全 文 ：Received 23 Oct. 2003 Accepted 21 Jun. 2004
Supported by the National Natural Science Foundation of China (30025044) and the State Key Program of Basic Research of China (“973”
project, 2002CB512807).
* Author for correspondence. Tel.: +86 (0)21 50806718; Fax: +86 (0)21 50807088; E-mail: .
http://www.chineseplantscience.com
Acta Botanica Sinica
植 物 学 报 2004, 46 (8): 1002-1008
Terpenoids and Phenols from Taiwania flousiana
XIANG Ying, YANG Sheng-Ping, ZHAN Zha-Jun, YUE Jian-Min*
(State Key Laboratory of Drug Research, Institute of Materia Medica, Shanghai Institutes for Biological Sciences,
The Chinese Academy of Sciences, Shanghai 201203, China)
Abstract: Two new terpenoids, namely taiwaniatriol (1) and senecrassidiol-9-O-b-D-glucopyranoside (8),
along with fifteen known compounds including five triterpenoids (2-6), one diterpene (7) and nine phenols
(9-17), were isolated from the root bark of Taiwania flousiana Gaussen. Taiwaniatriol was elucidated as
(24S)-3b-methoxy-5a-lanost-9(11)-ene-7b, 24, 25-triol. Their structures were established mainly by
spectral methods.
Key words: Taiwania flousiana; Taxodiaceae; triterpenoids; sesquiterpene glycoside; phenols
The genus Taiwania belonging to the family Taxodiaceae
has only two species. A number of sesquiterpenes (Cheng
et al., 1967; Kuo et al., 1969; He et al., 1997), diterpenes
(Lin et al., 1995; Lin et al., 1996; Lin et al., 1998a),
cycloadducts of diterpenes (Lin et al., 1996; Lin et al., 1997),
sterols (Lin et al., 1998a), lignans (Lin et al., 1967; Lin et al.,
1998b) and biflavones ( Kamil et al., 1977; Kamil et al.,
1981) were isolated from Taiwania cryptomerioides. Among
these compounds, a-cadinol showed selectively cytotoxic
activity against the human colon adenocarcinoma (HT-29)
cell line with an ED50 value of 0.778 mg/mL (He et al., 1997).
Ferruginol and taiwanin C exhibited significant antifungal
activity (Chang et al., 1999).
T. flousiana Gaussen, an evergreen tree with linear-tri-
angular leaves mainly distributed in China and northern
Burma, has not been previously investigated chemically.
In an effort to understand the chemical constituents of this
plant, seventeen compounds, including six triterpenoids,
one sesquiterpene glycoside, one diterpenoid, and nine
phenols were isolated from the root bark of T. flousiana.
Two of them are new compounds, namely (24S)-3b-methoxy-
5a-lanost-9(11)-ene-7b,24,25-triol (1) and senecrassidiol-9-
O-b-D-glucopyranoside (5). A trivial name taiwaniatriol was
given to compound 1. Their structures were established
mainly by spectral methods. Herein, we present the isola-
tion and structural elucidation of these compounds (Fig.1).
1 Results and Discussion
(24S)-3b-Methoxy-5a-lanost-9(11)-ene-7b,24,25-triol
(1), obtained as white powder, [a]20 D + 42.0º (c 0.14, CHCl3).
The molecular formula C31H54O4 was determined by HR-
EI-MS at m/z 490.400 8 [M]+ (calcd. 490.402 2). Its IR spec-
trum showed absorption bands at 3 547 cm-1 and 3 452
cm-1 ascribable to hydroxyl groups, and a medium absorp-
tion band at 1 628 cm-1 assignable to a double bond. In the
1H-NMR (see Experimental) and 13C-NMR spectra (Table
1), it exhibited signals for one secondary methyl, seven
tertiary methyls, one methoxyl group, three oxygenated ter-
tiary carbons, one oxygenated quaternary carbon, and one
trisubstituted double bond. The spectral data of compound
1 were remarkably similar to those of compound 2 except
for the presence of one more hydroxyl group attached to a
tertiary carbon. Compared with compound 2, the carbon
signals of C-6, C-7 and C-8 in compound 1 resonating at d
31.9, 72.5 and 50.4 were down-field shifted Dd 10.7, 44.5 and
8.6, respectively, indicating the presence of a C-7-OH (Fig.
1). The C-5 signal (d 49.2) of compound 1 was up-field shifted
Dd 3.8 compared with that of compound 2 caused by a
typical g-gauche effect of the C-7-OH, suggesting that the
C-7-OH took a b-orientation, which was confirmed by the
large coupling constants of H-7 (dt, J = 10.6, 4.9 Hz) taking
an axial position. Compared with the known compound
vietchiolide (Tanaka and Matshunaga, 1990) with a 7b-OH,
the carbon signals of the B-ring and the coupling constants
of 7a-H in compound 1 were dramatically matched with
those reported for vietchiolide. 2D-NMR experiment (HMQC
and HMBC) further confirmed the structure of compound 1
(Fig.2). The structure of compound 1 was thus elucidated
to be (24S)-3b-methoxy-5a-lanost-9(11)-en-7b, 24, 25-triol.
