全 文 ：Chemical Constituents of Thalictrum delavayi
WANG Ye1 ,2 , YANG Xiao_Sheng2 , LUO Bo2 , ZHAO Chao2 , HAO Xiao_Jiang1 ,2＊
(1.The State Laboratory of Phytochemistry and Plant Resources in West China , Kunming Institute of Botany ,
The Chinese Academy of Sciences , Kunming 650204 , China;
2.The Key Laboratory of Chemistry for Natural Products of Guizhou Province and The Chinese Academy of Sciences , Guiyang 550002, China)
Abstract:　Two new compounds , 5_hydro_N_methylcorydalidine (1)and 1_(4_methoxybenzyl)_2_N_methyl_6_
hydroxyl_5 , 7_dimethoxy_isoquinoline (2), together with seven known ones (3-9)were isolated from the
chloroform extract of the herb Thalictrum delavayi Franch., among which compound 7was firstly obtained from
the genus Thalictrum.Their structures were elucidated on the basis of spectroscopic evidence including HMQC
and HMBC experiments.
Key words:　Thalictrum delavayi;isoquinoline;benzyl isoquinoline
　　 Thalictrum delavayi Franch.is used as herb
medicine for anticancer , antibacterial , anti_inflammatory
as well as reducing blood pressure (Ma et al , 1980),
and rich in alkaloids.In order to find new bioactive com-
pounds , we investigated the chemical constituents of T .
delavayi collected in Lijang County , Yunnan Province ,
China.From the chloroform fraction of the ethanol extract
of T .delavayi , nine compounds , 5_hydro_N_methylcory-
dalidine (1), 1_(4_methoxybenzyl)_2_N_methyl_6_hy-
droxyl_5 ,7_dimethoxy_isoquinoline (2), N_methylcoryda-
line (3), thalactamine (4), 3 ,4_dihydro_6 ,7_dimethoxy-
isocarbostyril (5), 6 , 7_dimethoxy_2_methylisocarbostyril(6), 4_(4_methoxyphenyl)_3_buten_2_one (7), berber-
ine(8)and noroxyhydrastinine(9)were isolated , among
which 1 and 2were determined to be new isoquinoline and
benzyl isoquinoline , respectively.
1　Results and Discussion
Compound 1 was obtained as colorless plate crystal(CHCl3), mp 230-231 ℃.The IR spectra showed the
presence of hydroxyl group(3 532 cm-1)and conjugated
carbonyl group (1 643 cm-1).The high resolution
FABMS at m/ z 238.251 6 [M+H] + was in agreement
with the molecular formula C12H15NO4 (calcd.
238.252 0).Comparing the 1H- and 13C-NMR data of 1
with those of N_methylcorydaline (3)(Table 1), it was
indicated that they had the same skeleton.The most obvi-
ous difference between 1 and 3 was that the former con-
tained one hydroxyl group and the latter did not have hy-
droxyl substitution , which was further confirmed by the
1H_NMR signal at δH 5.86 (1H , br s , OH)and the
EIMS fragment ion peak at m/ z 220 (M -H2O).The
HMBC of 1(Fig.1)showed the cross peak between the
acylamide carbon atδ164.7 and the proton at δ7.27(H_8), suggesting that the hydroxyl group was located at
C_5.Therefore , compound 1was assigned to be 5_hydro_
N_methylcorydalidine.
Compound 2 was isolated as yellow oil.The HR_
FABMS(m/z 340.142 9 [M] +)determined the molecu-
lar formula to be C20H22NO4 (calcd.340.145 7).IR
spectra showed the absorption bond at 3 456 cm-1 and
1 633 cm
-1
due to a hydroxyl group and a conjugated
double bond.The 1H_ and 13C-NMR spectra indicated the
presence of an N_methyl function (δH 3.77 and δC
43.2), three methoxyl groups (δH 3.73 , 3.76 and
3.89).The 1H-NMR signals for eight protons in the
forms of two singlets and three doublets in the downfield.
One pair of doublets (δ7.10 and 7.29 , J =7.2 Hz)
were the characteristic H_3 and H_4 of the isoquinoline
ring system.The other two doublets belonged to an AA′
BB′system of a p_substituted benzyl moiety were assigned
to H_2′(H_6′)and H_3(H_5′), respectively.The pro-
ton signal atδ6.71(s)was assigned to H_8 based on the
1H_13C long_range correlations with the quaternary carbons
atδ165.6 , 158.4 and 147.0.The base peak (m/ z
339 , [M-H] +)in EI_MS spectra implied the hydroxyl
group(δ8.60)at the position of C_6.The substitutions
of all methoxyl and hydroxyl groups were further deter-
mined through the inspection of NMR data (proton , car-
bon , DEPT , HMQC and HMBC).Therefore , compound
2 was identified to be 1_(4_methoxybenzyl)_2_N_methyl_
6_hydroxyl_5 ,7_dimethoxy_isoquinoline.
