New triterpenes from Machaerocereus eruca

Article abstract of DOI:10.1021/np970364d

Four triterpenes, three lupanes, and a germanicane were isolated from Machaerocereus eruca. The germanicane derivative (1) was determined to be 3β, 19α-dihydroxygermanican-28-oic acid and named machaeroceric acid. The three new lupane derivatives were identified as 21-ketobetulinic acid (2), 16β-hydroxystellatogenin (4), respectively, on the basis of their spectroscpic data.

Full text of DOI:10.1021/np970364d

4
56
J . Nat. Prod. 1998, 61, 456-460
New Tr iter p en es fr om Ma ch a er ocer eu s er u ca
†
†
†
,†
‡
‡
Yang Ye, Kaoru Kinoshita, Kiyotaka Koyama, Kunio Takahashi,* Norio Kondo, and Hiroshi Yuasa
Department of Pharmacognosy and Phytochemistry, Meiji College of Pharmacy, 1-22-1, Yato-cho, Tanashi-city, Tokyo 188,
J apan, and Research Institute of Evolutionary Biology, 2-4-28, Kamiyoga, Setagaya-ku, Tokyo 142, J apan
Received J uly 29, 1997
Four triterpenes, three lupanes, and a germanicane were isolated from Machaerocereus eruca.
The germanicane derivative (1) was determined to be 3â,19R-dihydroxygermanican-28-oic acid
and named machaeroceric acid. The three new lupane derivatives were identified as
2
1-ketobetulinic acid (2), 16â-hydroxybetulinic acid (3), and 22â-hydroxystellatogenin (4),
respectively, on the basis of their spectroscopic data.
We have been interested in triterpenoids of cacti and
previously isolated six known sapogenins, and 10 new
ones, containing oleanane-type, lupane-type, and pacha-
nan-type triterpenes, from the acid hydrolysates of
methanol extracts of cactaceous plants.1-4 Pachanols
A, B, and C, which were new compounds posessing a
new skeleton named pachanan, and bridgesigenin C, a
as determined by HREIMS and confirmed by 13C NMR
and DEPT analysis. The IR spectrum of 1 exhibited
-1
-1
hydroxyl (3437 cm ) and carboxyl (1710 cm ) absorp-
1
3
tions. The C NMR spectrum revealed 30 carbon
signals, which were assigned by DEPT as seven methyl,
10 methylene, four methine, two alcoholic methine, and
seven quaternary (including a carboxyl) carbons. The
2
1
new compound, were isolated from T. pachanoi. Four
H NMR revealed seven singlet methyls, a doublet of
known triterpenes, stellatogenin, betulinic acid, olean-
olic acid, and thurberogenin, and a new compound,
machaerogenin, were also isolated from Machaerocereus
eruca Br. & R. (Cactaceae).4 Djerasii and co-workers
discovered that M. eruca contained stellatogenin and
betulinic acid in 1955. We now report four new triter-
penes (1-4) and four known triterpenes, morolic acid,
queretaroic acid, 27-desoxyphillyrigenin, and trelease-
genic acid (3â-hydroxytaraxastan-28,20â-olide) from the
acid hydrolysate of a MeOH extract.
