New routes to steroidal heterocyclic derivatives: Synthesis of biologically active pyrazolyl- and isoxazolylpregnene derivatives

Article abstract of DOI:10.1002/jhet.5570440102

(Chemical Equation Presented) Pyrazolyl- and isoxazolylpregnene derivatives were synthesized from the appropriate hydrazonoyl chlorides and hydroximoyl chlorides with enaminoprogesterone derivative. The newly synthesized compounds were elucidated by eleme

Full text of DOI:10.1002/jhet.5570440102

Jan-Feb 2007
7
New Routes to Steroidal Heterocyclic Derivatives: Synthesis of
Biologically Active Pyrazolyl- and Isoxazolylpregnene Derivatives.
Abdou O. Abdelhamida, Mervat M. Abdelhalimb and Gamal A. Elmegeedb
aChemistry Department, Faculty of Science, Cairo University, Giza 12613, Egypt
bHormone Department, National Research Centre, Dokki, Giza 12622, Egypt
Abdou_Abdelhamid@yahoo.com
Received October 19, 2005
R
O
R'
N
X
N
O
O
N
N
X
N
N2H4
i (ii)
ii- RCOC(Cl):NOH
X + NPh , O
i = RCOC(Cl):NNHPh
Pyrazolyl- and isoxazolylpregnene derivatives were synthesized from the appropriate hydrazonoyl
chlorides and hydroximoyl chlorides with enaminoprogesterone derivative. The newly synthesized
compounds were elucidated by elemental analysis, spectral data and chemical transformation. Some
products were tested towards some bacteria and some Fungal-plant pathogens
J. Heterocyclic Chem., 44, 7 (2007).
INTRODUCTION
pregnene derivatives have been found to possess a variety
of interesting pharmacological and biological activities
[4-7]. In continuation of the synthesis of modified steroids
[8-11], we report herein new and efficient procedures for
Attention has been devoted in the literature to the
synthesis of several steroidal heterocyclic derivatives that
exhibit marked medicinal activities [1-3]. Heterocyclic
Scheme 1
O
O
N
(CH3)2NCH(OCH3)2
+
2
O
O
1
3
RCOC(Cl):NNHPh
2 + 4 (5)
4
Et3N
-
O
N
R
+
RCOC:NNPh
R
O
O
5
O
N
N
N
Ph
Ph
4-7a, R =OC2H5
b, R = CONHPh
c, R = CH3
O
d, R = C6H5
O
6
7
8a, R' = OH
b, R' = CH3
c, R' = C6H5
N2H4
R'
N
N
N
N
Ph
8
O

8
A. O. Abdelhamid, M. M. Abdelhalim and G. A. Elmegeed
Vol 44
the synthesis of some pyrazolyl-, isoxazolyl-, pyra-
zolo[3,4-d]pyridazinyl- and isoxazolo[3,4-d]pyridazinyl-
pregnene derivatives.
Similarly, compound 3 was reacted with the appropriate
hydrazonoyl chlorides 4b-d in boiling benzene and
triethylamine afforded the corresponding pyrazolyl-
pregnene derivatives 6b-d, respectively (Scheme 1).
Compound 6a was reacted with hydrazine hydrate to
give pyrazolo[3,4-d]pyridazine 8a. Structure 8a was
confirmed by elemental analysis, spectral data and
alternative synthesis method. Thus, treatment of 6b with
boiling hydrazine hydrate gave product identical in all
respects (mp., mixed mp., and spectra) with 8a.
Also, pyrazolylpregnene derivatives 6c and 6d reacted
with hydrazine hydrate in ethanol to afford the corre-
sponding pyrazolo[3,4-d]pyridazinopregnene derivatives
8b and 8c, respectively (Scheme 1). Compound 3 was
reacted with the appropriate hydroximoyl chlorides 9a
and 9b in toluene containing triethylamine to afford the
isoxazolylpregnene derivatives 10a and 10b, respectively
(Scheme 2).
