Five new cadinane-type sesquiterpenes from the heartwood of Chamaecyparis obtusa var. formosana

Article abstract of DOI:10.1021/np0101402

Muurola-4,10(14)-dien-3-one (1), 10-O-acetyl-15-oxo-α-cadinol (2), 15-hydroxy-α-cadinol (3), 4α-hydroxy-5β-ethoxy-epi-cubenol (4), and 4α-hydroxy-5β-acetoxy-epi-cubenol (5), five new bicyclic sesquiterpenes, have been isolated from the heartwood of Chamae

Full text of DOI:10.1021/np0101402

J . Nat. Prod. 2002, 65, 25-28
25
F ive New Ca d in a n e-Typ e Sesqu iter p en es fr om th e Hea r tw ood of
Ch a m a ecypa r is obtu sa va r . for m osa n a
Yueh-Hsiung Kuo,*,† Chia-Hsien Chen,† Shih-Chang Chien,† and Yun-Lian Lin‡
Department of Chemistry, National Taiwan University, Taipei, Taiwan, Republic of China, and
National Research Institute of Chinese Medicine, Taipei, Taiwan, Republic of China
Received March 16, 2001
Muurola-4,10(14)-dien-3-one (1), 10-O-acetyl-15-oxo-R-cadinol (2), 15-hydroxy-R-cadinol (3), 4R-hydroxy-
5â-ethoxy-epi-cubenol (4), and 4R-hydroxy-5â-acetoxy-epi-cubenol (5), five new bicyclic sesquiterpenes,
have been isolated from the heartwood of Chamaecyparis obtusa var. formosana along with the known
compounds epi-cubenol, T-cadinol, T-muurolol, δ-cadinol, and R-cadinol. The structures of the new
constituents were elucidated through chemical and spectral studies.
There are seven species of the genus Chamaecyparis
(Cupressaceae), but only two endemic species, C. formosen-
sis and C. obtusa var. formosana, are found in the central
mountains of Taiwan. Both of these species are important
building materials, and the latter species is believed to be
more resistant to wood-decaying fungi. Although there are
several earlier studies on the chemical constituents of C.
obtusa var. formosana,1-4 only essential oils and simple
acidic components were isolated. We also recently reported
the isolation and identification of the novel diterpene
obtunone5 and three new abietane diterpenes6 from the
heartwood of the plant. In this paper, we report five new
bicyclic cadinane sesquiterpenes, muurola-4,10(14)-dien-
3-one (1), 10-O-acetyl-15-oxo-R-cadinol (2), 15-hydroxy-R-
cadinol (3), 4R-hydroxy-5â-ethoxy-epi-cubenol (4), and 4R-
hydroxy-5â-acetoxy-epi-cubenol (5), together with five known
sesquiterpenes, epi-cubenol (6),7 Τ-cadinol (7),8 Τ-muurolol
(8),8 δ-cadinol (9),9 and R-cadinol (10).10 Compound 3 was
purified as its monoacetate 11.
Resu lts a n d Discu ssion
HREIMS revealed compound 1 to be a sesquiterpene of
formula C15H22O [[M+] ) 218.1675]. The IR spectrum
suggested the presence of an R,â-unsaturated carbonyl
system with absorptions at νmax 1672, 1663 cm-1 and an
exocyclic double bond with absorption at 889 cm-1. The 13
C
NMR spectrum of 1 (Table 1) shows 15 carbon signals for
a carbonyl, two double bonds, three methylenes, four
methines, and three methyl groups. Five indices of hydro-
gen deficiency (IHD) were determined from the 13C NMR
spectrum and DEPT experiments. Four olefinic signals (δC
109.0, 134.9, 149.2, and 149.7) and the conjugated carbonyl
at δC 199.5 implicated a bicyclic molecule. The one-proton
doublet at δ 6.78 (J ) 5.0 Hz, H-5) could be assigned to a
vinylic hydrogen â to the carbonyl. A broad signal at δ 1.77
(3H) proved to be due to a methyl group on a double bond.
The signal at δC 109.0 is typical of the terminal methylene
carbon of an exocyclic double bond, while the singlet at δ
4.67 (2H) could be assigned to the terminal olefinic protons.
