Claims
- 1. A 17.alpha.,20-epoxy steroid of the formula ##STR5## and the C.sub.3 -protected forms of the 3.beta.-hydroxy-.DELTA.5-(C) A-ring where
- R.sub.6 is a hydrogen or fluorine atom or methyl group;
- R.sub.9 is nothing, a hydrogen, fluorine or oxygen atom which makes the C-ring
- (a) .DELTA.9(11) when R.sub.9 is nothing and
- (b) 9.beta.,11.beta.-epoxide when R.sub.9 and R.sub.11 taken together are an oxygen atom;
- R.sub.11 is a hydrogen or oxygen atom, two hydrogen atoms, or .alpha.- or .beta.-hydroxyl group or trimethylsilyl ether thereof which makes the C-ring
- (a) .DELTA.9(11) when R.sub.11 is a hydrogen atom,
- (b) 9.beta.,11.beta.-epoxide when R.sub.9 and R.sub.11 taken together are an oxygen atom and between C.sub.11 and R.sub.11 is a single bond, and
- (c) a ketone when R.sub.11 is an oxygen atom and between C.sub.11 and R.sub.11 is a double bond;
- R.sub.20 is alkyl of 1 thru 4 carbon atoms or phenyl, the R.sub.20 's can be the same or different;
- R.sub.21 is a hydrogen atom, --CO--R.sub.21 ' or --Si(R.sub.121).sub.3 ;
- R.sub.21 ' is alkyl of 1 thru 4 carbon atoms or phenyl;
- R.sub.121 is alkyl of 1 thru 4 carbon atoms or phenyl, the R.sub.121 's can be the same or different;
- .about. indicates that the attached group can be in either the .alpha. or .beta. configuration;
- is a single or double bond; and
- X is a hydrogen atom or nothing; when X is nothing the at C.sub.3 is a double bond and when X is a hydrogen atom the at C.sub.3 is a single bond.
- 2. A 17.alpha.,20-epoxy steroid according to claim 1 where the 17.alpha.,20-epoxy steroid (III A-C) is a .DELTA.4-3-keto (A) or .DELTA.1,4-3-keto (B) steroid.
- 3. A 17.alpha.,20-epoxy steroid according to claim 1 where the 17.alpha.,20-epoxy steroid (III A-C) is a 3.beta.-hydroxy .DELTA.5 (C)-steroid in the free form ##STR6## or C.sub.3 protected form selected from the group consisting of ##STR7## where R.sub.3 is alkyl of 1 thru 3 carbon atoms, a TMS, THP or EEE group;
- R.sub.3 ' is alkyl of 1 thru 5 carbon atoms or phenyl;
- TMS refers to trimethylsilyl;
- THP refers to tetrahydropyranyl;
- EEE refers to (1-ethoxy) ethyl ether [--O--CH(CH.sub.3)OCH.sub.2 CH.sub.3 ];
- where R.sub.6, R.sub.9, R.sub.1.sup.1, R.sub.20 and are defined in claim 1.
- 4. A 17.alpha.,20-epoxy steroid according to claim 1 where R.sub.6 is a hydrogen atom.
- 5. A 17.alpha.,20-epoxy steroid according to claim 1 where R.sub.9 is nothing or an oxygen atom and where R.sub.11 is a hydrogen atom or an oxygen atom making the C-ring .DELTA.9(11) or a 9.beta.,11.beta.-epoxide.
- 6. A 17.alpha.,20-epoxy steroid according to claim 1 where R.sub.20 is selected from the group consisting of methyl, isopropyl, t-butyl or phenyl.
- 7. A 17.alpha.,20-epoxy steroid according to claim 1 where R.sub.20 is methyl or phenyl.
- 8. A 17.alpha.,20-epoxy steroid according to claim 1 where R.sub.21 is --CO--R.sub.21 ' and R.sub.21 ' is selected from the group consisting of methyl, ethyl or phenyl.
- 9. A 17.alpha.,20-epoxy steroid according to claim 1 which is 17.alpha.,20-epoxy-20,21-dihydroxy-16.alpha.-methylpregna-1,4,9(11)-trien3-one 20-trimethylsilyl ether 21-acetate; 9.beta.,11.beta.;17.alpha.,20-diepoxy-20,21-dihydroxy-16.alpha.-methylpregna-1,4-dien-3-one 20-trimethylsilyl ether 21-acetate and 17.alpha.,20-epoxy-9.alpha.-fluoro-11.beta.,20,21-trihydroxy-16.alpha.-methylpregna-1,4-dien-3-one 11,20-bis(trimethylsilyl)ether 21-acetate.
