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Патент USA US3071589

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United States Patent ‘O??ce
,
3,071,579
Patented Jan. 1, 1963
1
2
containing up to 8 carbon atoms or acyloxy groups con
3,071,579
taining up to 12 carbon atoms. Typical examples of such
ester groups are the acetate, propionate, butyrate, hemi
7-ACYLTHIO DERIVATIVES 0F ZI-ACYLQXY-I'Ta
HYDROXY-M-PREGNENE-S,20-DIONES
succinate, enanthate, caproate, benzoate, aminoacetate,
Howard J. Ringold and Otto Halpern, Mexico City, Mex
ico, assignors, by mesne assignments, to Syntex Cor
trimethylacetate, phenoxyacetatc, cyclopentylpropionate,
phenylpropionate and ?-chloropropionate. The esteri?ed
poration, a corporation oi‘ Panama
compounds may also be in the form of water soluble salts
such as for example the alkali metal salts of hemisuccinate
or of an ester formed with phosphoric acid or the hydro
10 halides of esters formed with an aminoacid.
The present invention relates to novel cyclopentanophe
The ketal or acetal group is derived from an aliphatic
nanthrene compounds and to a process for preparing
ketone or aldehyde containing up to 8 carbon atoms of
No Drawing. Filed June 7, 1960, Ser. No. 34,369
Claims priority, application Mexico June 12, 1959
27 Claims. (Cl. 260—239.55)
same.
straight, branched, cyclic or cyclic-aliphatic chain, or from
More particularly the invention relates to novel acylthio
an aromatic or araliphatic ketone or aldehyde.
derivatives of 21~acy1oxy-l7a-hydroxy-A4-pregnene-3,20 15
diones which contain either a u-hydroxy, a-acyloxy,
a-methyl or B-methyl group at 0-16 or a cyclic acetal or
The cyclic ketal or acetal is formed by the reaction of
the 16,17-glycol With the ketone or aldehyde in the pres
ence of an acid catalyst such as perchloric acid. Typical
ketones and aldehydes employed are acetone, formalde
cyclic ketal group at C—l6,l7 and which may also con
tain an additional double bond at C—l,2 and/ or at C—6,7.
hyde, acetaldehyde, paraldehyde, acetophenone, benzophe
The novel compounds of the present invention are 20 none, methyl ethyl ketone, cyclohexanone or diethyl
potent diuretic agents which inhibit the activity of desoxy
ketone.
corticosterone and/or of aldosterone and can be repre
The Wavy line at ‘C—7 and at C—l6 indicates both the cc
sented by the following formulas:
and B steric con?guration.
The novel compounds of the present invention are pre
25 pared by a process illustrated by the following equation:
CHzOR3
30
O
i=0
AQHOR,
WW5
Oi/ WSC¢
\
i!
/chloranil
(EH20 R3
O
R
In the above formulas, Z indicates a double bond or
a saturated linkage between C-1 and C—2; R represents a 5 O
lower alkyl group containing up to 8 carbon atoms, an
aryl group or an aralkyl group containirn7 up to 10 carbon
atoms; R’ and R2 each represent hydrogen or an acyl
0Q
(‘31120183
Al?wm
I / selenium
eel;
(H)
dioxide
’ /
O
group; R’ and R2 jointly represent the grouping
55
R,
“VD
O
ARC
A
RC
%
SH
01310 R3
0
so
wherein R4 and R5 represent hydrogen or an aliphatic
hydrocarbon group containing up to 8 carbon atoms, of
straight, branched, cyclic or cyclic-aliphatic chain, satu
rated or unsaturated and including aromatic or araliphatic
65
groups; and R3 represents acyl.
‘The acyl groups are derived from hydrocarbon car
boxylic acids containing up to 12 carbon atoms or from
acids such as sulfuric or phosphoric. The carboxylic
acids may be saturated or unsaturated, straight chain or
branched chain aliphatic, cyclic-aliphatic, aromatic, and 70
may be substituted with amino, halogen, alkoxy groups
O
dioxide
R
(III)
l chldranil
(VII)
l chloranil
3,071,579
3
.
