全 文 ：Xerophinoid C , 旱生香茶菜中一个新的二萜糖苷化合物 ?
翁稚颖1 , 2 , 3 , 黄胜雄1 , 2 , 韩全斌1 , 肖伟烈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 中国科学院研究生院 , 北京 100039 ; 3 昆明医学院 , 云南 昆明 650031)
摘要 : 从旱生香茶菜 ( Isodon xeropene) 枝叶的乙酸乙酯部位分离到一个新的松香烷型二萜苷类化合物。通
过现代波谱技术 , 确定其结构为 16 , 18-二羟基-7 , 15 ( 17 )-二烯-对映-松香烷-3α- O-β-D-吡喃葡萄糖苷。
关键词 : 旱生香茶菜 ; 二萜糖苷 ; Xerophinoid C
中图分类号 : Q 946 文献标识码 : A 文章编号 : 0253 - 2700 (2007) 02 - 256 - 03
Xerophinoid C , a New Diterpene Glucoside Derivative
from Isodon xerophilus (Labiatae) *
WENG Zhi-Ying
1 , 2 , 3
, HUANG Sheng-Xiong
1 , 2
, HAN Quan-Bin
1
,
XIAO Wei-Lie1 , SUN Han-Dong1 * *
( 1 State Key Laboratory of Phytochemistry and Plant Resources in West China, Kunming Instituteof Botany, ChineseAcademy of
Sciences, Kunming 650204 , China; 2 Graduate School of the Chinese Academy of Sciences, Beijing 100039 , China;
3 Kunming Medical College, Kunming 650031 , China)
Abstract: A new ent-abieta-glucopyranoside was isolated fromthe ethyl acetate extract of Isodon xerophilus . The structure
was determined as 16 , 18-dihydroxy-7 , 15 (17) -dien-ent-abieta-3α- O-β-D-glucopyranoside by spectral methods .
Key words: Isodon xerophilus; Diterpene glucoside; Xerophinoid C
Isodon xerophilus ( C . Y . Wu & H . W . Li) H .
Hara is a perennial shrub native to Yunnan province .
The leaves of this plant have been used as a folk medi-
cine for the treatment of sore throat, inflammation, and
influenza . This plant is belong to the Isodongenus be-
ing rich in ent-kaurane diterpenoids ( Sun et al .
2001) . It’sthe first time to get an abietane deterpene
from I . xerophilus (Li et al . 2002) .
Results and Discussion
Xerophinoid C was isolated as brown amorphous
solid [α]28D - 29 .6° ( c 0 .65 MeOH ) . Its molecular
formula was deduced to be C26 H42 O8 on the basis of
NMR data and fromthenegativeHRESIMS that showed
an ion peak [M + Na] + at m?z 505 .2778 . Intense
absorption bands at 3419 , and 1645 cm- 1 were ob-
served in the IR spectrum of 1 , in accord with the pr-
esenceof hydroxyl groups and C = C double bond, re-
spectively . The 1 H NMR spectrum of 1 exhibited sig-
nals for aβ-glucopyranoside moiety in the structure .
The anomeric proton appeared atδH 4 .29 (1H, d, J =
7.6 Hz, H - 1′) , which correlated in the 1 H-1 H COSY
spectrumwith a downfield double doublet signal atδH
3.16 (1H, dd, J = 9.5, 7 .6 Hz, H - 2′) . In thesame
1 H-1 H COSY experiment, the H - 3′, H - 4′, H - 5′,
and H - 6′signals could be assigned unambiguously
云 南 植 物 研 究 2007 , 29 (2) : 256～258
Acta Botanica Yunnanica

?
?? ?Author for correspondence . Tel : + 86 - 871 - 5223251 ; E-mail : hdsun@ mail . kib. ac. cn
Received date: 2006 - 09 - 07 , Accepted date: 2006 - 10 - 11
作者简介 : 翁稚颖 (1975 - ) 女 , 博士研究生 , 主要从事天然药物化学和药理学研究。 ?
Foundation item: This study wasfinancially supported by theNatural ScienceFoundation of Yunnan Province ( 2004C0008Z) and theNational Natu-
ral Science Foundation of China (20502026 to Q .-B .Han .)
(Fig . 1 ) . The characteristic 13 C NMR signals atδC
102 .9 ( d) , 74 .9 ( d) , 77 .5 ( d) , 72 .7 ( d) , 78 .2
(d) , and 63 .4 ( t) also indicated the presence of a
glucopyranosyl group .
