One alkenylphenol and steroids from the aquatic plant Monochoria vaginalis

Article abstract of DOI:10.1002/jccs.200400035

Two new compounds have been isolated from the whole plant of Monochoria vaginalis and characterized as: (10Z)-1-(2,6-dihydroxyphenyl)octadec-10-en-1-one (1) (20R,24R)-campest-5-ene-3β,4β-diol (2) together with nine known ones. The structures of these comp

Full text of DOI:10.1002/jccs.200400035

Journal of the Chinese Chemical Society, 2004, 51, 225-228
225
One Alkenylphenol and Steroids from the Aquatic Plant Monochoria
vaginalis
a
b
c
Lie-Ching Row (
Fiber Research Division, Union Chemical Laboratories, Industrial Technology Research Institute, V400,
), Chiu-Ming Chen (
) and Jiau-Ching Ho * (
)
a
UCL/ITRI, Bldg, 9, 321 Sec. 2 Kuang Fu Road, Hsinchu, Taiwan 31040, R.O.C.
b
Department of Chemical Engineering, Ta-Hwa Institute of Technology,
Chung-Lin, Hsinchu, Taiwan 30703, R.O.C.
c
Department of Chemistry, National Tsing Hua University, Hsinchu, Taiwan 30043, R.O.C.
Two new compounds have been isolated from the whole plant of Monochoria vaginalis and characterized
as: (10Z)-1-(2,6-dihydroxyphenyl)octadec-10-en-1-one (1) (20R,24R)-campest-5-ene-3b,4b-diol (2) to-
gether with nine known ones. The structures of these compounds were elucidated on the basis of spectral data
and chemical evidence.
Keywords: Monochoria vaginalis; Pontederiaceae; Phenol; Sterol; Ozonolysis.
INTRODUCTION
The aquatic plant Monochoria vaginalis (BURM. f.)
OH
1
O
1'
1
0' 11'
18'
(
CH2)8
(CH2)6CH3
2
3
OH
PRESL (Pontederiaceae) is widely distributed in the south of
28
1
1
21
Taiwan and used for the treatment of asthma and fever. Re-
2
6
24
cently we reported the isolation and structural elucidation of
two new cerebrosides and one new acylglycosyl sterol from
18 20
17
25
27
1
9
1
1
2
M. vaginalis. As a continuing study, a new alkenylphenol,
1
4
9
14
(
10Z)-1-(2,6-dihydroxyphenyl)octadec-10-en-1-one (1) and
10
a new sterol, (20R,24R)-campest-5-ene-3b,4b-diol (2) to-
RO
6
gether with nine known compounds, 24-methylenelophenol
OR
2
R=H
3
-4
5
13 R=Ac
(
3), 4a-methyl-5a-ergosta-7,24(28)-diene-3b,4b-diol (4),
6
stigmast-4-en-3-one (5), 6b-hydroxystigmast-4-ene-3-one
6
7-8
9
(
6), cyclolauden-3b-ol (7), vomifoliol (8), dehydro-
1
0
11
12
vomifoliol (9), 3-oxo-a-ionol (10), and (-)-loliolide (11)
have been isolated and characterized by spectral and chemi-
cal evidence.
HO
R
3
R=H
4
R=OH
RESULTS AND DISCUSSION
The molecular formula of compound 1 was determined
to be C24
38 3
H O by high-resolution HR-EIMS. The IR spec-
-
1
trum revealed hydroxy (3310 cm ), chelating conjugated
O
-
1
-1
ketone (1635 cm ) and aromatic (1590, 1520 cm ) absorp-
R
tions. The UV spectrum exhibited absorption (lmax) in metha-
5
6
R=H
R=OH
1
nol at 223, 269 (sh) and 342 (sh) nm. The H-NMR spectrum
*
Corresponding author. Tel: +886-3-5927700-2857, 2851; fax: +886-3-5927310; e-mail: hochiao@yahoo.com.tw