4
The following examples serve to illustrate but are not
intended to limit the scope of the present invention:
CHZO R3
(‘1:0
:0
| _.._O H
(\l
0:
MN S C
I - -O H
NW R“
/
O
¢
\R
Example I
0 H2O Ra
i
selenium
dioxide
W Ra
/
0 —-
\/
—
0
S 0%
\R
(IV)
(V)
In the above formulas R and R3 have the same mean
45
A mixture of 5 g. of the 21-acetate of 16a-methyl-A4
pregnene-17a,21—diol-3,20-dione, described by Edwards
et al., J. Chem. Soc. 1959, 87, 200 cc. of t-butanol and
10 g. of chloranil was re?uxed under an atmosphere of
nitrogen for 8 hours, cooled, ?ltered and the ?lter was
Washed with ethyl acetate. The ?ltrate and washings
were combined, evaporated to dryness under reduced pres
sure, the residue was dissolved in ethyl acetate and the
solution was washed with cold aqueous sodium hydroxide
55 solution until the washings were colorless and then with
water to neutral. The solution was dried over anhydrous
sodium sulfate and the ethyl acetate was evaporated,
ing as set forth previously; R8 represents a-hydroxy,
?nally under reduced pressure; the residue was puri?ed
u-acyloxy, (a or [3)-methyl, or with the C-17a-hydroxyl
by recrystallization from acetone-hexane, thus yielding the
group, a cyclic ketal or acetal group of the type previ
21-acetate
of l6a-methyl - A416 - pregnadiene-l7a,2l-diol
60
ously set forth.
3,20-dione, M.P. 210-215" C., I max. 285 lTl/L, log 6 4.30.
In practicing the process outlined above, a 16-substi
A mixture of 2 g. of the above compound and 6 cc. of
tuted-2l-acyloxy-A‘i-pregnen-l7a-ol-3,20-dione (I) is re
thioacetic acid was heated on the steam bath for 3 hours,
?uxed with an excess of a quinone having an oxidation
cooled and the precipitate was collected by ?ltration and
reduction potential of less than —0.5, and preferably
those having potential of >-—0.65 or less, such as tetra
chloro-p-benzoquinone (chloranil), 1,2 or 1,4-naphtho
quinone, in an inert solvent such as tertiary butanol,
xylene or a mixture of ethyl acetate and acetic acid or
tertiary amyl acetate and acetic acid. The thus formed
16-substituted-21-acyloxy - A476 - pregnadien-l7et-ol-3,20
dione (II) is condensed with a thiolic acid, preferably
thioacetic acid, to form the 7-thioacetyl-16-substituted-21
washed with a little cold ether. There was thus obtained
the Zl-acetate of 7-thioacetyl-16oc-methyl-A4-pregnene
17a,21-diol-3,20-dione with its thioacetyl group predomi
nantly in the “position, M.P. 170~178° C., x max. 239
mp, log 6 4.25 and 306 mp, log 6 2.48.
A mixture of l g. of the above compound, 300 mg.
of selenium dioxide, 75 cc. of t-butanol and a few drops
of pyridine was re?uxed for 48 hours under an atmos
acyloxy-Ni-pregnen-17a-o1-3,20-dione (III). The latter,
phere of nitrogen and then ?ltered through celite; the solu
by incubation with Corynebacterium simplex ATCC 6946
to form the 7-thioacetyl-16-substituted-2l-acyloxy-AM
17a,2l-diol-3,20-dione.
tion Was evaporated to dryness under reduced pressure,
in which the C-7 substituent is predominantly in a steric
residue was dissolved in 50 cc. of acetone and re?uxed
con?guration, may then be dehydrogenated at C—l,2 by 75 the
with 2 g. of decolorizing charcoal for 1 hour. It was
re?uxing with an excess of selenium dioxide in a solvent
then ?ltered, the ?ltrate was evaporated to dryness and
such as tertiary butanol and in the presence of catalytic
the residue chromatographed on silica gel, thus affording
amounts of pyridine under an atmosphere of nitrogen for
the 21-acetate of 7-thioacetyl-16wmethyl-AIA-pregnadiene
about 48 hours, or by microbiological methods such as
pregnadiene-17a-ol-3,20-dione (VII), which compound
may be further dehydrogenated at C—6,7 as by treatment
with chloranil as set forth previously to produce the
7 - thioacetyl-16-substituted-21-aryloxy-A1AYG-PIegnatriene
17a-ol-3,20-dione (V).