Senecrassidiol-9-O-b-D-glucopyranoside (8) obtained
as pale gum, [a]20 D -34.0º (c 0.18, CH3OH), has the molecu-
lar formula C21H36O7 determined by HR-EI-MS at m/z
XIANG Ying et al.: Terpenoids and Phenols from Taiwania flousiana 1003
382.237 0 [M-H2O]+ (calcd. 382.235 5) and the 13C-NMR
spectra. A broad IR absorption band at 3 415 cm-1 was
ascribed to hydroxyl groups. The 1H-NMR spectrum
showed three angular methyl signals at d 0.87, 0.94 and 1.12
(each 3H, s). A typical fragmentation ion at m/z 220 [M-62-
H2O]+ and 13C-NMR spectral data suggested that the com-
pound 8 was likely a sesquiterpenoid glucoside. The 1H-
NMR and 13C-NMR (see Experimental) indicated the sugar
Fig.1. Structures of compounds 1-17.
Table 1 13C-NMR data of compounds 1-4 (CDCl3, 400 MHz)
No. 1 2 3 4 No. 1 2 3 4
1 36.2 36.0 36.1 36.7 17 50.2 51.0 51.0 50.9
2 28.6 28.1 29.7 33.6 18 14.3 14.4 14.4 14.4
3 88.4 88.6 78.9 217.3 19 22.0 22.2 22.2 22.0
4 38.9 39.0 39.1 47.7 20 36.4 36.4 36.4 36.4
5 49.2 53.0 52.5 53.4 21 18.6 18.5 18.5 18.5
6 31.9 21.2 21.4 22.5 22 33.7 33.9 33.9 34.9
7 72.5 28.0 28.1 28.0 23 28.8 28.7 28.7 27.7
8 50.4 41.8 41.8 41.9 24 79.6 79.6 79.6 79.6
9 146.3 148.7 148.5 147.1 25 73.3 73.2 73.2 73.2
10 39.1 39.4 39.4 39.1 26 26.6 26.5 26.5 25.6
11 117.2 114.7 114.9 116.2 27 23.3 23.2 23.2 23.2
12 36.9 37.2 37.1 37.2 28 18.3 18.5 18.5 18.5
13 45.1 44.3 44.3 44.3 29 28.2 28.2 28.1 26.5
14 46.5 47.0 47.0 47.0 30 16.3 16.4 15.6 21.8
15 36.7 33.6 33.9 33.9 OCH3 57.6 57.5
16 22.6 22.5 28.1 28.7
Acta Botanica Sinica 植物学报 Vol.46 No.8 20041004
moiety was glucose. The proton and carbon signals of the
anomeric center of the glucose (d H 4.31, 1H, d, J = 7.9 Hz; dC
100.7) suggested a b-configuration. The 1H-NMR and 13C-
NMR data of the aglycone moiety of compound 8 were
closely matched with those of senecrassidiol (Bohlman and
Ziesche, 1981; Iwabuchi et al., 1990), except for the C-9 at d
79.0 and the C-10 at d 22.8, the former was down-field shifted
ca. Dd 5, and the latter was up-field shifted ca. Dd 4 com-
pared with those of senecrassidiol resulting from
glycosylation, indicating that the sugar moiety was defi-
nitely linked to C-9. The structure of compound 8 was thus
elucidated as senecrassidiol-9-O-b-D-glucopyranoside.
Compounds 2 and 3 were respectively identified as
(24S)-3b-methoxy-5a-lanost-9(11)-ene-24,25-diol and (24S)-
5a-lanost-9(11)-ene-3b,24,25-triol on the basis of spectral
data (Kutney et al., 1981). As no 13C-NMR spectral data
have been reported for compounds 2 and 3 before, the
detail assignments of 13C-NMR data for compounds 2 and
3 were thus made for the first time (Table 1). Compound 4
was identified as 3-oxo-lanost-9(11)-ene-24S,25-diol (Wada
et al., 2001). The known serratene triterpenes, serrat-14-en-
3b,21b-diol (5) (Fang et al., 1991) and 29-acetoxy-3b-
methoxyserrat-14-en-21a-ol (6) (Wada et al., 2001) were
identified by comparison of the spectral data with those
reported. The known diterpenoid was identified as 9b,13b-
endoperoxide-abieta-8 (14)-en-18-oic acid (7) by compari-
son of its 1H- and 13C-NMR spectral data with those re-
ported values of its methyl ester (Monaco et al., 1987;
Barrero et al., 1991). This paper deals with the spectral data
in its original form (see experimental).
