Chemical constituents from the leaves of Aglaia perviridis

Article abstract of DOI:10.1080/10286020903565226

A new cinnamic acid-derived bisamide 1 and a new oplopanone-type sesquiterpenoid diglycoside 2, together with 11 known compounds, were isolated from the 95% ethanolic extract of the leaves of Aglaia perviridis. Their structures were elucidated by chemical and spectroscopic methods.

Full text of DOI:10.1080/10286020903565226

Journal of Asian Natural Products Research
Vol. 12, No. 3, March 2010, 215–219
ORIGINAL ARTICLE
Chemical constituents from the leaves of Aglaia perviridis
a
Ling Zhang , Jian-Hui Zhang , Shu-Ming Yang , Chang-Heng Tan *,
ab
bc
b
b
Hong-Feng Luo and Da-Yuan Zhu
b
a
Department of Chemical Engineering and Technology, College of Environmental and Chemical
b
Engineering, Shanghai University, Shanghai 200444, China; Department of Natural Medicinal
Chemistry, Shanghai Institute of Materia Medica, Chinese Academy of Sciences,
Shanghai 201203, China; School of Chemical Biology and Pharmaceutical Sciences, Capital
c
Medical University, Beijing 100069, China
(Received 26 October 2009; final version received 25 November 2009)
A new cinnamic acid-derived bisamide 1 and a new oplopanone-type sesquiterpenoid
diglycoside 2, together with 11 known compounds, were isolated from the 95%
ethanolic extract of the leaves of Aglaia perviridis. Their structures were elucidated by
chemical and spectroscopic methods.
Keywords: Aglaia perviridis Hiern; 4-hydroxypyramidatine; oplopanone 10-O-b-D-
(
5-O-syringoyl)-apiofuranosyl-(1 ! 2)-b-D-glucopyranoside
1
.
Introduction
together with 11 known compounds,
including three 3,4-secodammarane triter-
penoids: aglinin A [5], shoric acid, and
eichlerianic acid [6]; two C27 nortriter-
penoids: eichlerialactone [7] and cabralea-
hydroxylactone [8]; two pregnane-type
steroids: 2b,3b-dihydroxy-5a-pregn-
The genus Aglaia belongs to the family
Meliaceae, which is distributed in South
China, India, Malaysia, Indonesia, and
parts of the Western Pacific region.
Extracts of these plants have been used
for the treatment of fever, inflammation,
and abdominal tumors and as bactericides
and insecticides [1]. Previous phyto-
chemical studies on the genus Aglaia
have revealed the presence of a variety of
compounds with interesting biological
activities, including rocaglamides, aglains,
bisamides, triterpenoids, lignans, and
steroids [2]. In continuation of our
investigation on the chemistry of the
Aglaia plants [3,4], we undertook a
chemical constituent study on the 95%
ethanolic extract of the leaves of Aglaia
perviridis Hiern, which led to the isolation
of a new cinnamic acid-derived bisamide 1
and a new sesquiterpenoid diglycoside 2,
1
5
7(Z)-en-16-one and 2b,3b-dihydroxy-
a-pregn-17(E)-en-16-one [9]; two alka-
loids: pyramidatine [10] and piperine [11];
one lignan: (þ)-eudesmin [12]; and
one sterol: 7a-hydroxysitosterol [13].
Eichlerialactone was first reported from
this genus, and the other compounds were
obtained from this plant for the first time.
Herein, we report the isolation and
structural elucidation of 1 and 2.
2.
Results and discussion
Compound 1, obtained as a white amor-
phous powder, had quasi-molecular ion
þ
peaks at m/z 361 ([MþNa] ) and m/z 337
*Corresponding author. Email: chtan@mail.shcnc.ac.cn
ISSN 1028-6020 print/ISSN 1477-2213 online
q 2010 Taylor & Francis
DOI: 10.1080/10286020903565226
http://www.informaworld.com

