全 文 ：黑盖地花菌中一个新的 grifolin 衍生物?
张 凌1 , 2 , 董泽军1 , 刘吉开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 : 从黑盖地花菌 ( Albatrellus yasuda) 中分离得到 4 个 grifolin衍生物 : grifolene ( 1) , grifolin (2) , grifolic
acid (3) 和 neogrifolin (4) , 其中 1 为新化合物 , 它的化学结构通过波谱学方法鉴定。
关键词 : 黑盖地花菌 ; Grifolin; Grifolene
中图分类号 : Q 936 文献标识码 : A 文章编号 : 0253 - 2700 (2009) 02 - 187 - 03
A New Grifolin Derivative from the Mushroom
Albatrellus yasuda (Polyporaceae)
ZHANG Ling1 , 2 , DONG Ze-Jun1 , LIU Ji-Kai1 **
(1 State KeyLaboratory of Phytochemistry and Plant Resources in West China, Kunming Instituteof Botany, Chinese Academy of Sciences,
Kunming 650204 , China; 2 Graduate University of Chinese Academy of Sciences, Beijing 100049 , China)
Abstract : A newgrifolin derivative, named grifolene (1) , together withgrifolin (2) , neogrifolin (3) andgrifolic acid (4)
was isolated from the fruiting bodies of thefungus Albatrellusyasuda . The structureof 1 was elucidated onthe basis of ex-
tensive spectroscopic analysis .
Key words: Albatrellus yasuda; Grifolin; Grifolene
The fungus Albatrellus yasuda of the family Poly-
poraceae is mainly distributed in Yunnan, Sichuan,
Tibet and Fujian Provinces in China, which is a dis-
tinctive species by its pale yellow petaloid basidiomes,
simple septate hyphae and small non-amyloid ( Zheng
et al. , 2008 ) . By now, no any chemical investigations
have been reported on it . As part of our efforts to dis-
cover thestructurally diverseandbiologically significant
metabolites fromhigher fungi ( Liu, 2005 , 2006) , the
investigation of the fruitingbodies of A. yasuda has led
to the isolation of a newgrifolin derivative, named gri-
folene (1) , together with grifolin (2) , neogrifolin (3 )
and grifolic acid (4) .
Results and Discussion
Compound 1 , obtained as yellowoil , has amolec-
ular formula of C24 H32 O4 based on HRESI-MS ( pos .) ,
showing a quasi-molecular ion at m?z 385 .2369 ( cal-
cd . for C24 H33 O4 , 385 .2378) , requiring nine degrees
of unsaturation . The IR spectrum displayed absorption
bands of hydroxyl ( 3445 cm- 1 ) and double bond
(1650 cm- 1 ) groups . The 1 H NMR spectrum ( Table
1) of 1 in CDCl3 showed signals for threevinyl methyls
1 .83 ( 3H , s) , 1 . 82 ( 3H, s) , 1 . 58 ( 3H, s) , a
phenyl methyl 2 .46 (3H , s) , four substituted olefinic
protons, 6 . 13 (1H, d, J = 15 .5) , 5 . 61 (1H, dt, J
云 南 植 物 研 究 2009 , 31 (2) : 187～189
Acta Botanica Yunnanica DOI : 10 .3724?SP. J . 1143 .2009.08234
?
?? ?Author for correspondence; Tel : + 86 - 871 - 5216327 ; E-mail : jkliu@ mail .kib. ac. cn
Received date: 2009 - 01 - 04 , Accepted date: 2009 - 02 - 25
作者简介 : 张凌 ( 1982 - ) 女 , 在读硕士研究生 , 从事高等真菌化学研究。 ?
Foun ?dation items: National Basic Research Program of China ( 973 Program, 2009CB522300 ) , National Natural Science Foundation of China
(30830113 ) , and ChineseAcademy of Sciences ( KSCX1-YW-R-24 ; KSCX2-YW-G-025)
= 15.5, 7 .0) , 5 .27 (1H, t, J = 7 .1) , 5. 11 (1H, t,
J = 6.8) , and an aromatic proton 6 .23 ( 1H, s) . The
NMR spectra were similar to those of grifolic acid (4 )
(Mahiou et al. , 1995) , and the obvious NMR differ-
ences were as follows: the signals at δ 131 .0 ( s) ,
124.5 (d) , 26 .7 ( t) , 25 .7 ( q) , 17.7 (q) due to the
terminal isopentenyl unit in 4 were absent and replaced
by newlyarising resonances atδ142.2 (s) , 133 .9 (d) ,
128.9 (d) , 114.5 ( t) , 18.7 ( q) in 1 . In combination
with the HMBC correlations ( Table 1 ) : fromδH 1.83
(3H, s, H - 12′) toδC 133.9 ( d, C - 10′) and 114 .5
(t, C - 13′) , fromδH 4.88 ( 2H, s, H - 13′) toδC
133.9 ( d, C - 10′) and 18.7 ( q, C - 12′) , wesuggest-
ed that there was a 1, 3-pentadiene unit instead of the
isopentenyl group . Furthermore, thepositionof an addi-
tional methoxy group can be easily determined at the
carboxyl group in aromatic ring by the HMBC correla-
tions ( Table 1 ) . Consequently, the structure of 1 was
established as shown in Figure 1, named grifolene .
Comparison of the physical and spectroscopic data
with the reported data allowed for the identification of
compounds 2, 3 and 4, as grifolin (2) (Mahiou et al. ,
1995) , neogrifolin ( 3 ) ( Nukata et al. , 2002 ) and
grifolic acid (4) (Mahiou et al. , 1995) , respectively .