doublets at δ 3.41, and a doublet at δ 4.65. Unambigu-
1
13
ous assignments for the H and C NMR signals were
made by combination of the 1D difference homo-decou-
5-7
1
1
pling experiment, NOE difference spectra, H- H COSY,
1
13
HMBC, and HMQC. The H and C NMR chemical
shifts showed good agreement with similar data for the
A/B ring of oleanolic acid, and 1 had one more hydroxyl
2
group on the C/D/E ring. Compound 1 had no sp
2
3
carbons at positions 12 and 13. In J and J HMBC
experiments, the alcoholic methine proton at δ 4.65
showed correlation with the methyl carbons at C-29 (δ
3
0.8) and C-30 (δ 21.0) and with the methine carbons
at C-13 (δ 39.8) and C-18 (δ 46.4), respectively. These
findings indicated a hydroxyl group at C-19. The
stereochemistry of this alcoholic methine proton was
determined by analyzing the NOE difference spectrum
(Figure 1) and the value of coupling constant between
H-18 and H-19. From the difference decoupling spec-
trum, irradiation at H-19 (δ 4.65), H-18 was assigned
at δ 1.79 (t, J ) 10.3 Hz). This indicated that the
coupling constants of J 18-19 and J 18-13 were equal to
1
0.3 Hz. NOE enhancement of the H-13 (δ 2.92) proton
was observed by irradiation of H-19 (δ 4.65) and CH3-
6 (δ 1.07), respectively. In addition, NOE enhance-
2
ment was observed for H-18 and H-9, on irradiation of
CH3-27 (δ 1.17). Thus, H-18 was shown to be in the R
configuration. Furthermore, the alcoholic methine pro-
ton was determined to be in the â configuration from
the vicinal coupling constant (J 18-19 ) 10.3 Hz). The
1
13
H and C NMR assignments at the 29 and 30 positions
were made by NOE difference spectra. In the NOE
difference spectra, enhancement of the methyl protons
at δ 1.26 was observed by irradiation of H-19 (δ 4.65),
and, in turn, NOE enhancement of this methine proton
was observed by irradiation of the methyl protons.
Moreover, on irradiation of the methyl protons at δ 1.24,
NOE enhancement was observed at H-18 (δ 1.79)
(Figure 1). The methyl protons at δ 1.24 and δ 1.26
Resu lts a n d Discu ssion
Four new triterpenes 1-4 were isolated from M.
eruca. Compound 1 had molecular formula C30H50O4
*
To whom all correspondence should be addressed. Tel.: 0424-21-
0
394. Fax: 0424-21-1489.
†
Meiji College of Pharmacy.
Research Institute of Evolutionary Biology.
‡
S0163-3864(97)00364-9 CCC: $15.00
© 1998 American Chemical Society and American Society of Pharmacognosy
Published on Web 03/31/1998

New Triterpenes from Machaerocereus eruca
J ournal of Natural Products, 1998, Vol. 61, No. 4 457
of 3 (Table 2), as in 2, showed signals attributable to a
betulinic acid derivative, except for the signal due to a
proton attached to a carbon-bearing oxygen at δ 4.09.
In comparison with the data of betulinic acid, the carbon
signals for C-14, 15, 16, 17, and 18 appeared slightly or
largely shifted downfield (42.8 f 44.2, 31.2 f 40.1, 32.8
f 75.7, 56.6 f 61.5, and 47.7 f 49.4). These assign-
ments were performed by 1D and 2D NMR. From the
NOE difference spectrum, the hydroxy group was placed
at C-16, and H-16 was shown to be in the R configration.
Therefore, the structure of 3 was determined to be 16â-
hydroxybetulinic acid.
F igu r e 1. Observed positive NOEs for 1 from NOE-difference
spectra (indicated by arrows).
Compound 4 had molecular formula C30H48O5 as
1
3
determined by HREIMS and confirmed by C NMR and
DEPT analysis. The IR spectrum indicated the pres-
showed a cross peak in the HMQC spectrum at δ 21.0
and δ 30.8, respectively. Thus, the methyl protons and
carbon signals at δ 1.24 and δ 30.8 were assigned to
CH3-29 and the methyl protons and carbon signals at δ
-
1
ence of a hydroxyl (3457 cm ) and a five-membered
-
1
1
13
lactone (1759 cm ). H and C NMR of 4 (Table 2)
confirmed the characteristic feature for the stellatogenin
parent structure. In comparison with the NMR data
1.26 and δ 21.0 were assigned to CH3-30 (Table 1).
Therefore, the new compound 1 was determined to be
1
3
of stellatogenin, the C NMR chemical shifts were in
good agreement except for the D/E ring. The alcoholic
3
â,19R-dihydroxygermanican-28-oic acid and was named
1
13
methine proton (δ 5.23) had a long-range H- C
correlation with the carbonyl carbon. Thus, this hy-
droxy group was either at C-16 or C-22. Because the
machaeroceric acid.