The signals at δ 0.86 and 0.93 (each 3H, d, J ) 6.9 Hz,
H-12, -13) and 1.89 (1H, m, H-11; COSY correlation with
δ 0.86 and 0.93), together with the MS spectral fragment
at m/z at 175 [M+ - C3H7]+, established the presence of
an isopropyl group. On the basis of the above evidence, 1
had the skeleton of the cadinane type of sesquiterpene.11
* To whom correspondence should be addressed. Tel: +886-223638146.
Fax: +886-223636359. E-mail: yhkuo@ccms.ntu.edu.tw.
† National Taiwan University.
1
The H-1H COSY spectrum of 1 showed connectivities for
‡ National Research Institute of Chinese Medicine.
the H2-protons [δ 2.25 (1H, dd, J ) 16.9, 4.3 Hz) and 2.74
10.1021/np0101402 CCC: $22.00
© 2002 American Chemical Society and American Society of Pharmacognosy
Published on Web 12/20/2001

26 J ournal of Natural Products, 2002, Vol. 65, No. 1
Kuo et al.
Ta ble 1. 1H and 13C NMR Spectral Data of 1-5 and 11 (400 and 100 MHz in CDCl3)
1
2
3
11
4
5
no.
δC
δC
δC
δC
δH
δC
δH
δC
1
2
43.0
40.1
47.3
21.5
50.0
22.2
49.7
22.1
74.7
32.1
72.2
31.8
1.41m
1.64ma
1.57m
1.72m
1.51m
1.86mb
1.24m
1.85m
3
199.5
22.0
26.4
26.7
25.0
29.6
4
5
6
7
8
134.9
149.7
40.7
43.8
25.4
141.7
151.2
40.6
45.3
21.6
138.2
123.5
39.6
46.4
21.9
133.7
127.4
39.8
46.2
22.0
75.6
72.3
42.5
37.4
23.7
70.6
75.5
42.9
37.2
23.7
3.55br s
1.65a
1.72m
1.06m
1.67ma
5.05br s
1.83b
1.46m
1.05qd
(12.8, 6.8)
1.65qd
(12.8, 4.2)
1.42m
9
30.5
36.2
42.0
42.1
1.32m
1.49m
30.4
29.8
1.47m
10
11
149.2
27.5
84.2
26.2
72.3
25.9
72.3
26.0
1.32m
2.05sep d
(6.9, 3.0)
41.1
25.6
1.26m
41.5
25.5
1.82mb
12
13
14
15
16.3
21.4
109.0
16.0
15.2
21.3
17.4
194.4
22.6
170.5
15.1
21.4
20.6
67.2
15.1
21.4
20.7
68.8
21.0
171.0
0.71d(6.9)
0.91d(6.9)
0.83d(6.3)
1.20s
14.9
21.5
14.1
21.7
0.72d(6.9)
0.84d(6.9)
0.87d(6.7)
1.16s
14.8
21.4
14.6
27.8
21.1
169.2
OCOCH3
OCOCH3
OCH2CH3
OCH2CH3
2.08s
1.11t(6.9)
3.32dq
16.2
55.9
(14.0, 6.9)
3.37dq
(14.0, 6.9)
a,b
Overlapping each other.
(1H, dd, J ) 16.9, 12.8 Hz)] with the bridgehead proton
H-1 (δ 2.92, dt, J ) 12.8, 4.3 Hz), which in turn was
connected to the other bridgehead proton H-6 (δ 2.34, m).
H-6 was coupled to the methine proton at δ 1.59 (m, H-7),
and the coupling chain continued from H-7 to H-8 (δ 1.68-
1.73, m) and then to H-9 (δ 2.15-2.23, m). H-11 (δ 1.89,
m) showed a COSY correlation with H-7, H-12, and H-13
and also a NOESY correlation with H-5. This evidence
confirmed the location of the isopropyl group at C-7. The
relative stereochemistry of 1 was deduced from analyses
of coupling constants and the NOESY correlation between
to the carbonyl group (H-5). The COSY spectrum of 2
displayed the connectivity of H-5 to H-6 (δ 2.07, m), which
was also coupled to H-1 (δ 1.72, m) and H-7 (δ 1.23, m).
