全 文 ： 2013年 1月 第 11卷 第 1期 Chin J Nat Med Jan. 2013 Vol. 11 No. 1 81

Chinese Journal of Natural Medicines 2013, 11(1): 00810083
doi: 10.3724/SP.J.1009.2013.00081
Chinese
Journal of
Natural
Medicines







A new aristolactam alkaloid from the stems of
Dasymaschalon trichophorum
ZHOU Xiao-Lei1, 2, WU Jiu-Hong1*, BAI Jiao2, HU Xiao-Lan2, LI En-Zhen1, 3,
SHI Ning1, PEI Yue-Hu2
1Department of Pharmacy, The 306th hospital of PLA, Beijing 100101, China;
2School of Traditional Chinese Materia Medica, Shenyang Pharmaceutical University, Shenyang 110016, China;
3Institute of Pharmacology and Toxicology, Academy of Military Medical Sciences, Beijing 100850, China
Available online 20 Jan. 2013
[ABSTRACT] AIM: To study the chemical constituents of the stem of Dasymaschaon trichophorum Merr.. METHODS: The com-
pounds were isolated and purified by the methods of various chromatography. Their structures were elucidated on the basis of spectro-
scopic methods. RESULTS: Five aristolactam alkaloids were obtained and their structures were identified as 10-amino-3,6-dihy-
droxy-2,4-dimethoxyphenanthrene-1-carboxylic acid lactam (1), enterocarpam-II (2), oldhamactam (3), goniopedaline (4), and stig-
malactam (5), respectively. CONCLUSION: Compound 1 is a new aristolactam alkaloid, while compounds 2−5 are reported from this
genus for the first time.
[KEY WORDS] Annonaceae; Dasymaschaon trichophorum; Aristolactam alkaloids
[CLC Number] R284.1 [Document code] A [Article ID] 1672-3651(2013)01-0081-03

1 Introduction
 The genus Dasymaschalon Dalla Torre & Harms com-
prises about 16 species, three of which are distributed in the
south of China[1]. To date, only a few chemical constituents
of this genus have been reported, and most of them were
flavonoids and alkaloids[2-5]. In a phytochemical study on the
specie Dasymaschalon trichophorum Merr., five aristolactam
alkaloids were isolated and their structures were elucidated on
the basis of spectroscopic analysis as 10-amino-3, 6-dihy-
droxy-2, 4-dimethoxyphenanthrene-1-carboxylic acid lactam
(1), a new alkaloid, and four known aristolactam alkaloids,
enterocarpam-II (2), oldhamactam (3), goniopedaline (4), and
stigmalactam (5).
2 Results and Discussion
Alkaloid 1 was isolated as brownish yellow needles. The
molecular formula C17H13O5N was determined by

[Received on] 11-Apr.-2012
[Research funding] This project was supported by the National
Natural Science Foundation of China (No.81072546) and the Chi-
nese PLA National Science Fund for Distinguished Young Scholars
Grant during the 11th “Five-Year” Plan period (No.06J001).
[*Corresponding author] WU Jiu-Hong: Prof., Tel: 86-10-
66354564; Fax: 86-10-64879825, Email: jiuhongwu@hotmail.com
These authors have no conflict of interest to declare.
HR-ESI-MS at m/z 312.0867 [M + H]+ (Calcd. for C17H14O5
N1 312.086 6 ). The 13C NMR spectrum of alkaloid 1 indi-
cated the presence of 15 sp2 carbons (including a carbonyl
carbon at δ 166.9), which are typical for an aristolactam al-
kaloid[5-7]. Therefore, it was determined that 1 possesses an
aristolactam skeleton. Comparing its 1H and 13C NMR data
(see Table 1) with those of the known alkaloid goniopedaline
(4), 1 had an additional hydroxyl group. In the 1H-NMR
spectrum of 1, an ABX system for aromatic protons was ob-
served at δ 8.52 (1H, d, J = 2.5 Hz), 7.75 (1H, d, J = 8.6 Hz),
and 7.04 (1H, dd, J = 8.6, 2.5 Hz), attributable to H-5, H-8,
and H-7, respectively. A singlet at δ 7.05 (1H) was assigned
to H-9. These data resembled those of 5, 7, 8, 9-unsubstituted
aristolactams. The HMBC correlations (see Table 1) between
H-5 to C-6 and H-8 to C-6 confirmed the assignment of one
hydroxyl OH (δ 9.65) at C-6. The remaining two methoxyl
signals at δ 4.01 (3H, s) and 4.33 (3H, s) were assigned to
C-4 and C-2. The phenolic hydroxyl (δ 9.36) could be as-
signed to C-3. These assignments were verified by HMBC
correlations of the methoxyl protons at δ 4.01 with δ 150.1
(C-2), and δ 4.33 with δ 148.8 (C-4). The singlet signal at δ
10.73 was attributed to the amide NH, and this was con-
firmed by HMBC correlations between δ 10.73 to δ 109.9
(C-1), δ 132.4 (C-10) and δ 122.2 (C-10a). On the basis of
these results, 1 was established structurally as 10-amino-3, 6-
dihydroxy-2, 4-dimethoxyphenanthrene-1-carb-oxylic acid
lactam
ZHOU Xiao-Lei, et al. /Chinese Journal of Natural Medicines 2013, 11(1): 813
82 Chin J Nat Med Jan. 2013 Vol. 11 No. 1 2013年 1月 第 11卷 第 1期