The known lignans, icariside E4 (9) (Miyase et al., 1989),
(2R,3R)-2,3-dihydro-7-hydroxy-2-(4 ¢-hydroxy-3 ¢-
methoxyphenyl)-3-hydroxymethyl-5-benzofuranpropanol
4¢-O-(3-O-methyl-a-L-rhamnopyranoside) (10) (Pan and
Lundgren, 1995), (2R, 3R)-2, 3-dihydro-7-hydroxy-2-(4¢- hy-
droxy-3 ¢ -methoxyphenyl) -3 -hydroxymethyl -5 -
benzofuranpropanol-4¢-O-a-L-rhamnopyranoside (11)
(Popoff and Theander, 1975), and dihydrodehydrodiconif-
eryl alcohol 4¢-O-b-D-glucoside (12) (Abe and Yamauchi,
1986) were identified by spectral data.
The known compounds, monoaryl glycosides b-
hydroxypropiovanillone 3-O-b-D-glucopyranoside (13)
(Anderson and Lundgren, 1988), 3,4-dimethoxyphenyl-2-
O - ( 3 -O -m e t h y l - a - L - r h a mn o p y r a n o s y l ) - b - D -
glucopyranoside (14) (Pan and Lundgren, 1995), and three
known flavonoids taxifolin 3¢-O-b-D-glucopyranoside (15),
taxifolin (16) (Shen and Theander, 1985), and quercetin-3¢-
O-b-D-glucopyranoside (17) were also identified by com-
parison of their spectral data with those reported.
2 Experimental
2.1 General
Optical rotations were measured on a Perkin-Elmer 341
polarimeter (Na filter, l=589 nm). IR spectra were recorded
on a Perkin-Elmer 577 spectrometer. NMR spectra were re-
corded on a Bruker AM-400 (400 MHz) spectrometer with
TMS as internal standard. Mass spectra including high-
resolution mass spectra were recorded on a Finnigan MAT
95 mass spectrometer. All solvents used were of analytical
grade (Shanghai Chemical Plant). Silica gel (200-300 mesh)
was used for column chromatography, and pre-coated silica
gel GF254 plates (Qingdao Marine Chemical Plant) were
used for TLC. C-18 reversed-phase silica gel (150-200 mesh,
Merck) and MCI GEL CHP20P (75-150 m) (Mitsubishi
Chemical Industry Ltd.) were also used for column
chromatography.
2.2 Plant material
The root bark of Taiwania flousiana Gaussen was col-
lected in Lichuan, Hubei, China (May, 2001) and was au-
thenticated by Prof. ZHANG Chang-Gong (Tongji Medical
College, Huazhong University of Sciences and Technology,
Wuhan, China). A voucher specimen (20010102) has been
deposited in the Faculty of Pharmacognosy, Tongji Medi-
cal College, Huazhong University of Sciences and
Technology.
2.3 Extraction and isolation
The dried root bark (1.15 kg) was powdered and ex-
tracted with 95% ethanol to give crude extract (270 g). The
crude was dissolved in H2O and partitioned with petroleum
ether and EtOAc successively to afford petroleum ether
and EtOAc soluble fractions, respectively. The petroleum
ether soluble part (21 g) was subjected to silica gel chroma-
tography using a gradient mixture of petroleum ether-
Me2CO (from 1:0 to 1:1) as eluting solvent to give four
fractions. Fraction 1 was mainly composed of waxy materials.
Fig.2. Selected HMBC correlations of compound 1.
XIANG Ying et al.: Terpenoids and Phenols from Taiwania flousiana 1005
Fraction 2 was separated by CC on silica gel with a gradient
mixture of petroleum ether-CHCl3 (1:1 to CHCl3) to give
compound 5 (55 mg), and two sub-fractions 2a and 2b.
Sub-fraction 2a was subjected to a C-18 reversed-phase
silica gel CC using a gradient solvent H2O-Me2CO to give
compound 6 (2.3 mg). Sub-fraction 2b was separated by CC
on silica gel with mixture of petroleum ether-Me2CO (4:1) to
give compounds 2 (42 mg) and 4 (49 mg). Fraction 3 was
subjected to silica gel CC using petroleum ether with in-
creasing amount of iso-PrOH as solvent to give two sub-
fractions 3a and 3b, which were then subjected to C-18
reversed-phase silica gel CC to yield compounds 3 (8 mg)
and 7 (12 mg), respectively. Fraction 4 was subjected to
silica gel CC using petroleum ether with increasing amount
of iso-PrOH as solvent to give a major fraction, which was
further purified by C-18 reversed-phase silica gel CC to
obtain compound 1 (4.3 mg).
The ethyl acetate soluble part (42 g) was subjected to
silica gel CC using a gradient mixture of petroleum ether-
Me2CO (3:1 to Me2CO) as solvent to give eight fractions.
Fraction 4 was chromatographed over MCI-gel and silica
gel columns to give compound 16 (40 mg). Fraction 7 was
separated on column of MCI-gel, and then to column of C-
18 reversed-phase silica gel to give compounds 10 (80 mg),
15 (650 mg) and 17 (120 mg). Fraction 8 was separated by
column of MCI-gel and then silica gel CC with a gradient
mixture of CHCl3-MeOH to give eight sub-fractions (8a to
8h). Sub-fraction 8b was purified over column of C-18 re-
versed-phase silica gel to give compound 9 (10 mg). Sub-
fraction 8c was separated by silica gel CC to give a mixture
of two compounds, which were then purified by prepara-
tive TLC to obtain compounds 11 (90 mg) and 12 (20 mg).