RESULTS AND DISCUSSION
Progesterone (1) was reacted with dimethylformamide
dimethylacetal (2) to afford 17-(3-dimethylamino-acryl-
oyl)-10,13-dimethyl-1,2,6,7,8,9,10,11,12,13,14,15,16,17-
teteradecahydrocyclopenta[a]phen-anthren-3-one (3)
(Scheme 1). Structure 3 was confirmed by elemental
analysis, spectral data and chemical transportation. MS
1
spectrum showed molecular ion peaks at m/z = 369. H
NMR showed signals at ꢀ = 2.47 (s, 6H), 5.09 (d, 1H),
7.17 (d, 1H) that are characteristic signals of the
cyclopentanoperhydrophenanthrene moiety [12,13]. Thus,
compound 3 was reacted with C-ethoxycarbonyl-N-
phenylhydrazonoyl bromide (4a) in the presence of
triethylamine to give one isolable product, according to
tlc, whose mass spectrum and elemental analysis
indicated a molecular formula C32H38N2O4. The product
seemed to be one of two possible isomeric structures 6
Isoxazoloylpregnene derivatives 10a,b was reacted with
hydrazine hydrate to give isoxazolo[3,4-d]pyridazinyl-
pregnene derivatives 11a and 11b, respectively (Scheme
2). Structures 11a,b and 12a,b were elucidated based on
their elemental analyses and spectral data.
1
and 7 (Scheme 1). The H NMR spectrum of the product
showed, in addition to the expected signals of the
Scheme 2
R''
R''
N
N
O
N
N
O
O
N2H4
Et3N
O
3
R"CO(Cl):NOH
+
9
O
O
10
11
9-11a, R'' = C6H5
b, R'' = 2-C4H3S'
pregnene moiety [12,13], the presence of signals at ꢀ =
1.35 (t, 3H, CH3CH2), 4.25 (q, 2H, CH2CH3), 7.38-7.75
(m, 5H, ArH’s) and 8.12 (s, 1H, pyrazole H-5). The
product was easy to convert into pyrazolo[3,4-d]-
pyridazine 8a by its reaction with hydrazine hydrate,
therefore structure 7 was ruled out. Formation of 6 can be
explained via reaction of nitrilimine 5, which formed in
situ from hydrazonoyl chloride 4 and triethylamine, with
3 to afford cyclo adduct intermediate via 1,3-dipolar
cycloaddition followed by elimination of dimethylamine
to give pyrazole as the final product.
Antimicrobial Activity. Sensitivity of the selected
microorganisms to some synthesized compounds
were determined in vitro culture on three
concentrations (1, 2.5 and 5 mg/ml) that were
dissolved in N,N-dimethylformamide, the tests were
carried out using the filter paper and hole plate method
[14]. Studies on the biological activity of compounds in
comparison with chloroamphenicol and terbinafin are
shown in Tables 1 and 2. In general all tested compounds
were capable of inhibiting the growth of gram-positive
bacteria and gram-negative bacteria (Tables 1 and 2).
Table 1
Response of various microorganisms to some synthesized compounds in vitro (culture).
Microorganisms
Inhibition zone diamter (mm / mg sample)
6a
21
20
0.0
6b
00
00
0.0
6c
16
15
0.0
St.
18
12
3
Staphylococcus albus
Streptococcus facealis
Saccharomyces cervisiae
G+
G+
Fungus

Jan-Feb 2007
New Routes to Steroidal Heterocyclic Derivatives
9
Table 2
Response of various microorganisms to some synthesized compounds in vitro (culture).
Compounds
8a
8b
8c
11a
11b
St.
mg/ml
2.5
3
mg/ml
2.5
0
0
0
mg/ml
2.5
0
4
0
mg/ml
2.5
0
0
8
mg/ml
2.5
0
0
0
mg/ml
2.5
14
15
14
Concentration
Aspergillus fumigatus
Penicillium italicum
Syncephalastrum
racemosum
5
10
4
1
0
4
5
5
0
0
4
1
0
0
0
5
0
5
0
1
0
0
0
5
5
0
9
1
0
0
4
5
0
0
5
1
0
0
0
5
1
10
9
13
14
15
5
8
9
14
Candida albicans
Staphylococcus aureus
Pseudomonas areuginosa
Bacillus subtilis
5
0
0
4
0
0
0
0
0
0
5
0
0
0
0
0
9
8
0
5
0
9
5
0
0
0
4
0
0
0
0
0
3
4
0
0
0
0
0
5
0
0
0
0
5
5
0
4
0
0
0
0
3
0
0
0
0
0
0
0
0
0
0
5
0
0
0
0
3
0
0
0
0
0
0
9
9
15
12
8
10
10
14
13
9
9
8
9
10
10
Escherichia coli
St. Reference standerd; Chloramphenicol was used as a slandered antibacterial agent; Terbinafin was used as a slandered antifungal agent. Values
show zone of inhibition in mm. Diameter of the inhibition zones were: high (11-15 mm), moderate (6-10 mm), slight (1-5 mm) and negative (0).