2
16
L. Zhang et al.
2
[M2H] ) in the positive and negative
(
confirmed the fragment of 1,4-butanedi-
amine to be connected with the cinnamic
acid amide and p-hydroxybenzoic amide
through two terminal N atoms. Therefore,
the structure of 1 was elucidated to be
4-hydroxypyramidatine.
ESI-MS, respectively, in accord with the
molecular formula C H N O , which
was further confirmed by HR-ESI-MS
2
0 22 2 3
þ
(
O Na requires 361.1528). The H NMR
found [MþNa] 361.1523, C H N
2
0 22 2
1
3
spectrum of 1 showed signals for two
aromatic rings, of one 1,4-disubstituted at
Compound 2 was obtained as a white
amorphous powder, and it had the
d 7.81 (2H, d, J ¼ 8.4 Hz) and 6.87 (2H, d,
molecular formula C35H O15 deduced
52
H
J ¼ 8.4 Hz), and of one mono-substituted
from the quasi-molecular ion peak at m/z
þ
at d 7.57 (2H, br d, J ¼ 8.4 Hz), 7.40 (2H,
735.3209 ([MþNa] ) in the HR-ESI-MS.
H
br t, J ¼ 7.6 Hz), and 7.38 (1H, br t,
J ¼ 6.6 Hz), one pair of conjugated
Under acid hydrolysis, 2 gave D-glucose
1
and D-apiose as the sugar moiety. The H
1
3
E-double bond at d 7.54 and 6.70 (each
H
and C NMR spectra (Table 1) showed
signals for a syringoyl at d 7.41 (2H, s)
and 3.92 (6H, s) and d 166.3 (s), 148.1
(2C, s), 141.7 (s), 120.6 (s), 107.8 (2C, d),
56.4 (2C, q), a b-apiofuranosyl at d 5.58
(1H, br s) and d 109.3 (d), 78.2 (s), 78.1
1
amine fragment at d 7.84 and 7.70 (each
H, d, J ¼ 15.6 Hz), and a 1,4-butanedi-
H
H
C
1
H, br s), 3.41 (2H, br q, J ¼ 6.1 Hz), 3.36
(
2H, br q, J ¼ 6.1 Hz), and 1.64 (4H,
H
qui-like, J ¼ 6.0 Hz), indicating a cin-
C
namic acid-derived bisamide [10].
(d), 75.0 (t), 69.7 (t), one b-glucopyrano-
syl groups at d 4.63 (d, J ¼ 7.6 Hz) and
1
3
The C NMR spectral data of 1 were
similar to those of pyramidatine [10],
except for the signals for a p-hydroxy-
benzoic amide unit instead of those for the
benzoic amide fragment of the latter.
HMBC and HMQC experiments (Figure 1)
H
d
96.0 (d), 78.7 (d), 76.7 (d), 76.5 (d),
C
71.7 (d), 62.5 (t), and a sesquiternoid
segment (four methyls, four methylenes,
five methines, and two quaternary car-
bons). The aglycone was characterized
O
HO
1
'''
O
O
7
'''
O
5
''
HO
HO
3
''
O
1
''
OH
O
O
OH
OH
2
'
1
'
1
H
4
O
5
OH
O
1
0
4
'
H
N
6'
1
1
''
1
N
H
'
2
3
6
5
7
4
''
2''
1
O
H
4
1
1
1
7
''
O
12
1
13
2
5
Figure 1. The structures and the selective HMBC correlations (H ! C) of 1 and 2.

