2358
C. M. BENSASSON et al.
EtOAc±petrol (1:1) gave 3b, 7b-hydroxyandrost-5- tetrahydroxyandrostan-17-one (14) (146 mg) which
en-17-one (7) (482 mg) which crystallized from crystallized from EtOAc as prisms, mp 264±2668
EtOAc±petrol as needles, mp 2078 (lit. [11], 2158), (Found: C, 67.0; H, 8.9. C19H30O5 requires C, 67.4;
IR nmax cm 1; 3440, 1726. 1H NMR (pyridine-d5): H, 8.9%). IR nmax cm 1: 3200 (br), 1730 1H NMR
d 0.84 (3H, s, H3±18), 0.99 (3H, s, H3±19), 3.85 (pyridine-d5): d 0.78 (3H, s, H3±18), 3.94 (1H, d,
(1H, tt, J = 5 and 10.5 Hz, H±3a), 4.15 (1H, d, J = 2 Hz, H±6), 4.03 and 4.66 (1H, d, J = 12 Hz,
J = 7.5 Hz, H±7a), 5.71 (1H, s, H±6). Elution with H±19), 4.70 (1H, tt, J = 5 and 10.5 Hz, H±3a).
EtOAc±petrol (3:2) gave 3b, 7a-dihydroxyandrost-
5-en-17-one (6) (389 mg) which crystallized from
EtOAc±petrol as needles, mp 1778 (lit. [11],
182±1838), IR nmax cm 1: 3400, 1723. 1H NMR
REFERENCES
(pyridine-d5): d 0.86 (3H, s, H3±18), 1.02 (3H, s
H3±19), 3.75 (1H, tt, J = 4.5 and 11 Hz, H±3a),
4.15 (1H, br.s., H±7b), 5.89 (1H, br.s, H±6). Elution
with EtOAc±petrol (7:3) gave 3b, 11a-dihydroxy-
androst-5-en-17-one (8) (95 mg) which crystallized
from EtOA±petrol as prisms, mp 2108 (lit. [10],
211±2138), IR nmax cm 1: 3595, 1740. 1H NMR
(CDCl3): d 1.15(3H, s, H3±18), 1.33 (3H, s, H3±19),
3.54 (1H, tt, J = 5 and 10.5 Hz, H±3a), 3.89 (1H, t,
J = 11 Hz of d, J = 5 Hz, H±11b), 5.41 (1H, d,
J = 1.5 Hz, H±6). Elution with EtOAc±petrol (9:1)
gave 3b, 5a, 6b-trihydroxyandrostan-17-one (9)
(89 mg) which crystallized from EtOAc as prisms,
1. Mahato,
S.
Phytochemistry, 1993, 34, 883.
B.
and
Majumdar,
I.,
2. Farooq, A., Hanson, J. R. and Iqbal, Z.,
Phytochemistry, 1994, 37, 723.
3. Hanson, J. R., Nasir, H. and Parvez, A.,
Phytochemistry, 1996, 42, 411.
4. DeFaye, G., Luche, M. H. and Chambaz,
E. M., J. Steroid Biochem., 1978, 9, 331.
5. Crabb, T. A., Dawson, P. J. and Williams,
R. O., J. Chem. Soc., Perkin Trans. I, 1980,
2535.
6. Holland, H. L., Diakow, P. R. P. and Taylor,
G. J., Canad. J. Chem., 1978, 56, 3121.
7. Bridgeman, J. E., Cherry, P. C., Clegg, A. S.,
Evans, J. M., Jones, Sir E. R. H., Kumar, V.,
Meakins, G. D., Morisawa, Y. and Richards,
E. E., J. Chem. Soc. (C), 1970, 250.
8. Chambers, V. E. M., Jones, Sir E. R. H.,
Meakins, G. D., Miners, J. O. and Wilkins, J.,
J. Chem. Soc., Perkin Trans. I, 1975, 55.
9. Williams, K. I. H., Rosen®eld, R. S.,
Smulowitz, M. and Fukushima, Steroids, 1963,
1, 377.
1
mp 298±3018 (lit. [14], 292±2978) IR nmax cm 3551,
3444, 3348, 1726. 1H NMR (pyridine-d5): d 0.82
(3H, s, H3±18), 1.59 (3H, s, H3±19), 4.16 (1H, s,
H±6), 4.82 (1H, tt, J = 5.5 and 10.5 Hz, H±3a).
(c) 3b, 19-Dihydroxyandrost-5-en-17-one (10)
(1.6 g) in DMSO±EtOH (5:1, 30 ml) was evenly dis-
tributed between 50 ¯asks of a 3 day old culture.
After a further 8 days, the mycelium was ®ltered
and the broth extracted with EtOAc. The extract
was dried and the solvent evaporated to give a resi-
due which was chromatographed on silica. Elution 10. Bell, A. M., Browne, J. W., Denny, W. A.,
with EtOAc±petrol (7:3) gave the starting material
(635 mg). Elution with EtOAc±petrol (4:1) gave a
mixture of the starting material and a second com-
Denny, W. A., Jones, Sir E. R. H. and
Meakins, G. D., J. Chem. Soc, Perkin Trans. I,
1972, 2930.
pound which was further puri®ed by acetylation 11. Blunt, J. W. and Stothers, J. B., Organic
with Ac2O-pyridene overnight and chromatography. Magnetic Resonance, 1977, 9, 439.
Elution with EtOAc±petrol (1:4) gave 3b,17b,19- 12. Dodson, R. M., Nicholson, R. T. and Muir,
triacetoxy-androst-5-ene (13) (102 mg) which crys- R. D., J. Am. Chem. Soc., 1959, 81, 6295.
talized from EtOAc±petrol as plates, mp 908 13. Hanson, J. R. and Nasir, H., Phytochemistry,
1
(lit. [15], 88±898), H NMR (CDCl3): d 0.82 (3H, s,
H3±18), 2.03, 2.04 and 2.05 (each 3H, s, OAc), 3.96 14. Holland, H. L. and Diakow, P. R. P., Canad.
and 4.49 (1H, d, J = 12 Hz, H±19), 4.60 (1H, t, J. Chem., 1979, 57, 436.
J = 8.5 Hz, H±17a), 4.63 (1H, tt, J = 5 and 11 Hz, 15. Hill, R. A., Kirk, D. N., Makin, H. L. J. and
1993, 33, 831.
H±3a), 5.66 (1H, br.s, H±6). Elution of the original
column with MeOH±EtOAc (1:9) gave 3b,5a,6b,19-
Murphy, G. M., eds., Dictionary of Steroids.
Chapman and Hall, London, 1991, p. 60.