EXPERIMENTAL
carbonyl-1-phenylpyrazole-3-carboxylate (6a). This compound
was obtained as yellow crystals (ethanol), 2.60 g (51 %), mp
215°. ir (KBr): 3035 (CH aromatic), 2983, 2850 (CH aliphatic),
All melting points were determined on an Electrothermal
apparatus and are uncorrected. The IR spectra are expressed in
cm-1 and recorded in KBr pellets on
1
1695, 1715, 1720 (CO’s), 1640 (C=N) cm-1. H nmr (CDCl3):
1.16 (s, 3H), 1.26 (s, 3H), 1.27-1.71 (m, 14H), 1.35 (t, 3H,
CH3CH2), 1.99-2.01 (t, 3H), 2.35 (t, 1H), 2.99 (t, 2H), 4.25 (q,
2H, CH2CH3), 5.85 (s, 1H), 7.38-7.75 (m, 5H, ArH’s), and 8.12
(s, 1H, pyrazole H-5). ms: m/z 514 (55) (M+˙). Anal. Calcd. for
C32H38N2O4: C, 74.68; H, 7.44; N, 5.44. Found: C, 74.86; H,
7.23; N, 5.61.
a Pa-9721 IR
1
spectrometer. H NMR spectra were obtained on a Varian EM-
390 (90) MHz spectrometer in DMSO-d6 as solvent and TMS
as internal reference. Chemical shifts (ꢀ) are expressed in ppm.
Mass spectra were recorded on Kratos (75eV) MS equipment.
Elemental analysis ere carried out at Microanalytical Data Unit
at the National Research Center, Giza, Egypt. Antimicrobial
study of the new compounds were carried out at the laboratory
of Micro Analytical Center, Faculty of Science, Cairo
University, and the laboratory of The Regional Center for
Mycology and Biotechnology, El-Azher University, Egypt.
Hydrazonoyl chlorides and hydroximoyl chlorides were
prepared as previously methods [15-18].
4-(10,13-Dimethyl-3-oxo-2,3,6,7,8,9,10,11,12,13,14,15,16,17-
tetradecahydro-1H-cyclopenta[a]phenanthrene-17-carbonyl)-
3-phenylcarbamoyl-1-phenyl-1H-pyrazloe (6b). This compound
was obtained as yellow oil. ir (KBr): 3320 (NH), 3030 (CH-
aromatic), 2975, 2825 (CH- aliphatic), 1690, 1705, 1720 (CO’s),
1
1640 (C=N) cm-1. H nmr (CDCl3): 1.16 (s, 3H), 1.26 (s, 3H),
1.27-1.71 (m, 14H), 1.99-2.01 (t, 3H), 2.35 (t, 1H), 2.99 (t, 2H),
5.85 (s, 1H), 7.23-7.64 (m, 10H, ArH’s), 8.12 (s, 1H), pyrazole
C-5) and 9.23 (s, br., 1H, NH). ms: m/z: 561 (35) (M+˙). Anal.
Calcd. for C36H39N3O3 (561.73): C, 76.98 ; H, 7.00 ; N, 7.48.
Found : C, 76.89 ; H, 7.12 ; N, 7.53.
17-(3-dimethylaminoacryloyl)-10,13-dimethyl-1,2,6,7,8,9,10,
11,12,13,14,15,16,17-teteradecahydrocyclopenta[a]phenan-
thren-3-one (3). A solution of progesterone (1) (3.14 g, 0.01
mole) and DMF-DMA (1.69g, 0.01 mole) in dry xylene (30 mL)
was refluxed for 20 h. the solvent was removed under vacuum
and the residue triturated with petroleum ether (b.p. 40/60ºC).
The resulting solid was collected and crystallized from ethanol
to gave yellow crystals 3, yield 2.76 gm (75%), mp 110-112º, ir
(KBr): 2976, 2860 (CH), 1698, 1715 (C=O) cm-1. 1H nmr
(CDCl3): 1.16 (s, 3H), 1.26 (s, 3H), 1.27-1.71 (m, 14H), 1.99-
2.01 (t, 3H), 2.35 (t, 1H), 2.47 (s, 6H), 2.99 (t, 2H), 5.09 (d, 1H),
5.85 (s, 1H) and 7.17 (d, 1H). MS [m/z, (%)]: 369 (M+˙, 73 %).
