全 文 ： 98 Chin J Nat Med Mar. 2011 Vol. 9 No. 2 2011 年 3 月 第 9 卷 第 2 期

Chinese Journal of Natural Medicines 2011, 9(2): 0098−0100
doi: 10.3724/SP.J.1009.2011.00098
Chinese
Journal of
Natural
Medicines







A New Phragmalin-type Limonoid from
Chukrasia tabularis var. velutina
LUO Jun, WANG Jun-Song, CAO Wen-Jun, KONG Ling-Yi*
Department of Natural Medicinal Chemistry, China Pharmaceutical University, Nanjing 210009, China
Available online Mar. 2011
[ABSTRACT] AIM: To study the limonoid constituents of Chukrasia tabularis var. velutina. METHODS: The constituents were
isolated with silica gel, ODS column chromatography and preparative HPLC, their structures were elucidated on the basis of the NMR
and HRESIMS spectral data. RESULTS: Two phragmalin-type limonoids, tabulalin F (1) and tabulalin (2) were isolated.
CONCLUSION: Tabulalin F (1) was a new compound and tabulalin (2) was isolated from this plant for the first time.
[KEY WORDS] Meliaceae; Chukrasia tabularis var. velutina; Phragmalin-type limonoid
[CLC Number] R284.1 [Document code] A [Article ID] 1672-3651(2011)02-0098-03

1 Introduction
The plants of genus Chukrasia, a timber tree, grow
mainly in tropical areas of Asia such as India and southern
mainland China and contain C. tabularis and its variety, C.
tabularis var. velutina [1]. Its stem bark has been used tradi-
tionally as an astringent, antidiarrheal, and anti-influenza
agent in China [2]. Chemical constituents research indicated
that plants of chukrasia were rich source of phragmalin-type
limonoids [3]. In our ongoing research program on phragma-
lins from C. tabularis var. velutina, six C-15-acyl phrag-
malin-type limonoids featuring a C-16/C-30 δ-lactone ring
and a series of 16-norphragmalin-type limonoids were iso-
lated [4-6]. In this paper, we reported the isolation and struc-
tural elucidation of a new phragmalin limonoid, tabulalin F
(1), and known tabulalin (2) (Fig. 1).
2 Experimental
2.1 Apparatus and reagents
NMR spectra were recorded on Bruker ACF-300, 500, or
600 NMR instrument with TMS as internal standard. Mass

[Received on] 23-Nov.-2010
[Research Funding] This project was supported by the National Key
Scientific and Technological Special Projects of China (No. 2009ZX
09502-011).
[*Corresponding author] KONG ling-Yi: Prof., Tel: 86-25-8327
1405. Fax: 86-25-8530 1528， E-mail: cpu_lykong@126.com
These authors have no any conflict of interest to declare.

Fig. 1 Structures of compounds 1-2
spectra were obtained on a MS Agilent 1100 Series LC/MSD
iron-trap mass spectrometer (ESI-MS) and a Mariner
ESITOF spectrometer (HR-ESI-MS), respectively. All sol-
vents used were of analytical grade (Jiangsu Hanbang Sci-
ence and Technology Co., Ltd.). Silica gel (Qingdao Marine
Chemical Co., Ltd.), Sephadex LH-20 (Pharmacia), and Rp-
C18 (40-63 μm, Fuji) were used for column chromatography.
Preparative HPLC was carried out using Agilent 1100 Series
with Shimpark Rp-C18 column (20 mm × 200 mm) and a
1100 Series Multiple Wavelength detector.
2.2 Plant material
The air-dried stem bark of C. tabularis var. velutina was
collected from Xishuangbanna, Yunnan Province, China, in
March 2007, and was authenticated by Prof. Zhang Mian of
Research Department of Pharmacognosy, China Pharmaceu-
tical University. A voucher specimen (No. 2006-MML) had
been deposited in the Department of Natural Medicinal
Chemistry, China Pharmaceutical University.
LUO Jun, et al. /Chinese Journal of Natural Medicines 2011, 9(2): 98−100
2011 年 3 月 第 9 卷 第 2 期 Chin J Nat Med Mar. 2011 Vol. 9 No. 2 99