2
26 J. Chin. Chem. Soc., Vol. 51, No. 1, 2004
Row et al.
+
[
M -HOAc, C30
H
48
O
2
] by HR-EIMS. The diacetyl groups
were revealed by the NMR signals (Table 1) at d
H
2.05, 2.11
1
and d
C
21.1, 21.5, 170.1, 170.3. The H-NMR spectrum
showed six methyl signals at d 0.67 (3H, s, H
d, J = 6.8 Hz, H -28), 0.80 and 0.85 (each 3H, d, J = 6.7 Hz,
-26, -27), 0.91 (3H, d, J = 6.5 Hz, H -21) and 1.13 (3H, s,
-19). Two acetoxyl methine signals at d 4.74 (1H, ddd, J =
3
-18), 0.78 (3H,
3
H
H
3
3
3
HO
7
12.1, 4.4, 3.1Hz, H-3) and 5.50 (1H, d, J = 3.1 Hz, H-4)
should have 3S, 4R configurations by the J values at 12.1 and
1
3
.1 Hz, respectively. Additionally, the H-NMR spectrum
R1
R2
HO
showed one olefinic signal at d 5.82 (1H, dd, J = 5.1, 2.9 Hz,
O
1
3
H-6). The above data and C-NMR spectrum were almost
O
R3
identical with the authentic 3b,4b-diacetoxystigmast-5-
O
16
+
ene. The EI-MS spectrum signals at m/z 312 (M -HOAc-
11
+
C
9
H
19-H) and 271 (M -2HOAc-C
9
H
19) revealed the presence
8
9
R =R =OH, R =H
1 3 2
R , R =O, R =OH
of a saturated C
9
side chain. Furthermore, by comparing the
1
2
3
1
0 R =OH, R =R =H
1 2 3
chemical shift of H-21, H-26, H-27 and H-28 methyl signals
3
,5
suggested 20R,24R configurations. Thus the structure of 2
was elucidated as (20R,24R)-campest-5-ene-3b,4b-diol.
2
showed AM type aromatic protons at d 6.39 (2H, d, J = 8.0
Hz, H-4, 6) and 7.22 (1H, t, J = 8.0 Hz, H-5). The 8.0 Hz cou-
pling constant indicated that three protons were adjacent to
each other. Irradiation at d 6.39 collapsed the triplet at d 7.22
EXPERIMENTAL SECTION
1
to a singlet. The other peaks in the H-NMR spectrum showed
a terminal methyl group at d 0.86 (3H, t, J = 8.8 Hz, H-18¢), an
General Methods
alkyl chain at d 1.28 (CH
2 n
) , a methylene group at d 3.12 (2H,
EIMS spectra were taken with a JMS-HX-100 instru-
ment and HR-EIMS were recorded on a JEOL LMS-SX 102
system. UV spectra were recorded on a Perkin Elmer Lambda
t, J = 7.4 Hz, H-2¢) and a disubstituted double bond at d 5.35
1
3
(
2H, m, HC=CH). The C-NMR spectrum of 1 contained a
carbonyl group signal at d 207.8 (C-1¢), 1,2,3-trisubstituted
aromatic signals at d 108.5 (C-4, 6), 111.0 (C-2), 135.6 (C-5),
5
UV/VIS spectrophotometer. IR spectra were taken on a
JASCO FT-IR-110 infrared spectrophotometer. Optical ro-
tations were measured on a JASCO DIP-360 digital po-
1
61.2 (C-1, 3), and a disubstituted olefinic signal at d 130.0
HC=CH). These NMR data suggested compound 1 pos-
sesses one carbonyl group, two hydroxyl groups as well as a
(
1
13
larimeter. H- and C-NMR spectra were recorded on a
Bruker AM-400 NMR and Bruker DMX-600 NMR spec-
trometers. Column chromatography was performed using sil-
1
3,14
disubstituted double bond in the C18 side chain.
ence of a base fragmentation peak in HR-EIMS spectrum at
m/z 137.0243 (Calcd for C ; 137.0239) suggested the
existence of a dihydroxybenzoyl moiety in 1. The side chain
olefin adopting a Z configuration could be supported by CH
The pres-
OH
O
7
5 3
H O
1
2
3
1'
18'
10'
11'
2
OH
1
3
1
peaks at d 27.5, 27.7 (C-9¢, 12¢) in C-NMR spectrum since
the chemical shift values of allylic methylene were around d
O3 /CH2Cl2 , -78 ¢J
DMS
1
5
2
7 and 33 for cis and trans olefine, respectively. Ozonolysis
of 1 produced an aldehyde (12) (Fig. 1), which indicated that
the double bond of the side chain was located between C-10¢
and C-11¢. From the above evidence, the structure of 1 was
deduced as (10Z)-1-(2,6-dihydroxyphenyl)octadec-10-en-
OH
O
O
10'
O
H
H
+
1
-one.
The sterol 2 was isolated as a diacetyl derivative 13
which showed the pseudo-molecular peak at m/z 440.3635
OH
12
Fig. 1. Ozonolysis of compound 1.

