全 文 ：The Alkaloids from Leaves of Croton hemiargyerius var.
gymnodiscus
LIN Wen-han1＊ , FU Hong-zheng1 , LI Jun1 , CHENG Gang1 , and Roderick A Barnes2
(1 .StateKey Laboratory of Natural and Biomimetic Drugs , Peking University , Beijing 100083 , China;
2.Nucleo de Pesquisas de Produtos Naturais , Centro de Ciencias da Saude , Federal
University of Rio de Janeiro , Rio de Janeiro 21941 , Brasil)
Abstract:Aim　Investigation of alkaloids from the leaves of Brazilian medicinal plant Croton hemiargyerius var.
gymnodiscus.Methods　Silica gel column chromatography was used repeatedly for the isolation and purification , and their
structures were identified by extensive spectroscopy and comparison of the chemical and phy sical data with those of authentic
samples reported in literature.Results　Twelve alkaloids were isolated and their structures were identified.Conclusion　
Four new alkaloids named hemiargines A(1), B(5), C(6)and D(7), together with eight known alkaloids namely isoc-
orydine(2), corydine(3), norcorydine(4), salutaridine(8), glaucine(9), tetrahydropalmatrubine(10), xylopinoine
(11), and norlaudanosine(12)were isolated.
Key words:Csroton hemiargyerius;new alkaloids;hemiargines A , B , C , D
CLC number:R931.6　　　Document code:A　　　Article ID:1003-1057(2003)03-117-06
Introduction
The plants of Croton genus are quite abundant in the
central part of Brazil;only in the State of Rio de Janeiro
thirty-nine species of the genus have been identified.
They are largely used as folk medicine for wound healing.
A preliminary pharmacological investigation seemed to
confirm the healing activity of the alkaloids.In previous
work , Prof.R.A.Barnes and his group examined eight
of fifteen species of the genus showing positive test for
alkaloids
[ 1]
Croton salutaris contained salutaridine and its
racemic form salutarine
[ 2] , and C.celtidifolius possessed
two major alkaloids , isoboldine and thaliporphine[ 3 , 4] .
Croton hemiargerius from Friburgo of Rio yielded two al-
kaloids , salutaridine and glaucine.Croton hemiargyerius
Muel.var.gymnodiscus Muel collected in the State of
Sao Paulo was a new variety of hemiargyerius , and its
chemical constituents have not been submitted hitherto for
chemical investigation.We examined the alkaloids frac-
tions of its leaves in detail and isolated twelve alkaloids.
Their structures were determined by IR , MS , extensive
Received date:2003-03-25.
＊Corresponding author:Tel 010-62062210 , Fax 010-82802724 ,
E-mail whlin@bjmu.edu.cn
1D and 2D NMR spectrum analysis in combination with
chemical conversion and synthesis.
Results and Discussion
Twelve alkaloids were isolated and purified , of
which two major alkaloids , glaucine and isocorydine ,
contained 85%of the crude alkaloids , and the containing
minor alkaloids were lower than 1‰.Their chemical
stsuctures were further elucidated on the basis of IR , UV ,
MS (HRMS , EISM , CFMS), various 1D and 2D homo
and hetero NMR spectra in combination with comparison
of their physical and chemical properties with those of
their respective authentic compounds , and chemical conv-
ersion.Four of them were identified as new alkaloids
namely hemiargines A (1), B (5), C (6)and D(7),
and the known alkaloids were isocorydine (2)[ 5] ,
corydine (3)[ 6] , norcorydine (4)[ 7] , salutaridine (8)[ 8] ,
glaucine(9)[ 9] , tetrahydropalmatrubine (10)[ 9] , xylopi-
noine (11)[ 9] , and norlaudanosine (12)[ 9] .The berber-
ine type alkaloid xylopinine was found in Croton genus for
the first time.Hemiargine D was concluded to be simple
isoquinoline structure , which seemed to undergo biosyn-
thesis by special biogenetic pathway.
