全 文 ：鄂西香茶菜中一个新的苯取代二酮?
赵 勇1 , 2 ,3 , 黄胜雄1 , 杨黎彬1 , 3 , 李丽梅1 ,
肖伟烈1 , 普建新1 , 孙汉董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 云南师范大学化学化工学院 , 云南 昆明 650092; 3 中国科学院研究生院 , 北京 100049 )
摘要 : 从青海产鄂西香茶菜 ( Isodon henryi ) 的叶中分离得到 1 个新的苯取代二酮 , 利用波谱技术鉴定其结
构。同时 , 还得到了 8 个已知化合物。
关键词 : 唇形科 ; 鄂西香茶菜 ; 苯基二酮
中图分类号 : Q 946 文献标识码 : A 文章编号 : 0253 - 2700 (2008) 02 - 243 - 03
A New Phenyldione from Isodon henryi (Labiatae)
ZHAO Yong
1 , 2 , 3
, HUANG Sheng-Xiong
1
, YANG Li-Bin
1 , 3
, LI Li-Mei
1
,
XIAO Wei-Lie1 , PU Jian-Xin1 , SUN Han-Dong1 **
(1 State KeyLaboratory of Phytochemistry and Plant Resources in West China, Kunming Instituteof Botany, Chinese Academy of Sciences,
Kunming 650204 , China; 2 Collegeof Chemistry and Engineering, Yunnan Normal University, Kunming 650092 , China;
3 GraduateUniversity of Chinese Academy of Sciences, Beijing 100049 , China)
Abstract : A newphenyldionenamed henrydione (1) , together witheight known compounds (2 - 9) were isolated fromthe
ethyl acetate extract of Isodon henryi . The structure was elucidated on the basis of extensive NMR and MS means .
Key words: Labiatae; Isodon henryi ; Phenyldione
In past studies, avarietyof structurally interesting
diterpenoids with various biological activities, such as
antibacterial , anti-inflammatory and anticancer activi-
ties (Sun et al. , 2001) , werediscovered frommedici-
nal plants of thegenus Isodon (Labiatae) . In our con-
tinuing efforts to discover morenovel naturally bioactive
diterpenoids, we investigated the acetone extract of the
leaves of Isodon henryi collected from Qinghai prov-
ince, and isolated a series of ent-kaurane diterpenoids
( Zhao et al. , 2007 ) . Besides, a new phenyldione,
named henrydione, together with eight known com-
pounds (2 - 9) , cirsiliol (2 ) (Linuma et al. , 1980) ,
oleanolic acid (3) ( Tunmann and Baversfeld, 1975 ) ,
ursolic acid ( 4 ) ( Brieskom and Eberhardt, 1953 ) ,
asiatic acid (5 ) (Zhang et al. , 1997 ) , 5-hydroxy-7-
methoxychromone ( 6 ) ( Vasconcelos et al. , 1998 ) ,
10-undecenoic acid (7 ) ( Sharma et al. , 1995 ) , ros-
marinic acid ( 8 ) ( Eicher et al. , 1996 ) and methyl
rosmarinate ( 9 ) ( Lee et al. , 1992 ) were obtained .
Henrydione, as a new natural occurring product, was
the first isolation in thegenus of Isodon . Here, were-
ported the isolation and elucidation of this new com-
pound .
Henrydione (1) , obtained as an amorphoussolid,
云 南 植 物 研 究 2008 , 30 (2) : 243～245
Acta Botanica Yunnanica

?
?? ?Author for correspondence; Tel : + 86 - 871 - 5223251 ; E-mail : hdsun@ mail . kib. ac. cn
Received date: 2007 - 08 - 21 , Accepted date: 2007 - 11 - 29
作者简介 : 赵勇 ( 1967 - ) 男 , 在读博士研究生 , 主要从事天然产物化学研究。 ?
