US4041055A
Expired / Lapsed
US
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Process for the preparation of 17α-hydroxyprogesterones and corticoids from androstenes
Assignee: Pharmacia and Upjohn Co
•
Filing: 1975-11-17
•
Granted: 1977-08-09
•
Expires: 1995-11-17
Abstract
Abstract This invention discloses a general process for the production of corticoids from androstenes. This invention provides an economically viable alternative synthesis of 17 alpha -hydroxyprogesterones and the corticoids.
Inventors
- 👤 Kenneth Paul Shephard
- 👤 Verlan H. Van Rheenen
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-11-03 03:32
CPC Classifications
C; C07; C07J; C07J31/00; C07J31/003; C07J1/00; C07J1/0003; C07J1/0011; C07J1/0033; C07J1/004; C07J1/0048; C07J5/00; C07J5/0046; C07J5/0053; C07J5/0061; C07J5/0069; C07J5/0076; C07J7/00; C07J7/0005; C07J7/001; C07J7/004; C07J7/0045; C07J7/0065; C07J7/0075; C07J7/008; C07J7/0085
Claims Analysis
Total Claims: 126
Claim 1
Independent Claim
194 words
A process for the preparation of a steroid of the formula ##STR19## where R 3 is an oxygen atom (O) or a hydroxyl group (HO) with the proviso that when R 3 is (O) there are double bonds between C 3 and R 3 and between C 4 and C 5 , and when R 3 is (HO) there is a single bond between C 3 and R 3 with a double bond between C 5 and C 6 ; where R 6 is a hydrogen or fluorine atom or methyl group; where R 9 is a hydrogen, fluorine, chlorine, or bromine atom, or hydroxyl group; where R 11 is (H), (H,H), (H,αOH), (H,βOH) or (O); where R 16 is a hydrogen atom or methyl group; where ˜ indicates the attachment of the R 16 group in the alpha or beta configuration; and where is a single or double bond which comprises starting with a steroidal propargyl alcohol of the formula ##STR20## where R 3 , R 6 , R 9 , R 11 , R 16 , ˜, and are defined above and subjecting the steroidal propargyl alcohol IV to the following reactions:
Claim 2
Dependent Claim
194 words
A process for the preparation of a steroid of the formula ##STR19## where R 3 is an oxygen atom (O) or a hydroxyl group (HO) with the proviso that when R 3 is (O) there are double bonds between C 3 and R 3 and between C 4 and C 5 , and when R 3 is (HO) there is a single bond between C 3 and R 3 with a double bond between C 5 and C 6 ; where R 6 is a hydrogen or fluorine atom or methyl group; where R 9 is a hydrogen, fluorine, chlorine, or bromine atom, or hydroxyl group; where R 11 is (H), (H,H), (H,αOH), (H,βOH) or (O); where R 16 is a hydrogen atom or methyl group; where ˜ indicates the attachment of the R 16 group in the alpha or beta configuration; and where is a single or double bond which comprises starting with a steroidal propargyl alcohol of the formula ##STR20## where R 3 , R 6 , R 9 , R 11 , R 16 , ˜, and are defined above and subjecting the steroidal propargyl alcohol IV to the following reactions:
Claim 3
Dependent Claim
146 words
sulfenylating with a substituted sulfenylating agent of the formula R 17 -S-M; where M is a chlorine or bromine atom, phenylsulfone, phthalimide or imidazole group; where R 17 is alkyl of one thru 10 carbon atoms, trichloromethyl, phenyl or phenyl substituted with one thru 3 nitro groups or substituted with one thru 3 trifluoromethyl groups, aralkyl of 7 thru 12 carbon atoms, phthalimide, (R 121 ) 2 -N where R 121 is alkyl of one thru 10 carbon atoms, phenyl, phenyl substituted with alkyl of one thru 4 carbon atoms, aralkyl of 7 thru 12 carbon atoms with the proviso that the two R 121 groups may be the same or different, to form an allene sulfoxide of the formula ##STR21## where R 3 , R 6 , R 9 , R 11 , R 16 , R 17 , ˜, and are defined above; 2.