Compound 2 had molecular formula C30H46O4 as
determined by HREIMS and confirmed by 13C NMR and
DEPT analysis. The IR spectrum of 2 exhibited hy-
1
3
C NMR data of 4 (Table 2) was not in agreement with
4
that of 16â-hydroxystellatogenin, the hydroxyl group
was assumed to be at C-22. A combination of 1D homo-
decoupling and 2D NMR allowed assignments of all
protons and carbons. The stereochemistry of H-22 was
determined to be R by analyzing the NOE difference
spectrum. These facts indicated that 4 was 22â-hy-
droxystellatogenin.
-
1
-1
droxyl (3428 cm ), carboxyl (1700 cm ), and carbonyl
(
-1
1
1744 cm ) absorptions. The H NMR spectrum showed
five tertiary methyls (δ 0.82-1.23, CH3-23-27) and one
vinylic methyl (δ 1.86, CH3-30), two protons of an
isopropenyl moiety at δ 5.05 and 5.07 (each 1H, s, CH2-
2
9) and one alcoholic methine proton at δ 3.46 (1H, dd,
J ) 8.9, 7.4 Hz, CH-3â). The 13C NMR spectra of
compound 2 revealed 30 carbon signals, which were
assigned by DEPT as six methyl, nine methylene, five
methine, five quaternary, one alcoholic methine, one
carboxylic acid, and two olefinic (one dCH2 and one
Four known triterpenes were also isolated, and one
of the four was identical with morolic acid, which was
identified as the monoacetate derivative by comparing
1
3
with published C NMR data and physical character-
8
13
quaternary) carbons. The ∆2
0,29
istics. Unambiguous assignments of C NMR signals
were made by 2D NMR. The second known compound
was identified as queretaroic acid by direct comparison
with an authentic sample isolated from T. bridgesii.1
The other two compounds were confirmed to be 27-
-functionality of a lu-
pane skeleton was inferred for this compound from the
2
resonances of the sp carbons at C-29 (secondary carbon
signal deduced by DEPT pulse sequence) at δ 114.4 and
1
13
C-20 (quaternary carbon) at δ 144.9. The H and
C
9
desoxyphillygenin (3â-hydroxytaraxastan-28,20â-olide)
NMR (Table 1) confirmed the characteristic features for
a betulinic acid parent structure bearing one carbonyl
group on ring D or E for the compound. These assign-
1
0
and treleasegenic acid, respectively. This is the first
report of the isolation of morolic acid and 27-desoxy-
phillygenin from a cactus, and the first unambiguous
assignments of H and C NMR data for 27-desoxy-
phillygenin and treleasegenic acid are presented in the
Experimental Section.
1
13
ments were performed by H- C COSY and long-range
1
13
1
13
H- C COSY experiments. The signal of CH3-27 at δ
.07 had a long-range 1H- C correlation peak with
13
1
C-15. Methylene protons at C-15 and C-22 had same
correlation peak with C-17, and the methylene protons
at C-22 correlated with the carbon of the carbonyl group
Four new compounds were isolated, and three of the
four compounds (2, 3, and 4) were determined to be 21-
ketobetulinic acid, 16â-hydroybetulinic acid, and 22â-
hydroxystellatogenin, respectively. Compound 1 was
determined to be 3â,19R-dihydroxygermanican-28-oic
acid and was named machaeroceric acid. The stereo-
chemistry of 18-H in germanicanes is R in contrast to
the â configuration in oleananes. Germanicane-type
triterpenes reported earlier are characterized by the
(δ 215.0). These data indicated that the carbonyl group
was at C-21 or C-16. From the 1D homo-decoupling
spectrum, however, the methylene protons were as-
signed to C-16 by irradiation of the methylene protons
at C-15. Thus, the carbonyl group was placed at C-21.
In comparison with 13C NMR data of betulinic acid, the
carbons at C-19 and C-22 of 2 were deshielded (δ 49.7
f 59.0, 37.5 f 52.0), which supported the assignment
of the carbonyl group at C-21. Therefore, the new
compound was determined to be 21-ketobetulinic acid
1
8,19
13
∆
olefinic linkage in their molecules, except for a
1
1,12
few compounds having 18R-H.
Olean-12-ene-type
triterpenes are biosynthesized through germanicane-
type triterpenes from lupane-type triterpenes, and the
stereochemistry of 18-H in lupane-type triterpenes is
(2).
