14,19-Dioxygenated steroid compounds and their 14-dehydro analogs and process for the preparation thereof

Claim 2

A compound of the formula ##STR25## wherein R is o-pivalate or >-o-pivalate, R' is chosen from OH, O-acyl, and ═O, A-B is chosen from C(β-OH)-CH 2 ; C═CH; ##STR26## and C(β-OH)-CHBr; and Y is chosen from O-acyl, ═O, OH, H and O-tetrahydropyranyl ether, wherein acyl is chosen from formyl, acetyl, trimethyl acetyl and triethyl acetyl, and the Δ4, Δ5, Δ6, Δ7, Δ8 (9) dehydro analogues thereof.

Claim 3

A compound of the formula ##STR27## wherein R is OH or O-acyl, R' is chosen from OH and O-acyl, Y is chosen from OH, O-acyl, ═O and H, A-B is chosen from C(β-OH)CH 2 , C═CH and ##STR28## wherein acyl is formyl, acetyl, trimethyl acetal and triethyl acetyl, and the Δ4, Δ5, Δ6, Δ7, Δ8 (9) dehydro anloagues thereof.

Claim 4

A compound of the formula ##STR27## wherein R is OH or O-acyl, R' is chosen from OH and O-acyl, Y is chosen from OH, O-acyl, ═O and H, A-B is chosen from C(β-OH)CH 2 , C═CH and ##STR28## wherein acyl is formyl, acetyl, trimethyl acetal and triethyl acetyl, and the Δ4, Δ5, Δ6, Δ7, Δ8 (9) dehydro anloagues thereof.

Claim 5

A compound of the formula ##STR29## wherein R is >-OH or >-O-acyl, R' is OH or O-acyl, Y is OH, O-acyl, ═O, and H, A-B is C(β-OH)-CH 2 , ##STR30## C(β-OH)-CH 2 Br wherein acyl is chosen from formyl, acetyl, trimethyl acetyl and triethyl acetyl.

Claim 6

A compound of the formula ##STR29## wherein R is >-OH or >-O-acyl, R' is OH or O-acyl, Y is OH, O-acyl, ═O, and H, A-B is C(β-OH)-CH 2 , ##STR30## C(β-OH)-CH 2 Br wherein acyl is chosen from formyl, acetyl, trimethyl acetyl and triethyl acetyl.

Claim 7

A compound of the formula ##STR31## wherein R is ##STR32## R' is OH, Y is O-acyl, OH, H, A-B is C═CH, wherein acyl is chosen from formyl, acetyl, trimethyl acetyl and triethyl acetyl.

Claim 8

A compound of the formula ##STR31## wherein R is ##STR32## R' is OH, Y is O-acyl, OH, H, A-B is C═CH, wherein acyl is chosen from formyl, acetyl, trimethyl acetyl and triethyl acetyl.

Claim 9

A compound of the formula ##STR33## wherein R is >═O or >-OH, R' is OH or O-acyl, Y is H, OH, O-acyl, A-B is C═CH, C(β-OH)-CH 2 and ##STR34## wherein acyl is chosen from formyl, acetyl, trimethyl acetyl and triethyl acetyl.

Claim 10

A compound of the formula ##STR33## wherein R is >═O or >-OH, R' is OH or O-acyl, Y is H, OH, O-acyl, A-B is C═CH, C(β-OH)-CH 2 and ##STR34## wherein acyl is chosen from formyl, acetyl, trimethyl acetyl and triethyl acetyl.

Claim 11

A compound of the formula ##STR35## wherein R is COOH, R' is O-acyl, Y is H, A-B is C═CH, wherein acyl is chosen from formyl, acetyl, trimethyl acetyl and triethyl acetyl.

Claim 12

A compound of the formula ##STR35## wherein R is COOH, R' is O-acyl, Y is H, A-B is C═CH, wherein acyl is chosen from formyl, acetyl, trimethyl acetyl and triethyl acetyl.

Claim 13

A compound as defined in claim 1, wherein Y is H.

Claim 14

A compound as defined in claim 1, wherein R is O-pivalate and R' is O-acyl.

Claim 15

A compound as defined in claim 8, wherein A-B is C(β-OH)-CH 2 .

Claim 16

A compound as defined in claim 8, wherein Y is O-acyl.

Claim 17

A compound as defined in claim 1, wherein R is O-pivalate, R' is OH and A-B is C═CH.

Claim 18

A compound as defined in claim 1, wherein R is O-pivalate, R' is O-acyl and A-B is ##STR36##

Claim 19

A compound as defined in claim 1, wherein R' >-O-pivalate and A-B is C(β-OH)-CH 2 .

Claim 20

A compound as defined in claim 1, wherein R >-O-pivalate and R' and Y are O-acyl.