Journal of Asian Natural Products Research
217
1
Table 1. H (400 MHz) and
(
13
C NMR
100 MHz) spectral data of 2 (in acetone-d ).
those of (2)-oplopan-4-one-10-a-O-b-
glucose.
6
The glycone moiety was determined
as b-D-(5-O-syringoyl)-apiofuranosyl-
(1 ! 2)-b-D-glucopyranosyl based on the
Site
dH
dC
1
2
3
4
5
6
7
8
9
1.50 (m)
55.9
26.0
29.0
210.6
54.8
45.9
49.2
22.8
38.2
79.7
29.8
21.8
15.5
18.4
29.2
96.0
76.7
78.7
71.7
76.5
62.5
a: 1.25 (m); b: 1.81 (m)
a: 1.37 (m); b: 1.80 (m)
–
13
C NMR spectral data comparison with
those of albibrissinoside A [16], which has
thesamesugar moiety, aswellasthe HMBC
correlations (Figure 1). Furthermore, the
2.15 (m)
1.71 (m)
0
0.95 (br q, 12.1)
a: 0.90 (m); b: 1.50 (m)
a: 1.34 (m); b: 1.99 (m)
–
HMBC correlations between C-10 and H-1
demonstratedtheglyconeunittobeattached
on C-10. Consequently, the structure of 2
was finally determined to be oplopanone
10-O-b-D-(5-O-syringoyl)-apiofuranosyl-
(1 ! 2)-b-D-glucopyranoside.
1
1
1
1
1
1
1
2
3
4
5
6
0
1
2
3
4
1.28 (m)
0.86 (3H, d, 7.0)
0.59 (3H, d, 7.0)
1.21 (3H, s)
5
0
1.96 (3H, s)
4.63 (d, 7.6)
3. Experimental
0
0
0
0
0
3.39 (dd, 9.2, 7.8)
3.58 (dd, 9.1, 8.8)
3.33 (dd, 9.5, 8.4)
3.27 (ddd, 9.5, 5.4, 2.6)
3.79 (dd, 11.2, 2.6);
3.1 General experimental procedures
Optical rotations were determined on a
Perkin-Elmer 341 polarimeter. The IR
spectra were recorded on a Nicolet-
Magna-750-FTIR spectrometer. The
NMR spectra were taken on a Bruker
AV-400 spectrometer using TMS as an
internal standard. ESI-MS spectra were
measured on a Bruker Esquire 3000 plus
mass spectrometer. The HR-ESI-MS spec-
tra were obtained on a Finnigan LC
QDECA mass spectrometer. Silica gel
3
.62 (dd, 11.2, 5.4)
0
0
0
0
0
0
0
0
0
0
0
1
2
3
4
5
1
2
3
4
7
5.58 (br s)
3.99 (s)
109.3
78.1
78.2
75.0
69.7
120.6
107.8
148.1
141.7
166.3
56.4
0
0
–
4.31 (d, 10.0); 3.94 (d, 10.0)
4.45 (d, 11.0); 4.31 (d, 11.0)
–
7.41 (2H, s)
0
0
00
00 000
/6
/5
00 000
–
–
–
00
00
(200–300 mesh) or silica gel H (Qingdao
OMe
3.92 (6H, s)
Haiyang, Co., Qingdao, China), Sephadex
LH-20 (Pharmacia Biotech AB, Uppsala,
Sweden) were used for column chroma-
tography (CC), and silica gel HSGF254
(Yantai Jiangyou Guijiao Kaifa Co.,
Yantai, China) was used for TLC.
with an acetyl at d 210.6 (s), 29.2 (q) and
C
dH 1.96 (3H, s) and an isopropyl group at
dH 0.59 (d, J ¼ 7.0 Hz) and 0.86 (d,
J ¼ 7.0 Hz), indicative of an oplopanone-
1
3
type sesquiternoid [14]. The C NMR
data for the aglycone were nearly super-
posed with those of (2)-oplopan-4-one-
3.2 Plant material
The leaves of A. perviridis (Meliaceae)
were collected in Xishuangbanna County,
Yunnan Province, China, in July 2006.
The plant was identified by Prof. Jing-
Yun Cui of Xishuangbanna Tropical
Botanical Garden, CAS. A voucher speci-
men (No. 20061058) is deposited at the
Herbarium of Shanghai Institute of
Materia Medica.
1
0-a-O-b-glucose [15], demonstrating
oplopanone as the aglycone moiety of 2.
The NOESY spectrum revealed the NOE
cross-peaks of H-1/H-5, H-7, and H-8a,
1
4-Me/H-2b, H-6, and H-9b, indicating
that 2 had the same configurations of H-
a, H-5a, H-6b, H-7a, and 14-Meb as
1