Anal. Calcd. for C24H35NO2 (369.55): C, 78.00; H, 9.55; N;3.79.
Found: C, 77.92; H, 9.32; N, 3.65.
17-(3-Acetyl-1-phenyl-1H-pyrazole-4-carbonyl)-10,13-
dimethyl-1,2,6,7,8,9,10,11,12,13,14,15,16,17-tetradecahydro-
cyclopenta[a]phenanthren-3-one (6c). This compound was
obtained as yellow oil. ir (KBr): 3035 (CH-aromatic), 2983,
2850 (CH-aliphatic), 1695, 1715, 1720 (CO’s), 1640 (C=N)
1
cm-1. H nmr (CDCl3): 1.16 (s, 3H), 1.26 (s, 3H), 1.27-1.71 (m,
14H), 1.99-2.01 (t, 3H), 2.25 (s, 3H, CH3), 2.35 (t, 1H), 2.99 (t,
2H), 5.85 (s, 1H), 7.32-7.54 (m, 5H, C6H5), 8.12 (s, 1H),
pyrazole C-5). ms: m/z: 484 (55) (M+˙). Anal. Calcd. for
C31H36N2O3: C, 76.83; H, 7.49; N, 5.78. Found: C, 76.75; H,
6.56; N, 5.87.
Synthesis of 17-(3-Substituted 1-phenyl-1H-pyrazole-4-
carbonyl)-10,13-dimethyl-1,2,3,6,7,8,9,10,11,12,13,14,15,-16,
17-tetradecahydro-1H-cyclopenta[a]phenanthrene-one 6a-c.
General Procedure. To a mixture of compound 3 (3.96 g, 0.01
mole), the appropriate hydrazonoyl chlorides 4a-d (0.01 mole)
and triethylamine (1.5 mL, 0.01 mole) in dry benzene (30 mL),
was heated under reflux for 2 h then the solvent was removed
under vacuum and the oil was triturated with petroleum ether
(40/60ºC). The resulting solid was collected and crystallized
from ethanol to give 6a-d, respectively.
17-(3-benzoyl-1-phenyl-1H-pyrazol-4-carbonyl)-10,13-dimeth-
yl-1,2,6,7,8,9,10,11,12,13,14,15,16,17-tetradecahydrocyclo-penta-
[a]phenanthren-3-one (6d). This compound was obtained as
yellow crystals (EtOH), 3.40 g (63 %), mp 155-156° ir (KBr):
3030 (CH-aromatic), 2975, 2825 (CH-aliphatic), 1690, 1705,
1
1720 (CO’s), 1640 (C=N) cm-1. H nmr (CDCl3): 1.16 (s, 3H),
1.26 (s, 3H), 1.27-1.71 (m, 14H), 1.99-2.01 (t, 3H), 2.35 (t, 1H),
2.99 (t, 2H), 5.85 (s, 1H), 7.23-7.64 (m, 10H, ArH’s), 8.12 (s,
1H), pyrazole C-5). ms: m/z: 546 (35) (M+˙). Anal. Calcd. for
C36H38N2O3 (546.72): C, 79.09; H, 7.01; N, 5.12. Found: C,
79.21; H, 6.85; N, 4.92.
Ethyl 4-(10,13-Dimethyl-3-oxo-2,3,6,7,8,9,10,11,12,13,14,15,
16,17-tetradecahydro-1H-cyclopenta[a]phenanthrene-17-

10
A. O. Abdelhamid, M. M. Abdelhalim and G. A. Elmegeed
Vol 44
Synthesis of 10,13-Dimethyl-17-(7-substituted 2-phenyl-
penta[a]phenanthreen-3-one (10b). This compound was
obtained as oil, 2.5 g (53 %). ir (KBr): 3020 (CH-aromatic),
2H-pyrazolo[3,4-d]pyridazin-4-yl)-1,2,6,7,8,9,10,11,12,13,14,
15,16,17-tetradecahydro-cyclopenta[a]phenanthrenes 8a-c.
General Procedure. To a solution of the appropriate 6a-d
(0.005 mole) in absolute ethanol (20 ml) and hydrazine hydrate
(0.5 mL, 0.01 mole) was heated under reflux for 4 h and cooled.