Hemiargine A has the molecular formula C20H23NO4
afforded by HREIMS.Its 1H NMR showed very similar
117Journal of Chinese Pharmaceutical Sciences 2003 , 12(3)
signals with those of norcorydine.The typical aromatic
protons atδ6.85(d , J=8.0 Hz), δ6.79(d , J=8.0
Hz)and 6.62(s)were attributed to H-8 , H-9 and H-3 ,
respectively , by comparison of its NMR data with those of
known alkaloids 2-4.The presence of four methoxyl
groups [δ3.90(s);3.89(s);3.88(s);3.82 (s)]
and absence of a methyl group attached to nitrogen led to
propose its structure as 1-O-methylnorcorydine , named
hemiargine A.
Hemiargine B afforded a molecular formula as C19H19
NO4 by means of
1
H and
13
C NMR spectra in combination
with mass spectrum.It has one more unsaturation degree
than isocorydine.The typical signals at δ6.68 (d , J=
8.0 Hz), andδ6.72(d , J=8.0Hz), and the presence
of two of the three methoxyl groups substituted at C-1 and
C-2 were similar to those of isocorydine.A third methoxyl
group was considered to be attached to C-10 due to the
long range correlation between H-8(δ6.72 , d)and C-10
(δ146.62 , s), and between methoxyl protons δ3.90
(s , OCH3)and C-10.A couple of geminal protons atδ
4.28(d , J=15.2 Hz)and δ3.55 (d , J=15.2 Hz)
were assigned to CH2-7 , which implied that a double
bond was formed between the nitrogen and C-6a , and the
evidence was further supported by a typical carbon signal
atδ179.33(s)for C-6a.Thus , the structure was prop-
osed as 5.
Hemiargine C was a polar minor alkaloid , and its
molecular formula C19H21NO4 with ten unsaturatuon , was
afforded by the
1
H and
13
C NMR data in association with
MS spectrum(molecularweight as m z 327 [M] +).The
typical signals atδ7.62 (d , J=10.5 Hz)and δ7.81
(d , J=10.5Hz)in 1H NMR spectrum suggested that the
N-C6a bond was cleaved.The protons atδ9.12(s)andδ
7.05(s)were characteristic of protons H-11 and H-8 ,
respectively , in comparison with those of N-methylseco-
glaucine
[ 10] .Its difference from N-methylsecoglaucine was
the absence of a methoxyl group in hemiargine C , which
induced chemical shilft of H-3 to high field atδ6.91(s)
whereas that of N-methylsecoglaucine was δ7.19 (s).
The absence of correlation between hydroxyl proton and
H-3 in NOESY spectrum indicated that the hydroxyl group
was linked to C-1.The structure of 6 was therefore prop-
osed as shown.
Hemiargine D has a molecular formula C13 H19 N
(M+ , m z 189.2222)with five degrees of unsaturation.
IR absorption at 3 300 , 1 610 , 1 600 , 1 580 and 1 575
cm
-1
suggested the presence of NH and aromatic moiety.
13
C NMR data in combination with
1
H NMR data led to
conclude a simple isoquinoline alkaloid.On the basis of
DQF COSY spectrum , a methyl group atδ1.45(d , J=
6.8 Hz , 3H)coupled with the proton atδ3.36(q , J=
6.8Hz)was assigned to be connected to C-6a.A quater-
nary carbon at C-5 was substituted by a methyl δ1.18
(s , 3H)and an ethyl group (δ0.96 , t , J=7.2 Hz ,
3H;δ1.62 , q , J=7.2 Hz , 2H), respectively.The
geminal proton signalsδ2.74 (d , J=11.8 Hz)and δ
2.70 (d , J=11.8 Hz)were concluded to be CH2-4.
Four aromatic protons betweenδ7.09 and 7.28(m , 4H)
were concluded to be ring A of isoquinoline.The relative
configurations of C-5 and C-6a were determined by the
NOE correlation observed between the methyl protons H-7
and H-10.The structure was proposed as 7.
Experimental
General
The melting points were observed by using Kofler ap-
paratus and were uncorrected.The NMR spectra were
recorded for
1
H and
13
C NMR in Varian Germini 200.
The IR spectra were observed with Perkin Elmer model
559B , and MS spectra were examined using 70 eV with
the Micromass 12F and VG Autospec apparatus.The sili-
ca gel and aluminawere purchased from Merck Company.