Compound 3 had the molecular formula C30H48O4 as
1
3
determined by HREIMS and confirmed by C NMR
R. Compound 1, a germanicane derivative, does not
1
18,19
(
Table 2) and DEPT analysis. The H NMR spectrum
have the ∆
olefinic linkage but has the 18R-H,

4
58 J ournal of Natural Products, 1998, Vol. 61, No. 4
Ye et al.
Ta ble 1. 13C and 1H NMR Spectral Data of 1 and 2 in C5D5N
1
2
position
δC
δH
δC
δH
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
39.1
28.3
78.0
39.5
55.8
18.8
34.9
41.4
50.6
37.3
21.9
28.8
39.9
42.9
29.7
0.85 (m), 1.53 (m)
1.78 (m)
3.41 (dd, J ) 10.3, 5.7 Hz)
39.2
28.3
78.1
39.5
55.9
18.7
34.5
41.2
50.6
37.5
20.9
26.3
38.8
42.8
29.5
0.99 (m), 1.67 (m)
1.86 (m)
3.46 (dd, J ) 8.9, 7.4 Hz)
0.77 (m)
1.54 (m)
1.39 (m)
0.80 (d, J ) 9.1 Hz)
1.47 (m), 1.58 (m)
1.40 (m)
1.39 (d, J ) 12.6 Hz)a
1.70 (t, J ) 8.9 Hz)
1
1
1
1
1
1
1.54 (m)
1.78 (m), 2.95 (m)
2.92 (m)
1.35 (m)
1.29 (m), 1.75 (m)
2.53 (dt, J ) 12.1, 3.6 Hz)
1.27 (m),
1.28 (m),
1
.97 (ddd, J ) 14.1, 13.6, 3.8 Hz)
1.63 (dt, J ) 13.1, 3.8 Hz),
.41 (dt, J ) 13.1, 4.0 Hz)
2.27 (dt, J ) 13.6, 3.7 Hz)
1
6
35.5
32.1
1.70 (m),
2
2.63 (ddd, J ) 12.9, 3.7, 2.5 Hz)
1
1
1
2
2
2
7
8
9
0
1
2
52.3
46.5
75.9
37.6
36.2
34.4
50.8
48.7
59.0
1.79 (t, J ) 10.3 Hz)a
4.65 (d, J ) 10.3 Hz)
2.42 (t, J ) 12.1 Hz)
3.95 (d, J ) 12.1 Hz)
144.9
215.0
52.0
1.41 (m), 1.85 (m)
1.75 (m), 2.05 (m)
2.45 (d, J ) 16.9 Hz),
2
.92 (d, J ) 16.9 Hz)
2
2
2
2
2
2
2
3
3
4
5
6
7
8
9
0
28.7
16.3
16.4
16.5
15.2
178.8
21.0
30.8
1.23 (s)
1.00 (s)
0.80 (s)
1.07 (s)
1.17 (s)
28.7
16.3
16.3
16.3
14.9
178.5
114.4
21.5
1.23 (s)
1.02 (s)
0.82 (s)
1.07 (s)
1.14 (s)
1.24 (s)
1.26 (s)
5.04 (s), 5.06 (s)
1.86 (s)
a
Revealed by 1H difference decoupling spectrum and NOE difference experiment.
supporting this concept of the biosynthesis of triterpe-
noids. The ∆18,19 germanicanes, such as morolic acid,
may be intermediates to the oleananes.
°C for 2.5 h. The CHCl3-soluble fraction (4.41 g) was
subjected to column chromatography on Si gel (CHCl3-
MeOH) and purified by HPLC over Si gel (Nucleosil 50-
5
, 1 × 25 cm), eluted with CHCl3-MeOH, resulting in
Exp er im en ta l Section
the isolation of four new and four known triterpenes.
