全 文 ： 84 Chin J Nat Med Mar. 2010 Vol. 8 No. 2 2010 年 3 月 第 8 卷 第 2 期

Chinese Journal of Natural Medicines 2010, 8(2): 0084−0087
doi: 10.3724/SP.J.1009.2010.00084
Chinese
Journal of
Natural
Medicines








Polyoxygenated Seco-cyclohexene Derivatives from
Uvaria tonkinensis var. subglabra
ZHANG Chuan-Rui, WU Yan, YUE Jian-Min*
State Key Laboratory of Drug Research, Shanghai Institute of Materia Medica, Chinese Academy of Sciences, Shanghai, 201203, China
Available online 20 Mar. 2010
[ABSTRACT] AIM: To study the chemical constituents from the twigs of Uvaria tonkinensis var. subglabra. METHODS: Com-
pounds were obtained by silica gel chromatography, and their structures were assigned by spectroscopic methods. RESULTS: Two
new polyoxygenated seco-cyclohexenes, namely uvarisubols A (1) and B (2), along with seven known compounds zeylenol,
1,6-desoxypipoxide, 1-epizeylenol, uvamalol G, uvarirufol C, uvamalol F and ferrudiol, were isolated and structurally elucidated.
CONCLUSION: Uvarisubols A and B are two new polyoxygenated seco-cyclohexene analogues.
[KEY WORDS] Uvaria tonkinensis var. subglabra; Polyoxygenated seco-cyclohexenes; Uvarisubol A; Uvarisubol B
[CLC Number] R284.1 [Document code] A [Article ID]1672-3651(2010)02-0084-04

1 Introduction
The plants from Uvaria genus (Annonaceae) are widely
distributed over the tropical zone of Asia, Africa, and Austra-
lia, and there are about 10 species occurring in southern
China [1]. Chemical investigations on the genus Uvaria have
led to the isolation of an array of polyo- xygenated cyclo-
hexene derivatives [1-2], some of which showed biological
importance, such as antileukemic and antimalarial activities
[3], and nucleoside transport inhibitory activity [4]. Plant
Uvaria tonkinensis var. subglabra, which grows mainly in
Hainan, Guangdong and Yunnan provinces of China, has
been used as antifungal and anticancer agents [5]. Previous
chemical studies on this plant have afforded a number of
compounds, e.g. polyoxygenated cyclohexene derivatives and
cerebroside [6-8]. In the current study, two new polyoxygen-
ated seco-cyclohexene derivatives, uvarisubols A (1) and B (2)
(Fig. 1), together with seven known ones, were isolated from
the ethanolic extract of U. tonkinensis var. subglabra. We
present herein the isolation and structural elucidation of the
new compounds 1 and 2.
2 Results and Discussion
Uvarisubol A (1), a white amorphous powder, had a mo-

[Received on] 12-Jun-2009
[*Corresponding author] YUE Jian-Min: Prof., Tel: 86-21-5080
6718; Fax: 86-21-50806718; E-mail: jmyue@mail.shcnc.ac.cn


Fig. 1 Structures of compounds 1 and 2

lecular formula of C28H26O8 as determined by HR-EI-MS ion
at m/z 368.125 4 [M - BzOH]+ (calcd. 368.126 0) with 16
degrees of unsaturation. All of the 28 carbons in the molecu-
lar formula were resolved in the 13C NMR spectrum (Table 1),
and were classified as two methylenes, twenty methines and
six quaternary carbons by DEPT experiments. The IR ab-
sorptions exhibited the presence of monosubstitu- ted phenyl
rings (1 601, 1 452 and 710 cm−1) [9], ester ( 1 720 cm−1) and
hydroxyl (3 431 cm−1) groups. The presence of three benzoyl
groups was implied by 1H NMR signals at δ 7.41–8.08 (15H)
and 13C NMR (Table 1), and supported by the typical EI-MS
ions at m/z 77, 105 and 122 [BzOH]+. The 1H NMR spectra
showed the signals of additional nine protons, which included
two olefinic protons at δ 6.16 (dd, J = 15.8, 4.2 Hz) and δ
6.13 (dt, J = 15.8, 3.2 Hz). In addition, the proton signal of
ZHANG Chuan-Rui, et al. /Chinese Journal of Natural Medicines 2010, 8(2): 84−87
2010 年 3 月 第 8 卷 第 2 期 Chin J Nat Med Mar. 2010 Vol. 8 No. 2 85