Foundation item: This study was financially supported by theNatural Science Foundation of Yunnan Province (2004C0008Z)
has the molecular formula C11 H12 O5 from HRESIMS
( m?z: 247 .0589 [M + Na] + , calcd . 247 .0582) . IR
absorptions at 3430 , 1711 cm- 1 indicated the presence
of hydroxyl and carbonyl groups, respectively . The
13
C
NMR spectrum of 1 ( Table 1 ) along with analysis of
the DEPT spectra displayed 11 carbon signals corre-
sponding to one methyl , onemethylene, oneoxygenat-
ed methine (δ70 .1) , two carbonyl carbons (δ206 .4 ,
199 .0 ) and six phenyl carbons . The typical signals at
δ7 .91 (1H, d, J = 8 .2 Hz) , 7 . 24 ( 1H, d, J = 8 .2
Hz) and 8 .21 ( 1H, br s) observed in the 1 H NMR
spectrumrevealed the presenceof 1 , 2 , 4-trisubstitut-
ed phenolic moiety, which was also supported by the
HMBC correlations from H - 2′(δ8 .21) to C - 3′(δ
147 .5 ) , C - 4′(δ150 .2) and C - 6′(δ123 .8) , from
H - 5′(δ 7 .24 ) to C - 1′(δ 126 .9 ) , C - 3′ (δ
147 .5) and C - 4′(δ 150 .2 ) , and from H - 2′(δ
8 .21) to C - 6′(δ123 .8) .The side-chain of phenolic
cycle was established by the HMBC correlations fromH
- 2 (δ5 .94 ) and H - 3 (δ3 .04 , 3 .22) to C - 1 (δ
199 .0 ) , fromH - 2 (δ5 .94) , H - 3 (δ3 .04 , 3 .22)
and H - 5 (δ 2 .16 ) to C - 4 (δ 206 .4 ) . The cross-
peaks of H - 2′(δ8 .21) and H - 6′(δ7 .91) with C
- 1 (δ199 .0) (Fig . 1) helped in assigning the attach-
ment of the side-chain to be at C - 1′. Thus, com-
pound 1 was determined as 1 -( 3′, 4′-dihydroxyphe-
nyl )-2-hydroxypentane-1 , 4-dione .
Fig . 1 Key HMBC correlations for 1
The known compounds ( 2 - 9 ) were identified to
be cirsiliol ( 2) , oleanolic acid (3) , ursolic acid (4) ,
asiatic acid ( 5 ) , 5-hydroxy-7-methoxychromone ( 6 ) ,
10-undecenoic acid ( 7 ) , rosmarinic acid ( 8 ) and
methyl rosmarinate (9) by comparison of their spectral
data with literaturevalues .
Table 1 1 H and 13 C NMR spectral data of compound 1 in C5 D5 N
( 1 H: 400 MHz; 13 C: 100 MHz; δ: ppm)
No .
1 ?
C H
1 ?199 a. 0 (s)
2 ?70 J. 1 ( d) 5 . 94 ( dd, 4 . 5 , 7 . 9 )
3 ?49 R. 0 ( t) 3 ?. 04 ( dd, 8 ?. 0 , 16 .1 )
3 ?. 22 ( dd, 4 ?. 4 , 16 .1 )
4 ?206 a. 4 (s)
5 ?30 J. 7 ( q) 2 . 16 (s)
1 2′ 126 a. 9 (s)
2 2′ 116 \. 9 ( d) 8 ?. 21 ( br s)
3 2′ 147 a. 5 (s)
4 2′ 150 a. 2 (s)
5 2′ 116 \. 2 ( d) 7 ?. 24 ( d, 8 . 2 )
6 2′ 123 \. 8 ( d) 7 ?. 91 ( br d, 8 P. 2)
Experimental
General Experimental Procedures Optical rotationswere
measured using a Perkin-Elmer model 241 polarimeter . IR was
recorded on a Bio-Rad FTS-135 spectrometer with KBr pellets .