Alkenylphenol and Steroids from Monochoria vaginalis
J. Chin. Chem. Soc., Vol. 51, No. 1, 2004 227
1
13
Table 1. H- and C-NMR Data of Compound 13
1
3
1
13
1
Position
C
H
Position
C
H
1
2
3
4
5
6
7
8
9
1
1
1
1
1
1
36.8
22.5
72.9
76.2
138.2
131.7
32.0
31.9
50.2
36.1
25.5
39.6
42.3
56.8
24.2
16
17
18
19
20
21
22
23
24
25
26
27
28
OAc
OAc
28.2
56.0
11.8
20.2*
36.1
18.7
33.7
29.4
38.8
4.74 (ddd, 12.1, 4.4, 3.1)
5.50 (d, 3.1)
0.67 (s)
1.13 (s)
5.82 (dd, 5.1, 2.9)
0.91 (d, 6.5)
0
1
2
3
4
5
31.6
20.4*
20.5*
15.4
21.1; 170.1
21.5; 170.3
0.80 (d, 6.7)
0.85 (d, 6.7)
0.78 (d, 6.8)
2.08 (s)
2.01 (s)
1
13
4
*
00 MHz ( H) and 100 MHz ( C), CDCl
Assignments may be interchanged
3
ica gel (230-400 mesh, Merck) and charcoal activity (chro-
matography, Wako). Thin-layer chromatography (TLC) was
conducted on precoated Kiesel gel 60 F254 plates (0.25 mm,
Merck). Spots were located by ultraviolet illumination and by
spraying the ferric chloride reagent or 10% sulfuric acid fol-
lowing by heating. MPLC was carried out on a Buchi MPLC
system (pump, Buchi 688; detector, KAUER).
mg), 4 (23 mg), 5 (52 mg), 6 (26 mg), 7 (16 mg), 8 (22 mg), 9
(2 mg), 10 (3 mg), 11 (2 mg).
(Z)-1-(2,6-Dihydroxyphenyl)-octadec-10-en-1-one (1)
+
A colorless gum, HR-EIMS m/z: 374.2831 (M , Calcd
for C24
H
38
O
3
; 374.2821), m/z: 137.0243 (Calcd for C
7
H
5
O
3
;
+
137.0239). EI-MS m/z (rel. int.): 374 (M , 20), 330 (19), 189
(
18), 165 (73), 152 (76), 137 (100), 123 (14). IR (neat) nmax
-
1
Plant Material
cm : 3310, 2950, 1635, 1590, 1520, 1240, 1040, 720. UV
The dry whole plant (4.3 Kg) of M. vaginalis was col-
lected from the south of Taiwan in August 1998. A voucher
specimen was deposited at the Department of Chemical Engi-
neering, Ta-Hwa Institute of Technology, Hsinchu, Taiwan.
(MeOH) lmax nm (e): 342 (3000), 269 (11900), 223 (13800).
1
3
H-NMR (CDCl , 400 MHz) d: 0.86 (3H, t, J = 7.8 Hz,
H-18¢), 1.28 (H-4¢ to H-8¢; H-13¢ to H-17¢, br s), 1.62 (2H, m,
H-3¢), 2.02 (4H, m, H-9¢, 12¢), 3.12 (2H, t, J = 7.4 Hz, H-2¢),
5
.35 (center of AB system of H-10¢ and H-11¢, J10, 11~10 Hz),
Extraction and Separation
6.39 (2H, d, J = 8.0 Hz, H-4, 6), 7.22 (1H, t, J = 8.0 Hz, H-5),
1
3
Dried whole plants of M. vaginalis were extracted with
methanol (five times, each time 20 L) under reflux conditions
for 4-6 hr. The methanolic layer was chromatographed on a
3
9.60 (br s, OH). C-NMR (CDCl , 100 MHz) d: 14.1 (C-18¢),
27.5, 27.7 (C-9¢, 12¢), 22.3, 22.7, 29.2, 29.4, 33.3 (C-3¢ to
C-8¢; C-13¢ to C-17¢), 44.8 (C-2¢), 108.5 (C-4, 6), 111.0 (C-2),
130.0 (C-10¢, 11¢), 135.6 (C-5), 161.2 (C-1, 3), 207.8 (C-1¢).
Ozonolysis of 1: Compound 1 (5 mg) was dissolved and
stirred in dichloromethane 5 mL at -78 °C (acetone-dry ice),
and then ozone gas was blown in. The resulting solution was
treated with DMS (Dimethyl sulfide, 3 mL). After being
stirred for 12 hr, the homogeneous mixture was concentrated
charcoal column, eluting with MeOH, MeOH-CH
and CH Cl to afford three fractions. Each fraction was con-
centrated to give brownish viscous residue. The CH Cl layer
120 g) was chromatographed on a silica gel column (hex-
ane-ethyl acetate gradient) to give six fractions (Frs 1-6). Fr.
was further separated by MPLC using silica gel columns
25% ethyl acetate/n-hexane) and prep. TLC (silica gel, 5%
MeOH/CH Cl ) to afford 1, 5 and 7. Fr. 5 was separated by a
combination of MPLC (silica gel, 50% ethyl acetate/n-hex-
ane) and prep. TLC (silica gel, 10% MeOH/CH Cl ) to afford
-4, 6, 8-11. Yields: compound 1 (39 mg), 2 (3 mg), 3 (18
2 2
Cl (7:3)
2
2
2
2
(
3
(
and then partitioned by ether/H
2
O. The ether extract was pu-
2
2
rified by prep-TLC to give 12. Compound 12: A colorless
+
gum, HR-MS m/z: 278.1534 (M , Calcd for C16
H
22
O
4
).
+
2
2
EI-MS m/z (rel. int.): 278 (M , 8), 277(3), 137 (10), 149 (19),
-
1
2
87 (70), 74 (80), 18 (100). IR (neat) nmax cm : 3350, 2950,

