J. CHEM. RESEARCH (S), 1998 103
Diimide Reaction of 17-Oxoandrost-5-en-3 -yl Acetate (5).ÐTo a
stirred solution of 5 (200 mg, 0.6 mmol) in CH2Cl2 (10 ml) and
absolute MeOH (15 ml) dipotassium azodicarboxylate (1.0 g,
2.7 mmol) was added and the suspension cooled in an ice-bath.
To this mixture was added dropwise a solution of AcOH (0.6 ml)
in MeOH (6 ml) within ca. 30 min and stirring was continued
overnight at room temperature. Work-up as above aorded a
crystalline solid (220 mg) which was chromatographed on SiO2
(12 g). Elution with EtOAc gave a mixture of (Z)- and (E)-
hydrazones 6 (167 mg, 80.1%), mp 275±276 8C (decomp.);
/
max
0.87, 0.92 (3 H, parts of
1
cm (KBr) 3344, 1733, 1669, 1250;
H
two s, H-18 of Z and E isomers), 1.05 (3 H, s, H-19), 2.04 (3 H, s,
OCOCH3), 4.61 (1 H, m, H-3), 5.39 (1 H, d, J 5.0 Hz, H-6);
C
16.4, 16.6 (q, C-18), 19.2 (q, C-19), 20.5 (t, C-11), 21.3 (q,
OCOCH3), 23.2, 23.3 (t, C-15), 24.3 (t, C-2) 27.6 (t, C-7), 31.2
(d, C-8), 31.2 (t, C-12), 33.7, 33.9 (t, C-16), 36.6 (t,
C-1), 36.8 (s, C-10), 38.0 (t, C-4), 43.7, 43.9 (s, C-13), 50.2
(d, C-9), 53.5, 53.8 (d, C-14), 73.7 (d, C-3), 122.0 (d, C-6),
139.8 (s, C-5), 170.5 (s, OCOCH3), 165.9 173.6 (s, C-17); m/z 344
(M+).
Scheme 3
respective 17-oxo groups with hydrazine (accumulated by
diimide disproportionation) is the main process.
Diimide Reaction of 17-Oxo-7-norandrost-5-en-3 -yl Acetate (7).Ð
A
stirred ice-cooled suspension of
potassium azodicarboxylate (1.0 g, 2.7 mmol) in CH2Cl2 (10 ml) and
MeOH (15 ml) was treated with solution of AcOH (0.6 ml)
7 (200 mg, 0.63 mmol) and
a
Experimental
and MeOH (15 ml) as above. The mixture was left overnight at
room temperature and worked up as above. The residue (210 mg)
was puri®ed by column chromatography on SiO2 (12 g). Toluene±
Mps are uncorrected. IR spectra were recorded on a Perkin-
Elmer 337 spectrometer and NMR spectra on a Varian Gemini
2000 spectrometer (1H at 200 MHz, 13C at 50 MHz) in CDCl3
solution at room temperature, using SiMe4 as internal standard
(d in ppm, J in Hz). Mass spectra were measured on a Finnigan-
MAT 8230 spectrometer at 70 eV. Column chromatography was
carried out on silica gel 0.063±0.200 mm. TLC (control of reactions
and separation of products) was performed on silica gel G (Stahl)
(detection with 50% aqueous H2SO4).
EtOAc (6:4 and 1:1) eluted the hydrazone 8 (201 mg, 96.2%), mp
1
224±225 8C (decomp.); max/cm 3445, 1733, 1662, 1245;
0.92
(3 H, s, H-18), 0.93 (3 H, s, H-19), 2.04 (3 H, s, OCOCH3), 4.64
H
(1 H, m, H-3), 5.44 (1 H, br, s, H-6); 14.4 (q, C-18), 17.1 (q,
C
C-19), 20.5 (t, C-11), 21.3 (q, OCOCH3), 23.5 (t, C-15), 27.8 (t,
C-2), 29.6 (t, C-12), 32.7 (t, C-4), 34.1 (t, C-16), 36.7 (t, C-1), 44.7
(d, C-14), 45.6 (s, C-10), 45.7 (s, C-13), 51.3 (d, C-8), 62.5 (d, C-9),
73.5 (d, C-3), 125.1 (d, C-6), 148.5 (s, C-5), 170.4 (s, OCOCH3),
173.1 (s, C-17); m/z 330 (M+).
17-Oxo-5,8 -epidioxy-5 -androst-6-en-3 -yl Acetate (1)11.ÐMp
239±240 8C (from acetone±methanol); [ ]D= + 66.0 (c, 0.50 in
1
CHCl3); max/cm (KBr) 1748, 1735, 1248;
0.93 (3 H, s, H-18),
1.00 (3 H, s, H-19), 2.03 (3 H, s, OCOCH3), 5.00 (1 H, m, H-3),
H
6.32, 6.52 (2 H, AB, J 8.6 Hz, H-6, H-7) (Found: C, 69.75: H, 7.79.
C21H28O5 requires C, 69.98; H, 7.83%).