2.3 Extraction and isolation
The air-dried stem bark (10 kg) was extracted by reflux-
ing with 95% ethanol three times. The EtOH extract was
concentrated under reduced pressure (2 000 g) and then ex-
tracted with CHCl3 to give a chloroform extract (300 g). The
oily chloroform extract was dissolved in 2 L 50% MeOH and
H2O and then extracted with petroleum ether. After removal
of the fatty components, 210 g of extract was obtained, which
was subjected to pass over a silica gel column eluted with
CHCl3-MeOH in a gradient (1 : 0 to 1 : 2), to obtain eight
fractions (Fr. A-H) according to TLC monitor. Fr. E (20 g)
was chromatographed on a column of reversed-phase C18
silica gel eluted with MeOH-H2O (4 : 6 to 7 : 3) to give six
sub-fractions (Fr. E1-E6). Fr. E6 was chromatographed on a
column of reversed-phase C18 silica gel eluted with MeOH-
H2O (2 : 3 to 7 : 3) to give three sub-fractions (Fr. E6a-E6c),
Fr. E6b was separated by preparative HPLC using CH3CN
/H2O (40 : 60, 10 mL·min-1) as the mobile phase to give 2 (4
mg). Fr. G (6 g) was chromatographed on a column of silica
gel eluted successively with a gradient of petroleum ether-
EtOAc (1 : 1 to 1 : 4) to give four sub-fractions (Fr. G1-4). Fr.
G4 was chromatographed on a column of reversed-phase C18
silica gel eluted with MeOH-H2O (2 : 3 to 7 : 3), and then
separated by preparative HPLC using CH3OH-H2O (50 : 50,
10 mL·min-1) as the mobile phase to give 1 (4 mg).
3 Results and Discussion
Tabulalin F (1) was isolated as white amorphous powder.
Its HRESI-MS ion at m/z 583.215 6 [M + Na]+ indicated the
molecular formula to be C29H36O11 (Calcd.: C29H36O11Na,
583.215 0). In the 1H and 13C NMR spectra of 1, three
down-field shifted proton resonances at δH 7.57 (brs, H-21),
6.50 (brs, H-22), and 7.45 (t-like, J = 1.2 Hz, H-23) and four
carbon signals at δC 120.5 (C-20), 141.6 (C-21), 110.4 (C-22),
and 143.0 (C-23) were typical of a β-substituted furanyl moi-
ety. A pair of germinal doublets at δH 1.69 (d, J = 10.8 Hz)
and 2.03 (d, J = 10.8 Hz) were assigned to H-29 protons of
characteristic 4, 29, 1-ring-bridge in phragmalin, which was
confirmed by the HMBC correlations (Fig. 2) observed from
the H-29 protons to the quaternary carbons at δC 81.6 (C-1),
86.8 (C-3), 43.9 (C-4), 37.9.1 (C-5), and 44.2 (C-10). Afore-
mentioned information as well as other key information from
2D NMR studies (HMBC, HSQC and NOESY) suggested 1
was a phragmalin-type limonoid. The presences of a down-
field signal at δH 7.17 (H-15) and two olefinic carbon signals
at δC 165.8 (C-14) and 120.5 (C-15) suggested that a charac-
teristic ∆14, 15 α, β-unsaturated δ-lactone ring was existed in 1 [7].
Above analysis indicated that compound 1 was a phragma-
lin-type limonoid with ∆14, 15 double bond.