Claim 4
Dependent Claim
146 words
sulfenylating with a substituted sulfenylating agent of the formula R 17 -S-M; where M is a chlorine or bromine atom, phenylsulfone, phthalimide or imidazole group; where R 17 is alkyl of one thru 10 carbon atoms, trichloromethyl, phenyl or phenyl substituted with one thru 3 nitro groups or substituted with one thru 3 trifluoromethyl groups, aralkyl of 7 thru 12 carbon atoms, phthalimide, (R 121 ) 2 -N where R 121 is alkyl of one thru 10 carbon atoms, phenyl, phenyl substituted with alkyl of one thru 4 carbon atoms, aralkyl of 7 thru 12 carbon atoms with the proviso that the two R 121 groups may be the same or different, to form an allene sulfoxide of the formula ##STR21## where R 3 , R 6 , R 9 , R 11 , R 16 , R 17 , ˜, and are defined above; 2.
Claim 5
Dependent Claim
104 words
Michael addition to the allene sulfoxide of step (1) with an alkoxide, mercaptide or dialkyl amine to form a sulfoxide of the formula ##STR22## where R 3 , R 6 , R 9 , R 11 , R 16 , R 17 , ˜, and are defined above and where Z is -O-R 20 , -S-R 120 or -N-(R 120 ) 2 where R 20 is alkyl of one thru 5 carbon atoms, phenyl or phenyl substituted with one thru 4 carbon atoms, or alkyl of 7 thru 12 carbon atoms, and where R 120 is alkyl of one thru 5 carbon atoms; 3.
Claim 6
Dependent Claim
104 words
Michael addition to the allene sulfoxide of step (1) with an alkoxide, mercaptide or dialkyl amine to form a sulfoxide of the formula ##STR22## where R 3 , R 6 , R 9 , R 11 , R 16 , R 17 , ˜, and are defined above and where Z is -O-R 20 , -S-R 120 or -N-(R 120 ) 2 where R 20 is alkyl of one thru 5 carbon atoms, phenyl or phenyl substituted with one thru 4 carbon atoms, or alkyl of 7 thru 12 carbon atoms, and where R 120 is alkyl of one thru 5 carbon atoms; 3.
Claim 7
Dependent Claim
51 words
reacting the product of step (2) with a thiophile selected from the group consisting of trimethylphosphite and diethylamine to form a compound of the formula ##STR23## where R 3 , R 6 , R 9 , R 11 , R 16 , ˜, , and Z are defined above; and 4.
Claim 8
Dependent Claim
51 words
reacting the product of step (2) with a thiophile selected from the group consisting of trimethylphosphite and diethylamine to form a compound of the formula ##STR23## where R 3 , R 6 , R 9 , R 11 , R 16 , ˜, , and Z are defined above; and 4.
Claim 9
Dependent Claim
12 words
hydrolyzing the product of step (3) in the presence of an effective
Claim 10
Dependent Claim
12 words
hydrolyzing the product of step (3) in the presence of an effective
Claim 11
Dependent Claim
23 words
catalytic amount of an acid. 2. A process according to claim 1, where the substituted sulfenylating agent is an aromatic sulfenyl chloride, and
Claim 12
Dependent Claim
34 words
where the Michael addition is with an alkoxide. 3. A process according to claim 2, where the aromatic sulfenyl chloride is phenylsulfenyl chloride or tolylsulfenyl chloride and where the alkoxide is methoxide or ethoxide.
Claim 13
Dependent Claim
25 words
. A process according to claim 3, where the aromatic sulfenyl chloride is phenylsulfenyl chloride, where the alkoxide is methoxide and the thiophile is trimethylphosphite.
Claim 14
Dependent Claim
15 words
A process according to claim 4 where the steroid of formula X is flurogestone (9α-fluoro-11β,17α-dihydroxypregna-4-ene-3,20-dione).
Claim 15
Dependent Claim
15 words
A process according to claim 4, where the steroid of formula X is fluorometholone (9α-fluoro-11β,17α-dihydroxy-6α-methylpregna-1,4-diene-3,20-dione).