The structures of the known alkaloids (2−5) were identi-
fied by comparing their spectroscopic data (1H NMR and 13C
NMR) with those reported in the literature.
3 Experimental
3.1 General experimental procedures
HR-ESI-MS was recorded on a Varian QFT-ESI mass
spectrometer. 1H NMR and 13C NMR spectra were recorded
on Bruker AV-600 NMR spectrometers using TMS as an
internal standard. The chromatographic silica gel (54−74 μm)
was purchased from Qingdao Marine Chemical Factory
(Qingdao, China). Sephadex LH-20 was purchased from GE
Healthcare. RP-HPLC analysis and semi-preparation were
conducted using Hitachi L-6000 pumping system equipped
with a Hitachi L-7400 UV detector and performed with a C18
column (10 mm × 250 mm, GL science Co., Ltd., Japan).
Fractions were monitored by thin layer chromatography
(TLC), and spots were detected with a UV 254 nm lamp and
by spraying with 10% H2SO4 in EtOH followed by heating at
105 ºC for 5 min.
3.2 Plant material
The stems of Dasymaschaon trichophorum Merr. were
collected in Dec. 2010 in Beihai, Guangxi Zhuang Autono-
mous Region, China, and identified by Prof. FANG Ding
(Guangxi Institute of Chinese Medicine & Pharmaceutical
Sciences). A voucher specimen (No. 76773) was deposited in
The 306th Hospital of PLA.
3.3 Extraction and isolation
The dried and powered plant material (8.1 kg) was ex-
tracted with 95% EtOH three times under reflux. After con-
centration, the extract (750 g) was suspended in water and
partitioned with CHCl3 followed by EtOAc. The CHCl3
residue (15 g) was subjected to silica gel column chromatog-
raphy (600 g) and eluted with petroleum−EtOAc mixtures in
a gradient (1 : 0 →0 : 1) to yield 15 fractions (1−15) . Frac-
tion 10 was then subjected to column chromatography over
silica gel (90 g) eluted with CHCl3−MeOH (100 : 1 →100 : 5)
to give subfractions (Fr. A1−Fr. A5). Fr. A2 was purified by
Sephadex LH-20 (MeOH), followed by RP-HPLC
[MeOH/H2O (58 : 42), 4.0 mL·min1] to obtain 4 (2.3 mg). Fr.
A3 was further separated by silica gel chromatography, fol-
lowed by Sephadex LH-20 column chromatography to obtain
3 (12.5 mg). Fr. A4 was purified by Sephadex LH-20
(MeOH), followed by RP-HPLC [MeOH/H2O (54 : 46), 4.0
mL·min1] to obtain 5 (3.7 mg). Fraction 11 was subjected to
column chromatography over silica gel (55 g) eluted with
CHCl3−MeOH (9 : 2) to give subfractions (Fr. B1-Fr. B4). Fr.
B4 was purified by Sephadex LH-20 (MeOH), followed by
RP-HPLC [MeOH/H2O (52: 48), 4.0 mL·min-1] to obtain 2
(4.6 mg).
The EtOAc residue (12 g) was subjected to silica gel
column chromatography (220 g) and eluted with petroleum-
Me2CO mixtures in a gradient (1 : 0 → 0 : 1) to yield 11 frac-
tions (1−11). Fraction 6 was purified by Sephadex LH-20
(MeOH), followed by RP-HPLC [MeOH/H2O (50 : 50), 4.0
mL·min1] to obtain 1 (3.2 mg).
4 Structural Identification
10-Amino-3, 6-dihydroxy-2, 4- dimethoxyphenan-
threne-1-carboxylic acid lactam (1) Brownish yellow nee-
dles (MeOH), HR-ESI-MS m/z 312.086 7 [M + H]+ (Calcd.
for C17H14O5 N1, 312.086 6 ); 1H and 13C NMR data are
shown in Table 1.
Table 1 1H NMR and 13C NMR spectra for alkaloid 1 ( 600
MHz and 150 MHz, DMSO-d6)
Position δH mult. (J Hz) δC COSY HMBC
1 109.9
2 148.8
3 143.8
4 150.1
4a 127.1
4b 115.8
5 8.52, d (2.5) 111.0 H-7 C-4a, 4b, 6, 7, 8a
6 155.8
7 7.04,dd (8.6, 2.5) 116.8 H-8 C-5, 8a
8 7.75,d (8.6) 130.2 H-7 C-6, 8a, 9
8a 127.5
9 7.05, s 104.6 C-8a, 10a
10 132.4
10a 122.2
C=O 166.9
NH 10.73, s C-1, 10, 10a
2-OCH3 4.33, s 62.7 C-2
4-OCH3 4.01, s 60.0 C-4
3-OH 9.36, s
6-OH 9.65, s