Sub-fractions 8e, 8f and 8h were purified by Sephadex LH-
20 to give compounds 8 (2.2 mg), 13 (9 mg) and 14 (15 mg),
respectively.
2.4 Identification
Compound 1 White powder, C31H54O4, [a]20D +42.0º (c
0.14, CHCl3). 1H-NMR d (in CDCl3): 0.68 (3H, s, Me-18), 0.81
(3H, s, Me-30), 0.84 (3H, s, Me-28), 0.88 (1H, t, J = 6.9 Hz, H-
5), 0.92 (3H, d, J = 6.5 Hz, Me-21), 0.98 (3H, s, Me-29), 1.07
(3H, s, Me-19), 1.11 (1H, m, H-23), 1.17 (3H, s, Me-26), 1.22
(3H, s, Me-27), 1.30 (1H, m, H-16), 1.31 (1H, m, H-2), 1.32
(1H, m, H-1), 1.40 (2H, m, H-15), 1.53 (1H, br d, J = 12.6 Hz, H-
6), 1.63 (1H, m, H-20), 1.66 (1H, m, H-17), 1.79 (1H, m, H-23),
1.94 (1H, m, H-1), 1.98 (2H, m, H-16 and H-6), 1.99 (1H, m, H-
2), 2.11 (1H, br d, J = 9.5 Hz, H-12), 2.17 (1H, br d, J = 10.6 Hz,
H-8), 2.20 (1H, m, H-12), 2.34 (2H, m, H-22), 2.65 (1H, dd, J =
11.7, 4.1 Hz, H-3), 3.29 (1H, dd, J =10.0, 1.7 Hz, H-24), 3.37
(3H, s, OMe), 3.69 (1H, dt, J =10.6, 4.9 Hz, H-7), 5.30 (1H, d,
J = 6.2 Hz, H-11). 13C-NMR: see Table 1. IR (KBr) nmax: 3 547,
3 452, 2 918, 1 716, 1 628, 1 464, 1 371, 1 159, 1 097, 1 070, 978.
EI-MS m/z: 490 (M+, 2), 472 (23), 457 (54), 454 (62), 439 (53),
425 (18), 414 (26), 407 (40), 399 (26), 367 (25), 343 (100), 327
(31), 285 (21), 260 (22), 225 (23), 183 (38), 173 (49), 159 (34),
151 (33), 147 (32), 145 (38), 133 (45), 123 (45), 121 (68), 109
(63). HR-EI-MS: 490.400 8 [M+] (calcd. 490.402 2 for
C31H54O4).
Compound 2 White powder, C31H54O3, 1H-NMR d (in
CDCl3): 0.64 (3H, s, Me-18), 0.73 (3H, s, Me-28), 0.79 (3H, s,
Me-30), 0.89 (3H, d, J = 6.4 Hz, Me-21), 0.96 (3H, s, Me-29),
1.02 (3H, s, Me-19), 1.13 (3H, s, Me-26), 1.21 (3H, s, Me-27),
2.64 (1H, dd, J = 11.4, 4.1 Hz, H-3), 3.28 (1H, dd, J = 10.1, 1.8
Hz, H-24), 3.36 (3H, s, OMe), 5.21 (1H, d, J = 6.0 Hz, H-11).
13C-NMR: see Table 1.
Compound 3 White powder, C30H52O3, 1H-NMR d (in
CDCl3): 0.65 (3H, s, Me-18), 0.74 (3H, s, Me-28), 0.82 (3H, s,
Me-30), 0.90 (3H, d, J = 6.5 Hz, Me-21), 0.98 (3H, s, Me-29),
1.04 (3H, s, Me-19), 1.16 (3H, s, Me-26), 1.22 (3H, s, Me-27),
3.22 (1H, dd, J = 11.4, 4.2 Hz, H-3), 3.29 (1H, dd, J = 10.2, 2.1
Hz, H-24), 5.22 (1H, d, J = 6.2 Hz, H-11). 13C-NMR: see Table
1.
Compound 4 White powder, C30H50O3, 1H-NMR d (in
CDCl3): 0.65 (3H, s, Me-18), 0.74 (3H, s, Me-28), 0.90 (3H, d,
J = 6.4 Hz, Me-21), 1.06 (3H, s, Me-30), 1.07 (3H, s, Me-29),
1.22 (3H, s, Me-26), 1.22 (3H, s, Me-27), 3.29 (1H, br d, J =
9.3 Hz, H-24), 5.28 (1H, d, J = 5.9 Hz, H-11). 13C-NMR: see
Table 1.
Compound 5 White powder, C30H50O2, 1H-NMR d (in
CDCl3): 0.67 (3H, s, Me-28), 0.74 (3H, s, Me-24), 0.77 (3H, s,
Me-25), 0.81 (3H, s, Me-26), 0.86 (3H, s, Me-29), 0.91 (3H, s,
Me-30), 0.95 (3H, s, Me-23), 3.17 (1H, dd, J = 11.8, 4.9 Hz, H-
3), 3.43 (1H, dd, J = 2.9, 2.4 Hz, H-21), 5.30 (1H, br s, H-15).