Claim 16
Dependent Claim
15 words
A process according to claim 4, where the steroid of formula X is medroxyprogesterone (11β,17α-dihydroxy-6α-methylpregna-4-ene-3,20-dione).
Claim 17
Dependent Claim
60 words
A process for the preparation of a steroid of the formula ##STR24## where R 21 is a hydrogen atom or alkyl carboxylate of 2 thru 6 carbon atoms, or aromatic carboxylate of 7 thru 12 carbon atoms; which comprises starting with a steroidal propargyl alcohol of the formula ##STR25## and subjecting the steroidal propargyl alcohol IV to the following reactions:
Claim 18
Dependent Claim
60 words
A process for the preparation of a steroid of the formula ##STR24## where R 21 is a hydrogen atom or alkyl carboxylate of 2 thru 6 carbon atoms, or aromatic carboxylate of 7 thru 12 carbon atoms; which comprises starting with a steroidal propargyl alcohol of the formula ##STR25## and subjecting the steroidal propargyl alcohol IV to the following reactions:
Claim 19
Dependent Claim
21 words
sulfenylating with a substituted sulfenylating agent of the formula R 17 -S-M, to form an allene sulfoxide of the formula ##STR26##
Claim 20
Dependent Claim
21 words
sulfenylating with a substituted sulfenylating agent of the formula R 17 -S-M, to form an allene sulfoxide of the formula ##STR26##
Claim 21
Dependent Claim
24 words
Michael addition to the allene sulfoxide of step (1) with an alkoxide, mercaptide or dialkyl amine to form a sulfoxide of the formula ##STR27##
Claim 22
Dependent Claim
24 words
Michael addition to the allene sulfoxide of step (1) with an alkoxide, mercaptide or dialkyl amine to form a sulfoxide of the formula ##STR27##
Claim 23
Dependent Claim
26 words
reacting the product of step (2) with a thiophile selected from the group consisting of trimethylphosphite and diethylamine to form a compound of the formula ##STR28##
Claim 24
Dependent Claim
26 words
reacting the product of step (2) with a thiophile selected from the group consisting of trimethylphosphite and diethylamine to form a compound of the formula ##STR28##
Claim 25
Dependent Claim
49 words
and 4. adding a peracid to the product of step (3), where R 3 , R 6 , R 9 , R 11 , R 16 , R 17 , R 20 , R 120 , R 121 , ˜, , Z and M are defined in claim 1.
Claim 26
Dependent Claim
25 words
A process according to claim 8, where the substituted sulfenylating agent is an aromatic sulfenyl chloride and where the Michael addition is with an alkoxide.
Claim 27
Dependent Claim
25 words
The process according to claim 9, where the aromatic sulfenyl chloride is phenylsulfenyl chloride or tolylsulfenyl chloride and where the alkoxide is methoxide or ethoxide.
Claim 28
Dependent Claim
23 words
The process according to claim 10, where the aromatic sulfenyl chloride is phenylsulfenyl chloride, where the alkoxide is methoxide and thiophile is trimethylphosphite.
Claim 29
Dependent Claim
15 words
A process according to claim 11 where the steroid of formula XII is beclomethasone (9α-chloro-11β,17α,21-trihydroxy-16β-methylpregna-1,4-diene-3,20-dione).
Claim 30
Dependent Claim
15 words
A process according to claim 11, where the steroid of formula XII is betamethasone (9α-fluoro-11β,17α,21-trihydroxy-16β-methylpregna-1,4-diene-3,20-dione).
Claim 31
Dependent Claim
15 words
A process according to claim 11, where the steroid of formula XII is cortisone (17α,21-dihydroxypregna-4-ene-3,11,20-trione).
Claim 32
Dependent Claim
15 words
A process according to claim 11, where the steroid of formula XII is dexamethasone (9α-fluoro-11β,17α,21-trihydroxy-16α-methylpregna-1,4-diene-3,20-dione).
