全 文 ：Water-Soluble Constituents of Clerodendranthus spicatus
WANG Min , LIANG Jing-Yu＊ , CHEN Xue-Ying
Department of Natural Medicinal Chemistry , China Pharmaceutical University , Nanjing 210009 , China
【ABSTRACT】　AIM:To study the water-soluble constituents of the aerial parts of Clerodendranthus spicatus.METHOD:
The water soluble fractions were subjected to a series of chromatographic separation methods to afford six caffeic acid depsides ,
as well as free caffeic acid.Their structures were elucidated mainly by spectroscopic methods.RESULT:Seven compounds:
caffeic acid(1), rosmarinic acid(2), methyl rosmarinate (3), methyl lithospermate(4)and dimethyl lithospermate (5),
methyl lithospermate B(6), dimethyl lithospermate B (7)have been isolated from Clerodendranthus spicatus.CONCLU-
SION:Compounds 3～ 7 have been isolated from this plant for the first time.
【KEY WORDS】　Clerodendranthus spicatus;Polyphenolic constituents;Depsides
【CLC Number】　R284.1　　【Document code】　A　　【Ariticle ID】　1672-3651(2006)05-0027-04
【Received on】　2006-02-02
【＊Corresponding author】　LIANG Jing-Yu:Professor , Tel:96-25-
85391289 ,Fax:86-25-83353855 , E-mail:jyliang08@yahoo.com.cn.
　　Clerodendranthus spicatus (Thunb.)C.Y.Wu
ex H.W.Li (Lamiaceae)is a traditional medicinal
plant grown in Southeast Asia.This plant has been
widely used in treating chronic nephritis , urinary lithia-
sis , hepatitis , jaundice and biliary lithiasis[ 1] .In our
studies of the water soluble fractions of Cleroden-
dranthus spicatus , caffeic acid (1) and six other
polyphenolic constituents were isolated and elucidated
as:rosmarinic acid (2), methyl rosmarinate (3),
methyl lithospermate (4), dimethyl lithospermate (5),
methyl lithospermate B (6)and dimethyl lithospermate
B(7).Compounds 3 ～ 7 were isolated from this plant
for the first time.Compounds 2 ～ 7 are caffeic acid
depsides and it is reported that magnesium and ammoni-
um-potassium lithospermate B are the active components
having a uremia-preventive effect[ 2] , so we may make
further study on the pharmacological action of methyl
lithospermate B and dimethyl lithospermate B.
1　Apparatus and Reagents
X-4 micro melting point apparatus(uncorrected).
Nicolet Impact 410 spectrometer.JEOL JNM-EX 400
spectrometerwith TMS as internal standard.JASCO P-
1020 digital spectropolarimeter.Agilent 1100 series
LC/MSD Trap mass spectrometer.Silca gel (Qingdao
Marine Chemical Factory)was used for column chro-
matography and Silca gel GF254 for TLC.Sephadex LH-
20(Pharmacia)was used for column chromatography.
2　Plant Material
The leaves and stems of Clerodendranthus spicatus
were collected in Fuzhou , Fujian province , China , in
September 2002 , and identified by Prof.SONG Xue-
Hua.A voucher specimen (No.20020921)has been
deposited at the Department of Natural Medicinal Chem-
istry , China Pharmaceutical University.
3　Extraction and Isolation
Air-dried aerial parts of Clerodendranthus.spicatus
(18.5 kg)were extracted with 75% ethanol at 85 ℃
(reflux , 3 h×3), and the solvent was evaporated un-
der reduced pressure.The 75% ethanol extract was
suspended in H2O and partitioned successively with
petroleum ether (60 ～ 90 ℃), EtOAc.
The H2O layer was subjected to macroporous resins
and eluted with 25%/50%/75%/95% ethanol;and
the 50% ethanol fraction(27 g)was further subjected
to a series of chromatographic techniques , such as silica
gel column , ODS RP-18 column (CH3OH-H2O),
Sephadex LH-20 column chromatography (CH3OH),
yielding compounds 1 (30 mg), 2 (33 mg),
3(20 mg),4 (40 mg), 5 (10 mg), 6 (10 mg),
中国天然药物　2007年 1月　第 5卷　第 1期 Chin J Nat Med　Jan.2007　Vol.5　No.1　27　
7(25 mg).
