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Патент USA US3050525

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rates"
Patented Aug. 21, 1962
2
1
The process according to the invention for preparing
S-cyano and S-carbamyl analogs of the 4,5 derivatives of
steroidal A4-3-keto hormones essentially consists in the
reaction of such hormones with the cyanide, of an alkali
3,050,518
S-CYANO AND S-CARBAMYL STERGID
DERIVATHVES
Albert Bowers and Howard J. Ringold, Mexico City, Men‘
or alkaline earth metal, in the presence of a hydroxylated
ico, assignors, by niesne assignments, to Syntex Corps‘
ration, a corporation of Panama
No Drawing. Filed Inly 17, 195%, Ser. No. 827,679
organic solvent.
'
The starting compounds for carrying out this process
can be characterized by the following general ‘formula:
Claims priority, application Mexico Ziniy 22, 1958
2d Claims. (Qt. 26ti—239.55)
A
Y/\
This invention relates to certain new cyclopentanophen
anthrene derivatives and to a. process for their preparation.
More particularly, it relates to the novel S-cyano and
R 1,; j
42
S-carbamyl analogs of the 4,5-dihydro derivatives of ste
15
roidal M-hormones.
The new compounds which are the object of the present
invention exhibit valuable therapeutic properties: they
are antiestrogenic ‘agents and show anti-pituitary activity.
wherein A, R, X and Y have the same meaning as in the
These new anti-estrogenic agents and ‘anti-pituitary
preceding formula.
agents are 5~cyan0 and S-carbamyl analogs having the 20
The process of the invention can be represented by the
general formula:
following equation:
’
A
3
r
0t
A
R
3
30
R,
wherein A is a radical arrangement selected from the
'H
{lower aliphatic radical, flower aliphatic radical,
’
0H
,
I
R
I
“a
inhydfoxyéated OZL/
so ven
H
/
»
2'
,
,
00.0Ha
CO.CH2OH
I II
a/
A, R, R’, X and Y having the same meaning as ex
..
More speci?cally, ‘as starting material for the process ac
cording to our invention there can be used: testosterone,
testosterone or its esters, progesterone, desoxycorticoster
acyloxy
a’
/
A4-androsten-3,17~dione, a 17a-alky1 (alkenyl, alkinyl)
acyloxy
H
\
O:
_’ A‘
‘
plained hereinbefore.
i =0: <
\OH
,/
KON
group consisting of
'1
i
j,'/\
.
CO.CHa
bis-methylenedioxy(Bl\/iD), and
one, a 17a-acyloxy-progesterone, as well as the 19-nor
40 analogs of such compounds, all of which may optionally
‘be oxygenated at C-—l1 with a ,B-hydroxyl or a keto group
'and/ or ?uorinated at C~90t§ Formula I also represents the
17 ,20;2(),21 - bis - methylenedioxy derivatives’ of Reich
stein’s Compound “S,” of 19-nor-“S” and of their analogs
on
45 oxygenated at (3-11 and/ or ?uorinated at C-9u (cf. Sarett
et_al., J. Am. Chem. Soc., 80, 1517 (1958)).
O0.0HzOH
The process of the invention comprises the step of
reacting one of the above-mentioned starting compounds
while R is a member selected [from the group consisting
with potassium cyanide. Preferably, the starting com»
of hydrogen and methyl; X is a member selected from
the group consisting of hydrogen and ?uorine; Y is a mem 50 pound is re?uxed with potassium cyanide in mixture with
ethanol for a period of 1-5 hours and there is obtained a
ber of the group consisting of
mixture of the 5d. and 5,8 isomers of the S-cyano' and
H
\
OH
‘
‘rain
S-carbamyl analogs of the 4,5-dihydro derivatives of the
H
,
x
and
=0
‘on
respective A4-3-keto hormones, and the mixture is sep
55 arated into its components by chromatography.
Instead of potassium cyanide, there can be used another
and R’ is a radical selected from the group consisting of
alkali metal cyanide such as sodium cyanide or calcium
50c- and S?’cyano and -carbamyl.
cyanide. Instead of ethanol, other hydroxylated organic
By “lower aliphatic radical” we mean particular lower
alkyl as for example methyl or ethyl, lower alkenyl such
as vinyl, or propenyl, ‘and lower alkinyl such as ethinyl,
propinyl and the like; “acyloxy” is preferably the radical
derived from a hydrocarbon carboxylic acid having up to
solvents such as, for instance, a butanol, may be used.
one, there are obtained the 5oz- and Sift-isomers of S-cyano
12 ‘carbon atoms as is speci?cally set forth in the sub
Progesterone yields the 5a- and Sit-isomers of S-cyano
pregnan-3,20-dione and of 5-carbamyl-pregnan-3,ZO-dione;
sequent description of starting material.