Claim 33
Dependent Claim
16 words
A process according to claim 11, where the steroid of formula XII is difluorasone (6α,9α-difluoro-11β,17α,21-trihydroxy-16β-methyl-pregna-1,4-diene-3,20-dione 17,21-diacetate).
Claim 34
Dependent Claim
15 words
A process according to claim 11, where the steroid of formula XII is fludrocortisone (9α-fluoro-11β,17α,21-trihydroxypregna-4-ene-3,20-dione).
Claim 35
Dependent Claim
15 words
A process according to claim 11, where the steroid of formula XII is flumethasone (6α,9α-difluoro-11β,17α,21-trihydroxy-16α-methylpregna-1,4-diene-3,20-dione).
Claim 36
Dependent Claim
15 words
A process according to claim 11, where the steroid of formula XII is fluprednisolone (6α-fluoro-11β,17α,21-trihydroxypregna-1,4-diene-3,20-dione).
Claim 37
Dependent Claim
14 words
A process according to claim, where the steroid of formula XII is hydrocortisone (11β,17α,21-trihydroxypregna-4-ene-3,20-dione).
Claim 38
Dependent Claim
16 words
A process according to claim 11, where the steroid of formula XII is meprednisone (17α,21-dihydroxy-16β-methylpregna-1,4-diene 3,11,20-trione).
Claim 39
Dependent Claim
15 words
A process according to claim 11, where the steroid of formula XII is methylprednisolone (11β,17α,21-trihydroxy-6α-methylpregna-1,4-diene-3,20-dione).
Claim 40
Dependent Claim
16 words
A process according to claim 11, where a steroid of the formula XII is paramethasone (6α-fluoro-11β,17α,21-trihydroxy-16α-methylpregna-1,4-diene-3,20-dione).
Claim 41
Dependent Claim
16 words
A process according to claim 11, where a steroid of the formula XII is prednisolone (11β,17α,21-trihydroxypregna-1,4-diene-3,20-dione).
Claim 42
Dependent Claim
16 words
A process according to claim 11, where a steroid of the formula XII is prednisone (17α,21-dihydroxypregna-1,4-diene-3,11,20-trione).
Claim 43
Dependent Claim
34 words
A process for the preparation of a steroid of the formula ##STR29## which comprises starting with a steroidal propargyl alcohol of the formula ##STR30## and subjecting the steroidal propargyl alcohol IV to the following
Claim 44
Dependent Claim
34 words
A process for the preparation of a steroid of the formula ##STR29## which comprises starting with a steroidal propargyl alcohol of the formula ##STR30## and subjecting the steroidal propargyl alcohol IV to the following
Claim 45
Dependent Claim
23 words
reactions: 1. sulfenylating with a substituted sulfenylating agent of the formula R 17 -S-M, to form an allene sulfoxide of the formula ##STR31##
Claim 46
Dependent Claim
23 words
reactions: 1. sulfenylating with a substituted sulfenylating agent of the formula R 17 -S-M, to form an allene sulfoxide of the formula ##STR31##
Claim 47
Dependent Claim
24 words
Michael addition to the allene sulfoxide of step (1) with an alkoxide, mercaptide or dialkyl amine to form a sulfoxide of the formula ##STR32##
Claim 48
Dependent Claim
24 words
Michael addition to the allene sulfoxide of step (1) with an alkoxide, mercaptide or dialkyl amine to form a sulfoxide of the formula ##STR32##
Claim 49
Dependent Claim
26 words
reacting the product of step (2) with a thiophile selected from the group consisting of trimethylphosphite and diethylamine to form a compound of the formula ##STR33##
Claim 50
Dependent Claim
26 words
reacting the product of step (2) with a thiophile selected from the group consisting of trimethylphosphite and diethylamine to form a compound of the formula ##STR33##
Claim 51
Dependent Claim
17 words
adding a halogen to the product of step (3) to produce a compound of the formula ##STR34##
Claim 52
Dependent Claim
17 words
adding a halogen to the product of step (3) to produce a compound of the formula ##STR34##
Claim 53
Dependent Claim
74 words
where Y is a chlorine, bromine, or iodine atom; and 5. substituting an anion of the formula OR 21 for Y in the product of step (4) where R 3 , R 6 , R 9 , R 11 , R 16 , R 17 , R 20 , R 120 , R 121 , ˜, , Z and M are defined in claim 1 and where R 21 is defined in claim 8.
