Journal of Natural Proakts
Vol. 56, NO.12,pp. 2183-2185, D
2183
d 1993
A NEW TYPE OF TRITERPENE FROM TRZCHOCEREUS PACHANOZ TAKAOM TAKUWA,KAORU KINOSHITA,Krymm KOYM, KUNIOTAKAHASHI,* Department of Pharmacognosy and Phytochemistry, Meiji College of Pbarnacy, 1-22-1 Yato-cho, Tamshi City, Tokyo 188,Japan NORIOKONDO,HIROSHI YLJASA,
The Research Institute of Evolutiomry Biology, 4-28, 2-Chome, Kamiyoga, Setagaya-ku, Tokyo I 58,Japan and KEN-ICHIKAWN
Faculty of Pharmaceutical Sciences, Hoshi University,Ebara 2-4-41, Shimgawa-ku, Tokyo 142, Japan ~TRACT.-A new triterpene, pachanol A 111,which has a novel skeleton, was isolated from the hydrolysate of an MeOH extract of Trichocereuspachanoi (Cactaceae).
We have been interested in triterpenes of cacti and have isolated several known and unknown triterpenes from Hertrichocereus beneckei Backbg . and Trichocereus bridgesii Britt. & Rose ( 1 ) . Now we report the isolation and structural determination of a new triterpene, pachanol A 111, from Trzchocereuspachanoi Britt. & Rose (Cactaceae). This compound possesses a new skeleton named pachanane. Thestructureofpachanol A111 was determined by single-crystal X-ray diffraction, and the result is reported together with its assigned nmr data. The MeOH extract of T.pachanoi was hydrolyzed with 3.5% HCI, and the precipitates were chromatographed on a Si gel column with CHClJMeOH to obtain pachanol A, which was recrystallized from CHCl,/MeOH as colorless needles, mp >300', C30H4404 (mlz calcd 468.3241, found 468.3233).The molecular structure is illustrated in Figure 1 . The structure
H
FIGURE1.
The COLOC correlations (lH+13C) for pachanol A Ill.
illustrated in Figure 1 was confirmed on the basis of DEFT, 'H- 'H, 'H- I3CCOSY, and 'H- I3C long range COSY. The nmr assignments are summarized in Table 1 . CRYSTAL REFINEMENT DATA.'-
C3J-Ia04, M, 468, orthorhombic, space group P2,2,2, (No. 19),a=28.415(11), b=13.602(6), c=6.477(9) A, V=2503 ~ ; unique ( 4 )A3, Dc=1.244 g - ~ m - 1533 diffractometer data measured at ca. 295 K 128 max 100'; 28/w scan mode, monochromatic CuKa radiation ( h 1.5418 A)], 1312 with F > 3 a ( F ) considered observed and used in the block-matrix leastsquares refinement without absorption correction (p.,,=5.1 cm-'; specimen 0.50X0.15X0.10mm). Anisotropic thermal parameter refinement for C and 0; contribution of H ignored; R=0.094. An ORTEP drawing of 1 is shown in Figure 2 . EXPERIMENTAL %MATERIAL.-T. parhanot was cultivated in the Research Institute ofEvolutionary Biology, Setagaya-ku, Tokyo, Japan, and in Izu Natural History Park,Itoh, Shizuoka, Japan. This cactus was botanically identified by Dr. Hiroshi Yuasa.
'Atomic coordinates for this structure have been deposited with the Cambridge Crystallographic Data Centre and can be obtained on request from Dr. Olga Kennard, Cambridge Crystallographic Data Centre, 12 Union Road, Cambridge CB2 lEZ, UK.
Journal of Natural Products
2184
Wol . 56. No . 12
mts for Pachanol A [l Position
Multiplicity ( J in Hz)
1.................
39.1
2 3................. 4 ................. 5 ................. 7 .................
28.3 77.9 39.2 54.5 19.5 41.1
8 ................. 9 ................. 10 . . . . . . . . . . . . . . . . 11 . . . . . . . . . . . . . . . .
40.4 55.4 38.1 22.9
6.................