Plant material
The plant species was identified as Croton hemiargy-
erius var.gymnodiscus Muel.by Professor Arline Souza
Oliveira of the Department of Botany , the Federal Univer-
sity of Rio de Janeiro , and the sample was deposited in
State Key Laboratory of Natural and Biomimetic Drugs ,
Peking University.
Extraction and isolation
The dried leaves and stems(0.80 kg)were ground
and extracted by prolonged percolation with 95%EtOH.
After vacuum distillation , the residue was dissolved in
5%HCl solution.After filtration and extraction with CCl4
to remove chlorophyll , the acidic solution was made alka-
line with ammonia to pH 10 and subsequently extracted
with ether , EtOAc , and n-BuOH to afford three parts of
118 Journal of Chinese Pharmaceutical Sciences 2003 , 12(3)
crude alkaloids.The ether extract contained two major al-
kaloids with very similar Rf values when tested by TLC.
By repeated chromatography with columns of silica gel us-
ing hexane-acetone-ethylamine (1∶1∶0.1)as the eluting
solvents , the isolation of corydine(3)(250 mg)and iso-
corydine (2)(125 mg)was accomplished.From higher
Rf(higher than that of corydine)part of the collected
fractions ,hemiargine C(6)(11 mg), hemiargine D(7)
(14 mg), tetrahydropalmatrubine (10)(25 mg), and
glaucine (9)(12 mg)were isolated and purified by using
low pressure liquid chromatography with silica gel and
preparative TLC.From lower Rf parts of the collected
fractions , salutaridine (8)(10 mg)and hemiargine B
(5)(8 mg)were isolated.From EtOAc extract , norc-
orydine (4)(7 mg), norlaudanosine (12)(23 mg), xy-
lopinine (11)(18 mg), and hemiargine A(1)(10 mg)
were isolated and purified by repeated chromatography on
silica gel columns.
Structure identification:
Hemiargine A　Square crystal , mp 200-202℃,
[α] 25D +122.2℃ (c 3.6 , CHCl3).IR(KBr)cm-1:
3 350 , 1 630 , 1 615 , 1 600 , 1 583 , 1 560 , 1 500 ,
1 420 , 1 210 , 1 200 , 1 150 , 1 100.1H NMRδ(CDC-
l3):6.85 (d , J=8.0 Hz), 6.79 (d , J =8.0 Hz),
6.62(s), 3.90 (s , OCH3), 3.89 (s , OCH3), 3.88
(s , OCH3), 3.82 (s , OCH3), 4.22 (dd , J=10.2 ,
3.0 Hz , H-6a), 3.23 , 3.19(m , H-5), 3.20(dd , J=
12.5 , 3.0 Hz , H-7α), 2.70(dd , J=12.5 , 10.2 Hz ,
H-7β), 2.90 (m , H-4).13C NMR δ:145.79 (s , C-
1), 147.22(s , C-2), 126.23(s , C-1a), 117.11(s ,
C-1b), 112.43 (d , C-3), 128.47 (s , C-3a), 29.18
(t , C-4), 48.41 (t , C-5), 58.13(d , C-6a), 36.91
(t , C-7), 129.22 (s , C-7a), 119.47 (d , C-8),
112.71 (d , C-9), 150.00 (s , C-10), 146.04 (s ,
C-11), 130.02(s , C-11a), 56.87(q , OCH3), 59.21
(q , OCH3), 60.01 (q , OCH3), 55.86 (q , OCH3).
EI-MS m z:341 [M] + , 326 , 330 , 192(base peak),
176 , 151 , 150 , 147 , 131 , 118 , 107 , 92 , 77.HREI-
MS m z:341.1671(cacld.For C20H23NO4 341.1627).
Hemiargine B 　Amorphous , IR (KBr) cm-1:
3 330 , 2 970 , 1 635 , 1 610 , 1 600 , 1 580 , 1 555 ,
1 510 , 1 425 , 1 210 , 1 190 , 1 150 , 980 , 975 , 800.