Claim 54
Dependent Claim
25 words
A process according to claim 26, where the substituted sulfenylating agent is an aromatic sulfenyl chloride and where the Michael addition is with an alkoxide.
Claim 55
Dependent Claim
25 words
The process according to claim 27, where the aromatic sulfenyl chloride is phenylsulfenyl chloride or tolylsulfenyl chloride and where the alkoxide is methoxide or ethoxide.
Claim 56
Dependent Claim
24 words
A process according to claim 28, where the aromatic sulfenyl chloride is phenylsulfenyl chloride, where the alkoxide is methoxide and the thiophile is trimethylphosphite.
Claim 57
Dependent Claim
15 words
A process according to claim 29, where the steroid of formula XII is beclomethasone (9α-chloro-11β,17α,21-trihydroxy-16β-methylpregna-1,4-diene-3,20-dione).
Claim 58
Dependent Claim
15 words
A process according to claim 29, where the steroid of formula XII is betamethasone (9α-fluoro-11β,17α,21-trihydroxy-16β-methylpregna-1,4-diene-3,20-dione).
Claim 59
Dependent Claim
15 words
A process according to claim 29, where the steroid of formula XII is cortisone (17α,21-dihydroxypregna-4-ene-3,11,20-trione).
Claim 60
Dependent Claim
15 words
A process according to claim 29, where the steroid of formula XII is dexamethasone (9α-fluoro-11β,17α,21-trihydroxy-16α-methylpregna-1,4-diene-3,20-dione).
Claim 61
Dependent Claim
16 words
A process according to claim 29, where the steroid of formula XII is difluorasone (6α,9α-difluoro-11β,17α,21-trihydroxy-16β-methylpregna-1,4-diene-3,20-dione 17,21-diacetate).
Claim 62
Dependent Claim
15 words
A process according to claim 29, where the steroid of formula XII is fludrocortisone (9α-fluoro-11β,17α,21-trihydroxypregna-4-ene-3,20-dione).
Claim 63
Dependent Claim
16 words
A process according to claim 29, where the steroid of formula XII is flumethasone (6α,9α-difluoro-11β,17α,21-trihydroxy-16α-methylpregna-1,4-diene-3,20 -dione).
Claim 64
Dependent Claim
16 words
A process according to claim 29, where the steroid of formula XII is fluprednisolone (6α-fluoro-11β,17α, 21-trihydroxypregna-1,4-diene-3,20-dione).
Claim 65
Dependent Claim
15 words
A process according to claim 29, where the steroid of formula XII is hydrocortisone (11β,17α,21-trihydroxypregna-4-ene-3,20-dione).
Claim 66
Dependent Claim
16 words
A process according to claim 29, where the steroid of formula XII is meprednisone (17α,21-dihydroxy-16β-methylpregna-1,4-diene 3,11,20-trione).
Claim 67
Dependent Claim
15 words
A process according to claim 29, wherein the steroid of formula XII is methylprednisolone (11β,17α,21-trihydroxy-6α-methylpregna-1,4-diene-3,20-dione).
Claim 68
Dependent Claim
15 words
A process according to claim 29, where the steroid of formula XII is paramethasone (6α-fluoro-11β,17α,21-trihydroxy-16α-methylpregna-1,4-diene-3,20-dione).
Claim 69
Dependent Claim
15 words
A process according to claim 29, where the steroid of formula XII is prednisolone (11β,17α,21-trihydroxypregna-1,4-diene-3,20-dione).
Claim 70
Dependent Claim
15 words
A process according to claim 29, where the steroid of formula XII is prednisone (17α,21-dihydroxypregna-1,4-diene-3,11,20-trione).