methine bearing a benzoyloxy group resonated at δ 5.69 (m)
and the proton signals for two other methines bearing hy-
droxyl groups appeared at δ 4.11 (ddd, J = 11.8, 6.0, 1.9 Hz)
and δ 3.89 (dd, J = 7.6, 1.9 Hz), respec- tively. The proton
signals of two methylenes bearing the benzoyloxy groups as
found in the compounds of this structural class appeared at δ
4.88 (d, J = 3.2 Hz, 2H) and δ 4.50 (br d, J = 6.0 Hz, 2H).
The aforementioned three benzoyl groups and the only dou-
ble bond accounted for all the 16 degrees of unsaturation,
indicating that compound 1 is a polyoxygenated
seco-cyclohexene derivative [10-11]. On the basis of the
chemical shifts and coupling constants of key protons of 1 as
observed in the 1H NMR, along with the HMBC spectrum
(Fig. 2), the planar structure of 1 was finally assigned. In the
HMBC spectrum, three benzoyloxy groups were located at
C-1, C-4 and C-7 by the strong HMBC correlations of
H2-1/C-7′, H2-7/C-7″ and H-4/C-7″′, respectively; two hy-
droxyls were assigned to C-5 and C-6 by the mutual HMBC
correlations as depicted in Fig.2, and confirmed by the
chemical shifts of C-5 (δC 72.1) and C-6 (δC 68.1). The cou-
pling constant of H-2 and H-3 (J = 15.8 Hz) indicated that the
Δ2 double bond took the E-geometry. However, the relative or
the absolute configuration at C-4, C-5, and C-6 cannot be
assigned by the available data due to the free rotational fea-
ture of this type of compounds.
Uvarisubol B (2), a white amorphous powder, gave the
molecular formula of C21H22O7 as determined by HR-EI-MS
ion at m/z 264.101 1 [M - BzOH]+ (calcd. 264.099 8), and
supported by a positive mode of ESI-MS at m/z 409 [M +
Na]+. Comparison of the NMR data of 2 (Table 1) with those
of 1 suggested they are structurally close analogues, except
for the presence of a hydroxyl group at C-4 of 2 in the place

Table 1 1H and 13C NMR data of compounds 1 and 2
1a 2b
No.
δC δH (multi, J in Hz) δC δH (multi, J in Hz)
1 64.3 4.88 (d, 3.2, 2H) 65.3 4.84 (d, 5.9, 2H)
2 129.2 6.13 (dt, 15.8, 3.2) 125.3 6.06 (ddt, 15.5, 5.9, 1.5)
3 128.8 6.16 (dd, 15.8, 4.2) 136.4 6.18 (dd, 15.5, 5.3)
4 73.8 5.69 (m) 72.2 4.30 (m)
5 72.1 3.89 (dd, 7.6, 1.9) 73.7 3.64 (dd, 7.4, 2.1)
6 68.1 4.11 (ddd, 11.8, 6.0, 1. 9) 68.7 4.32 (m)
7 65.8 4.50 (brd, 6.0, 2H) 66.8 4.40 (brd, 6.3, 2H)
1′
1′′
1′′′
129.6
129.5
129.4
130.9 129.0
2′, 6′
2′′, 6′′
2′′′, 6′′′
129.8
129.7
129.6
8.03–8.08 (m, 6H) 129.9 129.8
8.03 (m, 2H)
8.01 (m, 2H)
3′, 5′
3′′, 5′′
3′′′, 5′′′
128.5
128.4
128.4
7.41–7.47 (m, 6H) 129.1 129.0
7.42 (m, 2H)
7.40 (m, 2H)
4′
4′′
4′′′
133.5
133.2
133.1
7.54–7.61 (m, 3H) 133.6 133.5
7.56 (m)
7.54 (m)
7′
7′′
7′′′
166.7
166.3
166.0
166.4 166.2
a Data were measured in CDCl3 at 400 MHz (1H) and 100 MHz (13C). b Data were measured in CD3COCD3 at 400 MHz (1H) and 100 MHz (13C).
Chemical shifts (δ) were expressed with TMS as the internal standard.



Fig. 2 Key HMBC (H→C) correlations of 1 and 2
ZHANG Chuan-Rui, et al. /Chinese Journal of Natural Medicines 2010, 8(2): 84−87
86 Chin J Nat Med Mar. 2010 Vol. 8 No. 2 2010 年 3 月 第 8 卷 第 2 期