2
28 J. Chin. Chem. Soc., Vol. 51, No. 1, 2004
Row et al.
2
850, 2710, 1720, 1620, 1590, 1460.
Previtera, L. Phytochemistry 1990, 29, 1797.
. Greca, M. D.; Monaco, P.; Previtera, L. Phytochemistry
989, 28, 629.
5. Greca, M. D.; Monaco, P.; Previtera, L. Tetrahedron 1991,
7, 7129.
4
1
(20R,24R)-3b,4b-Diacetoxycampest-5-ene (13)
2
2
Amorphous gum. [a] -45.5 (c = 0.1, CHCl
3
). HR-MS
D
+
4
m/z: 440.3635 [(M-HOAc) , Calcd for C30
H
48
O
2
; 440.3654].
6. Younus, M. S.; Carl, D. Tetrahedron 1974, 30, 4095.
EI-MS m/z (rel. int.): 440 (9), 399 (32), 398 (100), 396 (19),
7. Motoko, Y. A.; Yamazaki, S.; Ageta, H. Phytochemistry
-
1
3
1
12 (5), 271 (4). IR (neat) nmax cm : 2900, 2850, 1740, 1650,
1
991, 30, 3369.
1
13
220, 1060. H-NMR (CDCl
3
, 400 MHz) d: Table 1. C-
8. Dasai, M. C.; Singh, C. C. Tetrahedron 1982, 38, 201.
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NMR (CDCl
3
, 100 MHz) d: Table 1.
10. Takasugi, M.; Anetai, M.; Katsui, N.; Masamune, T. Chem.
Lett. 1973, 3, 245.
1
1. Murakami, T.; Kimura, T.; Wada, H.; Tanaka, N.; Saiki, Y.;
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