Claim 71
Dependent Claim
74 words
A process for the production of an allene sulfoxide of the formula ##STR35## which comprises starting with a steroidal propargyl alcohol of the formula ##STR36## and sulfenylating the steroidal propargyl alcohol IV with a substituted sulfenylating agent of the formula R 17 -S-M, where R 3 , R 6 , R 9 , R 11 , R 16 , R 17 , R 121 , ˜, , and M are defined in claim 1.
Claim 72
Dependent Claim
74 words
A process for the preparation of a sulfoxide of the formula ##STR37## which comprises starting with an allene sulfoxide of the formula ##STR38## and subjecting the allene sulfoxide VI to Michael addition with an alkoxide, mercaptide, or dialkylamine, where R 3 , R 6 , R 9 , R 11 , R 16 , R 17 , R 20 , R 120 , R 121 , ˜, and Z are defined in claim 1.
Claim 73
Dependent Claim
78 words
A process for the preparation of a 17α-hydroxy steroid of the formula ##STR39## which comprises starting with a sulfoxide of the formula ##STR40## and reacting the formula VII compound with a thiophile selected from the group consisting of trimethylphosphite and diethylamine where R 3 , R 6 , R 9 , R 11 , R 16 , R 17 , R 20 , R 120 , R 121 , ˜, , and Z are defined in claim 1.
Claim 74
Dependent Claim
69 words
A process for the preparation of a steroid of the formula ##STR41## which comprises starting with a 17α-hydroxy steroid of the formula ##STR42## and adding a peracid to compound IX, where R 3 , R 6 , R 9 , R 11 , R 16 , R 20 , R 120 , ˜, and Z are defined in claim 1 and where R 21 is defined in claim 8.
Claim 75
Dependent Claim
36 words
An allene sulfoxide of the formula ##STR43## where R 3 , R 6 , R 9 , R 11 , R 16 , R 17 , R 121 , ˜, and are defined in claim 1.
Claim 76
Dependent Claim
8 words
21-Phenylsulfinylpregna-4,17(20),20-triene-3-one an allene sulfoxide according to claim 48.
Claim 77
Dependent Claim
8 words
6α-Methyl-21-phenylsulfinylpregna-4,17(20),20-triene-3-one an allene sulfoxide according to claim 48.
Claim 78
Dependent Claim
8 words
11β-Hydroxy-21-phenylsulfinylpregna-4,17(20),20-triene-3-one an allene sulfoxide according to claim 48.
Claim 79
Dependent Claim
8 words
11β-Hydroxy-6α-methyl-21-phenylsulfinylpregna-4,17(20),20-triene-3-one an allene sulfoxide according to claim 48.
Claim 80
Dependent Claim
8 words
21-Phenylsulfinylpregna-4,9(11),17(20),20-tetraene-3-one an allene sulfoxide according to claim 48.
Claim 81
Dependent Claim
8 words
21-Phenylsulfinylpregna-1,4,9(11),17(20),20-pentaene-3-one an allene sulfoxide according to claim 48.
Claim 82
Dependent Claim
8 words
6α-Methyl-21-phenylsulfinylpregna-4,9(11),17(20),20-tetraene-3-one an allene sulfoxide according to claim 48.
Claim 83
Dependent Claim
8 words
6α-Methyl-21-phenylsulfinylpregna-1,4,9(11),17(20),20-pentaene-3-one an allene sulfoxide according to claim 48.
Claim 84
Dependent Claim
8 words
6α-Fluoro-21-phenylsulfinylpregna-4,9(11),17(20),20-tetraene-3-one an allene sulfoxide according to claim 48.
Claim 85
Dependent Claim
8 words
6α-Fluoro-21-phenylsulfinylpregna-1,4,9(11),17(20),20-pentaene-3-one an allene sulfoxide according to claim 48.
Claim 86
Dependent Claim
8 words
16α-Methyl-21-phenylsulfinylpregna-4,9,(11),17(20),20-tetraene-3-one an allene sulfoxide according to claim 48.
Claim 87
Dependent Claim
42 words
A sulfoxide of the formula ##STR44## where R 3 , R 6 , R 9 , R 11 , R 16 , R 17 , R 20 , R 120 , R 121 , ˜, and Z are defined in claim 1.