- 10. A process for the preparation of a 17.alpha.,20-epoxide of the formula ##STR8## which comprises contacting a .DELTA.17(20)-steroid of the formula ##STR9## with a peracid where R.sub.20 is alkyl of 1 thru 4 carbon atoms or phenyl, the R.sub.20 's can be the same or different,
- R.sub.21 is a hydrogen atom, --CO--R.sub.21 ' or --Si(R.sub.121).sub.3,
- R.sub.21 ' is alkyl of 1 thru 4 carbon atoms or phenyl,
- R.sub.121 is alkyl of 1 thru 4 carbon atoms or phenyl, the R.sub.121 's can be the same or different.
- 11. A process according to claim 10 where the .DELTA.17(20) steroid (II) is selected from the group consisting of
- .DELTA.4-3-keto steroids ##STR10##
- .DELTA.1. 4-3-keto steroids ##STR11## and 3.beta.-hydroxy-.DELTA.5 steroids ##STR12## and the C.sub.3 protected forms of the 3.beta.-hydroxy-.DELTA.5 (C) steroid ##STR13## where R.sub.3 is alkyl of 1 thru 3 carbon atoms, a TMS, THP, or EEE group,
- R.sub.3 ' is alkyl of 1 thru 5 carbon atoms or phenyl,
- R.sub.6 is a hydrogen or fluorine atom or methyl group,
- R.sub.9 is nothing, a hydrogen, fluorine or oxygen atom which makes the C-ring
- (a) .DELTA.9(11) when R.sub.9 is nothing and
- (b) 9.beta.,11.beta.-epoxide when R.sub.9 and R.sub.11 taken together are an oxygen atom,
- R.sub.11 is a hydrogen or oxygen atom, two hydrogen atoms, or .alpha.- or .beta.-hydroxyl group or trimethylsilyl ether thereof which makes the C-ring
- (a) .DELTA.9(11) when R.sub.11 is a hydrogen atom,
- (b) 9.beta.,11.beta.-epoxide when R.sub.9 and R.sub.11 taken together are an oxygen atom and between C.sub.11 and R.sub.11 is a single bond, and
- (c) a ketone when R.sub.11 is an oxygen atom and between C.sub.11 and R.sub.11 is a double bond,
- R.sub.20 is alkyl of 1 thru 4 carbon atoms or phenyl, the R.sub.20 's can be the same or different,
- R.sub.21 is a hydrogen atom, --CO--R.sub.21 ' or --Si(R.sub.121).sub.3,
- R.sub.21 ' is alkyl of 1 thru 4 carbon atoms or phenyl,
- R.sub.121 is alkyl of 1 thru 4 carbon atoms or phenyl, the R.sub.121 's can be the same or different,
- .about. indicates that the attached group can be in either the .alpha. or .beta. configuration,
- is a single or double bond,
- TMS refers to trimethylsilyl;
- THP refers to tetrahydropyranyl;
- EEE refers to (1-ethoxy) ethyl ether [--O--CH(CH.sub.3)OCH.sub.2 CH.sub.3 ].
- 12. A process according to claim 10 where the peracid is selected from the group consisting of peracetic, perbenzoic, m-chloroperbenzoic.
Parent Case Info
The present patent application is a divisional of application Ser. No. 870,364 filed June 6, 1986, now abandoned, which is a continuation-in-part patent application of co-pending patent application Ser. No. 724,380, filed Apr. 18, 1985 now U.S. Pat. No. 4,704,455 which is a continuation-in-part application of patent application Ser. No. 618,986, filed June 11, 1984, now abandoned.
US Referenced Citations (12)
Foreign Referenced Citations (1)
Number |
Date |
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2001990 |
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GBX |
Non-Patent Literature Citations (5)
Entry |
Organic Reactions in Steriod Chemistry, vol. II, J. Fried and J. A. Edwards, Van Nostrand Reinhold Co., NY (1972), pp. 75-76. |
J. Am. Chem. Soc. 80, pp. 3160-3161 (1958). |
J. Am. Chem. Soc. 80, p. 4428 (1958). |
E. J. Corey in Tetrahedron Letters 26, p. 6019 (1985). |
A. Alexakis in Tetrahedron Letters 27, p. 1047 (1986). |
Divisions (1)
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Number |
Date |
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Parent |
870364 |
Jun 1986 |
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Continuation in Parts (2)
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724380 |
Apr 1985 |
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Parent |
618986 |
Jun 1984 |
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