13C-NMR d (in CDCl3): 13.3 (C-28), 15.4 (C-26), 15.7 (C-23),
18.9 (C-6), 19.8 (C-24), 21.8 (C-30), 24.0 (C-16), 25.2 (C-2),
25.4 (C-11), 27.2 (C-12), 27.6 (C-20), 27.7 (C-29), 28.1 (C-25),
31.2 (C-19), 35.9 (C-10), 37.1 (C-18), 37.5 (C-22), 38.2 (C-4),
38.6 (C-1), 39.0 (C-8), 43.4 (C-17), 45.2 (C-7), 55.8 (C-5), 56.3
(C-27), 56.9 (C-13), 62.9 (C-9), 76.2 (C-21), 78.9 (C-3), 122.1
(C-15), 138.5 (C-14).
Compound 6 White powder, C33H54O4, 1H-NMR d (in
CDCl3): 0.65 (3H, s, Me-18), 0.74 (3H, s, Me-28), 0.82 (3H, s,
Me-30), 0.90 (3H, d, J = 6.5 Hz, Me-21), 0.98 (3H, s, Me-29),
1.04 (3H, s, Me-19), 1.16 (3H, s, Me-26), 1.22 (3H, s, Me-27),
3.22 (1H, dd, J = 11.4, 4.2 Hz, H-3), 3.29 (1H, dd, J = 10.2, 2.1
Hz, H-24), 5.22 (1H, d, J = 6.2 Hz, H-11). 13C-NMR d (in
CDCl3): 14.0 (C-28), 15.7 (C-25), 16.2 (C-24), 18.8 (C-6), 19.8
(C-26), 21.1 (OAc), 21.6 (C-30), 22.4 (C-2), 24.3 (C-16), 25.5
(C-11), 27.2 (C-12), 27.8 (C-20), 28.1 (C-23), 35.9 (C-18), 37.2
Acta Botanica Sinica 植物学报 Vol.46 No.8 20041006
(C-8), 37.3 (C-19), 38.2 (C-10), 38.5 (C-1), 38.9 (C-4), 42.0 (C-
22), 45.2 (C-7), 50.6 (C-17), 56.0 (C-27), 56.3 (C-5), 57.1 (C-
13), 57.5 (OMe), 62.8 (C-9), 64.7 (C-29), 79.4 (C-21), 88.5 (C-
3), 121.6 (C-15), 138.3 (C-14), 171.0 (OAc).
Compound 7 White powder, C20H30O4, 1H-NMR d (in
Me2CO-d6): 0.93 (3H, d, J = 6.9 Hz, H-16), 0.95 (3H, d, J =
6.9 Hz, H-17), 1.08 (3H, s, H-20), 1.30 (3H, s, H-19), 6.17 (1H,
t, J = 2.2 Hz, H-14). 13C-NMR d (in Me2CO-d6): 17.1 (C-17),
17.3 (C-16), 17.6 (C-19), 18.0 (C-2), 18.1 (C-20), 21.0 (C-6),
24.1 (C-11), 25.6 (C-12), 28.5 (C-7), 32.6 (C-15), 34.1 (C-1),
37.8 (C-3), 38.9 (C-10), 40.7 (C-5), 47.1 (C-4), 79.6 (C-13),
82.0 (C-9), 127.1 (C-14), 144.4 (C-8), 179.3 (C-18).
Compound 8 Pale gum, C21H36O7, [a]20D -34.0º (c 0.18,
CH3OH). 1H-NMR d (in CD3OD): 0.87 (3H, s, Me-13), 0.94
(3H, s, Me-15), 1.03 (1H, dd, J = 13.9, 12.6 Hz, H-8), 1.12 (3H,
s, Me-14), 1.29 (1H, m, H-11), 1.37 (1H, br d, J = 13.6 Hz, H-
12), 1.38 (2H, m, H-6), 1.45 (1H, m, H-8), 1.57 (1H, m, H-3),
1.63 (1H, m, H-10), 1.77 (1H, m, H-5), 1.78 (1H, m, H-12), 1.79
(1H, m, H-3), 1.80 (1H, m, H-10), 1.94 (1H, m, H-11), 2.42 (1H,
dd, J = 11.4, 7.5, 4.2 Hz, H-2), 3.19 (1H, m, H-2¢), 3.26 (1H, m,
H-3¢), 3.30 (1H, m, H-4¢), 3.37 (1H, m, H-9), 3.38 (1H, m, H-5¢),
3.62 (1H, dd, J = 11. 6, 5.4 Hz, H-6¢), 3.78 (1H, dd, J = 11.6,
2.6 Hz, H-6¢), 4.31 (1H, d, J= 7.9 Hz, H-1¢). 13C-NMR d (in
CD3OD): 22.6 (C-6), 22.8 (C-10), 24.6 (C-13), 29.0 (C-14),
31.0 (C-15), 34.2 (C-4), 35.5 (C-3), 36.6 (C-11), 37.0 (C-7),
37.4 (C-8), 38.8 (C-12), 42.6 (C-2), 49.7 (C-5), 62.8 (C-6¢), 71.7
(C-4¢), 72.4 (C-1), 74.7 (C-2¢), 77.1 (C-3¢), 77.7 (C-5¢), 79.0 (C-
9), 100.7 (C-1¢). IR (KBr) nmax: 3 415, 2 926, 1 464, 1 383, 1 078,
1 041. EI-MS m/z: 382 ([M-H2O]+, 7), 327 (12), 220 (12), 203
(100), 182 (24), 165 (35), 147 (46), 123 (86), 119 (24), 107 (36).
