公开(公告)号：ZA724554B

公开(公告)日：1973-04-25

申请号：ZA724554

申请日：1972-07-03

Applicant: HOFFMANN LA ROCHE

Inventor： KRUBINER A ,  OLIVETO E

IPC: C07J5/00 ,  C07J7/00 ,  C07J13/00 ,  C07C

Abstract: A process for converting 17 alpha -vinyl-17 beta -hydroxy steroids to 17-(2-haloethylidene)-steroids, known intermediates for antifungal and progestational agents, by treating the 17 alpha -vinyl-17 beta -hydroxy steroids with vanadium tetrahalide.

公开(公告)号：ZA7204554B

公开(公告)日：1973-04-25

申请号：ZA7204554

申请日：1972-07-03

Applicant: HOFFMANN LA ROCHE

Inventor： KRUBINER A ,  OLIVETO E

IPC: C07J5/00 ,  C07J7/00 ,  C07J13/00 ,  C07C

CPC classification number: C07J13/007 ,  C07J5/0053 ,  C07J7/0045

公开(公告)号：DK123297B

公开(公告)日：1972-06-05

申请号：DK340966

申请日：1966-07-01

Applicant: HOFFMANN LA ROCHE

Inventor： OLIVETO E ,  KRUBINER A

IPC: C07D317/72 ,  C07C171/00

Abstract: The invention comprises (a) a process for preparing 3a b - methyl - 3b - (1 - hydroxy -ethyl)-benz[e] -indene derivatives, including hydrogenated derivatives thereof, by reaction of a 3-oxo-3a b -methyl-benz-[e]-indene derivative, in which any keto groups other than in the 3-position are protected, with ethylidene-triphenyl phosphorono, to form a 3-ethylidene benz-[e]-indene derivative, if desired splitting off any ketone-protecting groups present, reducing any such keto group to an hydroxy group and converting this into its C1- 7 alkyl or 2-tetrahydropyranyl ether, and treating the 3-ethylidene compound so obtained first with a source of hydroboron radicals and then, at a pH greater than 7, with hydrogen peroxide, and (b) 3-ethylidene-intermediates of formula wherein R1 is a hydrogen atom or a C1- 7 alkyl group and Z is a carbonyl group, a group wherein R3 is a C1- 7 alkylene group, or a group wherein R2 is a hydrogen atom or a C1- 7 alkyl or 2-tetrahydropyranyl group. The 3b -hydroxy-ethyl side-chain may be oxidized to a 3b -acetyl side-chain. 3a b ,6(a or b )-dimethyl-3-oxo-7,7-ethylenedioxy-5a (a or b )-9ab -9ba -perhydro-benz-[e]-indenes are prepared by ketalization of the corresponding 7-oxo-3-hydroxy-compounds to form the 3-hydroxy-7,7-ethylenedioxy derivatives, followed by oxidation with chromium trioxide. 3a b ,6b - dimethyl - 3b - hydroxy - 7 - oxo - 5ab , 9ab ,9ba -perhydrobenz-[e]-indene is prepared by catalytic hydrogenation of the corresponding 5a,6-dehydro-compound. Progesterone and 20-hydroxy-3-oxo-D 4-9b ,10a -pregnane are prepared by condensation of the corresponding des-A-5-oxo-steroid with methyl vinyl ketone.

公开(公告)号：SE335978B

公开(公告)日：1971-06-21

申请号：SE902566

申请日：1966-07-01

Applicant: HOFFMANN LA ROCHE

Inventor： KRUBINER A ,  OLIVETO E

IPC: C07J5/00 ,  C07J7/00 ,  C07J75/00 ,  C07C167/20

Abstract: The invention comprises (1) a process for preparing 20-hydroxypregnanes, 19-nor-pregnanes and 10a -pregnanes by reacting a 17-keto steroid of the androstane, 10a -androstane or estrane series, in which any other keto groups are protected, with ethylidene-triphenylphosphorane to obtain a D 17(20)-pregnane, hydroborating this, and treating the product with hydrogen peroxide at a pH greater than 7 to obtain a 20-hydroxy-pregnane, followed if desired by one or more of (a) 20-esterification or oxidation; (b) regeneration of a protected keto group; (c) 3-etherification, esterification or oxidation; or (d) a Birch reduction, with optional isomerization of the product, (11) 3-hydroxy, C1- 7 alkoxy or C1- 7 alkanoyloxy-19-nor - pregna - 1,3,5(10), 17(20) - tetraenes, and (111) 3b -hydroxy, C1- 7 alkoxy, or tetrahydropyranyloxy, or 3,3 alkylene - 9b , 10a - pregn-17(20) enes. 3,3 - Ethylenedioxy - 5b , 9b , 10a - androstan-17b -ol is prepared by conversion of 5b ,9b ,10a -androstan - 17b - ol - 3 - one to its 3 - ethylene ketal, followed by oxidation with chromium trioxide. The 19-nor-pregna-1,3,5(10)-tetraenes of the invention have estrogenic activity and may be used in pharmaceutical compositions in combination with a carrier, for example in forms suitable for oral administration.

公开(公告)号：DK117489B

公开(公告)日：1970-05-04

申请号：DK340866

申请日：1966-07-01

Applicant: HOFFMANN LA ROCHE

Inventor： KRUBINER A ,  OLIVETO E

IPC: C07J5/00 ,  C07J7/00 ,  C07J75/00 ,  C07C167/20

Abstract: The invention comprises (1) a process for preparing 20-hydroxypregnanes, 19-nor-pregnanes and 10a -pregnanes by reacting a 17-keto steroid of the androstane, 10a -androstane or estrane series, in which any other keto groups are protected, with ethylidene-triphenylphosphorane to obtain a D 17(20)-pregnane, hydroborating this, and treating the product with hydrogen peroxide at a pH greater than 7 to obtain a 20-hydroxy-pregnane, followed if desired by one or more of (a) 20-esterification or oxidation; (b) regeneration of a protected keto group; (c) 3-etherification, esterification or oxidation; or (d) a Birch reduction, with optional isomerization of the product, (11) 3-hydroxy, C1- 7 alkoxy or C1- 7 alkanoyloxy-19-nor - pregna - 1,3,5(10), 17(20) - tetraenes, and (111) 3b -hydroxy, C1- 7 alkoxy, or tetrahydropyranyloxy, or 3,3 alkylene - 9b , 10a - pregn-17(20) enes. 3,3 - Ethylenedioxy - 5b , 9b , 10a - androstan-17b -ol is prepared by conversion of 5b ,9b ,10a -androstan - 17b - ol - 3 - one to its 3 - ethylene ketal, followed by oxidation with chromium trioxide. The 19-nor-pregna-1,3,5(10)-tetraenes of the invention have estrogenic activity and may be used in pharmaceutical compositions in combination with a carrier, for example in forms suitable for oral administration.