The resulting solid was collected and recrystallized from
benzene to give 8a-c, respectively.
4-(10,13-Dimethyl-3-oxo-2,3,6,7,8,9,10,11,12,13,14,15,16,17-
tetradecahydro-1H-cyclopenta[a]phenanthren-17-yl)-2-phenyl-
2,5-dihydropyrazolo[3,4-d]pyridazin-4-one (8a). This
compound was obtained as yellow crystals (benzene), 3.40 g (70
%), mp 248-250°. ir This compound was obtained as yellow
crystals (benzene), 3.40 g (70 %), mp 248-250°. iR (KBr):
(KBr): 3030 (CH-aromatic), 2984, 2850 (CH-aliphatic), 1705,
1680 (CO), 1647 (C=N) cm-1. 1H nmr (DMSO-d6): 1.16 (s, 3H),
1.26 (s, 3H), 1.27-1.71 (m, 14H), 1.99-2.01 (t, 3H), 2.35 (t, 1H),
2.99 (t, 2H), 5.85 (s, 1H), 7.50-7.68 (m, 5H, C6H5), 8.15 (s, 1H),
pyrazole C-5), 11.21 (s, br., 1H). ms: m/z: 483 (45) (M++1˙).
Anal. Calcd. for C30H34N4O2: C, 74.66; H, 7.10; N, 11.61.
Found: C, 74.37; H, 6.91; N, 11.72.
10,13-Dimethyl-17-(7-methyl-2-phenyl-2H-pyrazol[3,4-d]-
pyridazin-2-yl)-1,2,6,7,8,9,10,11,12,13,14,15,16,17-tetradeeca-
hydro-cyclopenta[a]phenanthren-3-one (8b). This compound
was obtained as yellow crystals (benzene), 3.10 g (64 %), mp
160-162°. ir (KBr): 3025 (CH-aromatic), 2980 (CH-aliphatic),
1690 (CO), 1640 (C=N) cm-1. 1H nmr (DMSO-d6): 1.16 (s, 3H),
1.26 (s, 3H), 1.27-1.71 (m, 14H), 1.99-2.01 (t, 3H), 2.35 (t, 1H),
2.38 (s, 3H, CH3) 2.99 (t, 2H), 5.85 (s, 1H), 6.95-7.30 (m, 5H,
C6H5), 8.12 (s, 1H), pyrazole C-5). ms: m/z: 479 (46) (M+-1˙).
Anal. Calcd. for C31H36N4O: C, 77.47; H, 7.55; N, 11.66. Found:
C, 77.65; H, 7.32; N, 11.72.
1
2985, 2835 (CH-aliphatic), 1685 (CO), 1625 (C=N) cm-1. H
nmr (CDCl3): 1.16 (s, 3H), 1.26 (s, 3H), 1.27-1.71 (m, 14H),
1.99-2.01 (t, 3H), 2.35 (t, 1H), 2.99 (t, 2H), 5.85 (s, 1H),
7.13-7.76 (m, 3H, ArH’s), 8.12 (s, 1H), oxazole C-5). ms:
m/z: 471 (28) (M+). Anal. Calcd. for C28H31NO4S: C, 70.41;
H, 6.54; N, 2.93; S, 6.71. Found: C, 70.30; H, 6.32; N, 2.80;
S, 6.82.
Synthesis of Isoxazolo[3,4-d]pyradiazines 11a,b.
General Procedure.
Equimolar amounts of 10a,b and
hydrazine hydrate (0.01 mole) and absolute ethanol (20 mL)
were heated under reflux for 3 h. The resulting solid was
collected by filtration and crystallized from benzene to afford
11a and 11b, respectively.
10,13-Dimethyl-17-(7-phenylisoxazolo[3,4-d]pyridazin-4-
yl)-1,2,6,7,8,9,10,11,12,13,14,15,16,17-tetradecahydrocyclo-
penta[a]phenanthren-3-one (11a). This compound was
obtained as yellow crystals (benzene), 2.60 g (60 %), mp 180-
182°. ir (KBr): 3030 (CH-aromatic), 2960, 2830 (CH-aliphatic),
1710 (CO), 1640 (C=N) cm-1 1H nmr (DMSO-d6): 1.16 (s, 3H),
1.26 (s, 3H), 1.27-1.71 (m, 14H), 1.99-2.01 (t, 3H), 2.35 (t, 1H),
2.99 (t, 2H), 5.85 (s, 1H), 7.13-7.76 (m, 5H, ArH’s), 8.12 (s,
1H), oxazole C-5). Anal. Calcd. for C30H33N3O2: C, 77.06; H,
7.11; N, 8.99. Found: C, 76.90; H, 7.20; N, 8.78.