The location of the isopropyl at C-7 was confirmed by the
NOESY correlations observed between H-5 and the two
methyls of the isopropyl group. The protons at δ 2.05 (m)
and 2.44 (m) were assigned to the allylic H-3 protons, which
were correlated in the COSY spectrum with H-2 [δ 1.64
and 2.06 (each 1H, m)]. H-1 showed a NOESY correlation
to H-2R, but no correlation to H-6. The signal for the olefinic
proton (H-5) appeared as a broad singlet and showed a
NOESY correlation to the methyls of the isopropyl group,
thus indicating a trans-fused ring and an equatorial
isopropyl.8,13,14 The 1H and 13C NMR data of 2 are very
similar to those of R-cadinyl acetate (12),15 except for
differences attributable to the aldehyde group in 2. On the
basis of the above evidence, as well as HMBC and NOESY
techniques, compound 2 was determined to be 10-O-acetyl-
15-oxo-R-cadinol. Saponification of 2 yielded alcohol 13 (see
below), which is an oxidative product from R-cadinol (10).
The chemical correlation further confirmed the structure
of 2.
1
H-1 and H-6. In the H NMR spectrum of 1, H-1 appears
as a doublet of triplets, with the larger doublet coupling
(J ) 12.8 Hz) to Hax-2 (δ 2.74) and smaller triplet couplings
(J ) 4.3 Hz) to Heq-2 (δ 2.25) and H-6 (δ 2.34). This evidence
established compound 1 as a cis-fused ring system. Ad-
ditionally, H-5 appears as a doublet coupled with H-6 (J )
5.0 Hz), providing further evidence for the cis-fusion: in
trans-fused isomers, such as T-cadinol (7), R-cadinol (10),
and 4-cadinene-9R-ol-3-one,12 the olefinic proton appears
as a broad singlet, while in cis-fused muurolene deriva-
tives8,13 the olefinic proton resonates as a doublet. Thus,
based on the above evidence, the structure of 1 was
established as muurola-4,10(14)-dien-3-one.
Compound 3 was purified as its monoacetate 11, ob-
tained by treating 3 with acetic anhydride in pyridine. The
molecular formula of 11 was assigned as C17H28O3 based
on HREIMS. The IR spectrum of 11 shows absorption
bands for a hydroxyl (νmax 3424 cm-1), a trisubstituted
double bond (νmax 3041, 1670, 825 cm-1), and an acetoxyl
Compound 2 was isolated as an oil and showed a
pseudomolecular ion at m/z 218 [M+ - AcOH], analyzing
for C17H26O3. The IR spectrum of 2 showed bonds attribut-
able to an acetoxyl group (1734, 1245, and 1160 cm-1),
geminal dimethyl group (1380 and 1369 cm-1), and a
conjugated aldehyde (2723, 1690, and 1642 cm-1). The
latter group was further confirmed from the UV absorption
1
group (νmax 1743 and 1245 cm-1). The H NMR spectrum
of 11 shows signals for an isopropyl group at δ 0.75, 0.90
(each 3H, d, J ) 6.9 Hz) and 2.09 (1H, m, COSY correlation
to two doublet methyl groups), a three-proton singlet (δ
1.09) for a methyl group attached to a quaternary carbon
bearing a hydroxyl group, an oxymethylene group (δ 4.44,
2H, s) linked between acetoxyl and olefinic groups, an
acetoxyl group (δ 2.05, s), and a trisubstituted olefinic
proton (δ 5.81, br s). By using COSY, HMQC, and HMBC
1
at λmax 232 nm. The H NMR spectrum shows signals for
an isopropyl group at δ 0.82, 0.96 (each 3H, d, J ) 6.9 Hz),
and 2.20 (1H, m, H-11), a three-proton singlet at δ 1.41
for a methyl attached to a quaternary carbon bearing an
acetoxyl group (δ 1.97, s), a conjugated aldehyde signal at
δ 9.43 (s), and a singlet at δ 6.84 for the olefinic proton â

Cadinane-Type Sesquiterpenes from Chamaecyparis
J ournal of Natural Products, 2002, Vol. 65, No. 1 27
spectral methods, all protons, carbons, and carbon-proton
connectivities were confirmed. The data were consistent
with a 15-acetoxycadinol general structure. The trans-fused
11 was revealed from the presence of a broad singlet for
the olefinic proton, H-5, and the C-7 equatorial isopropyl
was confirmed by observing a NOE correlation between H-5
and an isopropyl methyl group. The strong NOE correlation
between H3-14 and H-6 indicated an axial orientation (â)
of the methyl at C-10. By comparison of 13C NMR data of
11 with that of R-cadinol (Table 1), the structure of 11 was
determined as 15-acetoxy-R-cadinol. Saponification of com-
pound 11 yielded the purified natural product 3 (see
Experimental Section for physical data), which was also
chemically correlated to R-cadinol (10) and 13. Oxidation
of R-cadinol (10) with SeO2 under reflux in ethanol solution
gave four products, 13, 14,17 15,15 and 3.