Fig . 1 Structures of compounds 1 - 4
Table 1 NMR Spectral Data for Compound 1 in CDCl3
No . δC δH HMBC No . δC δH HMBC
1 ?111 .3 (s) 6′ 124 <. 6 ( d) 5 . 11 (1H , t, 6 . 8 ) C-4′, C-7′, C-14′
2 ?162 .6 (s) 7′ 134 @. 4 ( s)
3 ?105 .1 (s) 8′ 42 1. 9 ( t) 2 . 75 (2H , d, 7 . 0) C-6′, C-10′
4 ?159 .4 (s) 9′ 128 <. 9 ( d) 5 .61 (1H , dt, 15 .5, 7 B.0) C-7′, C-11′
5 ?111 .4 (d) 6 f. 23 ( 1H , s) C-1 7, C-3 , C-8 10′ 133 <. 9 ( d) 6 . 13 (1H , d, 15 .5) C-8′, C-12′, C-13′
6 ?140 .8 (s) 11′ 142 @. 2 ( s)
7 ?172 .7 (s) 12′ 18 ). 7 ( q) 1 . 83 (3H , s) C-10′, C-13′
8 ?24 .2 ( q) 2 f. 46 ( 3H , s) C-1 7, C-5 13′ 114 D. 5 ( t) 4 . 88 (2H , s) C-10′, C-12′
1 ?′ 22 .0 ( t) 3 f. 43 ( 2H , d, 7 I. 1 ) C-2 7, C-4 , C-3′ 14 ?′ 16 ). 2 ( q) 1 . 58 (3H , s) C-6′, C-8′
2 ?′ 121 .5 (d) 5 f. 27 ( 1H , t, 7 9. 1) C-3 7, C-4′, C-15′ 15 ?′ 16 ). 2 ( q) 1 . 82 (3H , s) C-2′, C-4′
3 ?′ 138 .9 (s) -OCH3 U51 ). 8 ( q) 3 . 92 (3H , s) C-7
4 ?′ 39 .6 ( t) 2 f. 09 ( 2H , t, 6 9. 3) C-2 7′, C-6′ 2-OH 12 . 10 (1H , s) C-1 , C-2 , C-3
5 ?′ 26 .3 ( t) 2 b. 13 (2H , dt, 6 4. 8, 6 .3) C-3 7′, C-7′
881 云 南 植 物 研 究 31 卷
Experimental
General UV spectra were recordedon a Shimadzu UV-
2401PC spectrophotometer . IR spectrum was obtained with a
Bruker Tensor 27 FT-IR spectrometer with KBr pellets . NMR
spectra were recorded with a Bruker DRX-500 spectrometer in
CDCl3 (δH = 7 .26 ppm, δC = 77 .00 ppm) at roomtemperature .
EIMS was taken on a Finnigan-MAT 90 instrument and HRESI-
MS recorded with API QSTAR Pulsar i spectrometer . Silica gel
(200 - 300 mesh, Qingdao Marine Chemical Inc . , China) and
Sephadex LH-20 ( Amersham Biosciences, Sweden) were used
for column chromatography . Fractions were monitored by TLC
and spots were visualized by heating silica gel plates immersed
with vanillin-H2 SO4 in ethanol .
Fungal material Thefresh fruiting bodies of A. yasuda
were purchased at the wild mushroommarket in Nanhua County
of Yunnan Province, China, inSeptember 2007 and identifiedby
Prof . Dr . YANG Zhu-Liang . A voucher specimen has been de-
posited in the Herbarium of Kunming Institute of Botany, CAS .
Extraction and isolation The fresh fruiting bodies of
A. yasuda were immersed in ethanol (1∶1 , v?v) and left at room
temperature . The ethanol extract (250 g) was applied on a silica
gel column, which eluted stepwise with petroleum ether?acetone
solvent system . Fraction 1 (2 .1 g) frompetroleum ether?acetone
(20∶1 , v?v) was isolated by silica gel ( CHCl3?petroleum ether
= 10∶1 , v?v) to afford 2 (1 .9 g) . Fraction 2 (1 .2 g) frompe-
troleum ether?acetone (15∶1 , v?v) was isolated by silica gel
(petroleum ether?acetone = 5∶1 , v?v) to afford 3 ( 34 mg) .
Fraction 3 (3 .8 g) from petroleum ether?acetone (10∶1 , v?v)
was isolated by silica gel (petroleum ether?acetone= 10∶1 , v?v)
to afford4 (2 .0 g) and a residuemainly containing 1 (petroleum
ether?acetone= 5∶1 , v?v) , which was further purified on Sepha-
dex LH-20 ( CHCl3?MeOH , 1?1) together with silica gel ( petro-
leumether?CHCl3 = 100∶1 , v?v) toyield purecompound 1 (3 .0
mg) as yellow oil .
Grifolene ( 1 ) : yellow oil . UV ( CHCl3 ) : λmax ( logε)
268 (3 .98) , 305 ( sh, 3 . 53 ) nm; IR (KBr) ν3445 , 2931 ,
1650 , 1454 , 1441 , 1319 , 1275 , 1196 , 1157 , 981 cm- 1 . NMR
data and key HMBC correlations: see Table 1 . EIMS: m?z
( % ) = 384 (1) [M] + , 285 (3 ) , 271 ( 6) , 248 (11 ) , 233
(14) , 217 ( 79) , 175 ( 26) , 163 (100) , 147 (16 ) . HRESI-
MS ( pos .) : 385 .2369 (calcd . for C24 H33 O4 , 385 .2378) .
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9812 期 ZHANG Ling et al. : A New Grifolin Derivative fromthe Mushroom Albatrellus yasuda (Polyporaceae)