123.7 (d, C - 6′) .
1 , 5 , 6-trihydroxy-3-methoxyxanthone ( 5 ) : C14 H10 O6 ,
yellow powder; 1 H NMR (400 MHz, DMSO) : δH 6 .34 (1H, d,
J = 1 .6 Hz, H - 2 ) , 6 . 57 ( 1H , d, J = 1 .6 Hz, H - 4 ) , 6 . 93
(1H , d, J = 7 .0 Hz, H - 7) , 7. 50 (1H , d, J = 7 .0 Hz, H -
8) ; 13 C NMR (100 MHz, DMSO) : δC 162 .6 (s, C - 1 ) , 96 .7
(d, C - 2) , 165.9 (s, C - 3 ) , 92.6 ( d, C - 4) , 157 .2 (s, C
- 4a) , 132 .5 (s, C - 5) , 152 .1 (s, C - 6) , 113 .2 ( d, C - 7) ,
115 .9 ( d, C - 8) , 179.9 (s, C - 9) , 102 .3 (s, C - 9a) , 146 .2
(s, C - 10a) , 56 .0 ( q, C - OMe) .
1 , 3 , 5 , 6-tetrahydroxyxanthone ( 6 ) : C13 H8 O6 , yellow
powder; 1 H NMR (400 MHz, DMSO) : δH 6.22 (1H, d, J =
1 .7 Hz, H - 2 ) , 6. 41 ( 1H, d, J = 1 .7 Hz, H - 4) , 6 . 97
(1H , d, J = 7 .0 Hz, H - 7) , 7. 61 (1H , d, J = 7 .0 Hz, H -
8) ; 13 C NMR (100 MHz, DMSO) : δC 164 .7 (s, C - 1 ) , 98 .8
(d, C - 2) , 165.8 (s, C - 3 ) , 94.7 ( d, C - 4) , 158 .7 (s, C
- 4a) , 133 .1 (s, C - 5) , 152 .1 (s, C - 6) , 113 .6 ( d, C - 7) ,
117 .4 ( d, C - 8) , 181.1 (s, C - 9) , 103 .0 (s, C - 9a) , 146 .8
(s, C - 10a) .
kielcorin (7) : C23 H18 O7 , yellow powder; 1 H NMR ( 400
MHz, DMSO) : δH 7.16 ( 1H , s, H - 1 ) , 7 . 65 (1H, d, J =
8 .4 Hz, H - 5) , 7. 82 ( 1H, m, H - 6 ) , 8 . 17 ( 1H , dd, J =
1 .5 , 7 .9 Hz, H - 8 ) , 7 .06 (1H, d, J = 1.8 Hz, H - 2′) ,
6 . 83 (1H, d, J = 8 .1 Hz, H - 5′) , 6 . 90 ( 1H , dd, J = 1 .8 ,
8 .2 Hz, H - 6′) , 5 . 06 ( 1H, d, J = 7 .9 Hz, H - 7′) , 4 . 38
(1H , m, H - 8′) , 3 . 44 (1H, m, H - 9′a) , 3. 71 (1H, m, H
- 9′b) , 3. 78 ( 3H , s, OMe) , 3 . 84 (3H, s, OMe) ; 13 C NMR
(100 MHz, DMSO) : δC 96 .6 ( d, C - 1) , 147 .4 ( s, C - 2 ) ,
139 .6 (s, C - 3) , 132 .5 (s, C - 4) , 155 .3 (s, C - 4a) , 141 .2
(s, C - 10a) , 118 .0 (d, C - 5) , 134 .7 (d, C - 6) , 124 .2 (d,
C - 7) , 125.8 (d, C - 8) , 113 .9 (s, C - 8a) , 174 .7 (s, C -
9) , 105 .8 (s, C - 9a) , 126 .6 (s, C - 1′) , 112 .2 ( d, C - 2′) ,
145 .8 (s, C - 3′) , 147 .7 ( s, C - 4′) , 115 .5 ( d, C - 5′) ,
134 .7 ( d, C - 6′) , 76.3 (d, C - 7′) , 77 .8 ( d, C - 8′) , 59 .9
(t, C - 9′) .
1 , 3 , 5 , 6-tetrahydroxy-4-prenylxanthone (8) : C18 H16 O6 ,
yellow powder; 1 H NMR (400 MHz, DMSO) : δH 6 .48 (1H, s,
H - 2) , 6 . 89 (1H , d, J = 8 .7 Hz, H - 7) , 7 . 48 ( 1H , d, J =
8 .7 Hz, H - 8) , 3 . 21 (2H, d, J = 6 .8 Hz, H - 1′) , 5 . 17
(1H , t, J = 6 .4 Hz, H - 2′) , 1 . 71 , 1 .61 ( each3H, 3′- Me) ;
13 C NMR (100 MHz, DMSO) : δC 93 .3 ( d, C - 2 ) , 159 .8 (s,
C - 3) , 109.7 (s, C - 4) , 155 .1 (s, C - 4a) , 132 .4 (s, C -
5) , 151 .8 (s, C - 6) , 113.0 ( d, C - 7 ) , 115 .9 ( d, C - 8 ) ,
112 .9 (s, C - 8a) , 179 .7 (s, C - 9 ) , 101 .2 ( s, C - 9a) ,
146 .0 ( s, C - 10 ) , 21 .0 ( t, C - 1′) , 122 .4 ( d, C - 2′) ,
130 .6 (s, C - 3′) , 17 .7 ( q, C - 4′) , 25 .5 ( q, C - 5′) .
Acknowledgements: The authors are grateful to the Analytical
Group, Laboratoryof Phytochemistry, Kunming Institute of Bota-
ny, CAS for the spectral measurements .
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