Fig. 2 Key HMBC and NOESY correlations of tabulalin F (1)
In 13C NMR spectra of 1, the presence of six oxygened
quaternary carbons at δC 81.6, 75.3, 86.8, 76.1, 80.0, and 66.9
indicated that the oxidized level of 1 was lower than that of
other phragmalins from chukrasia genus. Carefully analysis
the 2D NMR (HMBC and HSQC) spectra corresponding to
these carbons lead to assign their locations, which were at
C-1, C-2, C-3, C-8, C-17, and C-30 respectively. HMBC
correlations between proton signal (δH 4.77, H-3) of skeleton
and ester carbonyl carbon (δC 170.6) indicated that OH-3 was
acetylated. Thus, the planar structure of 1 was determined
finally.
The relative stereochemistry of 1 was elucidated by the
NOESY spectrum (Fig. 2). Strong cross-peaks from the H-30
to H-5 and H-15, H-17 to H-12β, H-3 to Me-28, Me-19 to
H-29a, indicated that H-5, H-30, H-17, and Me-28 were co-
facial and adopted an β-orientation, H-3, H-29, and Me-19
were α-orientated [7]. The correlations between H-17 to H-21
and Me-18 to H-22 indicated that the β-substituted furanyl
moiety and Me-18 were α-orientated. The α-orientation of
H-9 was determined by the correlation of H-9 with Me-19.
Thus, the structure of 1 was demonstrated as depicted (Fig. 1).
Compound 2 was isolated as white amorphous powder.
Negative ESI-MS m/z: 591.3 [M – H]- (100); positive ESI-
MS m/z 593.0 [M + H]+ (100). Its structure was identified to
be known tabulalin [7] by comparison of the NMR and MS
data with the published values.
LUO Jun, et al. /Chinese Journal of Natural Medicines 2011, 9(2): 98−100
100 Chin J Nat Med Mar. 2011 Vol. 9 No. 2 2011 年 3 月 第 9 卷 第 2 期

Table 1 1H NMR and 13C NMR data of 1 and 2
1a 2b No. H (J in Hz) C H (J in Hz) C
1 81.6 83.5
2 75.3 76.4
3 4.77, s 86.8 5.05, s 86.1
4 43.9 43.7
5 2.60, br s 37.9 2.14, d (10.4) 38.6
6 2.30, m, 2H c 34.0 2.40, m, 2H c 34.1
7 173.2 173.9
8 76.1 72.5
9 1.88, dd (10.8,2.4) 48.6 78.6
10 44.2 48.1
11α 1.40 m c 1.90 m c
11β 1.70 m c 20.1 2.10 m c 34.5
12α 1.30 m c 3.74 c 65.8
12β 1.90 m c 33.5
13 38.4 45.2
14 165.8 163.4
15 7.17, s 120.5 6.35, s 120.3
16 165.2 165.2
17 5.24, s 80.0 5.90, s 78.6
18 1.32, s, 3H 22.9 1.54, s, 3H 14.7
19a 1.14, s, 3H 1.37, s, 3H
19b 21.0 13.9
20 120.5 121.6
21 7.57, brs 141.6 7.61, br s 142.4
22 6.50, brs 110.4 6.60, br s 109.8
23 7.45, t-like (1.2) 143.0 7.51, t-like (1.2) 144.5
28 0.87, s, 3H 14.6 0.75, s, 3H 14.7
29a 2.03, d (10.8) 1.90, d (10.8) 1.66, d (10.8)
29b 1.69, d (10.8) 40.4 1.69, d (10.8) 40.1
30 4.24, s 66.9 4.41, s 68.3
OCH3-7 3.70, s, 3H 51.9 3.72, s, 3H 52.2
170.6 170.7 OAc-3 2.23, s, 3H 21.1 2.07, s, 3H 21.6
a Recorded at 600 MHz (1H) and 150 MHz (13C) in DMSO-d6, b Recorded at 300 MHz (1H) and 125 MHz (13C) in CDCl3, c Signal pattern unclear
due to overlapping.

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毛麻楝中的一个新 phragmalin柠檬苦素
罗 俊, 汪俊松, 曹文君, 孔令义*
中国药科大学天然药物化学教研室, 南京 210009
【摘 要】 目的：研究毛麻楝中结构新颖的 phragmalin 柠檬苦素。方法：应用各种分离方法对毛麻楝茎皮的乙醇提取物进
行分离纯化, 通过一维和二维 NMR 以及 HRESI-MS 方法鉴定化合物的结构。结果：分离鉴定了 2 个 phragmalin 柠檬苦素, 分
别为 tabulalin F (1) 和 tabulalin (2)。结论：Tabulalin F (1)为新化合物; tabulalin (2)首次从毛麻楝中分离得到。
【关键词】 楝科; 毛麻楝; Phragmalin 柠檬苦素

【基金项目】 国家“重大新药创制”科技重大专项(No. 2009ZX09502-011)