Alternatively, the 7-thioacetyl-l6-substituted-2l-acyl
OXy-A4-PI‘6gIl6l'l-170t-O1-3,20-dl011$ (III) may ?rst be de
hydrogenated at C—6,7 as by treatment with chloranil to
form 7-thioacetyl-16-substituted - 21 - acyloxy-M?-pregna
,dieneal7a-ol-3,20-dione(IV) which may further be dehy
drogenated at C—1,2 in ‘the same manner set forth above to
form the 7-thioacetyl-16~substituted - 21 - acyloxy-A1-4?
pregnatriene-l7a-ol-3,20-dione (V).
The above compound was then treated with chloranil,
exactly as described for the reaction of this substance with
the 2l-acetate of 16a-methyl-A4-pregnene-l7tx,2l-diol~
3,20-dione to produce the 21-acetate of 7-‘.hioacetyl-l6a
methyl-A1JM-pregnatriene-l7a,2l-diol-3,20-dione.
Example 11
A mixture of 5 g. of the 21-acetate of l6a-methyl-AL
. pregnenee'l7u,21-diol-3,20-dione, 10 g. of chloranil, 125 cc.
of ethyl acetate and 25 cc. of acetic acid was re?uxed
under an atmosphere of nitrogen for 72 hours; it was then
?ltered through celite, cooled and washed with cold 5%
aqueous sodium hydroxide solution until the washings
were colorless and then with water to neutral. After dry.
In another aspect of the invention, the 16-substituted 20 ing over anhydrous sodium sulfate the solvent was evapo
21-acyloxy - A416 - pregnadien-17a-ol-3,20-dione (II) may
rated and the residue puri?ed by recrystallization from
?rst be dehydrogenated at C—1,2 to form the correspond
acetone-hexane, thus furnishing the 21-acetate of 16a
ing AM?-pregnatriene compound (VI) and then subse
quently reacted with the thioacetic acid to form the 7-thio
acetyl-l6-substituted-2l-acyloxy _ AM - pregnadien-‘17a-ol
3,20-dione (VII), which upon further treatment with
chloranil is further dehydrogenated at C-6,7 to produce
the corresponding nll‘i-s-pregnatriene (V).
methyl-n‘iie-pregnadiene-17a,21~diol-3,20 - dione, identical
with the intermediary obtained in accordance with the
method described in the preceding example.
2 g. of the above compound was then re?uxed with 4 g.
of thiobenzoic acid in 50 cc. of benzene for 4 hours,
cooled, concentrated to a small volume, and diluted with
a little cold ether‘. The precipitate of the Zl-acetate of
The 021 acyloxy group may be conventionally saponi
?ed as by treatment with dilute methanolic potassium hy 30 7-thiobenzoyl-16rz-methyl-A‘1-pregnene - 1700,21 - dbl-3,20
droxide at 0° C. and then re-esteri?ed by conventional
dione formed was collected by ?ltration, washed with a
methods such as by reaction with an acid anhydride or
little cold ether and dried.
chloride in pyridine solution at room temperature. The
By subsequent reaction with selenium dioxide (cf. Ex
hydroxylgroup at C-16 is similarly esteri?ed by conven
ample I) there was obtained the 2l-acetate of 7-thio
tional methods while the 0-1706 hydroxyl group may be 35 benzoyl-16u-methyl - A14 - pregnadiene-l7u,2l-diol-3,20
esteri?ed by reaction with the acid anhydrides in benzene
dione, and then, by dehydrogenation with chloranil in
solution in the presence of p-toluenesulfonic acid at room
t-butanol
in accordance with the method of Example I,
temperature, with simultaneous esteri?cation of free hy
there was obtained the 2l-acetate of 7-thiobenzoyl-16rx
droxyl groups at C~l6 or C—2l. Thus the same or mixed
40 methyl-A1AG-pregnatriene-l7a,2l-diol-3,20-dione.
diesters or triesters can be produced.
3,071,579
5
a
Example III
preceding example as the starting material, there were
formed all of the products produced in such examples
having cyclopentylpropionoxy group at C-21 instead of
2 g. of the 2l-acetate of 7-thioacetyl-l6a-methyl-A4
pregnene-l7u,2l-diol-3,20-dione (see Example I) as well
the acetoxy group at C-21.
as 2 g. of the 2l-acetate of 7-thiobenzoyl-16rx-methyl
A4-pregnene-17a,2l-diol-3,2O-dione (see Example II) were
Example IX
In accordance with the method described in Example I
treated ?rst with chloranil, in accordance with the method
of Example I, and then with selenium dioxide, also in ac
there was introduced a double bond at C—6,7 in the 21
cordance with the procedure described in such example.