HR-EI-MS: 382.237 0 (calcd. 382.235 5 for C21H34O6 ([M-
H2O]+)).
Compound 9 White powder, C26H34O10, 1H-NMR d (in
CD3OD): 1.05 (3H, d, J = 6.2 Hz, Me-6¢¢), 1.64 (2H, m, H-8),
2.45 (2H, dd, J = 8.1, 7.3 Hz, H-7), 3.62 (3H, s, OMe), 3.68 (3H,
s, OMe), 5.17 (1H, d, J = 1.5 Hz, H-1¢¢), 5.38 (1H, d, J = 5.9 Hz,
H-7¢), 6.54 (1H, s, H-6), 6.56 (1H, s, H-2), 6.74 (1H, dd, J =
8.4, 1.8 Hz, H-6¢), 6.86 (1H, d, J = 1.8 Hz, H-2¢), 6.91 (1H, d,
J = 8.4 Hz, H-5¢). 13C-NMR d (in CD3OD): 18.4 (C-6¢¢), 33.4
(C-7), 36.3 (C-8), 56.1 (C-8¢), 56.9 (OMe), 57.2 (OMe),
62.7 (C-9), 65.5 (C-9¢), 71.3 (C-5¢¢), 72.5 (C-2¢¢), 72.6 (C-
3¢¢), 74.3 (C-4¢¢), 89.0 (C-7¢), 101.8 (C-1¢¢), 111.7 (C-2¢),
114.5 (C-2), 118.4 (C-6), 119.6 (C-6¢), 120.0 (C-5¢), 130.0 (C-
1), 137.5 (C-5), 139.2 (C-1¢), 145.7 (C-3), 147.0 (C-4), 147.9 (C-
4¢), 152.5 (C-3¢).
Compound 10 White powder, C26H34O10, 1H-NMR d
(in Me2CO-d6): 1.16 (2H, d, J = 6.2 Hz, Me-6¢¢), 1.74 (2H, m,
H-8), 2.52 (2H, dd, J = 8.1, 7.3 Hz, H-7), 3.44 (3H, s, 3¢¢-OMe),
3.81 (3H, s, 3¢-OMe), 4.27 (1H, t, J = 2.2 Hz, H-2¢¢), 5.39 (1H,
d, J = 1.5 Hz, H-1¢¢), 5.57 (1H, d, J = 5.9 Hz, H-7¢), 6.59 (1H, s,
H-6), 6.61 (1H, d, J = 1.5 Hz, H-2), 6.96 (1H, dd, J = 8.4, 1.8 Hz,
H-6¢), 7.10 (1H, d, J = 8.4 Hz, H-5¢), 7.12 (1H, d, J = 1.8 Hz, H-
2¢). 13C-NMR d (in Me2CO-d6): 17.7 (C-6¢¢), 31.9 (C-7), 35.2
(C-8), 55.0 (C-8¢), 55.9 (3¢-OMe), 56.8 (3¢¢-OMe), 61.3 (C-9),
64.4 (C-9¢), 67.1 (C-2¢¢), 69.9 (C-5¢¢), 71.5 (C-4¢¢), 81.3 (C-
3¢¢), 87.1 (C-7¢), 100.6 (C-1¢¢), 110.8 (C-2¢), 115.8 (C-2),
116.4 (C-6), 118.3 (C-6¢), 119.1 (C-5¢), 129.0 (C-1), 136.0 (C-
5), 138.4 (C-1¢), 141.3 (C-3), 145.5 (C-4), 145.5 (C-4¢), 151.2
(C-3¢).