1.82, 0.72, and 0.84 (isopropyl group), indicating an R-equa-
torial orientation of H-5. Therefore, hydroxyl and acetoxyl
groups were located at C-4 and C-5, respectively. Similarity
1
of the H and 13C NMR data of 5 and 4 and the absence of
a NOE correlation of H-10 to Hax-2 (δ 1.51) provided
evidence that 5 is a cis-fused decalin. The NOE observed
between H3-15 and both H-5 and H2-3 (δ 1.24 and 1.85)
suggested the â-equatorial orientation of H3-15. Thus,
compound 5 was identified as 4R-hydroxy-5â-acetoxy-epi-
cubenol.
Exp er im en ta l Section
Gen er a l Exp er im en ta l P r oced u r es. Melting points were
determined with a Yanagimoto micromelting point apparatus
and are uncorrected. IR spectra were recorded on a Perkin-
1
Elmer 983G spectrophotometer. H and 13C spectra were run
on a Bruker DMX-400 spectrometer. EIMS and specific rota-
tions were taken on a J EOL J MS-HX 300 mass spectrometer
and a J ASCO DIP-1000 digital polarimeter, respectively.
Extracts were chromatographed on silica gel (Merk 70-230
mesh, 230-400 mesh, ASTM) and purified with a semiprepara-
tive normal-phase HPLC column (250 × 10 mm, 7 µm,
LiChrosorb Si 60) taken on LDC Analytical-III.
P la n t Ma ter ia l. The heartwood of C. obtusa var. formosana
was collected from Taichung, Taiwan, in 1996. The plant was
identified by Mr. Muh-Tsuen Gun, formerly of the Department
of Botany, National Taiwan University. A voucher specimen
has been deposited at the Herbarium of the Department of
Botany, National Taiwan University, Taipei, Taiwan.
Compound 4 was isolated as an oil and shown by
HREIMS to have molecular formula C17H32O3. Only sp3
carbon signals, including three oxygenated carbon signals,
were observed in the 13C NMR spectrum of 4. The hydroxyl
group in 4 was evident from its IR spectrum (νmax 3418
cm-1). An ethoxyl group attached to a chiral carbon was
revealed from ethoxyl signals at δ 3.32, 3.37 (each 1H, dq,
J ) 14.0, 6.9 Hz), and 1.11 (3H, t, J ) 6.9 Hz). A broad
signal at δ 3.55 (1H, H-5, resonate at δC 72.3), which
showed HMBC correlation with δC 55.9 (-OCH2CH3) and
NOESY correlations with signals at δ 3.32 and 3.37
(-OCH2CH3), was assigned as geminal to an ethoxy group.
A doublet methyl signal (δ 0.83, d, J ) 6.3 Hz), a singlet
methyl signal (δ 1.20) on a carbon bearing a hydroxyl, and
an isopropyl group [δ 0.71, 0.91 (each 3H, d, J ) 6.9 Hz),
2.05 (1H, sep. d, J ) 6.9, 3.0 Hz)] were also observed.
Analysis of the 1H and 13C NMR (Table 1) of 4 clearly
showed it to be structurally similar to epi-cubenol (6), the
obvious differences being the absence of any double bonds
and the presence of an additional hydroxyl and one ethoxyl
group in 4. The placement of a hydroxyl and the ethoxyl
group at C-4 and C-5, respectively, was based on the
following data. The signal at δ 3.55 was assigned as C-5R
(equatorial) due to having NOESY (see structure 16)
correlation with H3-12 and H-11 of the isopropyl group. By
using HMQC and HMBC techniques, the 1H and 13C
signals were assigned. H-10 (δ 1.32, m) exhibited NOESY
correlations with H-6 (δ 1.65, overlapped with other
signals), Hâ-8 (δ 1.06, m), and H3-14, thus confirming the
equatorial orientation of the C-10 methyl group. The
absence of a NOE between H-10 and Hax-2 (δ 1.41)
suggested a cis-fused decaline structure, as in 16. The
presence of NOE cross-peaks between H-15 and H-4, and
H-15 and -OCH2CH3, clearly established the â-equatorial
orientation of the C-4 methyl. The ethoxy group on C-5 was
assigned the â-axial orientation, since -OCH2CH3 showed
NOE correlation with the Hâ-3 (δ 1.57) axial proton. Thus,
compound 4 was identified as 4R-hydroxy-5â-ethoxy-epi-
cubenol.