Claim 21

A compound as defined in claim 2, wherein R, R' and Y are each OH.

Claim 22

A compound as defined in claim 2, wherein R, R' and Y are each O-acyl.

Claim 23

A process of preparing a compound of the formula ##STR37## wherein R is chosen from O-pivalate, >-O-pivalate, OH, O-acyl, >-OH, >-O-acyl, ##STR38## and COOH, A-B is chosen from C(β-OH)-CH 2 , C═CH, ##STR39## and C(β-OH)-CHBr; R' is chosen from OH, O-acyl and ═0, Y is H, OH, O-acyl, ═O and O-tetrahydropryranyl ether, wherein acyl is chosen from formyl, acetyl, trimethyl acetyl and triethyl acetyl, and the Δ4, Δ5, Δ6, Δ7, and Δ8(9) dehydro analogues thereof, which process is selected from the group connsisting of (a) treating a compound of the formula ##STR40## wherein R, R' and Y are as defined above, with an oxidising agent, to form a compound of the formula (III) ##STR41## wherein R, R' and Y are as defined above, and subjecting the latter compound to a rearrangement process under hydrogenation or acidic conditions to form a compound of the formula (I) wherein the latter compound contains a 7-double bond and a 14β-hydroxy group; (b) treating a compound of the formula ##STR42## wherein R is as defined above, with an epoxidizing agent to form a compound of the formula ##STR43## treating the latter with an acetylating agent to form a compound of the formula ##STR44## and treating the latter with an acid to form the following compound of formula I ##STR45## wherein R is as defined above; (c) reducing a compound of the formula ##STR46## wherein R and R' are as defined above to form a compound of the formula ##STR47## wherein R and R' are as defined above; (d) reducing a compound of the formula ##STR48## wherein R and Y are as defined above, to form a compound of the formula I, ##STR49## wherein R and Y are as defined above and R" is H or Ac; (e) subjecting a compound of the formula ##STR50## wherein R and Y are as defined above, to hydrogenolysis, to form a compound of the formula ##STR51## wherein R and Y are as defined above, hydrogenating the latter compound to form a compound of the formula ##STR52## treating the latter with an acid or acid halide to form a compound of the formula ##STR53## wherein R and Y are as defined above, and treating the latter with a reducing agent to form a compound of the formula I, ##STR54## wherein R and Y are as defined above.

Claim 24

A process of preparing a compound of the formula ##STR37## wherein R is chosen from O-pivalate, >-O-pivalate, OH, O-acyl, >-OH, >-O-acyl, ##STR38## and COOH, A-B is chosen from C(β-OH)-CH 2 , C═CH, ##STR39## and C(β-OH)-CHBr; R' is chosen from OH, O-acyl and ═0, Y is H, OH, O-acyl, ═O and O-tetrahydropryranyl ether, wherein acyl is chosen from formyl, acetyl, trimethyl acetyl and triethyl acetyl, and the Δ4, Δ5, Δ6, Δ7, and Δ8(9) dehydro analogues thereof, which process is selected from the group connsisting of (a) treating a compound of the formula ##STR40## wherein R, R' and Y are as defined above, with an oxidising agent, to form a compound of the formula (III) ##STR41## wherein R, R' and Y are as defined above, and subjecting the latter compound to a rearrangement process under hydrogenation or acidic conditions to form a compound of the formula (I) wherein the latter compound contains a 7-double bond and a 14β-hydroxy group; (b) treating a compound of the formula ##STR42## wherein R is as defined above, with an epoxidizing agent to form a compound of the formula ##STR43## treating the latter with an acetylating agent to form a compound of the formula ##STR44## and treating the latter with an acid to form the following compound of formula I ##STR45## wherein R is as defined above; (c) reducing a compound of the formula ##STR46## wherein R and R' are as defined above to form a compound of the formula ##STR47## wherein R and R' are as defined above; (d) reducing a compound of the formula ##STR48## wherein R and Y are as defined above, to form a compound of the formula I, ##STR49## wherein R and Y are as defined above and R" is H or Ac; (e) subjecting a compound of the formula ##STR50## wherein R and Y are as defined above, to hydrogenolysis, to form a compound of the formula ##STR51## wherein R and Y are as defined above, hydrogenating the latter compound to form a compound of the formula ##STR52## treating the latter with an acid or acid halide to form a compound of the formula ##STR53## wherein R and Y are as defined above, and treating the latter with a reducing agent to form a compound of the formula I, ##STR54## wherein R and Y are as defined above.

Claim 25

A process as defined in claim 17, wherein said process comprises reducing a compound of the formula ##STR55## wherein R and Y are as defined above, to form a compound of the formula II ##STR56## wherein R and Y are as defined above the R" is H, formyl or acetyl.