1
H NMRδ(CDCl3):6.72(d , J=8.0 Hz), 6.68(d ,
J=8.0 Hz), 6.65 (s), 3.89 (s , OCH3 , 3.90 (s ,
OCH3), 3.91(s , OCH3), 4.28(d , J=15.2 Hz , H-
7), 3.55(d , J=15.2 Hz , H-7), 3.60(dd , J=12.5 ,
3.0Hz , H-5), 3.20(dd , J=12.5 , 11.5 Hz , H-5),
2.85(dd , J=12.0 , 11.5 Hz , H-4), 2.70 (dd , J=
12.5 , 3.0 Hz , H-4).2.90 (m , H-4).13 C NMR δ
(CDCl3):144.42 (s , C-1), 121.45 (s , C-1a),
114.45(s , C-1b), 146.62(s , C-2), 110.98(d , C-
3), 137.71(s , C-3a), 31.22(t , C-4), 51.52(C-5),
179.33(s , C-6a), 32.11 (t , C-7), 136.62 (s , C-
7a), 120.78(d , C-8), 114.43(d , C-9), 146.62(s ,
C-10), 144.11(s , C-11), 123.35(s , C-11a), 58.81
(q , OCH3), 55 ,53 (q , OCH3), 55.78 (q , OCH3).
EI-MS m z:325 [M] + , 300 , 286 , 192 , 176.
Hemiargine C 　Amorphous , IR(KBr)cm-1:
3 450 , 3 300 , 1 635 , 1 610 , 1 600 , 1 510 , 1 500 ,
1 420 , 1 380 , 1 300 , 1 190 , 1 150.1H NMR δ
(CD3OD):9.12(s , H-11), 7.81(d , J=10.5Hz , H-
7), 7.62 (d , J=10.5 Hz , H-6a), 6.91 (s , H-3),
7.03(s , H-5), 3.98 (s , OCH3), 3.95(s , OCH3),
3.94 (s , OCH3), 3.51(t , J =7.5 Hz , 2H , H-5),
2.87(t , J =7.5 Hz , H-4).13 C NMR δ(CD3OD):
148.32(s , C-1), 151.45(s , C-2), 109.72(d , C-3),
125.10(s , C-3a), 134.31(s , C-1b), 124.62 (s , C-
1a), 115.41 (d , C-6a), 124.12 (d , C-7), 128.32
(s , C-7a), 109.00 (d , C-8), 148.45 (s , C-9),
144.87(s , C-9), 107.11(d , C-11), 31.31(t , C-4),
42.67 (t , C-5).58.81 (q , OCH3), 55.51 (q ,
OCH3), 55.72(q , OCH3).EI-MS m z:327 [M] + ,
312 , 296 , 297 , 265.
Hemiargine D 　Amorphous , IR(KBr) cm-1:
3 220 , 1 600 , 1 510 , 1 500 , 1 420 , 1 352 , 1151 ,
987 , 760.CI-MS m z:190 [M+H] + , 147 , 71 , 43.
1
H and
13
C NMR data were shown in Table 1.
Isocorydine 　Square crystal , mp 240 -242℃,
[ α] 25D +182.3°(c 1.3 , CHCl3).IR(KBr)cm-1:
3 300 , 1 650 , 1 620 , 1 570 , 1 480 , 1 460 , 1 435 ,
1 150 , 1 095 , 920 , 834.EI-MS m z:341 [ M] + ,
326 , 310 , 295 , 281 , 266 , 167 , 150 , 149 , 139 , 125 ,
105 , 83 , 71.1H NMRδ:6.86(s , H-3), 2.46(ddd ,
J=17.3 , 3.9 , 3.4 Hz , H-4a), 2.70 (dd , J=17.3 ,
3.4 Hz , H-4b), 3.06 (dd , J=13.0 , 17.3 , H-5b),
3.19(ddd , J=17.3 , 17.3 , 3.9 Hz , H-5a), 4.22(m ,
119Journal of Chinese Pharmaceutical Sciences 2003 , 12(3)
H-6a), 2.88(d , J=12.8 Hz , H-7a), 2.44(dd , J=
12.8 , 12.8 Hz , H-7b), 6.82(d , J=8.0 Hz , H-8),
6.84(d , J =8.0 Hz , H-9), 2.53 (N-CH3), 3.90
(OCH3):3.90 (OCH3), 3.70 (OCH3).13 C NMR δ
142.19(s , C-1), 125.00 (s , C-1a), 118.89 (s , C-
1b), 149.11(s , C-2), 111.12(d , C-3), 129.22(s ,
C-3a), 29.26 (t , C-4), 52.67 (t , C-5), 62.83(d ,
C-6a), 35.85 (t , C-7), 129.87 (s , C-7a), 118.13
(d , C-8), 111.17 (d , C-9), 151.21 (s , C-10),
144.04(s , C-11), 129.22(s , C-11a), 43.77(q , N-
CH3), 55.81 (q , OCH3), 55.82(q , OCH3), 61.91
(q , OCH3).