E xt r a ct ion a n d Isola t ion . The dried heartwood of C.
obtusa var. formosana (11 kg) was extracted with Me2CO (120
L) at room temperature (3 days × 2). To the evaporated Me2-
CO extract was added H2O to bring the total volume to 1 L,
and this phase was then partitioned with ethyl acetate (1 L ×
3). The combined ethyl acetate layer afforded a black syrup
(680 g) that was chromatographed on Si gel and by HPLC
(normal phase on Lichrosorb Si 60), repeatedly using a
hexane-EtOAc gradient solvent system. Muurola-4,10(14)-
diene-3-one (1) (5.5 mg), epi-cubenol (6) (11.8 mg), T-cadinol
(7) (11.2 mg), T-muurolol (8) (9.3 mg), δ-cadinol (9) (5.8 mg),
R-cadinol (10) (16.7 mg), 10-O-acetyl-15-oxo-R-cadinol (2) (5.1
mg), 15-hydroxy-R-cadinol (3) (crude weight 15 mg), 4R-
hydroxy-5â-ethoxy-epi-cubenol (4) (6.5 mg), and 4R-hydroxy-
5â-acetoxy-epi-cubenol (5) (5.6 mg) were eluted with 5%, 5%,
10%, 10%, 10%, 10%, 20%, 30%, 50%, and 50% EtOAc in
hexane solvent systems, respectively. Acetylation of crude 3
(15 mg) with Ac2O and pyridine yielded 11 (14 mg).
Mu u r ola-4,10(14)-dien -3-on e (1): colorless oil; [R]25D -12.8°
(c 0.31, CHCl3); IR (KBr) νmax 1672, 1663, 1655, 889, 830 cm-1
;
1
UV (MeOH) λmax (log ꢀ) 238 (3.91) nm; H NMR (CDCl3, 400
MHz) δ 0.86, 0.93 (each 3H, d, J ) 6.9 Hz, H-12, -13), 1.59
(1H, m, H-7), 1.67-1.73 (2H, m, H-8), 1.77 (3H, br s, H-15),
1.89 (1H, m, H-11), 2.15-2.23 (2H, m, H-9), 2.25 (1H, dd, J )
16.9, 4.2 Hz, Ha-2), 2.34 (1H, m, H-6), 2.74 (1H, dd, J ) 16.9,
12.8 Hz, Hb-2), 2.92 (1H, dt, J ) 12.8, 4.3 Hz, H-1), 4.67 (2H,
br s, H-14), 6.78 (1H, d, J ) 5.0 Hz, H-5); 13C NMR data, see
Table 1; EIMS m/z 218 [M]+ (6), 203 (3), 190 (70), 175 (45),
147 (100), 133 (40), 119 (41), 105 (68), 91 (80), 69 (48); HREIMS
m/z 218.1675 (calcd for C15H22O, 218.1671).
10-O-Acetyl-15-oxo-r-ca d in ol (2): colorless oil; [R]25
D
The IR spectrum of 5 suggested the presence of hydroxyl
(νmax 3430 cm-1) and acetoxyl groups (νmax 1735 and 1224
-18.3° (c 0.75, CHCl3); IR (KBr) νmax 2723, 1734, 1690, 1642,
1380, 1369, 1245, 1114, 1025 cm-1; UV (MeOH) λmax (log ꢀ)
1
1
cm-1), which was further supported by H and 13C NMR
232 (4.04) nm; H NMR (CDCl3, 400 MHz) δ 0.82, 0.96 (each
3H,d J ) 6.9 Hz, H-12, -13), 1.14-1.18 (2H, m, H-8), 1.23 (1H,
m, H-7), 1.41(3H, s, H-14), 1.64 (2H, m, Ha-2, Ha-9), 1.72 (1H,
m, H-1), 1.97 (3H, s, OCdOCH3), 2.05 (1H, m, Ha-3), 2.06 (1H,
m, Hb-2), 2.07 (1H, m, H-6), 2.20 (1H, m, H-1), 2.44 (1H, m,
Hb-3), 2.64 (1H, d, J ) 12.4 Hz, Hb-9), 6.84 (1H, br s, H-5),
and 9.43 (1H, s, H-15); 13C NMR data, see Table 1; EIMS m/z
218 [M+ - HOAc] (82), 189 (74), 175 (100), 157 (23), 148 (31),
105 (34); HREIMS m/z 218.1682 (calcd for C15H22O, 218.1671).
