全 文 ：半枝莲的一个新的克罗烷二萜?
朱 锋1 , 2 , 刘玲丽1 , 邸迎彤1 , 郝小江1 * * , 何红平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 : 从半枝莲 ( Scutellaria barbata) 植物地上部分的甲醇提取物中分离得到一个新的克罗烷二萜。通过现
代波谱技术鉴定为 15β-甲氧基-6α- O-乙酰基-19- O-丙酰基-4α, 18 ; 11 , 16; 15 , 16-环氧-新克罗烷二萜。
关键词 : 半枝莲 ; 唇形科 ; 克罗烷二萜
中图分类号 : Q 946 文献标识码 : A 文章编号 : 0253 - 2700 (2009) 05 - 474 - 03
Scutellin A , a New Neoclerodane Diterpenoid from
Scutellaria barbata (Labiatae)
ZHU Feng
1 , 2
, LIU Ling-Li
1
, DI Ying-Tong
1
, HAO Xiao-Jiang
1 * *
, HE Hong-Ping
1 **
(1 State Key Laboratory of Phytochemistry and Plant Resources in West China, Kunming Institute of Botany, Chinese Academic
of Sciences, Kunming 650204 , China; 2 Graduate University of ChineseAcademy of Sciences, Beijing 100049 , China)
Abstract : A new neoclerodane diterpenoid was isolated fromthe ethyl acetate extract of Scutellaria barbata . The structure
was determined as 15β-methoxy-6α-acetoxy-19-propanoyloxy-4α, 18 ; 11 , 16 ; 15 , 16-triepoxy-neoclerodan .
Key words: Scutellaria barbata; Labiatae; Neoclerodane diterpenoid
Thedriedwhole herb of Scutellaria barbata D . Don
(named in Chinese as“Ban Zhi Lian”) has been used in
folk medicine for the treatment of tumors, heptitis, liver
cirrhosis and other diseases in China (Kan, 1978) . In
previous researches, therewereseveral reports about cyto-
toxic neoclerodane diterpenoids isolated from this species
(Dai et al. , 2006; Dai et al. , 2007) . Theisolationof
themethanol extraction of the aerial part of Scutellaria
barbata led to obtain a new neoclerodane diterpenoid,
Scutellin A (1) . The structure was elucidated by 1D,
2D NMR and HRESIMS data .
Results and Discussion
Scutellin A ( 1 ) was isolated as white solid . Its
molecular formula was deduced to be C26 H40 O8 on the
basis of NMR data and the positive HRESIMS at m?z
503 .2622 [M + Na] + . Intensive absorption bands at
1725 cm- 1 observed in IR spectra indicate the presence
of carbonyl groups .
1
H and
13
C NMR spectraof Scute-
llin A exhibited characteristic signals of 4α, 18 ; 11 ,
16; 15 , 16-triepoxy neoclerodanediterpenoid [δH 0 .94
(s, H - 20 ) , 0 . 84 ( d, J = 6 .4 , H - 17 ) , δ 2 .97
( dd, J = 3 .6 , 2 .4 , Ha- 18) 2 .18 ( d, J = 3 .6 , Hb
- 18) , 3. 99 (dd, J = 12 .4 , H - 11) , 5 . 08 ( d, J =
4 .8 , H - 15 ) , 5 . 69 ( d, J = 5 .4 , H - 16 ) , δC 13 .9
(q, C - 20) , 17 .4 ( q, C - 17) , 48 .3 ( t, C - 18 ) ,
83 .5 ( d, C - 11 ) , 104 .8 ( d, C - 15 ) , 107 .2 ( d, C
- 16) ] ( Lin et al. , 1989; Ohno et al. , 1996 ) . The
1
H and
13
C NMR data also gave signals of one methyl-
ene [δH 4 .39 ( d, J = 12 .0 , Ha - 19) , 4 . 83 ( d, J =
云 南 植 物 研 究 2009 , 31 (5) : 474～476
Acta Botanica Yunnanica DOI : 10 .3724?SP. J . 1143 .2009.09114
?