The structureof aglycon and positions of the sugar
moiety could be deduced from a series of 2D NMR
measurements, including its
1
H-
1
H COSY , ROESY ,
HMQC , and HMBC spectra . The structure of the agly-
con was shown to be a diterpene from the presence of
20 carbon signals in the13 C NMR spectrumin addition
to the carbon signals of the sugar moiety . Moreover,
the 1 H NMR spectrum showed only two tetrial methyl
signals atδH 0 .88 and 0 .77 , while the 13 C NMR and
DEPT spectra showed one trisubstituted double bond
(δC 138 .2 , s andδC 121 .2 , d) , and one 1 , 1-disub-
stituted double bond (δC 155 .0 , s andδC 107 .9 , t) .
Three oxygenated carbons found atδC 80 .5 ( d) , 65 .2
( t) and 64 .5 ( t) were correlated in the HMQC spec-
trumwith theproton signals atδH 3 .67 (1H, dd, J =
10 .8 , 5 .2 Hz, H - 3) , δH 4 .03 ( 2H, br s, H2 - 16) ,
andδH 3 .57 and 3 .17 ( each 1H , d, J = 11 .7 Hz, H2
- 18) , respectively .These NMR datatogether with the
molecular formula showed that the diterpene aglycon
must be tricyclic . Interpretation of the
1
H-
1
H COSY
and HMBC data readily suggested that it was an ent-
abietane diterpenoid . Observation of HMBC correla-
tions fromH - 3 to C - 1 , C - 18 , C - 19 , and C - 5 ,
and fromH2 - 16 to C - 15 , C - 17 , and C - 13 allowed
for the assignment of a hydroxyl group at C - 3 , C - 18
and C - 16 , respectively, while HMBC correlations
from H - 7 (δH 5 .40 , br s) to C - 8 , C - 9 , and C - 5
led to the location of a double bond at C - 7 and C - 8
(Figure 1) . The position of the sugar moietiy was de-
termined fromthe HMBC correlationsof H - 3 withC -
1′and H - 1′with C - 3 . The ROESY correlations be-
tween H - 3 and H2 - 18 indicated theβ-orientation of
Fig . 1 COSY ( — ) and Selected HMBC ( → )
correlations of compound
H - 3 . Its acid hydrolysis afforded D-glucose, which
was detected by TLC and identified by its optical rota-
tion value . Accordingly, xerophinoid C was elucidat-
ed as 16 , 18-dihydroxy-7 , 15 (17 ) -dien-ent-abieta-
3α- O-β-D-glucopyranoside .
Acid Hydrolysis . Xerophinoid C ( 10 mg) was
heated with 2 mL of 2 .5 M HCl at 65℃ for 4 h . After
4 mL of H2 O was added and the mixture was extracted
with EtOAc, the aqueous phasewas evaporated invac-
uo to yield 3 mg of D-glucose, which was detected by
TLC and optical rotation, [α]19D + 58 .5° ( c 0 .20 ,
H2 O) .
Experimeatal
General experimental procedures All melting points
weremeasured on an XRC-1 micro melting point apparatus and
are uncorrected . Optical rotationswere taken on a Perkin-Elmer
model 241 polarimeter . IR spectrometer weremeasured in aBio-
Rad FTS-135 spectrometer with KBr pellets . MS were recorded
on a VG Auto spec-3000 spectrometer or on a Finnigan MAT 90
instrument . 1D and 2D NMR spectra were taken on a Bruker
AM-400 and a Bruker DRX-500 instrument with TMS as internal
standard, respectively . Semipreparative HPLC was performed on
an Agilent 1100 liquid chromatograph with a Zorbax SB-C18 ,
9 .4 mm× 25 cm column . Column chromatography were per-
formed either on silica gel ( 200 - 300 mesh . Qingdao Marine
Chemical Inc . , China) , silica gel H (10 - 40μm, Qingdao Ma-
rineChemical Inc . , China) , or Lichroprep RP-18 gel (40 - 63
μm, Merck, Dramstadt, Germany) .
Plant material The leaves of I . xerophilus were collected
in Yuanyang prefecture of Yunnan Province in November, 1998 ,
and air-dried . The identityof plant material was verifiedby Prof .
Zhong-WenLin, and a voucher specimen (KIB 98 - 11 - 25 Lin)
was deposited at the State Key Laboratory of Phytochemistry and
Plant resources in West China, Kunming Institute of Botany,
Chinese Academy of Sciences .