15-Hyd r oxy-r-ca d in ol (3): amorphous solid; [R]25D -30.6°
(c 0.85, CHCl3); IR (KBr) νmax 3363, 3020, 1687, 1214, 1066,
signals at δ 2.08 (s), δC 21.1, and 169.2. The molecular
formula of C17H30O4 was established by HREIMS. Besides
the acetyl group, signals for 15 carbons were evident in
the 13C NMR spectrum. Thus, 5 was proposed to be a
sesquiterpene. The signals at δ 0.87 (3H, d, J ) 6.7 Hz,
H-14), 1.16 (3H, s, H-15), 5.05 (1H, br s, H-5), 1.82 (1H, m,
H-11), 0.72 and 0.84 (each 3H, d, J ) 6.9 Hz, H-12, -13),
suggested 5 is an epi-cubenol derivative. The signal for H-5
(δ 5.05) showed an NOE correlation with the signals at δ

28 J ournal of Natural Products, 2002, Vol. 65, No. 1
Kuo et al.
1027, 757 cm-1; 1H NMR (CDCl3, 400 MHz) δ 0.73, 0.88 (each
3H, d, J ) 6.9 Hz, H-12, -13), 1.03 (2H, m, H-7), 1.06 (3H, s,
H-14), 1.21 (1H, m, H-1), 1.17, 1.58 (each 1H, m, H-8), 1.39
(1H, td, J ) 12.5, 3.7 Hz, H-9), 1.72 (1H, m, H-6), 1.76 (1H,
dt, J ) 12.5, 2.9 Hz, H-9), 2.08 (2H, m, H-2), 2.12 (1H, m,
H-11), 2.18 (2H, m, H-3), 3.94, 3.97 (each 1H, d, J ) 13.0 Hz,
H-15); 13C NMR data, see Table 1; EIMS m/z 238 [M+] (2),
220 (M+ - H2O)(26), 193 (54), 190 (93), 159 (100), 147 (78),
119 (68), 91 (100); HREIMS m/z 238.1935 (calcd for C15H26O2,
238.1926).
reaction mixture was filtrated through Celite, and the filtrate
was purified by SiO2 chromatography and then HPLC to yield
four products: 13 (100 mg), 14 (264 mg),15 3 (81 mg), and 15
(123 mg).15 The physical data of 13 are as follows: amorphous
solid; [R]30 -6.3° (c 3.52, CHCl3); IR (KBr) νmax 3432, 3031,
D
2735, 1683, 1639, 1129, 1070 cm-1; 1H NMR (CDCl3, 200 MHz)
δ 0.81, 0.95 (each 3H, d, J ) 7.0 Hz), 1.10 (3H, s), 6.82 (1H, br
s), and 9.40 (1H, s); EIMS m/z 236 [M+] (6), 218 (42), 193 (100),
178 (44), 175 (75), 135 (44), 91 (80).
4r-Hyd r oxy-5â-eth oxy-epi-cu ben ol (4): amorphous solid;
D
1013, 875, 775 cm-1; 1H and 13C NMR data, see Table 1; EIMS
m/z 284 [M+] (3), 185 (65), 149 (13), 100 (100), 86 (14); HREIMS
m/z 284.2354 (calcd for C17H32O3, 284.2351).
Ack n ow led gm en t. This research was supported by the
National Science Council of Republic of China.
[R]25 -9.9° (c 0.12, CHCl3); IR (KBr) νmax 3418, 1113, 1069,
Refer en ces a n d Notes
(1) Kafuku, K.; Nozoe, T. Bull. Chem. Soc. J pn. 1931, 6, 65-74.
(2) Nozoe, T. Bull. Chem. Soc. J pn. 1936, 11, 295-298.
(3) Lin, Y. T.; Wang, K. T.; Chang, L. H. J . Chin. Chem. Soc. 1955, 2,
126-128.