Enterocarpam-II (2) Brownish yellow needles
(MeOH). 1H NMR (600 MHz, DMSO-d6) δ: 10.77 (1H, s,
NH), 10.10 (1H, s, 3-OH), 8.62 (1H, d, J = 8.02 Hz, H-5),
7.85 (1H, s, H-9), 7.42 (1H, s, H-2) ,7.36 (1H, t, J = 8.02 Hz,
H-6), 7.08 (1H, d, J = 8.02, H-7), 4.05 (3H, s, 4-OMe), 4.01
(3H, s, 8-OMe); 13C NMR (150 MHz, DMSO-d6) δ:168.3
(C=O), 154.2 (C-3), 153.7 (C-8), 150.5 (C-4), 133.9 (C-10),
127.0 (C-8a), 125.7 (C-1), 123.9 (C-6), 123.3 (C-6), 121.6
(C-5), 120.2 (C-10a), 117.9 (C-4b), 112.1 (C-7), 109.9 (C-2),
98.7 (C-9), 59.8 (4-OMe), 56.9 (8-OMe). Alkaloid 2 was
identified as 10-amino-3-hydroxy-4, 8-dimethoxyphenan-
threne-1-carboxylic acid lactam by comparison of the spec-
tral data with the literature[8].
Oldhamactam (3) Brownish yellow needles (MeOH),
1H NMR (600 MHz, DMSO-d6) δ: 10.91 (1H, s, NH), 10.15
(1H, s, 8-OH), 8.58 (1H, d, J = 8.4 Hz, H-5), 7.53 (1H, s,
H-9), 7.35 (1H, t, H-6), 7.03 (1H, d, J = 8.4 Hz, H-7), 4.39
(3H, s, H-2), 4.08 (3H, s, 4-OMe), 3.91 (3H, s, 3-OMe); 13C
NMR (150 MHz, DMSO-d6) δ: 166.2 (C=O), 156.3 (C-8),
153.5 (C-2), 153.3 (C-4), 146.0 (C-3), 133.2 (C-10), 126.8
(C-6), 125.7 (C-8a), 125.0 (C-4a), 122.9 (C-10a), 116.9 (C-5),
115.7 (C-1), 110.7 (C-8), 109.6 (C-4b), 99.5 (C-9), 62.4 (2-
OMe), 61.3 (4-OMe), 60.7 (3-OMe). Alkaloid 3 was iden-
ZHOU Xiao-Lei, et al. /Chinese Journal of Natural Medicines 2013, 11(1): 813
2013年 1月 第 11卷 第 1期 Chin J Nat Med Jan. 2013 Jan. 11 No. 1 83

tified as 10-amino-8-hydroxy-2, 3, 4-trimethoxyphenanthrene
-1-carboxylic acid lactam by comparison of the spectral data
with the literature[9].