More particularly, if the starting compound is testoster
androstan-17p-ol-3-one and of S-carbamyl-androstan
17?-ol-3-one.
,
3,050,518
3
4
and desoxycorticosterone aifords the Sot- and S?-isomers
of S-cyan'o-pregnan-Zl-ol-3,20-dione ‘and of 5-carbarnyl
The following speci?c examples serve to illustrate but
are not intended to limit the present invention.
pregnan-21-ol-3,20-dione.
‘EXAMPLE I
A testosterone substituted at C-17a with the residue of
a lower aliphatic hydrocarbon, saturated or unsaturated, 5
A mixture of 5 g. of testosterone, 8 g. of potassium
used as the starting compound la?ords the 506- and 55
cyanide and 200 cc. of 95% ethanol was re?uxed for 3
isomers of the respective 17a-alkyl(alkenyl or alkinyl)
hours, cooled diluted with water and extracted with
S-cyano-androstan-175-ol-3-one and of the corresponding
17a—all<yl(a1kenyl or alkinyl)~5-carbamyl-androstan-17,8
ol-3-one.
ether.
The extract was washed with water, dried over
anhydrous sodium sulfate and evaporated to dryness.
The residue consisted of a mixture of S-cyano-dihydro
A 17-ester of one of the last mentioned testosterone
derivatives used as the starting compound yields the cor
testosterone (50a), of S-cyano-testan-l75-ol-3-one (5,8),
of 5-carbamyl-dihydrotestosterone (5a) and of S-car
bamyl-testan-17?-ol-3-one (5,8). vBy chromatography on
responding S-cyano ‘and S-carbamyl compounds esteri?ed
at 0-17, ‘and a 17-ester of 17a-hydroxy-progesterone per
neutral alumina there were separated the S-cyano from
mits to obtain the 511- land SB-isomers of the corresponding 15 the S-carbamyl compounds and the 506- and S?-isomers
17-ester of 5-cyanoapregnan-l7a-ol-3,ZO-dione and of
were isolated.
S-carbamyl-pregnan-17u-ol-3,20-dione.
EXAMPLE II
In the compounds of Formula II having a primary
hydroxyl group at 0-21 or a secondary hydroxyl group
at 0-175, these groups can be esteri?ed by reaction with
the anhydride of a hydrocarbon carboxylic acid of up to
12 carbon atoms, in pyridine solution; the anhydride may
be derived from a hydrocarbon carboxylic acid of up to
12 carbon atoms, saturated or unsaturated, of straight,
branched, cyclic or mixed cyclic-aliphatic chain, with or
without methoxy, halogen or other substituents in the
the mixture was re?uxed for 5 hours, with the same ?nal
results.
Following the procedures of the previous examples, the
?nal products listed in Table I given hereinafter can be
obtained from the indicated starting materials:
Table l
chain. We prepared among others, such esters as the
‘acetates, propionates, butyrates, t-butyrates, hemisucci
nates, enanthates, caproates, benzoates, trimethylacetates,
phenylpropionates, phenoxyacetates, ‘cyclopentylpropio
ExlaImple
Starting Compound
Products
19-nor-testosterone ____ ._
5a and ?ts-isomers of 5~cyano-l9
0.
30
mates and ?-chloropropionates; the starting compounds
(I) may possess similar ester groups’and, therefore, the
III ______ ._
nor-androstan-l7?p1-8-one and
5-oarbamyl - 19 - nor-androstan
reaction products obtained from the cyanide treatment
according to the invention are correspondingly esteri?ed.
17/3-ol-3-one.
IV ______ __ ll-keto-testosterone--_-_
From the bis-methylenedioxy (BMD) derivatives there 35
were obtained the BMD derivatives, wherein the dihy
droxyacetone side chain was regenerated by treatment
with an aqueous organic acid.
and 5-carbamyl-androstan-N?
0l-3,l1-dione.
V _______ __ ll?-hydroxy-
5a and 5B-isorners of 5-cyano
testosterone.
androstan - 115,176 - diol - 3- one
and 5-carbamyl-androstan-ll?
17?-diol-3-0ne.