MS wereobtained on a VG Auto spec-3000 spectrometer or on a
Finnigan MAT 90 instrument . 1D and 2D NMR spectra were
measured on Bruker AM-400 and Bruker DRX-500 instrument
with TMS as internal standard, respectively . The EtOAc layer
was decolored on MCI-gel CHP 20P . Column chromatograph
were performed either on silica gel ( 200 - 300 mesh . Qingdao
MarineChemical Inc ., China) , Lichroprep RP-18 gel (40 - 63
μm, Merck, Dramstadt, Germany) and Sephadex-LH-20 ( 25 -
100μm, AmershamBiosciences, Sweden) . Thin- layer chromato-
graph (TLC) was carried out on silica gel 60 F254 on glass plates
(Merck) using various solvent systems .
Plant Material The leaves of I . henryi were collected in
MinheCounty, Qinghai province, People′s Republic of China,
in July 2005 and identified by Prof . LI Xi-Wen, and a voucher
specimens (KIB 200507014 ) has been deposited in theStateKey
Laboratoryof Phytochemistry and Plant ResourcesinWest China,
Kunming Institute of Botany, Chinese Academy of Sciences .
Extraction and Purification The milled plant material
(3. 5 kg) was extracted with 70% aq . acetone (3×20 L ) at r .
t . overnight . The extractwas partitioned between H2 O and EtO-
Ac . The EtOAc layer ( 81 g) was chromatographed on MCI-gel
CHP 20P ( eluted with 90 % CH3 OH-H2 O, then 100%
CH3 OH) . The 90 % CH3 OH fraction ( 58 g) was chromato-
graphed over silicagel (200 - 300 mesh) , eluted ina step gradi-
ent manner with CH3 Cl3 -Me2 CO ( 1∶0 to 0∶1 ) to afford seven
fractions (A-G) . Fraction B ( 4. 53 g) was isolated by silica gel
column chromatography [200 - 300 mesh, petroleum-acetone (9∶
442 云 南 植 物 研 究 30 卷
1 - 1∶1 ) ] to give three isolates 3 (32 mg) , 4 (4 mg) and 5 ( 17
mg) . Fractions C (3 .60 g) was chromatographed over silica gel
(200 - 300 mesh) and divided into eight subfractions (1 - 8 ) .
Compound1 (8 mg) was obtained by RP-18 (eluted with 42%
CH3 OH) from fraction C - 2 ( 173 mg) . Compound 2 (20 mg)
and 6 (17 mg) was purified by Sephadex-LH-20 fromfractions C
- 3 (1 .14 g) . Fraction D (2 . 3 g) was further purified by silica
gel column chromatography [200 - 300 mesh, eluted with petro-
leum-acetone (3∶1) ] to give compound 8 (5 mg) and compound
9 (5 mg) . Fraction E (2 . 6 g) afforded compound 7 (7 mg) by
silica gel column chromatography [ 200 - 300 mesh, eluted with
petroleum-acetone ( 3∶1 ) ] and RP-18 ( eluted with 30%
CH3 OH) successively .
2-hydroxy-1 - ( 3′, 4′-dihydroxyphenyl )-pentane-1 , 4-di-
one (1) : an amorphoussolid; [α] 25D + 145 .7 ( c 0.1 , C5 H5 N) ;
IRνKBrmax cm- 1 : 3430 , 2923 , 1711 , 1612 ; ESIMS m?z: 247 [M
+ Na] + ( 100 ) , 471 [ 2M + Na] + ( 6 ) ; HRESIMS m?z:
247 .0589 ( cacld . for C11 H12 O5 Na 247 .0582 ) ; 1 H NMR
(C5 D5 N, 400 MHz) and 13 C NMR (C5 D5 N, 100 MHz) data see
Table 1 .
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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5422 期 ZHAO Yong et al. : A New Phenyldione from Isodon henryi (Labiatae)