There were thus obtained as intermediates the 21-acetate
of 7-thi0aCBtyl-l6cc-InBlLhYl-A4'G-PIBgHZ‘1diGHE-170¢,Z1-(llOl-3,
acetate of A4-pregnene-16a,l7a,2l-triol-3,20-dione, thio
10 acetic acid was then added to the latter to produce the
2l-acetate of 7-thioacetyl-Mpregnene-l6u,17a,21-triol
20‘-dione and 21-acetate of 7-thiobenzoyl-l6u-methyl
A‘LG-pregnadiene17a,2l-diol-3,20-dione and then the ?nal
3,20-dione.
Example IV
In accordance with the methods described in the pre
1 g. of this compound was then treated with
propionic anhydride in 6 cc. of pyridine, kept overnight
1,4,6-trienes.
at room temperature, poured into water, heated for half
15 an hour on the steam bath, cooled and the precipitate was
collected, washed with water, dried and recrystallized
from acetone-hexane, thus producing the 16-propionate
ZI-acetate of 'I-thioacetyl-M-pregnene-l6a,17a,21-triol
3,20-dione. By subsequent reaction with selenium di
ceding examples, the 21-propionate of 165-rnethyl-A4
pregnene-l7a,21-diol-3,20-dione described in copending
application Serial No. 824,199, ?led July 1, 1959, was
converted into its 6-dehydro derivative and subsequently
treated with thioacetic acid to form the 21-propionate of
oxide, in accordance with the method described in Exam~
ple I, there was obtained the 16-propionate-21-acetate of
7 - thioacetyl - 16p - methyl - A4 - pregnene - 17cc,21 - diol
7-thioacetyl - A1-4 - pregnadiene - 16ot,17oc,21 - triol - 3,20‘
3,20-dione.
dione. 550 mg. of this diene was then treated with 12.5
cc. of acetic acid, 2.5 cc. of acetic anhydride and 500 mg.
The latter was then converted into the 1
dehydro, 6-dehydro and 1,6-bis-dehydro derivatives in the
same manner as described in the previous examples.
25 of p~toluenesulfonic acid, kept overnight at room tempera
Example V
ture, poured into water, extracted with methylene chlo
3.0 g. of the 21-acetate of A4-pregnene-16a,17a,21
ride‘ and the extract was washed with water to neutral,
dried over anhydrous sodium sulfate and evaporated. Re
crystallization of the residue from acetone-hexane af
triol-3,20-dione in 40 cc. of acetone was treated with 0.4
cc. of 70% perchloric acid and stirred for 1 hour at room
temperature, poured into 200 cc. of 10% aqueous sodium
bicarbonate solution and the precipitate was collected by
?ltration, washed with Water, dried and recrystallized
from acetone-hexane.
There was thus obtained the ace
tonide of A4-pregnene-16a,l7a,21-triol-3,2O>dione 2i1-ace 35
tate.
By following the methods described in Examples I, II,
and III, the latter compound was converted into the 21
acetate of 7-thiocetyl-16rx,17a-isopropylidenedioxy-A4
pregnene-Zl-ol-3,20-dione and then into its l-dehydro, 6
dehydro and 1,6-bis-dehydro derivatives and into the cor
responding 7-thiobenzoyl derivatives of the foregoing
compounds.
forded the l6-propionate-17,21-diacetate of 7-thioacetyl
A1-4—pregnadiene-16a,17a,21-triol-3,20-dione. Finally, by
the reaction with chloranil described in Example I, there
was produced the l6-propionate-17,21-diacetate of 7-thio
acetyl-A1A?-pregnatriene-l6e,17a,21-triol-3,2(l-dione.