12 . . . . . . . . . . . . . . . . 13 . . . . . . . . . . . . . . . . 14 . . . . . . . . . . . . . . . . 15 . . . . . . . . . . . . . . . . 16 . . . . . . . . . . . . . . . .
124.0 132.0 140.0 125.4 42.4
17 . . . . . . . . . . . . . . . . 18 . . . . . . . . . . . . . . . . 19 . . . . . . . . . . . . . . . .
45.2 39.3 29.0
20 . . . . . . . . . . . . . . . . 21 . . . . . . . . . . . . . . . . 22 . . . . . . . . . . . . . . . .
38.7 80.2 33.0
23 . . . . . . . . . . . . . . . . 24 . . . . . . . . . . . . . . . . 25 . . . . . . . . . . . . . . . . 26 . . . . . . . . . . . . . . . . 27 . . . . . . . . . . . . . . . . 28 . . . . . . . . . . . . . . . . 29 . . . . . . . . . . . . . . . . 30 . . . . . . . . . . . . . . . .
28.6 16.4 16.6 19.0 23.8 180.3 21.8 68.9
‘H- 13CLong-range correlations
0.92 1.65 1.83 3.34
m m m dd (5.7, 10.4)
c.3. c-5
0.89 1.60 1.54 2.57
d (11.9) rn m rn
C-25 c.8. c-10 C.5. C.9. C-26
1.28
m
2.09 2.25
m
C.12. C-13
5.99
m bs
C.9. C-14
1.96 2.97
d (18.7) d (18.7)
C.14. C.15. C.17. C.18 .C-28
2.49 1.57 2.16
bs m d (15.6)
C.13. C.17. C.21. C-29
4.85 1.82 2.43 1.26 1.06 0.95 1.09 1.86
d (5.7) m d (11.9)
1.36 3.55 3.89
S
S S
s s S
d (10.4) d (10.4)
23
FIGURE2 . ORTEP drawing of 1.
C-28 C.3. C 4 . C.5. C-24 C.5. C-23 c.5. c.9. c-10 C.7. C.8. C.9. C-14 C.14. C.15. C-16 C.19. C.20. C-21 c-21
December 19931
Takizawa et a/.: Triterpene from Trzchocereus
This specimen is deposited at the Research Institute ofEvolutionaryBiology,Setagaya-kuTokyo,Japan. INSTRUMENTS.-M~ was determined with a Yanagimoto MP micro mp apparatus. 'H- and 13 C-nmr spectra were recorded using aJEOL GSX400 ('H 400 and "C 100 MHz) spectrometer in C,D,N with TMS as an internal standard. The chemical shifts are expressed in ppm (6)(Table 1). The [a]Dvalues were determined with a JASCO DIP-140 digital polarimeter. Cc was carried out on 70-230 mesh Si gel (Merck). Hrms and eims spectra were obtained using a JEOL JMS-DX 302. EXTRACTION AND ISOLATION OF PACHANOL A T. parbunoi (196.9 g) was extracted [l].-Dry with CHCI, and then repeatedly with MeOH. The MeOH extract (12.9 g ) was hydrolyzed with 3.5% HCI at 110' for 2.5 h. The precipitates (2.98 g) produced were subjected to cc on Si gel (CHC1,I MeOH) and purified by hplc on a Si gel column
2185
(Nucleosil60-5, 1 X25 cm), eluted with CHC1,MeOH(50:1),resultinginpachanolA(15.0mg). Crystallization from MeOH gave pachanol A 111: mp >300°(dec), [ a l -89.O0(r=0.145; ~ CHCI,); ir v max (KBr) 3500, 3450, 2950, 2900, 1740 cm-'; uv A max (MeOH) 255 ( ~ ~ 8 7 0 0'H) ;and 13 C nmr see Table 1; eims mlz {MI' 468 (93) 450 (30),422 (32), 383 (loo), 351 (38), 214 (29), 201 (591, 189 (35), 135 (27). ACKNOWLEDGMENTS The authors thank Dr. Shoji Shibata, the Laboratory ofNatural Medicinal Materials, for his suggestion. LITERATURE CITED 1.
K. Kinoshita, K. Koyarna, and K. Takahashi, J. Nat. Prod., 55, 953 (1992).
Received 29 April 1993