Compounds 3 , 4 , 5 and 6 were identified as N_
methylcorydaline , thalactamine , 3 ,4_dihydro_6 ,
7_dimethoxyisocarbostyril and 6 ,7_dimethoxy_2_methyliso-
carbostyril , respectively , by comparison with the authen-
tic samples.Compounds 8 and 9 were identified as
berberine (Janssen et al , 1989)and noroxoyhydrastinine(Doskotch et al , 1969), respectively , by comparison of
their spectral data with the literature values.
2　Experimental
2.1　General experimental procedures
Melting point was measured with XT_4 , and the
temperature was uncorrected.1H_NMR and 13C_NMR
spectra and HMBC were recorded at INOVA_400 instru-
ment using TMS as internal standard.FABMS was mea-
sured with HP_5973 mass spectrometer.IR was recorded
Received:2002-07-23　Accepted:2002-10-12
＊Author for correspondence.
植　物　学　报　　　　　　　　　　　　　　　　　　　　　　　　　　　　　　　　　　　　　　　　　　　　　　　　　　　
Acta Botanica Sinica　2003 , 45(4):500-502 http://www.chineseplantscience.com
Table 1　The 1H_NMR(CDCl3 , 400MHz)and 13C_NMR(CDCl3 , 100 MHz)data of compounds 1 and 3
C
1
1H_NMR 13C_NMR C
3
1H_NMR 13C_NMR
1
2
3
4
5
6
7
8
9
10
11
12
13
HO_5
-
-
3.11(2H , t , 6.8)
2.90(2H , t , 6.8)
-
7.27(1H , s)
3.93(3H , s)
3.88(3H , s)
3.11(3H , s)
5.86(1H , br s)
164.1(s)
-
48.2(t)
20.9(t)
145.1(s)
137.9(s)
150.7(s)
103.5(d)
124.8(s)
117.7(s)
61.0(q)
56.0(q)
35.3(q)
-
1
2
3
4
5
6
7
8
9
10
11
12
13
-
-
-
3.49(2H , t , 6.8)
2.88(2H , t , 6.8)
6.57(1H , s)
7.54(1H , s)
3.90(3H , s)
3.86(3H , s)
3.08(3H , s)
-
164.8(s)
-
48.3(t)
27.4(t)
110.4(d)
151.6(s)
147.8(s)
109.8(d)
121.9(s)
131.5(s)
56.1(q)
56.0(q)
35.1(q)
-
Table 2　The 1H_NMR(CDCl3 , 400MHz)and 13C_NMR(CDCl3 , 100 MHz)data for compound 2
C δC δH HMBC
1 147(s) - -
2 - - -
3 131.4(d) 7.10(1H , d, 7.2) C_1 , 10 , N_CH3
4 110.9(d) 7.29(1H , d, 7.2) C_3 , 5 , 9
5 139.9(s) - -
6 165.6(s) - -
7 158.4(s) - -
8 99.7(s) 6.71(1H , s) C_1 , 6 , 7
9 128.5(s) - -
10 114.8(s) - -
CH2 33.1(t) 4.34(2H , s) C_1 , 1′, 2′, 3′, 5′, 6′
1′ 126.7(s) - -
2′ 129.0(d) 6.93 (H , d , 8.4)C_4′, 6′, CH2
3′ 114.6(d) 6.78 (H , d , 8.4)C_1′, 4′, 5′
4′ 158.8(s) - -
5′ 114.6(d) 6.78 (H , d , 8.4)C_1′, 3′, 4′
6′ 129.0(d) 6.93 (H , d , 8.4)C_2′, 4′, CH2
CH3N_2
CH3O_5
CH3O_7
CH3O_4′
HO_6
43.2(q)
59.3(q)
55.5(q)
55.3(q)
-
3.77(3H , s)
3.89(3H , s)
3.76(3H , s)
3.73(3H , s)
8.60(1H , br s)
C_1 , 3
C_5
C_7
C_4′
C_6
Fig.1.　The key HMBC correlations of compound 1.
with Bruker VICTOR_22 spectrometer.Silica gel for TLC
and column chromatography was performed with the
product of Qingdao Ocean Chemical Factory.
2.2　Plant material
Thalictrum delavayi Franch.was collected from Li-
jang County of Yunnan Province , China and identified by
Prof.MIN Tian_Lu of the Kunming Institute of Botany ,
The Chinese Academy of Sciences.
2.3　Extraction and isolation
Dried leaves of plant (5 kg)were powdered and
extracted with 95% EtOH at room temperature three
times.The extract was evaporated in vacuum , and the
residue was partitionized in 5%HCl.After filtrated , the
acidic solution was extracted three times with petroleum
ether and then basified with 25%ammonia to pH 9-10.