Corydine　mp 150-152℃, [ α] 25D +207°(c 1.0 ,
CHCl3).IR(KBr)cm-1:3 450 , 2 980 , 1 620 , 1 550 ,
1 450 , 1 200 , 1 150 , 820 , 730.1H NMRδ(CDCl3):
6.71(s , H-3), 2.50(dd , J=13.5 , 17.0 Hz , H-4α),
3.10(dd , J=13.5 , 4.0 Hz , H-5β), 2.65 (dd , J=
17.0 , 2.5 Hz), 3.20(ddd , J=17.0 , 17.0 , 4.0 Hz ,
H-5α), 2.70(dd , J=13.0 , 2.0 Hz , H-4), 7.11(d ,
J=8.0 , H-8), 6.90(d , J=8.0 Hz , H-8), 3.96(s ,
OCH3), 3.95(s , OCH3), 3.76(s , OCH3), 2.60(s ,
N-CH3).EI-MS m z:341 [ M] + , 326 , 310 , 298 ,
324 , 280 , 268 , 252 , 170 , 155 , 139 , 120 , 105 , 91 ,
74.
Norcorydine　Amorphous , [α] 25D +67.2°(c 3.2 ,
CHCl3).IR(KBr)cm-1:3 450 , 3 300 , 2 970 , 2 960 ,
1 632 , 1 610 , 1 550 , 1 520 , 1 420 , 1 400 , 1 220 ,
1 200 , 1 170 , 1 100 , 850 , 720 , 700.1H NMR δ
(CDCl3):6.77(s , H-3), 7.15(d , J=8.0 Hz), 6.95
(d , J=8.0 Hz), 3.99(s , OCH3), 3.89(s , OCH3),
3.80 (s , OCH3), 2.55 (dd , J =14.0 , 14.5 Hz ,
H-4α), 3.05(m), 3.10 (m), 2.70(m), 2.60 (dd ,
J=14.0 , 2.5 Hz), 2.92 (dd , J =16.0 , 14.0 Hz).
EI-MS m z :327 [M] + , 326 , 312 , 310 , 298 , 163.
Salutaridine　mp 223-225℃, [ α] 25D +140°(c
2.0 , CHCl3).IR(KBr)cm-1:3 320 , 2 980 , 1 670
(CO), 1 600 , 1 580 , 1 460 , 1 400 , 1 250 , 1 170 ,
1 020 , 1 000 , 830 , 790 , 750.1H NMR δ(CDCl3):
6.81 (d , J=8.3 Hz , H-1), 6.72 (d , J =8.3 Hz ,
H-2), 7.60 (s , H-5), 6.38 (s , H-8), 3.95 (s ,
OCH3), 3.80 (s , OCH3), 3.40 (d , J=18.5 Hz),
3.05(dd , J=18.5 , 6.5 Hz), 3.75(d , J=6.5 Hz),
2.50(N-CH3), 2.25(dd , J=16.5 , 8.5 Hz , H-15),
1.82 (ddd , J =16.5 , 16.5 , 6.5 Hz , H-15), 2.65
(m), 2.40(m , H-16).EI-MS m z:326 [M] + , 190 ,
178 , 58 , 39.