Example X
l g. of the 21-acetate of A4—pregnene-l6a,17u,21-triol
3,20~dione was treated with chloranil, in accordance with
the method of Example I, then with thioacetic acid; then
there were introduced the double bonds at C—1,2 and
C—6,7, also in accordance with such example; there was
thus obtained the 2l-acetate of 7-thioacetyl-A1Ats-pregna
'
triene-l6a,l7a,21-triol-3,20-dione. 1 g. of this com
Example VI
pound in 50 cc. of anhydrous benzene was treated with
By conventional methods of esteri?cation A4-pregnene 45 3 g. of propionic anhydride and l g. of p-toluenesulfonic
acid monohydrate for 48 hours at room temperature;
160a,170t,2.1—tTlOl-3,20-dl0t1€ was converted into the 16,21
the mixture was washed with water, dried over anhydrous
dipropionate thereof, which, in accordance with the meth~
sodium sulfate and the benzene was evaporated. Re
ods described in Examples I, II and III, was transformed
crystallization of the residue from acetone-hexane fur
into the 16,2l-dipropionatc of 7-thioacetyl-M-pregnene
l6a,l7a,2l-triol-3,20-dione; the 16,21-dipropionate of 7
thioacetyl - A114 - pregnadiene - 16ot,17u,2l - triol - 3,20‘
dione; the 16,2l-dipropionate of 7-thioacetyl-A4Y5-preg
nadiene-l6a,l70:,21#triol-8,20-dione; the 16,2l-dipropio
nate of 7-thioacetyl-AlAs-pregnatriene-16a,17a,21-triol
3,20-dione as well as the corresponding 7-thiobenzoyl de
rivatives of the foregoing compounds.
Example VII
By following an analogous procedure to that described
in Example V, there was prepared instead of the 16,17
acetonide the 16,17-ethylidenedioxy acetal by substitut
nished the 16,17-dipropionate-2l-acetate of 7-thioacetyl
A1'4'6-pregnatriene-16u,l7a,2l-triol-3,20-dione.
We claim:
1. 7-thioacetyl - 160a - methyl~A1'4-pregnadiene-17a,2l
dial-3,20-dione-2l-acetate.
2. 7-thiobenzoyl-l6ot-methyl - A4 - pregnene — 170:,21
diol-3,20-dione 21-acetate.
3. 7-ithiobenzoyl-l6a-methyl ~ A1‘4 - pregn-adiene - 17a,
2 l-diol-3 ,20-dione 21-acetate.
4. 7-thioacetyl-l6?-rnethyl - A4 - pregnene-l7a,2l-diol
3,20-dione 21-propionate.
5. A compound of the following formula:
ing the acetone by acetaldehyde, and, by following the
procedures described in Examples I, ‘III and II, there were
formed the ZI-acetate of 7-thioacetyl-16a,17a-ethylidene
dioxy-M-pregnen-Zl-ol-3,20-dione, the 21-acetate of 7 65
CHzO Rs
C=O
252cm
thioacetyl - 1641,17“ - ethylidenedioxy — A4,“ - pregnadien
2l-ol-3,20-dione, the 21-acetate of 7-thi0acetyl-16a,17a
ethylidenedioxy -A‘-i4 - pregnadien - 21- 01 - 3,20 - dione
and. the 21-acetate of 7-thioacetyl-16u,17a-ethylidene
dioxy-A1tt-s-pregnatrien-2l-ol-3,20-dione as well as the
corresponding 7-thiobenzoyl derivatives.
Example VIII
Z/\l
/
I,
——SCOR
wherein R is selected from the group consisting of alkyl
containing up to 8 carbon atoms, aryl and aralkyl con
mate of A4-pregnene-16m,17a,21-triol-3,20-dione in the 75 taining up to 10 carbon atoms; R2 is selected from the
By employing the corresponding 21-cyclopentylpropio
3,071,579
8
17. The 16-propionate-21-acetatc of 7-thioacetyl-A416
group consisting of hydrogen and a hydrocarbon car
boxylic acyl group containing up to 12 carbon atoms; R3
pregnadiene-l6a,17a,21-triol-3,20-dione.
is a hydrocarbon carboxylic acyl group containing up to
> 18. The 16,21-dipropionate of 7-thioacetyl-AM?-preg
12 carbon atoms and Z is selected from the group con
sisting of a double bond between C—1 and C-—2 and a
natriene-16a,17u,21-triol-3,20-dionc.
19. The 16-propionate-17,21-diacetate of 7-thioacetyl
ALM-pregnatriene-16ml7a,21-trio1-3,20-dione.
20. The 16,17-dipropionate-2l-acetate of 7-thioacetyl
Alv‘m-pregnatriene16a,17a,21-triol-3,20-dione.
saturated linkage between C-1 and C-2.
6. 7-thioacctyl-16a - methyl - A114’6 - pregnatriene-17a,
21—diol-3,20-dione-2l-acetate.
21. A compound of the following formula:
7. 7-thioacetyl - 16a - methyl-M?-pregnadiene-17a,2l
10
diol-3,20-dione-2l-acetate.