Compound 11 White powder, C25H32O10, 1H-NMR d
(in Me2CO-d6): 1.17 (3H, d, J = 6.2 Hz, Me-6¢¢), 1.74 (2H, m,
H-8), 2.53 (2H, dd, J = 8.0, 7.3 Hz, H-7), 3.80 (3H, s, 3¢-OMe),
5.37 (1H, s, H-1¢¢), 5.56 (1H, d, J = 5.9 Hz, H-7), 6.60 (1H, s, H-
6), 6.61 (1H, s, H-2), 6.95 (1H, d, J = 8.0 Hz, H-6¢), 7.10 (1H, d,
J = 8.0 Hz, H-5¢), 7.11 (1H, s, H-2¢). 13C-NMR d (in Me2CO-
d6): 17.7 (C-6¢¢), 32.1 (C-7), 35.5 (C-8), 55.0 (C-8¢), 56.0 (3¢-
OMe), 61.5 (C-9), 64.6 (C-9¢), 69.9 (C-5¢¢), 71.4 (C-2¢¢), 71.9
(C-3¢¢), 73.2 (C-4¢¢), 87.4 (C-7¢), 100.5 (C-1¢¢), 111.1 (C-2¢),
116.0 (C-2), 116.6 (C-6), 118.6 (C-6¢), 119.0 (C-5¢), 129.2 (C-1),
136.1 (C-5), 138.1 (C-1¢), 141.3 (C-3), 145.6 (C-4), 145.9 (C-4¢),
151.3 (C-3¢).
Compound 12 White powder, C25H32O11, 1H-NMR d
(in CD3OD): 1.80 (2H, m, H-8), 2.62 (2H, dd, J = 8.1, 7.3 Hz, H-
7), 3.82 (3H, s, OMe), 3.85 (3H, s, OMe), 4.84 (1H, d, J = 7.2
Hz, H-1¢¢), 5.54 (1H, d, J = 5.9 Hz, H-7¢), 6.71 (1H, s, H-6),
6.73 (1H, s, H-2), 6.92 (1H, dd, J = 8.4, 1.8 Hz, H-6¢), 7.02 (1H,
d, J = 1.8 Hz, H-2¢), 7.13 (1H, d, J = 8.4 Hz, H-5¢). 13C-NMR d
(in CD3OD): 33.4 (C-7), 36.3 (C-8), 56.1 (C-8¢), 57.2 (OMe),
57.2 (OMe), 62.7 (C-9), 63.0 (C-6¢¢), 65.5 (C-9¢), 71.8 (C-4¢¢),
75.4 (C-2¢¢), 78.3 (C-5¢¢), 78.6 (C-3¢¢), 89.0 (C-7¢), 103.2 (C-
1¢¢), 111.7 (C-2¢), 114.6 (C-2), 118.4 (C-6), 118.4 (C-6¢), 119.9
(C-5¢), 130.1 (C-1), 137.6 (C-5), 138.8 (C-1¢), 145.7 (C-3),
148.1 (C-4), 148.1 (C-4¢), 151.4 (C-3¢).
Compound 13 White powder, C16H22O9, 1H-NMR d (in
CD3OD): 3.17 (1H, dd, J = 8.8, 8.1 Hz, H-2¢¢), 3.30 (overlapped
with the signals of solvents, H-3¢¢ and H-4¢¢), 3.34 (2H, s, H-
2), 3.38 (1H, m, H-5¢¢), 3.68 (1H, dd, J = 13.2, 4.4 Hz, H-6¢¢),
3.85 (1H, dd, J = 13.2, 5.9 Hz, H-6¢¢), 3.89 (3H, s, OMe), 3.97
(1H, m, H-3), 4.26 (1H, m, H-3), 4.34 (1H, d, J = 8.1 Hz, H-1¢¢),
6.83 (1H, d, J = 8.4 Hz, H-5¢), 7.53 (1H, s, H-2¢), 7.59 (1H, d, J
= 8.4 Hz, H-6¢). 13C-NMR d (in CD3OD): 39.6 (C-2), 56.8
(OMe), 63.9 (C-6¢¢), 66.8 (C-3), 71.9 (C-4¢¢), 75.4 (C-2¢¢), 78.4
(C-5¢¢), 78.4 (C-3¢¢), 104.9 (C-1¢¢), 112.3 (C-5¢), 116.7 (C-2¢),
125.7 (C-6¢), 137.1 (C-1¢), 150.0 (C-4¢), 155.7 (C-3¢), 199.9
(C-1).
Compound 14 White powder, C19H28O12, 1H-NMR d
(in CD3OD): 1.30 (3H, d, J = 6.3 Hz, Me-6¢¢), 3.31 (1H, m, H-
3¢), 3.35 (1H, m, H-4¢), 3.40 (3H, s, 3¢¢-OMe), 3.41 (1H, m, H-
XIANG Ying et al.: Terpenoids and Phenols from Taiwania flousiana 1007
5¢), 3.47 (1H, t, J = 9.5 Hz, H-4¢¢), 3.58 (1H, dd, J = 9.1, 8.4 Hz,
H-3¢), 3.63 (1H, d, J = 7.7 Hz, H-2¢), 3.68 (1H, br d, J = 12.7 Hz,
H-6¢), 3.77 (3H, s, 4-OMe), 3.81 (3H, s, 3-OMe), 3.90 (1H, dd,
12.1, 2.2 Hz, H-6¢), 4.12 (1H, m, H-5¢¢), 4.15 (1H, m, H-2¢¢),
4.89 (1H, d, J = 7.8 Hz, H-1¢), 5.32 (1H, d, J = 1.8 Hz, H-1¢¢),
6.64 (1H, dd, J = 8.8, 2.9 Hz, H-6), 6.75 (1H, d, J = 2.9 Hz, H-
2), 6.85 (1H, d, J = 8.8 Hz, H-5). 13C-NMR d (in CD3OD):
18.7 (C-6¢¢), 56.9 (3-OMe), 57.7 (4-OMe), 57.7 (3¢-OMe),
63.1 (C-6¢), 68.5 (C-2¢¢), 70.4 (C-5¢¢), 72.1 (C-4¢), 73.2 (C-4¢¢),
78.6 (C-5¢), 79.4 (C-2¢), 79.7 (C-3¢), 82.4 (C-3¢¢), 102.0 (C-1¢),
102.8 (C-1¢¢), 104.0 (C-2), 108.9 (C-5), 114.5 (C-6), 146.4 (C-1),
151.7 (C-4), 154.2 (C-3).