Table 1 　The 1H and 13 C NMR data of hemiargine D in
CDCl3
No. 13C(δ) 1H(δ) Hz
1a 126.20 d 7.23 d 7.6
1 126.56 d 7.28 d 7.6 , 7.8
2 126.55 d 7.09 d 7.8 , 7.8
3 131.09 d 7.23 d 7.8
3a 135.00 s
1b 137.50 s
4 29.59 t 1.74 d 11.8
2.70 d 11.8
5 55.31 s
6a 61.34 d 3.36 q 6.8
7 18.74 q 1.45 d 6.8
8 21.64 t 1.62 q 7.2
9 11.81 q 0.96 t 7.2
10 18.02 q 1.18 s
Glaucine　mp 120-122℃, [α] 25D +128°(c 6.9 ,
CHCl3).IR(KBr)cm-1:2 800 , 1 610 , 1 605 , 1 585 ,
1 450 , 1 320 , 1 200 , 1 105 , 970 , 950.1H NMRδ
(CDCl3):8.10(s , H-11), 6.98(s , H-8), 6.63(s ,
H-3), 3.90 (s , OCH3), 3.88(s , OCH3), 3.78 (s ,
OCH3), 3.70 (s , OCH3), 2.52 (s , N-CH3).EI-MS
m z:355 [M] + , 254 , 340 , 324 , 312 , 297 , 281.
Tetrahydropalmatrubine　Amorphous , IR(KBr)
cm
-1:2 980 , 2 976 , 1 615 , 1 600 , 1 550 , 1 520 , 1 430 ,
1 400 , 1 355 , 1 200 , 1 150 , 990 , 875 , 730.1H NMRδ
(CDCl3):6.78(d , J=8.0 Hz), 6.73(d , J=8.0Hz),
7.00(s), 6.62(s), 4.28(d , J=15.0 Hz), 3.90(s ,
9H), 3.52(d , J=15.0 Hz), 3.30(dd , J=14.2 , 3.0
Hz), 3.15 (m), 3.00-2.50 (m , 6H).13 C NMRδ
(CDCl3):147.37(s), 147.30(s), 143.95(s), 141.42
(s), 129.53(s), 127.83(s), 126.68(s), 121.00(s),
119.13(d), 111.26 (d), 108.89 (d), 108.51 (d),
59.13(d), 56.03(q), 55.56 (q), 55.73(q), 51.27
(t), 36.15 (t), 28.90 (t).EI-MS m z:327 [M] + ,
326 , 312 , 310 , 298 , 163.
120 Journal of Chinese Pharmaceutical Sciences 2003 , 12(3)
Xylopinoine　mp 182-183℃, IR(KBr)cm-1:
2 980 , 2 975 , 1 610 , 1 580 , 1 550 , 1 510 , 1 420 ,
1 215 , 1 155 , 870 , 720.1H NMRδ(CDCl3):6.71
(s), 6.70 (s), 6.62 (s), 6.55(s), 4.26(dd , J=
12.0 , 3.5 Hz), 4.12 (dd , J=14.0 , 6.0 Hz), 3.90
(s , OCH3), 3.98 (d , J =15.2 Hz), 3.70 (d , J =
15.2 Hz), 3.30 -2.60 (m , 6H).13 C NMR δ
(CDCl3):129.60 (s , C-1a), 108.46 (d , C-1),
147.38(s , C-2), 147.38(s , C-3), 147.38(s , C-3),
111.24(d , C-4), 126.60(s , C-4a), 29.25(t , C-5),
51.23(5 , C-6), 58.20 (t , C-8), 59.50 (d , C-9),
35.97(t , C-10), 126.20 (s , C-11), 109.14(d , C-
12), 147.30 (s , C-13), 147.30 (s , C-14), 111.43
(d , C-15), 55.95 (q , 4x OCH3).EI-MS m z :355
[M] + , 354 , 340 , 324 , 281 , 94.