?? ?Author for correspondence; E-mail: haoxj@mail .kib. ac.cn, hehongping@ mail .kib.ac. cn; Tel : + 86- 871 - 5223263; Fax: + 86 -871- 5223070
Received date: 2009 - 06 - 11 , Accepted date: 2009 - 07 - 22
作者简介 : 朱锋 ( 1984 - ) 男 , 硕士 , 主要从事天然产物化学研究。 ?
Foundation item: The Natural Science Foundation of Yunnan Province (2009CD112)
12 .0 , Hb - 19) , δC 62 .0 ( t, C - 19 ) ] , one methine
[ 4 . 66 ( dd, J = 11 .4 , 4 .6 , H - 6 ) , δC 71 .9 (d, C -
6) ] and three substitutions, including an acetoxyl [δH
1 .92 ( s, 3H) , δC 170 .1 ( s) , 21 .2 ( q) ] , a pro-
panoyloxyl [δH 2 .37 ( dq, 7 . 6 , 1 . 6 , 2H) , 1 . 15 ( t,
7 . 6 , 3H) , δC 174 .2 ( s) , 29 .6 ( t) , 9 . 1 ( q) ] and
one methoxyl group [δH 3 .30 ( s, 3H ) , δC 54 .6
( q) ] . The HMBC cross-peaks of H - 6?C - 1′, H2 -
19?C - 1″, H - 3″?C - 2″, C - 1″established the acetoxyl
group at C - 6 and the propanoyloxyl group at C - 19 .
Meanwhile, the correlations ofδH 3 .30?C - 15 estab-
lished themethoxyl group at C - 15 . Detailed 2D NMR
analysis (Fig.1 ) further established the planar struc-
ture of Scutellin A . The relativeconfiguration of Scute-
llin A was deduced by its ROESY data . The ROESY
correlations of H - 11?H3 - 20 , H3 - 17 , H - 15 and H3
- 20?H2 - 19 indicated they areon the samesideof the
decalin andβ-orientation . H - 6 , H - 10 , Hβ - 18 in-
dicated they areon the other sideof thedecalin andβ-
orientation . Thus, Scutellin A was determined to be
15β-methoxy-6α-acetoxy-19-propanoyloxy-4α, 18 ; 11 ,
16; 15 , 16-triepoxy-neoclerodan .
Fig . 1 COSY (━ ) and selected HMBC (→ )
correlations of Scutellin A
Experimental
General Experimental Procedures Optical rotations were
measured on a JASCO DIP-370 digital polarimeter . A Tenor 27
spectrophotometer was used for scanning IR spectroscopy . NMR
spectra were recorded on Bruker AM-400 and DRX-500 spec-
trometers withTMS asinternal standard . ESIMSwas recordedona
finniganMAT 90 instrument, HRESIMS spectraon VG Auto Spec-
3000 spectrometer . Columnchromatographywas performedon sili-
ca gel (200 - 300 mesh; Qingdao Marine Chemical Inc ., Qingd-
ao, People′s Republic of China) , Sephadex LH-20 (40 - 70μm,
Amersham Pharmacia Biotech AB, Uppsala, Sweden) , and Li-
chroprep RP-18 gel (40 - 63μm, Merck Darmstadt, Germany) .
Plant Material Thedried aerial part of Scutellaria barbata
(20 kg) collected in Guangxi Province of China was bought in
Kunming Juhuamedicinal material market inSeptember, 2007 and
a voucher specimen (HH2007092801 ) is deposited at the State
Key Laboratoryof Phytochemistry and Plant ResouresinWest Chi-
na, Kunming Instituteof Botony, Chinese Academic of Science .