VI ______ __
one, there are obtained the 50c- and Sit-isomers of 5 4.0
11 - keto ‘ 19 - nor - testosterone.
,
5a and 5,8-isomers of ?-oyano
19 - nor - androstan 417B - o1 - 3,
ll-dione and of ?-earbamyl-IQ
cyano - 17,20;20,21 - bis - methylenedioxy - pregnan - 3
nor - androstan - 17B - ol - 3,
ll-djone.
one and of 5-carbamyl-17,20;20,2Ibis-methylenedioxy
VII ..... ..
pregnan-3-one.
,
113 - hydroxy - 19 - nortestosterone.
5a and 5?-isomers of 5~cyauo
19 - nor - androstan-11?,17?-diol
VIII ____ __ 17a- acetoxy- progester-
50¢ and ??-isomers of 5~cyano
3-one and of 5-earbamyl~19-nor
Starting compounds which have at 0-10 a hydrogen
atom instead of the ‘angular methyl group, yield the 5
cyano and 5~carbamyl derivatives of the 19-nor-analogs
of the above mentioned compounds.
one.
androstan-ll?,l7B-diol~3-one.
17a-acetoxy-pregnan-3,20 - dlone
and of ?-carbamyl-Haacetoxy _
pregnan-3,20-dione.
IX ______ -_ ll-clesoxycorticosterone.. 5a and 5,8-isomers of 5~eyano
In accordance with a further feature of the process ac~
pregnan - 21 - ol_3,20-dione
cording to the invention, the starting compounds are oxy
and
5-earbamYLprcgnau-21 - o l-3,20
50
dione.
X _______ __
Gortlcosterone ________ ._
5a and ??-isomers of 5-eyan0
pregnau-11B,21-diol ~ 3,20 - dione
XI ______ __
A4- pregnen ~ 21 - 01-3,
5a and 5?-isomers of 5-cya110
genated at 0-11 and ?uorinated at C-90t, to produce the
?nal compounds of the type described ‘above correspond
and
5~carbamyl-pregnan-lll9,
2l-diol-3,20-dione.
ingly ‘substituted at (3-11 or at C-11 and C-9.
11,20-trione.
The above-mentioned ‘17,20;20,21-bis-methylenedioxy
pregnan - 21 - ol - 3,11,20 - trione
'
compounds and their 19-nor analogs or' ll-oxygenated or
XII _____ ._
9ot-?uorinated derivatives ‘are treated with an aqueous or
19-1101‘' 11 - desoxycor-
tlcosterone.
ganic acid in order to regenerate the dihydroxyacetone
side chain, for example by heating with aqueous formic
acid; there are thus treated the bis-methylenedioxy deriv
atives of the 50C- ‘and SIS-isomers of 5-cyano-pregnan-17a, 60
and 5-oarbarnyl-pregnan-2l-ol
3,11,20-trione.
5c: and 5?-isomers of ?-cyano
l9-nor-pregnan-2l-ol-3,20 - dione
and 5-carbarnyl-19~nor-pregnan
21-o1-3,20-dione.
XIII ____ __
19-nor-corticosterone._._
,
V
5a and 5?-isomers .of 5-cyano
19 - nor - pregnan- 115,21 - diol-H,
20-dione and 5-carbamyl-19
nor - pregnan ~ 115,21 - diol —3,20
dione.
21-diol-3,20-d.ione and of the corresponding compounds
of the 19-nor-series, ‘as well as those having an oxygen
XIV ____ __
19-nor—A4~pregnen - 21 ol-3,11,20-trione.
5a: and 5B-is0mers of 5~cyano
lll-nor- pregnan - 21 - ol - 3,11,20
XV _____ __
17,20;20,21 - bis - methylenedioxy - pregnan-
5a and 5B-isomers of 5-eyano
17,20;20,21 - bis - methylene
trione and 5-earbamyl-l9-nor
function at 0-11 or an oxygen function at 'C—11 and a
pregnan - 21 - 0l - 3,11,20 - trione.
?uorine ‘atom at C-9a; there are obtained the respective
S-cyano and S-carbamyl analogs of pregnan-17a,21-diol
5n: and ??-isomers of 5-cyano
androstan - 17B - ol-3,11 - dione
Thus, if the starting com
pound is 17,20;20,21-bis-methylenedioxy-A‘l-pregnen-3
genated at 0-11 with a ?-hydroxyl or keto group, or oxy
i’w
In another experiment, in accordance with the preced
ing example, methanol was substituted for ethanol, and
65
3,20-dione with or without the angular methyl group at
3-one.
dioxy-pregnan-3-one - and
oarbamyl -
5
17,20;20,21 - bis
methylenedioxy-pregnan-ii‘one.