Norlaudanosine 　Amorphous , IR(KBr)cm-1:
3 350 , 1 610 , 1 600 , 1 550 , 1 515 , 1 440 , 1 400 ,
1 335 , 990 , 980 , 780.1H NMR δ(CDCl3):6.80
(dd , J=8.0 1.8 Hz), 6.78 (d , J=8.0 Hz), 6.80
(d , J=1.8 Hz), 6.58 (s), 6.52 (s), 4.26 (br),
3.88(s , OCH3), 3.87(s , OCH3), 3.86(s , OCH3),
3.72(s , OCH3), 3.20-2.75 (m , 6H).13C NMRδ
(CDCl3):111.17(d , C-1), 147.70(s , C-2), 147.70
(s , C-3), 112.45(d , C-4), 28.00 (t , C-5), 41.55
(t , C-6), 56.15(d , C-8), 128.50(s , C-9), 126.80
(s , C-10), 40.06 (t , C-11), 130.07 (s , C-12),
111.53(d , C-13), 148.84(s , C-14), 146.99(s , C-
15), 109.38 (d , C-16), 121.49 (d , C-17), 55.69
(q), 55.76(q), 55.67(q), 55.97(q).EI-MS m z:
343 [M] + , 327 , 191 , 151.
Figure 1　Structure of compounds 1-12
121Journal of Chinese Pharmaceutical Sciences 2003 , 12(3)
　　Acknowlegement　Dr.Lin wishes to thank CNPq
for the financial support in the work.This paper is on the
memorial to Professor Barnes R.A.for his great contribu-
tion to phytochemistry in Brazil.
References
[ 1] Barnes RA , Gilbert MEA.The alkaloids from Croton geuns
[ J] .Biol Inst Qui Agric , 1959 , 58:1.
[ 2] Barnes RA.The isolation and structural determination of iso-
quinoline alkaloids from Croton salutaris [ J] .An Acad Bras
Cienc , 1964 , 36:238.
[ 3] Barnes RA , Soeiro OM.Alkaloids from Croton salutaris [ J] .
Phytochemistry , 1981 , 26:343.
[ 4] Jane ALB.MSc thesis , Chemical constituents from Croton
celtidifolius[ D] .Universidade Federal de Rio de Janeiro ,
1982.
[ 5] Istatkova K , Philipov SA.Alkaloids from Isopyrum thalictroi-
des [ J] .Phytochemistry , 2000 , 54:959.
[ 6] Lin QS.Chemistry of Chinese Herb Medicines [ M] .Beijing:
Beijing Science Publishing House , 1977.735.
[ 7] Johns RS , Lamberton JA , Li CS , et al.Aporphinoid type al-
kaloids from Croton genus [ J] .Aust J Chem , 1970 , 23:
307.
[ 8] Barnes RA , Soeiro OM.The alkaloids from plant Croton salu-
taris [ J] .Phytochemistry , 1981 , 26:343
[ 9] Shamma M , Hindenlang DM.Carbon-13NMR Shift Assign-
ment of Amine and alkaloids [ M] .New York:and London:
Plenum Press , 1979.
[ 10] Blanco OM , Castedo L , Villaverde MC.Alkaloids from
Platycapnos spicata [ J] .Phytochemistry , 1993 , 32:1055.
巴豆属植物 Croton hemiargyerius var.gymnodiscus 中生物碱的研究
林文翰1 , 付宏征1 , 李 军1 , 程 刚1 , Roderick A.Barnes2
(1.北京大学天然药物及仿生药物国家重点实验室 , 100083 北京;
2.里约联邦大学天然产物研究中心 , 里约热内卢 21941 巴西)
摘要:目的　从巴西巴豆属药用植物的一新变种复制Muel的叶中分离生物碱成分。方法　应用硅胶柱层析法分离和纯
化 ,波谱分析与已知化合物的波谱和理化性质比较得以确定化合物结构。结果　分离得到 12 个生物碱 , 其中 4 个为新生物
碱 ,命名为 hemiargine A(1), B(5), C(6)和 D(7);8个已知生物碱为 isocorydine(2), corydine(3), norcorydine(4), salutari-
dine(8), glaucine(9), tetrahydropalmatrubine(10), xy lopinoine(11)和 norlaudanosine(12)。结论　获得 4种新化合物 , 除生物碱
(8),其余生物碱均为首次从该属植物中获得 。
关键词:Croton hemiargyerius;生物碱;hemiargine A , B , C 和 D
122 Journal of Chinese Pharmaceutical Sciences 2003 , 12(3)