Gen er al Exper im en tal P r ocedu r es. Melting points
were determined on a Yanagimoto MP micromelting
point apparatus. The IR spectra were measured with
Ma ch a er ocer ic a cid (1): white amorphous powder
20
(
3.2 mg); mp 271-274 °C; [R] D +5.98° (c 0.35, CHCl3-
-1
MeOH 1:1); IR νmax (KBr) cm 3437, 3125, 2934, 2868
1
13
1
a J ASCO A-102 IR spectrophotometer. The H and
C
(
8
(
sh), 1710, 1692, 1642, 1462, 1385, 1261, 1100, 1036,
NMR spectra were recorded using a J EOL GSX-400 ( H
+
02; EIMS m/z (rel int %) 474 (M , 47), 456 (44), 438
4
00 and 13C 100 MHz) spectrometer in pyridine-d5.
35) 207 (100), 189 (92); HREIMS m/z 474.3714, calcd
Chemical shifts are recorded in parts per million (δ) in
pyridine-d5. The [R]D values were determined with a
J ASCO DIP-140 digital polarimeter. Column chroma-
tography was carried out on 70-230 mesh Si gel
1
13
for C30H50O4, 474.3708; H and C NMR, see Table 1.
2
1-Ketobetu lin ic a cid (2): white amorphous powder
2
0
(
15 mg); mp 214-217 °C; [R] D +26.2° (c 0.53, CHCl3-
MeOH 1:1); IR νmax (KBr) cm 3425, 2950, 2870 (sh),
-
1
(Merck). HPLC was performed using an SSC-3100-J
1
732, 1690, 1442, 1260, 1090, 1025, 800; EIMS m/z (rel
pump with an Oyo-Bunko Uvilog 7 UV detector. HRMS
and EIMS spectra were obtained using a J EOL J MS-
DX 302.
+
int %) 470 (M , 100); 452 (34), 437 (23), 207 (64), 189
(
4
97); HREIMS m/z 470.3393, calcd for C30H46O4,
1
13
70.3396; H and C NMR, see Table 1.
P la n t Ma ter ia l. M. eruca Br. & R. (Cactaceae) was
cultivated originally at the Research Institute of Evo-
lutionary Biology (Setagaya-ku, Tokyo, J apan), Izu
National History Park (Itoh, Shizuoka, J apan), and the
J apan Cactus Planning Co. (Fukushima City, Fuku-
shima, J apan). These cacti were identified by Drs. N.
Kondo and H. Yuasa. A voucher specimen is deposited
at the Research Institute of Evolutionary Biology.
Extr a ction a n d Isola tion . Dry M. eruca was ex-
tracted with CHCl3 and then repeatedly with MeOH.
Extraction of the entire plant of M. eruca with MeOH
was performed as described previously.4 The MeOH
extract (17.9 g) was hydrolyzed with 3.5% HCl at 110
1
6â-Hyd r oxybetu lin ic a cid (3): white amorphous
2
0
powder (30 mg); mp 271-274 °C; [R] D -14.3° (c 0.34,
MeOH); IR νmax (KBr) cm
370, 1250, 1180, 1020, 880, 790; EIMS m/z (rel int %)
72 (M , 20), 454 (76), 246 (44), 207 (81), 189 (100);
HREIMS m/z 472.3552, calcd for C30H48O4, 472.3553;
H and C NMR, see Table 2.