The aqueous layer was extracted with CHCl3 and removal
of the CHCl3 gave residue (150 g).Part of the residue(50 g)was subjected to the silica gel column with CHCl3∶MeOH∶Et2NH (200∶10∶1)as eluant to afford 1 (15
mg), 2(48 mg), 3(25 mg), 4(34 mg), 5(17 mg),
6(27 mg), 7(35 mg), 8(180 mg)and 9(31 mg).
2.4　Identification
Compound 1　Colorless plate crystal(CHCl3), mp
230-231 ℃.HR_FABMS m/z 238.251 6([M+H] + ,
C12H15NO4 , calc.238.252 0).IRνKBrmax cm-1:3 532
(OH), 1 643(C O).1H_NMR and 13C_NMR data are
shown in Table 1.
Compound 2 　 Yellow oil , HR_FABMS m/ z
340.142 9 ([M] + , C20H21NO4 , calc.340.145 7).
WANG Ye et al:Chemical Constituents of Thalictrum delavayi 501　
Fig.2.　The structures of compounds 2-9.
1H_NMR and 13C_NMR data are shown in Table 2.
Compound 3　Colorless needle crystal (MeOH),
mp 125-126 ℃.1H_NMR and 13C_NMR data are shown
in Table 1.
Compound 4　Colorless plate crystal(MeOH), mp
112-114 ℃, and it was identified as thalactamine by
comparison of the mixed melting point and Rf value (on
TLC)with an authentic sample.
Compound 5　Colorless prisms crystal(benzene),
mp 174-175 ℃, it was identified as 3 , 4_dihydro_6 , 7_
dimethoxyisocarbostyril by comparison of the mixed melt-
ing point and Rf value (on TLC)with an authentic sam-
ple.
Compound 6　Colorless needle crystal(CHCl3),
mp 112-113 ℃, it was identified as 6 ,7_dimethoxy_2_
methylisocarbostyril by comparison of the mixed melting
point and Rf value with an authentic sample.
Compound 7　Colorless plate crystal(CHCl3), mp
142-143 ℃, it was identified as 4_(4_methoxyphenyl)_
3_buten_2_one by 1H_NMR , 13C_NMR and MS spectral
data.EIMS m/ z(%):176(100), 161(97).1H_NMRδ(CDCl3 , 400MHz):2.32(3H , s), 3.80(3H , s),
6.57(1H , d , J =16.4 Hz), 6.87 (2H , m), 7.44
(1H , d , J =16.4 Hz), 7.45 (2H , m).13C_NMRδ(CDCl3 , 100 MHZ):27.27(q), 55.29(q), 114.35(d), 124.90(d), 126.96(s), 129.89(d), 143.24(d), 161.54(s), 198.41(s).
Compound 8　Yellow powder , it was identified as
berberine by comparison of its spectral data with the liter-
ature values.
Compound 9　Colorless plate crystal(MeOH), it
was identified as noroxyhydrastinine by comparison of its
spectral data with the literature values.
References:
Doskotch R W , Schiff P L , Beal J L.1969.Alkaloids of Thalic-
trum.Ⅺ.Two new alkaloids from T.minus var.adianati-
folium noroxyhydrastinine and thalifoline.Tetrahedron , 25:
469-475.
Janssen RH A M , Lousberg R J J Ch , Wijkens P , Kruk C , Theuns
H G.1989.Assignment of 1H_ and 13C-NMR resonances of
some isoquinoline alkaloids. Phytochemistry , 28:2833-
2839.
Ma Z_Q(马竹青), Xin S_M (辛顺妹), Shen X_C (沈兴昶).
1980.The antitumor activity of thalidasine and its toxicities.
Chin Tradit Herb Drugs(中草药), 11:217-219.(in Chi-
nese with English abstract)
(Managing editor:WANG Wei)
偏翅唐松草化学成分的研究
汪　冶1, 2　杨小生2　罗　波2　赵　超2　郝小江1, 2＊
(1.中国科学院昆明植物研究所植物化学与西部植物资源国家重点实验室 , 昆明 650204;
2.贵州省 、中国科学院天然产物化学重点实验室 , 贵阳 550002)
摘要:　从偏翅唐松草(Thalictrum delavayi Franch.)的乙醇提取物的氯仿部分分离到 9 个化合物(1-9)。其中化合
物1 和 2 为新化合物 , 分别为 5_hydro_N_methylcorydalidine (1)和 1_(4_methoxybenzyl)_2_N_methyl_6_hydroxy l_5 , 7_
dimethoxy_isoquinoline(2)。化合物 7 为首次从唐松草属中分离到。它们的结构经波谱方法(包括HMQC 和HMBC)得
到鉴定。
关键词:　偏翅唐松草;异喹啉;苄基异喹啉
中图分类号:Q914　　　文献标识码:A　　　文章编号:0577-7496(2003)04-0500-03
收稿日期:2002-07-23　接收日期:2002-10-12
＊通讯作者。 (责任编辑:王　葳)
502　 植物学报　Acta Botanica Sinica　Vol.45　No.4　2003