Extraction and isolation The dried and powdered leaves
7522 期 WENG Zhi-Ying et al .: Xerophinoid C, a New Diterpene Glucoside Derivative from . . .
(1. 5 kg) were extractedwith 70% Me2 CO and filtered . The fil-
trate was concentrated and extracted with EtOAc and n-BuOH
successively . The EtOAc layer (50 g) was decolourized on MCI-
gel CHP 20P (90% CH3 OH-H2 O, 100% MeOH ) . The 90%
CH3 OH fraction (46 g) waschromatographed over silicagel (200
- 300 mesh, 330 g) , eluted in a step gradient manner with
CHCl3 -acetone (1∶0 to 0∶1) to yield fractions Ⅰ-Ⅶ . Fraction
Ⅵ was further purified by chromatography over RP-18 ( CH3 OH-
H2 O, from 30% to 100% ) and further submitted to repeated
column chromatographyover silica gel ( petroleum ether-Me2 CO,
8∶2 - 1∶1) to get compound 1 (45 mg) .
Xerophinoid C (1) C26 H42 O8 , brown amorphous solid
[α] 28D - 25.52°( c= 0 .15 , MeOH) . Positive ESIMS: m?z 505
[M + Na] + ; positive HRESIMS [M + Na] + m?z 505 .2778
(calcd for C26 H42 O8 Na, 505 .2777) . UVλMeOHmax nm ( logε) : 203
(3 .84) . IRνKBrmax cm- 1 : 3467 , 2954 , 1748 , 1705 , 1647 , 1432 ,
1371 , 1232 , 1288 , 1049 , 1014 , 960 . 1 H NMR ( pyridine-d5 )
δ1 .76 , 1 .17 ( each 1H , overlap, H2 - 1 ) , 1 . 68 , 1 .64 ( each
1H, overlap, H2 - 2) , 3 .67 (1H, dd, J = 10 .8 , 5 .2 Hz, H -
3) , 1 . 68 (1H, overlap, H - 5) , 1 . 78 , 1 .73 (each 1H , over-
lap, H2 - 6) , 5 .40 (1H , br s, H - 7) , 1 . 75 ( 1H , overlap, H
- 9) , 1 .81 , 1 .21 ( each 1H, overlap, H2 - 11 ) , 1. 85 , 1 .23
(each 1H, overlap, H2 - 12 ) , 1 . 48 ( 1H , m, H - 13 ) , 2 . 34
(1H, br d, J = 10 .9 Hz, H - 14a) , 1 . 86 (1H, overlap, H -
14b) , 4 . 03 (2H, br s, H2 - 16) , 5 . 00 , 4 .73 ( each1H, br s,
H2 - 17) , 3 . 57 , 3 .17 ( each1H, d, J = 11 .7 , H2 - 18 ) , 0 . 77
(3H , s, H3 - 19) , 0 . 88 (3H, s, H3 - 20) , 4. 29 (1H, d, J =
7 .6 Hz, H - 1′) , 3. 16 ( 1H , dd, J = 9 .5 , 7 .6 Hz, H - 2′) ,
3 . 30 ( 1H, overlap, H - 3′) , 3 .00 ( 1H, overlap, H - 4′) ,
3 . 35 (1H, m, H - 5′) , 3 .89 (1H , dd, J = 11 .2 , 2 .0 , H - 6′
a ) , 3 . 52 (1H, dd, J = 11 .2 , 2 .0 , H - 6′b ) . 13 C NMR
(pyridine-d5 ) δ: 38 .8 (t, C - 1 ) , 24 .4 ( t, C - 2) , 80 .5 ( d,
C- 3) , 43 .5 (s, C - 4 ) , 42 .4 ( d, C - 5 ) , 23 .6 ( t, C - 6 ) ,
121 .2 ( d, C - 7) , 138 .2 (s, C - 8 ) , 53 .6 ( d, C - 9) , 35 .9
(s, C - 10) , 26 .7 ( t, C - 11) , 32 .9 (t, C - 12) , 42 .6 ( d, C
- 13) , 42 .1 ( t, C - 14) , 155 .0 (s, C - 15) , 65.2 ( t, C - 16) ,
107 .9 (t, C - 17) , 64 .5 ( t, C - 18 ) , 13.6 ( q, C - 19 ) , 16 .2
(q, C - 20) , 102 .9 ( d, C - 1′) , 74 .9 ( d, C - 2′) , 77 .5 ( d,
C - 3′) , 72 .7 (d, C - 4′) , 78 .2 ( d, C - 5′) , 63 .4 (t, C - 6′) .
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