-
1
3400, 2910, 1680, 1440,
1
4
+
1
13
22â-Hyd r oxystella togen in (4): white amorphous
powder (6.3 mg), mp 296-298 °C; [R] D -10.0° (c 0.31,
MeOH); IR νmax (KBr) cm
1370, 1260, 110, 990, 800; EIMS m/z (rel int %) 488 (M ,
1), 470 (100), 427 (68), 205 (34), 189 (86); HREIMS m/z
2
0
-
1
3450, 2855, 1758, 1440,
+

New Triterpenes from Machaerocereus eruca
J ournal of Natural Products, 1998, Vol. 61, No. 4 459
Ta ble 2. 13C and 1H NMR Spectral Data of 3 and 4 in C5D5N
3
4
position
δC
δH
δC
δH
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
39.3
28.3
78.0
39.5
55.9
18.7
34.8
41.2
50.5
37.5
21.1
25.6
38.0
44.2
40.1
0.80 (m), 1.66 (m)
1.84 (m)
3.45 (br t, J ) 8.1 Hz)
39.2
28.3
78.1
39.5
55.8
18.7
34.9
41.4
50.8
37.5
21.3
28.0
40.8
43.4
26.8
0.99 (m), 1.60 (m)
1.87 (m)
3.45 (br t, J ) 7.9 Hz)
0.80 (m)
1.36 (m), 1.54 (m)
1.42 (m)
0.80 (m)
1.40 (m)
1.43 (m)
1.28 (t, J ) 8.9 Hz)
1.30 (m)
1
1
1
1
1
1
1.18 (m), 1.38 (m)
1.15 (m), 1.91 (m)
2.64 (m)
1.47 (m)
1.31 (m), 1.56 (m)
1.55 (m)
a
1.80 (m),
1.78 (m), 2.82 (ddd, J ) 13.3, 13.1, 5.2 Hz)
2
.21 (t, J ) 12.2 Hz)
1
6
75.7
4.09 (dd, J ) 11.5, 4.1 Hz)
22.3
1.20 (m),a
2
.50 (dt, J ) 13.9, 5.2 Hz)
1
1
1
2
2
2
2
2
2
2
2
2
2
3
7
8
9
0
1
2
3
4
5
6
7
8
9
0
61.5
49.4
48.1
150.5
31.4
36.0
28.6
16.3 (16.30)
16.4 (16.36)
16.4 (16.43)
16.2
56.0
39.7
54.2
69.3
86.3
81.8
28.6
16.5
16.4
16.4
14.2
179.5
31.1
31.0
1.80 (m)
3.52 (m)
2.35 (dd, J ) 11.9, 6.0 Hz)
2.00 (d, J ) 6.0)
5.14 (br s)
5.23 (br s)
1.25 (s)
1.15 (s)
0.84 (s)
1.80 (m), 1.66 (m)
1.21 (s)
1.01 (s)
0.83 (s)
1.13 (s)
1.03 (s)
0.95 (s)
1.12 (s)
177.7
110.2
19.4
4.77 (s), 4.92 (s)
1.77 (s)
1.53 (s)
1.43 (s)
a
Assignments may be interchanged.
4
88.3501; calcd for C30H48O5, 488.3502; 1H and 13
NMR, see Table 2.
C
(3-C), 39.5 (4-C), 55.9 (5-C), 18.6 (6-C), 34.3 (7-C), 40.8
(8-C), 50.9 (9-C), 37.4 (10-C), 21.2 (11-C), 25.4 (12-C),
43.2 (13-C), 41.3 (14-C), 27.7 (15-C), 28.1 (16-C), 42.2
(17-C), 48.3 (18-C), 42.4 (19-C), 83.9 (20-C), 27.3 (21-
C), 32.2 (22-C), 28.6 (23-C), 16.3 (24-C), 16.5 (25-C), 15.9
(26-C), 14.3 (27-C), 176.6 (28-C), 18.6 (29-C), 24.1 (30-
Mor olic a cid : white amorphous powder (5.3 mg);
+
EIMS m/z (rel int %) 456 (M , 79), 410 (30), 248 (97),
2
calcd for C30H48O3, 456.3603; C NMR (C5D5N) δ 39.4
36 (70), 207 (100), 189 (95); HREIMS m/z 456.3608,
1
3
1
(1-C), 28.3 (2-C), 78.0 (3-C), 39.5 (4-C), 56.0 (5-C), 18.7
(6-C), 34.2 (7-C), 41.0 (8-C), 51.5 (9-C), 37.5 (10-C), 21.3
(11-C), 26.5 (12-C), 41.6 (13-C), 43.0 (14-C), 30.3 (15-
C); H NMR (C5D5N) δ 0.96 (m), 1.66 (dt, J ) 12.9, 3.4
Hz) (1-CH2), 1.86 (m) (2-CH2), 3.45 (br t, J ) 8.1 Hz)
(3-CH), 0.78 (m) (5-CH), 1.35 (m), 1.52 (m) (6-CH2), 1.34
(m) (7-CH2), 1.31 (br s) (9-CH), 1.12 (m), 1.46 (m) (11-
CH2), 0.91 (m), 1.54 (m) (12-CH2), 1.23 (m) (13-CH), 1.09
(m), 2.28 (dt, J ) 13.1, 4.2 Hz) (15-CH2), 1.19 (m), 2.01
(ddd, J ) 13.7, 4.3, 2.5 Hz) (16-CH2), 1.04 (m) (18-CH),
1.58 (m) (19-CH), 1.50 (m), 1.79 (m) (21-CH2), 1.49 (m)
(22-CH2), 1.22 (s) (23-CH3), 1.02 (s) (24-CH3), 0.82 (s)
(25-CH3), 0.90 (s) (26-CH3), 0.89 (s) (27-CH3), 0.87 (d, J
) 6.9 Hz) (29-CH3), 1.26 (s) (30-CH3).