2
18
L. Zhang et al.
5:1). Fraction I gave pyramidatine (1.5g) as
crystals. Fraction II was subjected to silica
3
.3 Extraction and isolation
The dry leaves of A. perviridis (5kg) were
extracted with 20 liters of 95% EtOH at
room temperature for three times. The
concentrated extract was partitioned
between H O and petroleum ether, CHCl ,
gel CC (CHCl –MeOH, 15:1) to yield
3
fractions II.1–II.4. Compound 1 (15 mg)
was isolated from fraction II.3 through CC
(Sephadex LH-20, MeOH). Compound 2
(12 mg) was acquired from fraction III after
2
3
EtOAc, and BuOH, respectively. The
CHCl fraction (142g) was subjected to
chromatography of a silica gel column (i.d.
purification of a silica gel column (CHCl3–
MeOH, 8:1), and then of a Sephadex LH-20
column (MeOH).
3
10£80 cm) with the gradient CHCl –
Me CO (1:0, 25:1, 10:1, 5:1, 2:1, 0:1) as
3
2
eluents to give six fractions (A–F).
Fraction A yielded solids, which was
further purified by silica gel CC (CHCl3–
MeOH, 30:1) to afford 7a-hydroxysito-
sterol (100mg). Fraction B was subjected
to silica gel CC (CHCl –Me CO, 15:1) to
3
.3.1 4-Hydroxypyramidatine (1)
White amorphous powder. UV (MeOH)
lmax (log 1): 202 (4.87), 267 (4.72) nm. IR
nmax: 3292, 1701, 1655, 1626, 1540.9,
1508, 1248, 848, 768 cm
spectral data (acetone-d , 400 MHz): d
2
1
1
.
H NMR
3
2
6
yield fractions B1–B5. Fraction B2 furn-
ished (þ)-eudesmin (40 mg) after purifi-
0
7
.84 (1H, br s, H-6 ), 7.81 (2H, d,
J ¼ 8.4 Hz, H-3 and H-7), 7.70 (1H, br s,
cation of silica gel CC (CHCl –MeOH,
3
0
0
00
H-1 ), 7.57 (2H, br d, J ¼ 8.4 Hz, H-5 and
2
5:1). Fraction C was subjected to silica gel
0
00
00
H-9 ), 7.54 (1H, d, J ¼ 15.6 Hz, H-3 ),
CC (CHCl –Me CO, 10:1) to obtain
2
00
3
7
7
.40 (2H, br t, J ¼ 7.6 Hz, H-6 and H-8 ),
fractions C1–C6. Fraction C5 gave piper-
ine (40 mg) after purification of silica gel
CC (CHCl –Me CO, 5:1). Fraction D was
00
.38 (1H, br t, J ¼ 6.6 Hz, H-7 ), 6.87
(
(
2H, d, J ¼ 8.4 Hz, H-4 and H-6), 6.70
3
2
00
1H, d, J ¼ 15.6 Hz, H-2 ), 3.41 (2H,
separated into fractions D1–D5 through a
silica gel column (CHCl –MeOH, 15:1).
0
br t, J ¼ 6.1 Hz, H -5 ), 3.36 (2H, br t,
2
3
0
J ¼ 6.1 Hz, H -2 ), 1.64 (4H, qui-like,
2
Fractions D4 and D5 furnished aglinin A
(1.6g) and eichlerialactone (1.0g), respect-
0
0
13
J ¼ 6.0 Hz, H -3 and H -4 ). C NMR
2
2
00
00
(
acetone-d , 100 MHz): d 167.0 (C-1 ),
6
ively, by methods of recrystallization.
Fraction E was further isolated by silica
gel CC (CHCl –MeOH, 15:1) to provide
1
65.9 (C-1), 160.7 (C-5), 139.7 (C-3 ),
00
00
135.9 (C-4 ), 129.8 (C-7 ), 129.5 (C-3 and
C-7), 129.3 (C-6 and C-8 ), 128.1 (C-5
00
00
00
3
fractions E1–E6. Shoric acid (1.5g) and
eichlerianic acid (1.3g) were obtained as
crystals from fractions E3 and E4, respect-
ively. Fraction E5 was purified by silica gel
00
00
and C-9 ), 126.5 (C-2), 122.5 (C-2 ),
0
1
15.3 (C-4 and C-6), 39.4 (C-5 ), 39.2
0
0
0
(
C-2 ), 27.5 (C-3 ), 27.4 (C-4 ). ESI-MS
positive or negative): m/z 361.1
(
þ
þ
CC (CHCl –MeOH, 10:1) to afford cabra-
3
[MþNa] , 699.3 [2MþNa] , 337.1
2
M2H] ; HR-ESI-MS: m/z 361.1523
leahydroxylactone (60 mg). Fraction F was
subjected to silica gel CC (CHCl –MeOH,
[
þ
3
[MþNa] (calcd for C H N O Na,
2
0
22
2
3
10:1) to gain fractions F1–F6. Fraction F4
yielded mixed solids, which were further
3
61.1528).
isolated by silica gel CC (CHCl –MeOH,
3
3
.3.2 Oplopanone 10-O-b-D-(5-O-
1
1
0:1) to obtain 2b,3b-dihydroxy-5a-pregn-
7(Z)-en-16-one (7 mg) and 2b,3b-dihy-
syringoyl)apiofuranosyl-(1 ! 2)-b-D-
glucopyranoside (2)
droxy-5a-pregn-17(E)-en-16-one (8 mg).
The EtOAc-soluble fraction (60 g) was
separated into fractions I–IV by silica gel
25
White amorphous powder. ½aꢀ : 213.2
D
(c ¼ 0.600, MeOH). UV (MeOH) l
max
CC (CHCl –MeOH, 30:1, 20:1, 10:1, and
3
(log1): 219 (3.95), 279 (4.66) nm. IR n
:
max