0-10 and/or with an oxygen function at C_11 or an
oxygen function at C-ll and a ?uorine atom at (1-904.
XVI ____ _. IQ-nor-analog of starting
According to another variation in practicing the proc
ess of invention, the 17,20;20,21-bis~rnethylenedioxy com
XVII_____ 11f] - hydroxy ~ analog of
ll?-hydroxy-analogs of products
and the products resulting from this reaction are acety
lated at 0-21 by treatment with acetic anhydride in py
starting compound of
Example XV.
XVIII_.__ ll-keto-analog of starting
compound of Example
XV (17,20;20,2l~
ll-keto-analogs of products of
Example XV.
ridine solution.
XIX ____ __ 9a-?uoro analog of start-
2cgrupound of Example
70
pounds are treated with aqueous acetic acid in the hot
There are thus obtained the above men
tioned ?nal compounds in the form of their 21-acetates. 75
B MID-cortisone).
ing material of Example XV.
l9-nor analog of products of
Example XV.
of Example XV.
-
‘.lcr-?uoro analogs of products of
Example I.
3,050,518
Table I-Cont1nued
Exlalmple
Table III
Starting Compound
Products
ExlaImple Starting Material Acid Anhydride
0.
,
Final Product
o.
5
XX _____ _. l7a-propyl~testosterone__ 5a and 5,8-iso1ners of the 5-cyano.
and B-carbamyl analogs of 17a-
XXXIII. _- 5a-cyano prodnot of Ex-
propyl - androstan - l7B-ol-3,ll -
ample I.
dione.
XXXIV_-__ 5;‘3‘cyano prod-
XXI ____ _- 17a-vinyl-testosterone-__ 5a and ??-isomers of the S-cyano
’
and 5-carbarnyl analogs of 17a-
not of Ex-
XXII..-» 17a - iso - propen(-l)y -
progesterone.
ample V.
XXXVL... ??-carhamyl
product of
dione.
17-propionate of 5?~
ample I.
cyano product of
Example V.
17-lbenzoate of 5a
dride.
‘Example VI.
and ?-carbamyl analogs of 17a-
iso - propenyl - pregnan - 3,20 -
propionic anhybenzoio anhy-
product of
5a and B?-isorners of the 5-cyano
17-acetate of 5a-Cy
ano product of Ex
dride.
vinyl - endrostan - 1713 - ol - 3,11- 10 XXXV_-._. EQ-carbamyl
dione.
acetic anhydride. .
carbamyl product
of Example VI.
cyclopentyl-pro- 2l-cyclopentylprd
picnic anhy-
Example X.
pioante of 5B-oar—
dride.
hamyl-pregnan
XXIII____ IYa-alkyl-testosterone. __ 5a and BB-isomers of the E-cyano
115,21-diol-3,20
and 5-carbamyl analogs of 17a-
dione.
alkyl - androstan - 17B » ol > 3,11- 15 XXXVII_-_. 5?-cyano prod-
-,
XXIV-__- 17a - pentenyl-proges-
tcrone.
dione.
5a and BIS-isomers of the 5-cyano
and S-oarbamyl analogs of 17a-
not of Example V.
XXXVIIL- 5?-cyan0 prod-
pentenyl -pregnan - 3,20 - dione.
XXV___-_ 17a - ethiny~ corticosterone.
.
XXVI..-" 17a - propin(-l)yl - tes-
tosterone‘
not of Ex-
butyric anhy-
17-Ebutyrate of 5
dride.
cyano testan-17?
ol-3-0ne.
17-capr0ate of 5
caproic anhydride.
5a and ??-isomers of the ?-cyano
ample I.
and S-carbamyl analogs of 17a‘ XXXIX--- 5?<oyano prodethinyl - prcgnan- 11,8,2l-diol-3,
not of Ex20-dione.
20
ample I.
cyano tcstan-UB- '
ol-3-one.
17-oyclopentylpro
pionate of 5>cyano
testan-l75~ol-3~one.
cyclopentyl-proVpionio anhydride.
5a and ??'isomers of the 5-cyano
and S-carbarnyl analogs of 17a
projpinyl - androstan - 17?-ol-3,
1- ione.
25
.