Fig 1　Structures of compounds 1～ 7
4　Structure Elucidation
Compound 2:amorphous yellowish powder , mp 205
～ 208 ℃(MeOH);ESI-MS(-)m/z 359 [M-H] - ,
IRνKBrmax (cm-1)3 425 , 1 682 , 1 607 , 1 519 , 1 442 ,
1 263 , 1 182 , 1 114 cm-1.1H NMR(400MHz , DMSO-
d6)unit A:δ7.05 (1H , br s , H-2), 6.76(1H , d ,
J =8.4 Hz , H-5), 6.96(1H , d , J =8.0 Hz , H-6),
7.40(1H ,d , J =15.6Hz , H-7), 6.20(1H ,d , J =
15.6 Hz , H-8);unit B:δ6.68 (1H , br s , H-2),
6.50(1H , d , J =8.1 Hz , H-5), 6.61(1H , d , J =
8.1 Hz , H-6), 3.01 (1H , br d , J =12.7 Hz ,
H-7α), 2.83 (1H , dd , J =12.7 Hz , 7.6 Hz ,
H-7β), 4.97 (1H , d , J =7.6 Hz , H-8).13C NMR
data in Table 2.Compound 2 was characterized as ros-
marinic acid by the comparison of the physical and
spectral data with the reported data
[ 3] .
Compound 3:amorphous yellowish powder , mp 72
～ 75℃(MeOH);[α] 21D +61.20°(c 0.05 , CH3OH);
ESI-MS(-) m/z 373 [ M-H] - , IR(KBr)υ3 421 ,
2 937 , 2 854 , 1 685 , 1 604 , 1 523 , 1 444 , 1 380 ,
1 269 , 1 182 , 1 116 cm-1.1H NMR(400 MHz , DM-
SO-d6)unit A:δ7.06(1H , br s , H-2), 6.76(1H ,
d , J =8.4 Hz , H-5), 7.00(1H , br d , J =8.4 Hz ,
H-6), 7.48(1H , d , J =16.0 Hz , H-7), 6.26(1H ,
d , J =16.0 Hz , H-8);unit B:δ6.64 (1H , br s ,
H-2 , overlap), 6.49 (1H , d , J =8.0 Hz , H-5),
6.63(1H , d , J =8.0 Hz , H-6), 3.38 (1H , m ,
H-7α), 2.95(1H , m , H-7β), 5.10(1H , t , J =6.4
Hz , H-8), 3.66(3H , s , -OCH3).13C NMR data in
Table 2.Compound 3 was determined to be methyl ros-
marinate by the comparison of the physical and spectral
data with the reported data
[ 3] .
Compound 4:amorphous white powder , mp 105 ～
108 ℃(Me2 CO);[ α] 21D +153.00°(c 0.10 ,
CH3OH);ESI-MS(-)m/ z 551[M-H] - , IR(KBr)υ
3 402 , 2 956 , 1 731 , 1 695 , 1 612 , 1 515 , 1 446 ,
1 367 , 1 286 , 1 186 , 1 114 cm-1.1H NMR and
13CNMR data in Tables 1 and 2.Compound 4was elu-
cidated as methyl lithospermate by the comparison of the
physical and spectral data with the reported data
[ 4] .
Compound 5:amorphous yellowish powder , mp
112 ～ 115 ℃(Me2CO);[ α] 21D +37.00°(c 0.10 ,
CH3OH);ESI-MS(-):m/z 565[M-H] - , IR(KBr)υ
3 751 , 3 404 , 2 954 , 2 852 , 1 716 , 1 610 , 1 515 ,
1 444 , 1 365 , 1 286 cm-1.1H NMR and 13C NMR da-
ta in Tables 1 and 2.Compound 5 was identified as
dimethyl lithospermate by the comparison of the physical
and spectral data with the reported data[ 4] .
Compound 6:amorphous white powder , mp 121 ～
123 ℃(Me2CO);[α] 21D +13.50°(c 0.14 , CH3OH);
ESI-MS(-) m/z 731 [ M-H] - , IR(KBr)υ3 416 ,
2 956 , 2 852 , 1 735 , 1 612 , 1 517 , 1 446 , 1 365 ,
1 286 , 1 186 , 1 112 cm-1.1H NMR and 13C NMR da-
ta in Tables 1 and 2.Compound 6 was characteized as
methyl lithospermate B by the comparison of the physi-
cal and spectral data with the reported data[ 5] .