4r-Hydr oxy-5â-acetoxy-epi-cu ben ol (5): amorphous solid;
[R]25 +10.2° (c 0.12, CHCl3); IR (KBr) νmax 3430, 1735, 1224,
D
1016, 996 cm-1; 1H and 13C NMR data, see Table 1; EIMS m/z
298 [M+] (1), 280 (28), 227 (36), 220 (25), 195 (30), 177 (60),
167 (100), 159 (22); HREIMS m/z 298.2148 (calcd for C17H30O4,
298.2144).
(4) Lin, Y. T.; Wang, K. T.; Chang, L. H. J . Chin. Chem. Soc. 1963, 10,
139-145.
(5) Kuo, Y. H.; Chen, C. H.; Huang, S. L. Chem. Pharm. Bull. 1998, 46,
181-183.
15-Acetoxy-r-ca d in ol (11): amorphous solid; [R]25D -34.7°
(c 0.36, CHCl3); IR (KBr) νmax 3424, 3041, 1743, 1670, 1245,
(6) Kuo, Y. H.; Chen, C. H.; Huang, S. L. J . Nat. Prod. 1998, 46, 829-
831.
(7) Ohta, Y.; Hirose, Y. Tetrahedron Lett. 1967, 2073-2075.
(8) Cheng, Y. S.; Kuo, Y. H.; Lin, Y. T. J . Chem. Soc., Chem. Commun.
1967, 565-567.
(9) Kuo, Y. H.; Wu, T. R.; Cheng, M. C.; Wang, Y. Chem. Pharm. Bull
1990, 38, 3195-3201.
(10) Cheng, Y. S.; Kuo, Y. H.; Lin, Y. T. Chemistry 1968, 47-51.
(11) Bordoloi, M.; Shukla, V. S.; Nath, S. C.; Sharma, R. Phytochemistry
1989, 28, 2007-2037.
(12) Lin, Y. T.; Cheng, Y. S.; Kuo, Y. H. Tetrahedron Lett. 1968, 3881-
3882.
1
1123, 1026 cm-1; H NMR (CDCl3, 400 MHz) δ 1.10 (1H, m,
H-7), 1.12, 1.62 (each 1H, m, H-8), 1.24 (1H, m, H-1), 1.24,
2.07 (each 1H, m, H-2), 1.41, 1.79 (each 1H, m, H-9), 1.76 (1H,
m, H-6), 2.00-2.10 (2H, m, H-3); 13C NMR data, see Table 1;
EIMS m/z 262 [M+ - H2O] (4), 187 (12), 177 (19), 159 (100),
147 (18), 119 (26), 105 (23); HREIMS m/z 262.1941 (calcd for
C
17H26O2, 262.1933).
Sa p on ifica tion of 2 a n d 11 in Meth a n olic Na OH.
(13) Kuo, Y. H.; Cheng, Y. S.; Lin, Y. T. Tetrahedron Lett. 1969, 2375-
Compound 2 (5 mg) or 11 (5 mg) was dissolved in 1 N NaOH
methanolic solution (1 mL) for 5 h under stirring, and the
solution was quenched with 15 mL of H2O. After removal of
MeOH by evaporating in vacuo, the product was extracted with
CH2Cl2 and dried (MgSO4) to afford 13 (3 mg) or 3 (3 mg).
Oxid a tion of r-Ca d in ol (10) w ith Selen iu m Dioxid e.
R-Cadinol (10) (from Taiwania cryptomerioides with same
specific rotation from C. obtusa var. formosana) (1.543 g) and
SeO2 (1.06 g) in 30 mL of 95% ethanol were refluxed 6 h. The
2377.
(14) He, K.; Shi, G.; Zhao, G. X.; Kozlowski, J . K.; McLaughlin, J . L. J .
Nat. Prod. 1997, 60, 38-40.
(15) Nishimura, H.; Hasegawa, H.; Seo, A.; Nakano, H.; Mizutani, J . Agric.
Biol. Chem. 1979, 43, 2397-2398.
(16) Connolly, J . D.; Philips, W. R.; Huneck, S. Phytochemistry 1982, 21,
233-234.
(17) Lin, Y. T.; Cheng, Y. S.; Kuo, Y. H.; Lin, K. C. J . Chin. Chem. Soc.
1974, 21, 31-35.
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