EXAMPLE
XL
Alternatively, the dlhydroxyacetone side chain was re
generated by heating a S-cyano or 5~carbamyl-17,201;
20,21-bis-methylenedioxy-pregnane with 50% acetic acid
for 7 hours at 100° C.; the product was precipitated by
diluting with water ‘and then acetylated at C-21 by the
EXAMPLE XXVII
A mixture of 5 g. of 5oz-cyano-17,20;20,2l-bls-methylene-droxy-pregnan-l 1,8-01-3-one, the BMD compound
produced 1n the preceding Example XVII and 100 cc. of 30
method of Example XXXI. There was thus prepared,
60% formic acid was stirred on a steam bath for 1 hour
for example, 5ot-cyano-4,5-dihydro-cortisone 2l‘acetate.
and cooled; the precipitate was collected by ?ltration,
washed with water, dried and recrystallized from acetone
hexane. There was thus obtained Sa-cyanoépregnan
11p,17a,21 - triol - 3,20 -dione, namely 50: - cyano - 4,5
We claim:
'1. A process for preparing S-cyano and S-carbamyl
analogs of certain 4,5 dihydro derivatives of steroidal
35 A‘i-3-keto—hormones, comprising the steps of reacting a
starting compound having the general formula:
' dihydro-hydrocortisone.
Following the procedure of Example XXVH, the ?nal
products listed in Table 11 below can be obtained from
the indicated starting materials:
40
Table Ii
Example
No.
Starting Material
Final Product
.
45
XXVIIL. Final products of Exam-
5e: and 5B-isomers of S-cyano
ple XV.
wherein A is a radical arrangement selected from the
group consisting of
pregnan-17a,2l-diol ~ 3,20 - dione
and
XXIX- __- Final products of Exam;
ple XVIII.
5'carbamyl-pregnan-l7a,
21-diol-3,20-dione.
5a and ??-isomers of 5-cyano- and
?-carbamyl analogs of 4,5
dihydrocortisone.
50
H
[lower aliphatic radical [lower aliphatic radical
XXX.____ Final products of Exam- 5a and SE-isomers of o-cyano and
ple XIX.
5-carbamyl analogs of 9:1
?noro - 4,5 - dihydro-hydrccorti
sone.
tacyloxy,
.
,
55
‘EXAMPLE
A mixture of 1 g. of 5ct-cyano-pregnan-115,17a-21
, \
CO~OH5
,
CO-OHzOH
/
CH-GH2
bis-methylenedioxy, and
‘OH
triol~3,20-dione, obtained as described in Example XX,
(JO-CHaOH
5 cc. of acetic anhydride and 10 cc. of pyridine Was kept 60
overnight at room temperature and then poured‘ into
wherein the acyl ‘radical is derived from a hydrocarbon
water, heated for 1 hour on a steam bath and cooled; the
precipitate was collected, washed with water, dried and
recrystallized ‘from acetone-hexane, thus producing 5a
cyano~pregnan-11,8,17a,21-triol-3,20-dione 2l-acetate.
EXAMPLE XXXII
By following the procedure of Example XXXI, there
was prepared SB-carbamyl-dihydrotestosterone l7-propi
onate by reaction of the free compound with propionic
anhydride.
Following the procedure of iExample XPQQ‘I, the ?nal
products‘ listed in Table .111 below. can be obtained from
the starting compounds indicated.
carboxylic acid of less than 12 carbon atoms; R is a mem
ber selected from the group consisting of hydrogen and
methyl, X is an atom selected from the group consisting
65 of hydrogen and ?uorine, and Y is a member selected
from the group consisting of H,
OH
g
, and =0
H
with the. cyanide of a metal selected from the group
consisting of the alkali-metals and the alkaline earth
75 metals, in the presence of a hydroxy'lated organic solvent,
3,050,518
7
8. A compound of the following formula:
so as to produce a new mixture of analogs being of the
general formula:
'
A
X
R
,"
01W2
10_.
RI
wherein A, R, X and Y have the same signi?cance as in
the general formula of said starting material; and R’ is
selected from the group consisting of cyano and carbamyl,
and separating the mixture to isolate the individual analogs
therefrom.
2. The process according to claim 1, characterized in
that the starting compound is re?uxed for from about one
to five hours with potassium cyanide in mixture with a
I solvent which is a lower fatty alcohol.
wherein R is selected from the group consisting of hy- /
drogen and methyl; R1 is selected from the group consist
ing of cyano and carbamyl; Y is selected from the group
consisting of hydrogen, B-hydroxyl, a-hydroxyl and keto;
X is selected from the group consisting of hydrogen and
fluorine and R4 is selected from the group consisting of
hydrogen, hydroxy and hydrocarbon carboxylic acyloxy
20I of less than 12 carbon atoms.