Extraction and isolation Driedandpowered aerial part of
S. barbata (20 kg) was extracted three times with 95 % MeOH
at 50℃ . After evaporating the solvents, the residue was dis-
solved in H2 O and extracted successively with petroleum ether,
EtOAc, and n-BuOH , respectively . The EtOAc extract (220 g)
was chromatographed over silica gel (200 - 300 mesh) and eluted
with petroleumether-EtOAc (9∶1 , 7∶3 , 1∶1 , 0∶1) to give four
fractions (A-D) . Fraction A ( 54 g) was purified by column
chromatography over MCI gel by using 90 % MeOH?H2 O and
MeOH as the eluents . The fraction eluted by 90 % MeOH was
further purified by Sephadex LH-20 (eluted withMeOH) and sil-
ica gel (elutedwith petroleumether?Me2 CO 9∶1) to give Scutell-
in A (54 mg) .
Scutellin A (1) : C26 H40 O8 , white solide; [α] 28D = - 32 .7
( c= 0 .15 , CHCl3 ) ; Positive ESIMS m?z 503 [M + Na] + ;
HRESIMS m?z 503 .2622 [M + Na] + ( calcd 503 .2620 ) . IR
νKBrmax cm- 1 : 3432 , 1724 , 1636 , 1628 , 1464 , 1372 , 1255 ,
1020 , 983 , 863; 1 H and 13 C NMR data, see Table1 .
References:
Dai ?SJ , Tao JY , Liu K et al. , 2006 . Neo-clerodane diterpenoids from
Sctuellaria barbata with cytotoxic activities [ J ] . Phytochemistry, 13 :
1326—1330
Dai ?SJ , Wang GF , Chen M et al. , 2007 . Five new neo-clerodanediter-
penoid alkaloids from Scutellaria barbata with cytotoxic activities
[ J ] . Chemical Pharmaceutical Bulletin , 55 : 1218—1221
Kan ?WS, 1978 . Manual of Vegetable Drugs in Taiwan [ M ] . Vol . 2 ,
Taipei : Chinese Medicine Publishing, 57
Lin ?YL , Kuo YH , Chen YL , 1989 . Two new clerodane-type diterpe-
noids, clerodindins A and B , from Cleodendron brachyanthumSchau-
er [ J ] . Chemical Pharmaceutical Bulletin , 37 : 2191—2193
Ohno ?A, Kizu H , Tomimori T, 1996 . Studies on nepalese crudedrugs XXI .
on the diterpenoid constituents of the aerial part of Scutllaria discolor
colebr [ J ] . Chemical Pharmaceutical Bulletin, 44: 1540—1545
5745 期 ZHU Feng et al. : Scutellin A , a New Neoclerodane Diterpenoid from Scutellaria barbata (Labiatae)
表 1 化合物 Scutelin A ( 1) 的氢谱和碳谱数据
Table 1 The NMR data for Scutelin A (1) in CDCl3
No ?. δC δH No. δC δH