Diimide Reduction of 17-Oxo-5,8 -epidioxy-5 -androst-6-en-3 -yl
We thank the Serbian Academy of Sciences and Arts and
the Ministry of Sciences and Technology of Serbia for ®nan-
cial support.
Acetate (1).ÐTo a stirred solution of 1 (1.08 g, 3 mmol) in CH2Cl2
(50 ml) and absolute MeOH (70 ml) dipotassium azodicarboxylate
(5 g, 13.5 mmol) was added and the suspension cooled in an ice-
bath. To this mixture was added dropwise a solution of AcOH
(3 ml) in absolute MeOH (30 ml) within ca. 1 h. Stirring was
continued at room temperature for an additional 20 h, when the
yellow colour disappeared. The mixture was taken up in water
(250 ml) and extracted twice with CH2Cl2, the combined organic
extract was washed with saturated aq. NaHCO3 solution and water,
Received, 9th September 1997; Accepted, 31st October 1997
Paper E/7/06570A
References
1 D. J. Pasto, Reduction of C1C and C2C by Noncatalytic
Chemical Methods in Comprehensive Organic Synthesis, ed. B. M.
Trost and I. Fleming, Pergamon, Oxford, 1991, vol. 8, p. 471.
2 E. E. van Tamelen, M. Davis and M. F. Deem, Chem.
Commun., 1965, 71.
dried (Na2SO4) and evaporated and the residue
( 1.2 g) was
chromatographed on SiO2 (50 g). Elution with toluene±EtOAc 9:1
and 8:2 aorded 5,8 -epidioxy-17-oxo-5 -androstan-3 -yl acetate
(2) (182 mg, 16.1%), mp (141 8C), IR and 1H NMR identical with
those of an authentic sample.7
3 S. Uemura, A. Onoe, H. Okazaki, M. Okano and K. Ichikawa,
Bull. Chem. Soc. Jpn., 1976, 49, 1437.
Toluene±EtOAc 2:8 and EtOAc eluted a mixture of (Z)- and (E)-
hydrazone 3 (655 mg, 58.1%): max/cm (KBr) 3450, 1733, 1661,
4 E. E. van Tamelen, R. S. Dewey, M. F. Lease and W. H. Pirkle,
J. Am. Chem. Soc., 1961, 83, 4302.
1
1252; dH 0.92, 0.98 (3 H, parts of two s, H-18 of Z and E isomers),
1.03 (3 H, s, H-19), 2.00 (3 H, s, OCOCH3), 4.81 (1 H, m, H-3).
5 G. Dauben and C. H. Schallhorn, J. Am. Chem. Soc., 1971, 93,
2254.
Upon recrystallization from acetone±methanol, hydrazone
3
6 W. Adam and H. J. Eggelte, J. Org. Chem., 1977, 42, 3987.
7 Lj. Lorenc, L. Bondarenko, V. Pavlovic, H. Fuhrer, G. Rihs,
J. Kalvoda and M. Lj. Mihailovic, Helv. Chim. Acta, 1989, 72,
608.
aorded 5,8a-epidioxy-17-isopropylidenehydrazono-5a-androstan-3b-
1
yl acetate 4 (384 mg), mp 205 8C; max/cm (KBr) 1742, 1670,
1254; dH 0.98 (3 H, s, H-18), 1.04 (3 H, s, H-19), 1.81, 1.99 [6 H,
2 s, N=C(CH3)2],, 2.00 (3 H, s, OCOCH3), 4.82 (1 H, m, H-3); dC
17.3 (q, C-18), 17.5 (q, C-19), 18.0 (q, CH3C=N), 19.3 (t, C-11),
20.9 (t, C-2), 21.0 (q, OCOCH3), 21.5 (t, C-15), 24.7 (q, CH3C=N),
25.7 (t, C-1), 26.4 (t, C-6), 27.9 (t, C-16), 33.5 (t, C-4) 35.4 (t, C-7),
35.5 (s, C-10), 36.0 (t, C-12), 44.8 (s, C-13), 51.7 (s, C-9), 51.9 (d,
C-14), 69.4 (d, C-3), 78.5 (s, C-8), 80.4 (s, C-5), 159.3 [s,
8 R. Tang, M. L. McKee and D. M. Stanbury, J. Am. Chem.
Soc., 1995, 117, 8967.
9 A successful diimide reduction of the ole®nic double bond in
some
5-B-nor-steroids has been recently reported,10 using
toluene-p-sulfonyl hydrazide in collidine at 150 8C.
10 A. Kasal, H. Chodounska and W. J. Szczepek, Tetrahedron
Lett., 1996, 37, 6221.
N=C(CH3)2], 169.7 (s, OCOCH3), 173.2 (s, C-17); m/z 416 (M+
)
(Found: C, 68.83; H, 8.50; N, 7.11. C24H36N2O4 requires C, 69.20;
H, 8.71; N, 7.44%).
11 L. Bondarenko-Gheorghiu, Ph.D. Thesis, University of
Belgrade, 1986.