Compound 15 White powder, C21H22O12, 1H-NMR d
(in CD3OD): 3.21 - 3.38 (4H, m, H-2¢¢ - H-5¢¢), 3.50 (1H, dd,
J = 12.1, 5.9 Hz, H-6¢¢), 3.73 (1H, dd, J = 12.1, 1.8 Hz, H-6¢¢),
4.41 (1H, d, J = 11.7 Hz, H-3), 4.67 (1H, d, J = 7.3 Hz, H-1¢¢),
4.81 (1H, d, J = 11.7 Hz, H-2), 5.71 (1H, d, J = 2.2 Hz, H-6),
5.75 (1H, d, J = 2.2 Hz, H-8), 6.73 (1H, d, J = 8.4 Hz, H-5¢),
6.93 (1H, dd, J = 8.4, 1.8 Hz, H-6¢), 7.21 (1H, d, J = 1.8 Hz, H-
2¢). 13C-NMR d (in CD3OD): 63.0 (C-6¢¢), 71.9 (C-4¢¢), 73.9
(C-3), 75.3 (C-2¢¢), 78.0 (C-3¢¢), 78.7 (C-5¢¢), 85.3 (C-2), 96.8
(C-8), 97.8 (C-6), 102.3 (C-10), 104.4 (C-1¢¢), 117.4 (C-5¢),
118.6 (C-2¢), 125.1 (C-6¢), 130.4 (C-1¢), 147.0 (C-3¢), 149.4 (C-
4¢), 164.8 (C-9), 165.7 (C-7), 169.1 (C-5), 198.8 (C-4).
Compound 16 White powder, C15H12O7, 1H-NMR d
(in Me2CO-d6): 4.59 (1H, d, J = 11.4 Hz, H-3) 4.99 (1H, d,
J = 11.4 Hz, H-2), 5.92 (1H, d, J = 1.8 Hz, H-6), 5.97 (1H, d, J
= 1.8 Hz, H-8), 6.87 (2H, m, H-5¢, H-6¢), 7.05 (1H, d, J = 1.1 Hz,
H-2¢). 13C-NMR d (in DMCO-d6): 72.6 (C-3), 84.1 (C-2), 95.6
(C-8), 96.6 (C-6), 100.9 (C-10), 115.4 (C-2¢), 115.4 (C-5¢),
120.3 (C-6¢), 129.1 (C-1¢), 145.4 (C-3¢), 146.2 (C-4¢), 163.6 (C-
9), 164.2 (C-7), 167.7 (C-5), 197.7 (C-4).
Compound 17 Yellow powder, C21H20O12, 1H-NMR d
(in CD3OD): 3.33 - 3.46 (4H, m, H-2¢¢ - H-5¢¢), 3.64 (1H, dd,
J = 11.7, 3.3 Hz, H-6¢¢), 3.81 (1H, br d, J = 11.7 Hz, H-6¢¢), 4.71
(1H, d, J = 7.0 Hz, H-1¢¢), 5.99 (1H, d, J = 1.7 Hz, H-6), 6.25
(1H, d, J = 1.7 Hz, H-8), 6.78 (1H, d, J = 8.4 Hz, H-5¢), 7.69 (1H,
d, J = 8.4 Hz, H-6¢), 7.96 (1H, s, H-2¢). 13C-NMR d (in CD3OD):
62.9 (C-6¢¢), 71.7 (C-4¢¢), 75.3 (C-2¢¢), 78.1 (C-3¢¢), 78.9 (C-
5¢¢), 95.1 (C-8), 99.9 (C-6), 104.9 (C-1¢¢), 104.9 (C-10), 117.6
(C-2¢), 118.4 (C-5¢), 124.8 (C-1¢), 125.5 (C-6¢), 138.0 (C-3),
147.2 (C-2), 147.8 (C-3¢), 150.9 (C-4¢), 158.7 (C-9), 163.0 (C-5),
166.5 (C-7), 177.9 (C-4).
Acknowledgements: The authors are grateful to Prof.
ZHANG Chang-Gong (Tongj i Medica l Col lege ,
Huazhong University of Sciences and Technology,
Wuhan, China) for the plant material collection and
identification.
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