9. A compound of the following formula:
3. The process according to claim 1, characterized in
that the cyanide is sodium cyanide.
4. The process as described in claim. 1, characterized in
011201215v ‘
that the starting compound is 17,20;20,2l-bis-methylene
dioxy-A4~pregnen-3-one, and further comprising the step
of heating the resulting compounds in aqueous organic
acid in order to regenerate the dihydroacetone side chain
of the aforesaid starting compound;
5. The process as described in claim 1, further com
prising the step of reacting a resulting analog with the an
hydride of a carboXylic acid having up to 12 carbon atoms,
so as to produce the corresponding ester of the analog
having the primary and secondary hydroxyl groups
wherein R is selected from the group consisting of hy
drogen and methyl; R1 is selected from the group consist
thereof esteri?ed.
‘6. A compound of the following formula:
ing of cyano and carbamyl; R2 is selected from the group
consisting of hydrogen and a hydrocarbon carboxylic acyl
0 R2
group of less than 12 carbon atoms; Y isgsel'ected from
the group consisting of hydrogen, lS-hydroxyl, a-hydroxyl ’
40 and keto and X is selected from the group consisting of
hydrogen and ?uorine.
10. A compound of the following formula:
Y
X
R
0_
,r’
OHZORZ
5
R1
45
wherein R is, selected from the group consisting of hy
drogen and methyl; R1 is selected from the group con
1
sisting of cyano and carbamyl; R2 is selected from the
group consisting of hydrogen and a hydrocarbon car
boxylic acyl group of less than 12 carbon atoms; ’Y is
,
I
/\
0%;
selected from the group consisting of hydrogen, B-hy
droXyl, oc-hYdI‘OXYl and keto and X is selected from the
31
group consisting of hydrogen and ?uorine.
wherein
R1
is
selected
from
the group consisting of cyano
7. A compound of the following formula:
55 and carbamyl; R2 ‘is selected from the ‘group consisting of
hydrogen and a hydrocarbon carboxylic acyl group of
OR2
less than 12 carbon atoms; Y is selected from the group
consisting of hydrogen, B-hydroxyl, whydroxyl and keto
and X is selected from the group consisting of hydrogen
60 and ?uorine.
A
H wherein R is selected from the group consisting of hy
drogen and methyl; R1 is selected from the group con
’
11. A compound of the following formula:
65
sisting of cyano and carbamyl; R2 is selected from the
group consisting of hydrogen and a hydrocarbon car
boxylic acyl group of less than 12 carbon atoms; R3 is
selected from the group consisting of lower alkyl, lower
alkenyl and lower alkinyl radicals; Y is selected from
the group consisting of hydrogen, ,B-hydroxyl, a-hydroxyl
and keto and X is selected from the group consisting of
hydrogen and ?uorine.
wherein R is selected from the group consisting of hydro
gen and methyl; R1 is selected from the group consisting
75 of cyano and carbamyl; and R2 is selected from the group
3,050,518
10
9
of cyano and carbamyl; X is selected from the group con
consisting of hydrogen and a hydrocarbon carboxylic
sisting of hydrogen and ?uorine and Y is selected from
acyl group of less than 112 carbon atoms.
the group consisting of hydrogen, p-hydroxyl, oc-hydroxyl
'12. A compound of the following formula:
and keto.
o-om
13.
14.
15.
~16.
CH2
5-cyano-dihydrotestosterone.
5?-carbamyl-dihydrotestosterone-l7-propionate.
5a-cyano-4,5-dihydro-cortisone-Zl-acetate.
5a-cyano-4,5-dihydro-hydrocortisone~21-acetate.
17. The hydrocarbon carboxylic acid esters of less than
10 12 carbon atoms of S-cyano-l7a-hydroxy-pregnane-3,20
dione.
18. The hydrocarbon canboxylic acid esters of less than
12 carbon atoms of S-carbamyl-17a-hydroxy-pregnane
15
R1
wherein R is selected from the group consisting of hydro
gen and methyl; R1 is selected from the group consisting
3,20-dione.
119. S-cyano-pregnane-17u,21-diol-‘3,20>dione.
20. S-carbamyl-pregnane-17u,21-dio1-3,20-dione.
No references cited.
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