10,13-Dimethyl-17-(7-(4-thien-2yl)isoxazolo[3,4-d]pyrida-
zin-4-yl)-1,2,6,7,8,9,10,11,-12,13,14,15,16,17-tetradecahydro-
cyclopenta[a]phenanthren-3-one (11b). This compound was
obtained as yellow crystals from (benzene), 3.21 g (68 %), mp
165-167°. ir (KBr): 2984, 2850 (CH3, CH2), 1705, (CO), 1647
1
(C=N). H NMR (ꢀ ppm): 1.16 (s, 3H), 1.26 (s, 3H), 1.27-1.71
(m, 14H), 1.99-2.01 (t, 3H), 2.35 (t, 1H), 2.99 (t, 2H), 5.85 (s,
1H), 6.92-7.31 (m, 3H), 9.25 (s, 1H, isoxazole C-5). Anal.
Calcd. for C28H31N3O2S: C, 71.01; H, 6.60; N, 8.87; S, 6.77.
Found: C, 70.85; H, 6.40; N, 8.78; S, 6.54.
17-(2,7-Diphenyl-2H-pyrazolo[3,4-d]pyridazin-4-yl)-10,13-
dimethyl-1,2,6,7,8,9,10,-11,12,13,14,15,16,17-tetradecahydro-
cyclopenta[a]phenanthren-3-one (8c). This compound was
obtained as yellow crystals (benzene), 3.20 g (59 %), mp 238-
240°. ir (KBr): 3026 (CH-aromatic), 2985, 2835 (CH-aliphatic),
REFERENCES AND NOTES
1
1690 (CO), 1645 (C=N) cm-1. H NMR (DMSO-d6): 1.16 (s,
3H), 1.26 (s, 3H), 1.27-1.71 (m, 14H), 1.99-2.01 (t, 3H), 2.35 (t,
1H), 2.99 (t, 2H), 5.85 (s, 1H), 7.53-7.76 (m, 10H, ArH’s), 8.12
(s, 1H), pyrazole C-5) and characteristic signals of cyclopenta-
noperhydrophenanthrene moiety. ms: m/z: 542 (35) (M+). Anal.
Calcd. for C36H38N4O: C, 79.67; H, 7.06; N, 10.32. Found: C,
79.76; H, 6.90; N, 10.05.
Synthesis of Isoxazoles 10a,b. General Procedure. A
mixture of 3 (3.96 g, 0.01 mol), the appropriate hydroximoyl
chloride 9a,b (0.01 mol) and triethylamine (1.5 mL, 0.01 mole)
in dry toluene (20 mL) was stirred at 0ºC. The stirring was
continued for 3 h. The reaction mixture was concentrated under
vacuum to give the oily products 10a,b respectively.
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17-(3-Benzoylisoxazole-3-carbonyl)-10,13-dimethyl-1,2,6,7,
8,9,10,11,12,13,14,15,16,-17-tetradecahydrocyclopenta[a]phen-
anthreen-3-one (10a). This compound was obtained as oil, 2.8
g (59 %). ir (KBr): 3026 (CH-aromatic), 2985, 2835 (CH-
1
aliphatic), 1690 (CO), 1645 (C=N) cm-1. H nmr (CDCl3): 1.16
(s, 3H), 1.26 (s, 3H), 1.27-1.71 (m, 14H), 1.99-2.01 (t, 3H), 2.35
(t, 1H), 2.99 (t, 2H), 5.85 (s, 1H), 7.53-7.76 (m, 5H, ArH’s), (s,
1H), oxazole C-5). ms: m/z: 471 (28) (M+). Anal. Calcd. for
C30H33NO4: C, 76.41; H, 7.05; N, 2.97. Found: C, 76.30; H,
6.82; N, 3.12.
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bonyl-1,2,6,7,8,9,10,11,-12,13,14,15,16,17-tetradecahydrocyclo-
[12] W. B. Smith, Mag. Reson. Chem. 37(2), 103 (1999).
[13] N. S. Bhacca, D. H. William, "Application of NMR spectroscopy

Jan-Feb 2007
New Routes to Steroidal Heterocyclic Derivatives
11
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