Claim 88
Dependent Claim
7 words
20-Methoxy-21-phenylsulfinylpregna-4,17(20)-diene-3-one a sulfoxide according to claim 60.
Claim 89
Dependent Claim
7 words
20-Methoxy-6α-methyl-21-phenylsulfinylpregna-4,17(20)-diene-3-one a sulfoxide according to claim 60.
Claim 90
Dependent Claim
7 words
11β-Hydroxy-20-methoxy-21-phenylsulfinylpregna-4,17(20)-diene-3-one a sulfoxide according to claim 60.
Claim 91
Dependent Claim
7 words
11β-Hydroxy-20-methoxy-6α-methyl-21-phenylsulfinylpregna-4,17(20)-diene-3-one a sulfoxide according to claim 60.
Claim 92
Dependent Claim
7 words
20-Methoxy-21-phenylsulfinylpregna-4,9(11),17(20)-triene-3-one a sulfoxide according to claim 60.
Claim 93
Dependent Claim
7 words
20-Methoxy-21-phenylsulfinylpregna-1,4,9(11),17(20)-tetraene-3-one a sulfoxide according to claim 60.
Claim 94
Dependent Claim
7 words
20-Methoxy-6α-methyl-21-phenylsulfinylpregna-4,9(11),17(20)-triene-3-one a sulfoxide according to claim 60.
Claim 95
Dependent Claim
7 words
20-Methoxy-6α-methyl-21-phenylsulfinylpregna-1,4,9(11),17(20)-tetraene-3-one a sulfoxide according to claim 60.
Claim 96
Dependent Claim
7 words
6α-Fluoro-20-methoxy-21-phenylsulfinylpregna-4,9(11),17(20)-triene-3-one a sulfoxide according to claim 60.
Claim 97
Dependent Claim
7 words
6.alpha.-Fluoro-20-methoxy-21-phenylsulfinylpregna-1,4,9(11),17(20)-tetraene-3-one a sulfoxide according to claim 60.
Claim 98
Dependent Claim
7 words
20-Methoxy-16α-methyl-21-phenylsulfinylpregna-4,9(11),17(20)-triene-3-one a sulfoxide according to claim 60.
Claim 99
Dependent Claim
34 words
A 17α-hydroxy steroid of the formula ##STR45## where R 3 , R 6 , R 9 , R 11 , R 16 , R 120 , ˜, and Z are defined in claim 1.
Claim 100
Dependent Claim
8 words
17α-Hydroxy-20-methoxypregna-4,20-diene-3-one a 17α-hydroxy steroid according to claim 72.
Claim 101
Dependent Claim
8 words
17α-Hydroxy-20-methoxy-6α-methylpregna-4,20-diene-3-one a 17α-hydroxy steroid according to claim 72.
Claim 102
Dependent Claim
8 words
11β,17α-Dihydroxy-20-methoxypregna-4,20-diene-3-one a 17α-hydroxy steroid according to claim 72.
Claim 103
Dependent Claim
8 words
11β,17α-Dihydroxy-20-methoxy-6.alpha.-methylpregna-4,20-diene-3-one a 17α-hydroxy steroid according to claim 72.
Claim 104
Dependent Claim
8 words
17α-Hydroxy-20-methoxypregna-4,9(11),20-triene-3-one a 17α-hydroxy steroid according to claim 72.
Claim 105
Dependent Claim
8 words
17α-Hydroxy-20-methoxypregna-1,4,9(11),20-tetraene-3-one a 17α-hydroxy steroid according to claim 72.
Claim 106
Dependent Claim
8 words
17α-Hydroxy-20-methoxy-6α-methylpregna-4,9(11),20-triene-3-one a 17α-hydroxy steroid according to claim 72.
Claim 107
Dependent Claim
8 words
17.alpha.-Hydroxy-20-methoxy-6α-methylpregna-1,4,9(11),20-tetraene-3-one a 17α-hydroxy steroid according to claim 72.