Fig. 1 Structures of alkaloids 1-5

Fig. 2 Key HMBC correlations of alkaloiud 2
Goniopedaline (4) Brownish yellow needles (MeOH),
1H NMR (600 MHz, DMSO-d6) δ: 10.90 (1H, s, NH), 9.52
(1H, s, 3-OH), 9.10 (1H, d, J = 7.38 Hz, H-5), 7.95 (1H, d, J
= 7.38 Hz, H-8), 7.54 (2H, m, H-6, 7), 7.17 (1H, s, H-9), 4.36
(3H, s, H-2), 4.04 (3H, s, 4-OMe); 13C NMR (150 MHz,
DMSO-d6) δ:166.6 (C=O), 149.6 (C-2), 148.5 (C-3),
143.9(C-4), 134.7 (C-10), 133.6 (C-4a), 128.7 (C-8), 126.3
(C-5), 125.9 (C-7), 125.6 (C-6), 122.0 (C-8a), 121.3 (C-10a),
115.7 (C-4b), 109.2 (C-1), 103.7 (C-9), 62.3 (2-OMe), 59.5
(4-OMe). Alkaloid 4 was identified as 10-amino-3-hydroxy-2,
4-dimethoxyphenanthrene-1-carboxylic acid lactam by com-
parison of the spectral data with the literature [10].
Stigmalactam (5) Brownish yellow needles (MeOH),
1H NMR (600 MHz, DMSO-d6 ) δ:10.83 (1H, s, NH), 9.72
(1H, s, 6-OH), 8.52 (1H, d, J = 2.46 Hz, H-5), 7.79 (1H, d, J
= 8.7 Hz, H-8), 7.15(1H, s, H-9), 7.06 (1H, dd, J = 8.7, 2.46
Hz, H-7), 4.37 (3H, s, H-2), 4.10 (3H, s, 4-OMe ), 3.91 (3H, s,
3-OMe); 13C NMR (150 MHz, DMSO-d6) δ: 166.5 (C=O),
155.8 (C-2), 146.1 (C-3), 156.6(C-4), 153.7(C-6), 132.1
(C-10), 130.3 (C-8), 127.6 (C-8a), 126.9 (C-10a), 125.8
(C-4a), 117.0 (C-7), 115.6 (C-4b), 111.1 (C-1), 110.3 (C-5),
106.1 (C-9), 63.2 (2-OMe), 61.9 (3-OMe), 61.2 (4-OMe).
Alkaloid 5 was identified as 10-amino-6-hydroxy-2,3,4-
trimethoxyphenanthrene-1-carbo-xylic acid lactam by com-
parison of the spectral data with the literature [11].
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皂帽花中的一个新生物碱
周晓磊 1, 2, 吴久鸿 1*, 白 皎 2, 胡晓兰 2，厉恩振 1, 3，史 宁 1，裴月湖 2
1解放军第 306医院药学部, 北京 100101;
2沈阳药科大学中药学院, 沈阳 110016;
3军事医学科学院毒物药物研究所, 北京 100850
【摘 要】 目的：对皂帽花化学成分的研究。方法：运用柱层析等方法分离纯化化合物, 通过波谱解析和理化鉴别进行结
构鉴定。结果：从皂帽花中分离得到 5个生物碱，分别是：10-amino-3, 6-dihydroxy-2, 4-dimethoxyphenanthrene-1-carboxylic acid
lactam (1), enterocarpam-II(2), oldhamactam (3), goniopedaline (4) 和 stigmalactam (5) 。结论：化合物 1 为新化合物, 化合物 2~5
均为首次从该属植物中分离得到。
【关键词】 番荔枝科; 皂帽花; 生物碱

【基金项目】 国家自然科学基金(No. 81072546)和全军“十一五”杰出人才基金（No. 06J001）资助项目