CH2OR3
8. 7-thiobenzoyl116a-methyl - A1416 - pregnatriene-17a,
2l-diol-3,20-dione-2l-acetate.
9. 7-thiobenzoyl-16a-methyl - A‘i-G - pregnadiene - 17a,
2l-diol-3,20-dione-2l-acetate.
10. 7-thioacetyl116?-methyl - A416 - pregnadiene-l7a,21
15
diol-3,20-dione-2l-propionate.
11. 7-thioacetyl-16f3-methyl - A1,“ - pregnatriene-17a,
21-diol~3,20-dione-2l-propionate.
12. A compound of the following formula:
wherein R is selected from the group consisting of alkyl
containing up to 8 carbon atoms, aryl and aralkyl con
(511120 R3
r=<>-on1
z
0-
/]: Ton’
l
taining up to 10 carbon atoms; R3 is a hydrocarbon car
boxylic acyl group containing up to 12 carbon atoms;
25 R4 and R5 are selected from the group consisting of
hydrogen and an aliphatic hydrocarbon group containing
vup to 8 carbon atoms, and Z is selected from the group
consisting of a double bond between 0-1 and C-2 and
a saturated linkage between 0-1 and C-2.
\ MSCOR
30
22. 7 - thioacetyl - 16a,17ot - isopropylidenedioxy - A4
wherein R is selected from the group consisting of alkyl
containing up to 8 carbon atoms, aryl and aralkyl con
pregnen-21-ol-3,20-dione 2l-acetate.
taining up to 10 carbon atoms; R’ and R2 are selected
pregnadien-21-ol~3,20'-dione-2l-acetate.
_
24. 7 - thioacetyl - 1604,17a - ethylidenedioxy - A4
23. 7 - thioacetyl - 1‘6a,l7a - isopropylidenedioxy - A114
from the group consisting of hydrogen and a hydrocarbon
carboxylic acyl group containing up to 12 carbon atoms; 35 pregnen-21-ol-3,20-dione-2l-cyclopentylpropionate.
' 25. A compound of the following formula:
R3 is a hydrocarbon carboxylic ‘acyl group containing up
to 12 carbon atoms; and Z is selected from the group con
CHZORa
sisting of a double bond between C-1 and C-2 and a
saturated linkage between 0'1 and C-2.
13. The 16,21-dipropionate of 7-thioacetyl-A4-preg
news-16a,17a,21-triol-3,20-dione.
14. The 16,2l-dipropionate of 7-thioacetyl-AL4-pregna
Cll6n€~16oz,l7a,21-tfi0l—3,20-di0116.
15'. The 16-propionate-17,21-diacetate of 7—thioacetyl
A1'4-pregnadiene-16a,17a,21-triol-3,2O-dione.
oi/vmoon
45
16. A compound of the following formula:
wherein R is selected from the group consisting of alkyl
containing up to 8 carbon atoms, aryl and aralkyl con
taining up to 10 carbon atoms; R3 is a hydrocarbon car
z- I/
IQ“
/
O-QVESCOR
boxylic acyl group containing up to 12 carbon atoms;
R4 and R5 are selected from the group consisting of hy
drogen and an aliphatic hydrocarbon group containing
up to 8 carbon atoms; and Z is selected from the group
55 consisting of a double ‘bond between C-—1 and C-2 and a
saturated linkage between C-1 and C-2.
wherein R is selected from the group consisting of alkyl
containing up to 8 carbon atoms, aryl and aralkyl con
taining up to 10 carbon atoms; R’ and R2 are selected 60
from the group consisting of hydrogen and a hydrocarbon
carboxylic acyl group containing up to 12 carbon atoms;
R3 is a hydrocarbon carboxylic acyl group containing up
to 12 carbon atoms; and Z is selected from the group con
sisting of a double bond between C-1 and C-2 and a 65
saturated linkage between C~l and C—2.
26. 7 - thioacetyl - 16a,17a - isopropylidenedioXy-AM
pregnadiene-Zl-ol-3,20-dione-2l-acetate.
27. 7 - thioacetyl - 1‘6oc,170t - ethylidenedioxy - A1315
pregnatriene-Zl-ol-3,20-dione-2l-cyclopentylpropionate.
References Cited in the ?le of this patent
UNITED STATES PATENTS
2,837,464
2,904,560
Nobile et al. __________ __ June 3, 1958
Dodson et al __________ __ Sept. 15, 1959
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