C), 34.3 (16-C), 48.6 (17-C), 139.0 (18-C), 132.0 (19-C),
2.4 (20-C), 34.2 (21-C), 34.2 (22-C), 28.6 (23-C), 16.3
24-C), 16.3 (25-C), 16.9 (26-C), 15.3 (27-C), 179.1 (28-
3
(
C), 30.8 (29-C), 29.4 (30-C).
Acetyla tion of Mor olic Acid . Morolic acid (2 mg)
in 0.5 mL pyridine was treated with 0.5 mL of anhy-
drous acetic acid. After 24 h at room temperature, the
reaction mixture was applied to Si gel column chroma-
8
10
tography to obtain the monoacetate.
Tr elea segen ic a cid : white amorphous powder (6
Qu er eta r oic a cid :1
,14,15
white amorphous powder
mg); IR νmax (KBr) cm 3450, 2950, 1700, 1460, 1260,
-1
-
1
+
(
1
10 mg); mp >300 °C; IR νmax (KBr) cm : 3400, 2950,
1120; EIMS m/z (rel int %) 488 (M , 1), 470 (2), 442 (39),
+
695, 1460, 1030; EIMS m/z (rel int %) 472 (M , 5), 264
424 (100), 393 (21), 234 (44), 216 (52), 190 (46); HREIMS
m/z 488.3503, calcd for C30H48O5, 488.3502; 13C NMR
(C5D5N) δ 38.9 (1-C), 28.1 (2-C), 78.1 (3-C), 39.4 (4-C),
55.8 (5-C), 18.8 (6-C), 33.3 (7-C), 39.7 (8-C), 48.1 (9-C),
37.4 (10-C), 23.8 (11-C), 123.2 (12-C), 143.9 (13-C), 42.2
(14-C), 28.4 (15-C), 25.1 (16-C), 48.7 (17-C), 41.4 (18-
C), 43.0 (19-C), 40.6 (20-C), 74.0 (21-C), 42.1 (22-C), 28.7
(23-C), 16.5 (24-C), 15.5 (25-C), 17.5 (26-C), 26.1 (27-
C), 179.3 (28-C), 25.2 (29-C), 64.3 (30-C); 1H NMR
(C5D5N) δ: 0.98 (m), 1.53 (m) (1-CH2), 1.82 (m) (2-CH2),
3.45 (dd, J ) 9.9, 6.4 Hz) (3-CH), 0.89 (m) (5-CH), 1.35
(m), 1.55 (m) (6-CH2), 1.32 (m), 1.45 (m) (7-CH2), 1.70
(t, J ) 8.9 Hz) (9-CH), 1.85 (m), 1.92 (dd, J ) 8.9, 3.1
(73), 234 (100), 207 (52), 187 (36); HREIMS m/z 472.3550,
1
3
calcd for C30H48O4, 472.3540; C NMR (C5D5N) δ 38.9
(1-C), 28.1 (2-C), 78.0 (3-C), 39.7* (4-C), 55.8 (5-C), 18.8
(6-C), 33.2 (7-C), 37.3* (8-C), 48.1 (9-C), 37.9 (10-C), 23.8
(11-C), 122.7 (12-C), 144.7 (13-C), 42.2 (14-C), 28.3 (15-
C), 24.0 (16-C), 46.6 (17-C), 41.6 (18-C), 42.0 (19-C), 35.9
20-C), 29.6 (21-C), 32.9 (22-C), 28.4 (23-C), 16.5 (24-
C), 15.3 (25-C), 17.4 (26-C), 26.2 (27-C), 180.2 (28-C),
8.8 (29-C), 65.5 (30-C), (* may be interchanged).