28　　Chin J Nat Med　Jan.2007　Vol.5　No.1 中国天然药物　2007年 1月　第 5卷　第 1期
Table 1　1H-NMR data of compounds 4～ 7(400 MHz in(CD3)2CO)
Unit H 4 5 6 7
A 5 6.90(d , 8.4 Hz) 6.90(d , 8.4 Hz) 6.90(d, 8.8 Hz) 6.90(d , 8.4 Hz)
6 7.26(d , 8.4) 7.28(d , 8.4) 7.27(d, 8.8) 7.30(d , 8.4)
7 7.72(d , 15.6) 7.74(d , 16.0) 7.65(d, 16.0) 7.68(d , 15.6)
8 6.16(d , 15.6) 6.32(d , 16.0) 6.32(d, 16.0) 6.33(d , 15.6)
B 2 6.79(d , 2.0)a 6.80(d , 2.0)a 6.80(d, 2.0)a 6.80(d , 2.0)a
5 6.74(d , 8.0) 6.74(d , 8.0) 6.73(d, 8.0) 6.73(d , 8.0)
6 6.62(dd, 2.0 , 8.0) 6.63(dd , 2.0, 8.0) 6.64(dd, 2.0 , 8.0)b 6.61(dd , 2.0 , 8.0)b
7α 3.03(m) 3.02(m) 3.03(m) 3.03(m)
7β 2.98(m) 2.89(m) 2.93(m) 2.95(m)
8 5.16(dd , 4.6 , 7.8) 5.20(dd ,5.0, 10.0) 5.20(dd , 5.2, 7.4) 5.20(dd , 5.2 , 7.4)
10 　　　- 3.66(3H , s) 　　　- 3.61(3H , s)b
C 2 6.79(d , 2.0)a 6.80(d , 2.0)a 6.80(d, 2.0)a 6.80(d , 2.0)a
5 6.76(d , 8.0) 6.76(d , 8.0) 6.80(d, 8.0)a 6.80(d , 8.0)a
6 6.72(dd , 2.0, 8.0) 6.72(dd , 2.0 , 8.0) 6.70(dd , 2.0 , 8.0)ab 6.70(dd, 2.0 , 8.0)ab
7 5.80(d , 4.0) 5.95(d , 5.2) 5.82(d, 4.4) 5.82(d , 4.4)
8 4.46(d , 4.0) 4.56(d , 5.2) 4.48(d, 4.4) 4.49(d , 4.4)
10 3.67(3H , s) 3.70(3H , s) 　　　- 　　　-
D 2 6.70(d, 2.0)a 6.70(d , 2.0)a
5 6.70(d, 8.0)a 6.70(d , 8.0)a
6 6.46(br d , 8.0) 6.46(dd, 2.0 , 8.0)
7α 3.03(m) 3.03(m)
7β 2.93(m) 2.95(m)
8 5.20(dd , 5.2, 7.4) 5.20(dd, 5.2 , 7.4)
10 3.62(3H , s) 3.62(3H , s)b
aOverlapped wi th other signals;bAssignments may be interchanged in each column
Table 2　13C-NMR data of compounds 2～ 7(100 MHz , 2 ～ 3 in DMSO-d6;4 ～ 7 in(CD3)2CO)
NO. C-1 C-2 C-3 C-4 C-5 C-6 C-7 C-8 C-9 -OCH3
2 unit A 125.3 113.9 144.9 148.4 115.3 121.2 145.5 114.7 165.9
B 128.4 116.5 144.7 143.6 115.7 119.7 36.6 79.2
3 unit A 125.1 112.7 145.4 148.6 115.3 121.6 146.2 114.8 165.7
B 126.5 116.5 144.8 143.9 115.6 119.9 36.2 72.8 169.7 52.0
4 unit A 124.6 125.6 148.2 145.9 117.1 121.4 142.9 115.7 166.2
B 128.3 118.0 145.7 144.5 116.1 120.5 37.4 74.1 174.8
C 133.7 113.0 145.3 144.5 115.8 118.1 87.2 57.2 170.3 52.3
5 unit A 124.1 126.6 148.1 146.1 117.1 121.4 142.9 115.8 166.2
B 128.4 118.0 145.9 144.6 115.9 121.4 37.4 73.9 172.2 52.9
C 132.8 113.3 145.5 144.4 116.3 118.1 87.6 56.5 170.4 52.2
6 unit A 124.3 125.8 148.2 145.9 117.1 121.5 142.6 115.8 166.3
B 128.5 118.0 145.7 144.5 115.9 121.4 37.0 73.9 171.1
C 133.0 113.0 145.2 144.4 116.3 118.0 87.3 56.8 169.8
D 128.1 117.0 145.3 144.5 116.4 121.4 37.4 74.9 170.9 52.4
7 unit A 124.2 125.8 148.3 146.0 117.0 121.5 143.0 115.8 166.3
B 128.4 118.0 145.8 144.6 115.9 121.4 37.0 73.9 170.5 52.2
C 132.9 113.0 145.3 144.3 116.0 118.1 87.3 56.6 169.8
D 128.1 116.9 145.4 144.6 116.1 121.4 37.4 74.9 170.9 52.4
　　Compound 7:amorphous white powder , mp 95 ～
98 ℃(Me2CO);[α] 21D +74.00°(c 0.10 , CH3OH);
ESI-MS(-)m/z 745 [ M-H ] - , IR(KBr)υ3 410 ,
2 956 , 2 852 , 1 735 , 1 612 , 1 517 , 1 446 , 1 365 ,
1 286 , 1 178 , 1 114 cm-1.1H NMR and 13C NMR da-
ta in Tables 1 and 2.Compound 7was determined to be
dimethyl lithospermate B by the comparison of the phys-
ical and spectral data with the reported data[ 5] .