Claim 108
Dependent Claim
8 words
6α-Fluoro-17α-hydroxy-20-methoxypregna-4,9(11),20-triene-3-one a 17α-hydroxy steroid according to claim 72.
Claim 109
Dependent Claim
8 words
6.alpha.-Fluoro-17α-hydroxy-20-methoxypregna-1,4,9(11),20-tetraene-3-one a 17α-hydroxy steroid according to claim 72.
Claim 110
Dependent Claim
8 words
17α-Hydroxy-20-methoxy-16α-methylpregna-4,9(11),20-triene-3-one a 17α-hydroxy steroid according to claim 72.
Claim 111
Dependent Claim
4 words
21-Bromo-17α-hydroxypregna-4,9(11)-diene-3,20-dione a 21-halo steroid.
Claim 112
Dependent Claim
4 words
21-Bromo-17α-hydroxypregna-4,9(11)-diene-3,20-dione a 21-halo steroid.
Claim 113
Dependent Claim
4 words
21-Bromo-17α-hydroxypregna-1,4,9(11)-triene-3,20-dione a 21-halo steroid.
Claim 114
Dependent Claim
4 words
21-Bromo-17α-hydroxypregna-1,4,9(11)-triene-3,20-dione a 21-halo steroid.
Claim 115
Dependent Claim
4 words
21-Bromo-17α-hydroxy-6α-methylpregna-4,9(11)-diene-3,20-dione a 21-halo steroid.
Claim 116
Dependent Claim
4 words
21-Bromo-17α-hydroxy-6α-methylpregna-4,9(11)-diene-3,20-dione a 21-halo steroid.
Claim 117
Dependent Claim
4 words
21-Bromo-17.alpha.-hydroxy-6α-methylpregna-1,4,9(11)-triene-3,20-dione a 21-halo steroid.
Claim 118
Dependent Claim
4 words
21-Bromo-17.alpha.-hydroxy-6α-methylpregna-1,4,9(11)-triene-3,20-dione a 21-halo steroid.
Claim 119
Dependent Claim
4 words
21-Bromo-6α-fluoro-17α-hydroxypregna-4,9(11)-diene-3,20-dione a 21-halo steroid.
Claim 120
Dependent Claim
4 words
21-Bromo-6α-fluoro-17α-hydroxypregna-4,9(11)-diene-3,20-dione a 21-halo steroid.
Claim 121
Dependent Claim
4 words
21-Bromo-6.alpha.-fluoro-17α-hydroxypregna-1,4,9(11)-triene-3,20-dione a 21-halo steroid.
Claim 122
Dependent Claim
4 words
21-Bromo-6.alpha.-fluoro-17α-hydroxypregna-1,4,9(11)-triene-3,20-dione a 21-halo steroid.
Claim 123
Dependent Claim
4 words
21-Bromo-17α-hydroxy-16α-methylpregna-4,9(11)-diene-3,20-dione a 21-halo steroid.
Claim 124
Dependent Claim
4 words
21-Bromo-17α-hydroxy-16α-methylpregna-4,9(11)-diene-3,20-dione a 21-halo steroid.
Claim 125
Dependent Claim
15 words
A process according to claim 11 where the steroid of formula XII is 17α,21-dihydroxypregna-4,9(11)-diene-3,20-dione 21-acetate.
Claim 126
Dependent Claim
15 words
A process according to claim 29 where the steroid of formula XII is 17α,21-dihydroxypregna-4,9(11)-diene-3,20-dione 21-acetate.
References Cited (Backward Citations)
GB902293A
Cited
US3992422A
Cited
USPTO Annuity & Maintenance Windows
| Annuity Stage | Window Opens | Payment Deadline | Surcharge Period Until | Estimated Fee | Status |
|---|---|---|---|---|---|
| 3.5 Years (Year 4) | 1980-08-08 | 1981-02-07 | 1981-08-09 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1984-08-08 | 1985-02-07 | 1985-08-09 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 1988-08-08 | 1989-02-07 | 1989-08-09 | $7700.00 | Window Closed / Lapsed |