(
2
9
2
7-Desoxyp h illyr igen in : white amorphous powder
65 mg); HREIMS m/z 456.3610, calcd for C30H48O3,
(
1
3
4
56.3603; C NMR (C5D5N) δ 39.3 (1-C), 28.3 (2-C), 78.1

4
60 J ournal of Natural Products, 1998, Vol. 61, No. 4
Ye et al.
Hz) (11-CH2), 5.57 (t-like, J ) 3.1 Hz) (12-CH), 1.20 (m),
.20 (m) (15-CH2), 2.20 (m) (16-CH2), 3.61 (t, J ) 9.5
Hz) (18-CH), 1.98 (t, J ) 9.5 Hz) (19-CH2), 4.22 (m) (21-
CH), 2.46 (dd, J ) 12.3, 4.7 Hz), 2.57 (dd, J ) 12.7, 12.3
Hz) (22-CH2), 1.24 (s) (23-CH3), 1.02 (s) (24-CH3), 0.88
J .; Geller, L. E.; McDonald, R. N.; Taylor. B. J . J . Am. Chem.
Soc. 1955, 77, 1200-1203.
2
(
(
(
(
6) Djerassi, C.; Farkas E.; Lui, L. H.; Thomas, G. H. J . Am. Chem.
Soc. 1955, 77, 5330-5336.
7) Marx, M.; Leckereq, J .; Tursch, B.; Djirassi, C. J . Org. Chem.
1
955, 32, 3150-3155.
8) Gonz a´ ez, A. G.; Fraga, B. M.; Gonz a´ ez, P.; Hernandez, M. G.;
Ravelo, A. G. Phytochemistry 1981, 20, 1919-1921.
(s) (25-CH3), 1.02 (s) (26-CH3), 1.32 (s) (27-CH3), 1.59
(s) (29-CH3), 4.20 (d, J ) 10.7 Hz), 4.65 (d, J ) 10.7 Hz)
(30-CH2).
9) Errington, S. G.; J efferies, P. R. Phytochemistry 1988, 27, 543-
5
45.
(
(
10) Djerassi, C.; Mills J . S. J . Am. Chem. Soc. 1958, 80, 1236-1243.
11) Siddqui, S.; Faizi, S.; Siddiqui, B. S.; Sultana, N. Phytochemistry
1
989, 28, 2433-2438.
Refer en ces a n d Notes
(
12) Pym, J . G.; Ray, J . E.; Smith, G. W.; Whitehead, E. V. Anal.
(
(
(
(
(
1) Kinoshita, K.; Koyama, K.; Takahashi, K.; Kondo, N.; Yuasa,
Chem. 1975, 47, 1617-1622.
H. J . Nat. Prod. 1992, 55, 953-955.
2) Kinoshita, K.; Koyama, K.; Takahashi, K.; Kondo, N.; Yuasa,
H. J . Nat. Prod. 1995, 58, 1739-1744.
(13) Dev, S.; Gupta, A. A.; Patwardhen, S. A. Handbook of Terpenoids,
Triterpenoids; CRC Press: Boca Raton, FL, 1989; pp 37-41.
(14) Djerassi, C.; Henry, J . A.; Lemin, A., Rios, T.; Thomas, G. H. J .
Am. Chem. Soc. 1956, 78, 3783-3785.
3) Takizawa, T.; Kinoshita, K.; Koyama, K.; Takahashi, K.; Kondo,
N.; Yuasa, H. J . Nat. Prod. 1995, 58, 1913-1914.
4) Koyama, K.; Kinoshita, K.; Takahashi, K.; Kondo, N.; Yuasa,
H. J . Nat. Prod. 1993, 56, 2201-2203.
(15) Tori, K.; Seo, S.; Shimaoka, A.; Tomita, T. Tetrahedron Lett.
1974, 48, 4227-4230.
5) Djerassi, C.; Lui, L. H.; Farkas, E.; Lippman, A. E.; Lemin, A.
NP970364D