中国天然药物　2007年 1月　第 5卷　第 1期 Chin J Nat Med　Jan.2007　Vol.5　No.1　29　
Reference
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[ 2] 　Tanaka T , Morimoto S , Nonaka GI , et al.Magnesium and ammoni-
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a-preventive effect from Salvia miltiorrhiza[ J] .Chem Pharm Bull ,
1989 , 37(2):340-344.
[ 3] 　Wu ZJ , Ouyang MA , Yang CR.Polyphenolic constituents of Salvia
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[ 4] 　Kohda H , Takeda O , Tanaka S , et al.Isolation of inhibitors of
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肾茶的水溶性成分
王　敏 ,梁敬钰＊ ,陈雪英
中国药科大学天然药物化学教研室 , 南京 210009
【摘　要】　目的:研究肾茶(Clerodendranthus spicatus)地上部位的水溶性成分。方法:应用大孔吸附树脂层析 , 硅胶柱
层析 , 反相柱层析和 Sephadex LH-20柱层析等多种方法进行分离纯化 , 通过波谱解析和理化鉴别进行结构鉴定。结果:分
离得到 7 个化合物 ,分别为:咖啡酸(caffeic acid , 1)、迷迭香酸(rosmarinic acid , 2)、迷迭香酸甲酯(methyl rosmarinate , 3)、紫草
酸单甲酯(methyl lithospermate , 4)、紫草酸二甲酯(dimethyl lithospermate , 5)、紫草酸乙单甲酯(methyl lithospermate B , 6)、紫草
酸乙二甲酯(dimethy l lithospermate B , 7)。结论:化合物3 ～ 7均为首次从该植物中分得。
【关键词】　肾茶;多酚类化合物;缩酸
·信　　息·
2007年第 67届世界药学大会 、中国药学会百年庆典
主办单位:国际药学联合会 中国药学会　　　时　　间:2007年 9 月 1日～ 6 日
地　　点:北京
国际药学联合会(International Pharmaceutical Federation , 简称 FIP)成立于 1912年 ,总部设在荷兰海牙 , 目前有来自
80多个国家的 130多个团体会员 , 是世界上最大的国际药学组织。 FIP 每年召开一次世界药学大会 , 在五大洲轮流
举办 , 参加会议人数约 3 000 人 ,是世界药学领域的传统盛会。世界药学大会会议内容广泛 , 涉及药学科研 、教育 、实
践等各个领域 , 至今已经召开了 66届 , 有力地促进了国际药学界的交流与合作。中国药学会于 1992 年恢复在国际
药学联合会的活动 , 是国际药学联合会理事单位。
中国药学会成立于 1907 年 , 是我国最早成立的学术团体之一 , 到目前为止 ,中国药学会有会员近 10 万人 , 高级
会员近 3 000 人 ,团体会员35个。学会下设 6 个工作委员会 , 15 个专业委员会 , 主办 19 种学术期刊。中国药学会自
创立以来 , 紧跟时代步伐 ,不断发展壮大 , 已经成为在国内药学界具有广泛影响的重要学术团体 , 成为推动我国药学
事业发展的一支重要社会力量。特别是改革开放以来 , 中国药学会坚持学会宗旨和民主办会原则 , 做了大量卓有成
效的工作 , 为提高我国药学科技水平 、繁荣医药卫生事业 、保障人民群众身体健康 、促进经济社会发展发挥了重要作
用 , 赢得了广大药学科技工作者的依赖 ,得到了广大人民群众的好评。
2007 年第 67届世界药学大会 , 会议内容广泛涉及药学科研 、教育 、实践等各个领域 , 将就国际药学领域的热点 、
难点问题 , 展开务实而广泛的研讨 ,会议内容将涵盖药学流行病学 、药学经济学 、天然药物 、药物质量 、放射药学 、生
物药学 、社区药学 、医院药学 、工业药学 、药事管理 、药学教育 、实验室与药物控制 、军事与急救药学 、药学信息 、临床
生物学等众多领域 , 对于促进我国药学技术的发展 , 促进与国际药学届的交流与合作 ,必将产生积极而深远的影响。
30　　Chin J Nat Med　Jan.2007　Vol.5　No.1 中国天然药物　2007年 1月　第 5卷　第 1期