Journal of Asian Natural Products Research
219
2
1
3
408, 1709, 1610, 1516, 1464, 1221cm
13
.
H and C NMR: see Table 1. ESI-MS
References
1
[1] C.M. Pannell, Kew Bull. Additional Ser.
16, 379 (1992).
[2] G. Brader, S. Vajrodaya, H. Greger, M.
Bacher, H. Kalchhauser, and O. Hofer,
J. Nat. Prod. 61, 1482 (1998).
þ
(
positive or negative): m/z 735 [MþNa] ,
þ
2
447 [2MþNa] , 711 [M2H] ; HR-ESI-
1
þ
MS: m/z 735.3209 [MþNa] (calcd for
C H O Na, 735.3204).
3
5
52 15
[3] S.M. Yang, C.H. Tan, H.F. Luo, D.X.
Wang, and D.Y. Zhu, Helv. Chim. Acta
9
1, 333 (2008).
[
4] S.M. Yang, W.W. Fu, D.X. Wang, C.H.
Tan, and D.Y. Zhu, J. Asian Nat. Prod.
Res. 10, 459 (2008).
3
.3.3 Acid hydrolysis of 2
Two milligrams of 2 were dissolved in
ml of 2 M HCl–dioxane (1:1), and then
[
5] K. Mohamad, T. SeAvene, V. Dumontet,
M. Pais, M. Van Tri, H. Hadi, K. Awang,
and M.T. Martin, Phytochemistry 51,
1031 (1999).
2
the solution was refluxed for 2 h. After
cooling, the solution was neutralized with
NaHCO , and then filtered to remove the
[
[
[
6] D. Roux, M.T. Martin, M.T. Adeline, T.
Sevenet, A.H.A. Hadi, and M. Pais,
Phytochemistry 49, 1745 (1998).
7] J. Phongmaykin, T. Kumamoto, T.
Ishikawa, R. Suttisri, and E. Saifah,
Arch. Pharm. Res. 31, 21 (2008).
8] B.N. Su, H. Chai, Q. Mi, S. Riswan, L.B.
Kardono, J.J. Afriastini, B.D. Santarsiero,
A.D. Mesecar, N.R. Farnsworth, G.A.
Cordell, S.M. Swanson, and A.D. King-
horn, Bioorg. Med. Chem. 14, 960 (2006).
3
solid. The filtrate was subjected to CC
(Sephadex LH-20, MeOH–H O, 1:1) to
2
afford a sugar fraction. This sugar fraction
and standard D-glucose and D-apiose
(Sigma, St Louis, MO, USA) were each
treated with L-cysteine methyl ester
hydrochloride (2 mg) in pyridine (1 ml) at
6
08C for 1 h. Then, the solution was treated
with N,O-bis(trimethylsilyl)trifluoroace-
tamide (0.02 ml) at 608C for 1 h. Sub-
sequently, the supernatant was subjected
to GC analysis (2308C, flow rate
15 ml/min; Supelco, Bellefonte, PA,
USA). D-Glucose (tR 24.2 min) and D-
[9] A. Inada, H. Murata, Y. Inatomi, T.
Nakanishi, and D. Darnaedi, Phytochem-
istry 45, 1225 (1997).
10] E. Saifah, J. Puripattanavong, K. Likhit-
witayawuid, G.A. Cordell, H. Chai, and
J.M. Pezzuto, J. Nat. Prod. 56, 473
(1993).
[
[
[
[
11] W. Ternes and E.L. Krause, Anal.
Bioanal. Chem. 374, 155 (2002).
12] J. Latip, T.G. Hartley, and P.G. Water-
man, Phytochemistry 51, 107 (1999).
13] M.D. Ecap, I. Onaco, and L. Revitera,
J. Nat. Prod. 53, 1430 (1990).
apiose (t 14.2 min) were detected.
R
Acknowledgements
The authors thank the National Science &
Technology Major Project ‘Key New Drug
Creation and Manufacturing Program’, China
[14] K. Takeda, H. Minato, and M. Ishikawa,
Tetrahedron Suppl. 7, 219 (1965).
[15] K.H. Lee, S.U. Choi, and K.R. Lee, Arch.
Pharm. Res. 28, 280 (2005).
(
2009ZX09301-001), the National Science
Foundation of China (No. 20602037), and the
Shanghai Leading Academic Disciplines
[16] M.J. Jung, S.S. Kang, Y.J. Jung, and J.S.
Choi, Chem. Pharm. Bull. 52, 1501
(2004).
(
S30109) for generous financial support.

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