of the benzoyloxy group at C-4 of 1. In the 1H NMR spec-
trum of 2, the H-4 (δ 4.30, m) up-field shifted ca. Δδ 1.39 as
compared with that of 1, indicating that a hydroxyl group was
located at C-4 (δ 72.2) of 2. The planar structure of 2 was
further confirmed by the analysis of HMBC spec- trum (Fig.
2).
Seven known compounds were identified to be zeylenol
[12], 1,6-desoxypipoxide [13], 1-epizeylenol [14], uvamalol G [11],
uvarirufol C [15], uvamalol F [16], and Ferrudiol [17] on the
basis of their 1H, 13C NMR and EI-MS data.
3 Experimental
3.1 General
IR spectra were recorded on a Perkin-Elmer 577 spec-
trometer (KBr disc). UV spectra were measured on a Shima-
dze UV-2550 UV-visible spectrophotometer. Optical rota-
tions were made on a Perkin-Elmer 341 polarimeter at room
temperature. NMR spectra were measured on a Bruker
AM-400 spectrometer with TMS as internal standard. EI-MS
(70 eV) and ESIMS were carried out on a Finnigan MAT 95
mass spectrometer and an Esquire 3000plus LC-MS instru-
ment, respectively. All solvents used were of analytical grade
(Shanghai Chemical Plant, Shanghai, People’s Republic of
China). Silica gel (200-300 mesh), silica gel H60 and MCI gel
(CHP20P, 75-150 μm, Mitsubishi Chemical Industries Ltd.)
were used for column chromatography, and pre-coated Sigel
GF254 plates (Qingdao Marine Chemical Plant, Qingdao,
China) were used for TLC.
3.2 Plant Material
The twigs of U. tonkinensis var. subglabra were col-
lected from Hainan island of China and authenticated by
Professor Shi-Man Huang of Hainan University. A voucher
specimen has been deposited in Shanghai Institute of Materia
Medica (accession number Uv-tonsubglabra-2004-1Y).
3.3 Extraction and Isolation
The powder of dried twigs (2 kg) of U. tonkinensis var.
subglabra was extracted with 95% ethanol at room tempera-
ture to give a green-dark residue (282 g), which was parti-
tioned between EtOAc and water to give an EtOAc- soluble
fraction E (61 g). The E fraction was subjected to a MCI gel
column eluting with MeOH-H2O (6∶4 to 9∶1) to give three
subfractions (F1-F3). F1 was subjected to CC on silica gel
eluting with petrol-EtOAc (2∶1) to obtain a major com-
pound, which was then purified by silica gel CC eluting with
petrol-Me2CO (4∶1) to yield 2 (60 mg) and zeylenol (25
mg). F2 was subjected to silica gel CC eluting with pet-
rol-EtOAc (5∶1 to 2∶1) to afford five fractions (F2a– F2e).
F2a and F2d were subjected to silica gel CC eluting with
petrol-Me2CO (6∶1 and 4∶1) to give 1, 6-desoxy- pipoxide
(21 mg) and 1-epizeylenol (45 mg), respectively. F3 was
separated on a silica gel CC eluting with petrol-EtOAc (5∶1
to 2∶1) to afford five fractions (F3a-F3e). F3a was chroma-
tographed on a silica gel column eluting with CHCl3-MeOH
(300∶1) to give uvamalol G (38 mg) and uvarirufol C (5
mg). F3b and F3d were purified by silica gel CC eluting with
CHCl3-MeOH (200∶1) to yield the uvamalol F (10 mg) and
Ferrudiol (40 mg), respectively. F3e was subjected to silica
gel CC eluting with petrol-Me2CO (4 ∶ 1) and then
CHCl3-MeOH (200∶1) to give 1 (30 mg).
Uvarisubol A (1): white amorphous powder; [α]20D
+ 42.3 (c 0.800, CHCl3); UV (MeOH): λmax (log ε) 228 (4.89),
273 (4.06) nm. IR (KBr) vmax 3 431, 1 720, 1 703, 1 601, 1
452, 1 317, 1 275, 1 111, 1 070, 710 cm-1; for 1H and 13C
NMR data, see Table 1; EI-MS m/z 368 (0.1) [M - BzOH]+,
351 (0.1), 325 (0.1), 311 (0.3), 282 (0.8), 228 (0.8), 203 (18),
122 (3), 105 (100), 77 (14); HR-EI-MS: 368.125 4 ([M -
H2O]+, C21H20O6+; calcd. 368.126 0).
Uvarisubol B (2): white amorphous powder; [α]20D
+34.3 (c 0.900, CHCl3); UV (MeOH): λmax (log ε) 228 (4.67),
273 (3.85) nm. IR (KBr) vmax 3 489, 3 367, 1 718, 1 695,
1 452, 1 379, 1 279, 1 113, 1 092, 1 066, 717 cm-1; for 1H and
13C NMR data, see Table 1; ESI-MS m/z 409 [M + Na]+;
EI-MS m/z 264 (0.1) [M - BzOH]+, 246 (0.1), 233 (0.2), 203
(1.1), 195 (11), 123 (10), 105 (100), 77 (16); HR-EI-MS:
264.101 1 ([M - BzOH]+, C14H16O5+; calcd. 264.099 8).
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乌藤中的裂环多氧取代环己烯类化合物
张传瑞, 吴 艳, 岳建民*
中国科学院上海药物研究所国家新药研究重点实验室, 上海 201203
【摘 要】 目的：研究乌藤中的化学成分。方法: 运用硅胶柱色谱技术分离化合物并用光谱技术鉴定其结构。结果: 从乌
藤中分离并鉴定得到 2 个新的裂环多氧取代环己烯衍生物 uvarisubol A 和 uvarisubol B, 以及 7 个已知化合物。 结论：Uvarisubol
A 和 uvarisubol B 是 2 个新的裂环多氧取代环己烯。
【关键词】 乌藤; 裂环多氧取代环己烯; Uvarisubol A; Uvarisubol B

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