1 ?22 v. 1 t 2 G. 13 ( m) ; 1 . 57 ( m) 14 38 P. 0 t 2 5. 17 ( m) ; 1 . 65 (m)
2 ?24 v. 9 t 1 G. 86 ( m) ; 1 . 38 ( m) 15 104 Z. 8 d 5 5. 08 ( d, 4 x. 8 )
3 ?32 v. 7 t 0 G. 99 brd; 2 . 08 ( m) 16 107 Z. 2 d 5 5. 69 ( d, 5 x. 4 )
4 ?65 s. 0 s — 17 16 H. 4 q 0 5. 84 ( d, 6 x. 4 , 3H)
5 ?45 s. 5 s — 18 48 P. 3 t 2 5. 97 ( dd, 3 . 6 , 2 A. 4 ) ; 2 ?. 18 ( d, 3 Q. 6)
6 ?71 n. 9 d 4 G. 66 ( dd, 11 . 4 , 4 .6 ) 19 62 P. 0 t 4 5. 39 ( d, 12 .0 ) ; 4 y. 83 ( d, 12 .0)
7 ?33 v. 3 t 1 G. 44 ( m) ; 1 . 64 ( m) 20 13 H. 9 q 0 5. 94 (s, 3H )
8 ?36 n. 1 d 1 G. 44 ( m) 6 q-O- - 荷COCH3 170 _. 1 s —
9 ?40 s. 0 s — 6 q-O-CO - ?CH ?3 21 H. 2 q 1 5. 92 (s, 3H )
10 ?48 n. 5 d 1 G. 59 ( m) 19-O- - 唬COCH2 CH3 174 _. 2 s —
11 ?83 n. 5 d 3 G. 99 ( dd, 12 . 0 , 4 .0 ) 19-O-CO - ?CH ?2 CH3 29 P. 6 t 2 5. 37 ( dq, 7 . 6 , 1 . 6 , 2H)
12 ?32 v. 1 t 1 G. 71 ( m) ; 1 . 48 ( m) 19-O-COCH2 - 紌CH - 紌3 9 5. 1 q 1 .15 (t, 7 h. 6 , 3H )
13 ?39 n. 9 d 2 G. 98 ( m) 15-OCH3 54 H. 6 q 3 5. 30 (s, 3H )
a: 1 H and 13 C NMR spectrawereobtained at 400 and 100 MHz, respectively
b: Coupling constants were presented in Hertz, unless otherwise indicated, all proton signals integrate to 1H
* * * * * * * * * * * * * * *
《云南植物研究》 征订启事
《云南植物研究》 是国家科委 (79) 国科发条字 341 号文批准创办的植物学专业学报 , 是中国科
学院主管的全国性自然科学期刊。现为我国植物科学研究发表论文的主要学术性刊物之一 , 并被评为
“中国自然科学核心期刊”,“中国生物学类科技核心期刊”。本刊荣获中科院优秀期刊二等奖 (1996)
及一等奖 ( 2000)、第二届全国优秀期刊三等奖 (1997 ) 及云南省优秀科技期刊一等奖 (1997 ) 等 ,
并作为中国科学院首批向美国 SCI 推荐的刊物之一。并入选国家“双效期刊”。本刊所发表的论文在
国内生物、农林、医药、轻工等二次文献刊物都有摘报 ; 国外 CA ( 美国化学文摘 )、BA ( 美国生物
学文摘 ) 等从 1980 年起就连续摘报 , 还有生物科学的当代进展 ( CABS)、科学引文索引 (SCI ) 的 CI
部分以及俄罗斯文摘杂志 ( PЖ ) 和国际农业科技情报系统 (Agris) 等摘报。乌利希国际期刊指南
(UIPD) 从 80 年代就刊载本刊出版事宜。现我刊已同 30 多个国家和地区有发行和交换关系 ; 在国内
外同行中有一定的影响。本刊现已加中国学术期刊光盘版、中国学术期刊网及万方数据库资源系统。
本刊主要报道植物学各分支学科具有创造性或较高学术水平的研究论文和简报 ; 植物学领域的新
发现及重大应用价值的新成果 ; 有关植物学资源开发利用和保护的创新性研究成果 ; 植物学研究的新
技术、新方法 ; 反映本学科重要领域的国内外植物科学研究的最新进展的评述 , 中英文稿件均受欢
迎。本刊设有植物系统学与生物地理学、植物化学与化学生物学、生物多样性保护与民族植物学、植
物生态学与资源管理、植物生理与分子生物学 5 个专栏。
《云南植物研究》 为双月刊 , 双月 25 日出版 , 2010 年每期 25 元 , 邮发代号 : 64 - 11 , 若在邮局漏
订的读者可直接与编辑部联系订阅。
联系地址 : 云南昆明市北郊黑龙潭 中国科学院昆明植物研究所 , 邮政编码 : 650204
E-mail : bianji@mail . kib. ac. cn http:??journal . kib. ac. cn Tel & Fax: 0871 - 5223032
674 云 南 植 物 研 究 31 卷