| 摘要 |
1,257,522. 16α-Alkyl steroids. ORGANON LABORATORIES Ltd. 28 Jan., 1969 [1 Feb., 1968], No. 4715/69. Heading C2U. Novel compounds of formula wherein R 1 is H or CH 3 , R 2 is OH, OAcyl or F, R 3 is H(OH), H(OAcyl) or oxo, R 4 is C 2-4 alkyl, and the 6,7-bond may be saturated or unsaturated, are prepared from 16α-(C 2 _ 4 alkyl)-progesterones or -19-norprogesterones or the corresponding 3 - (hydroxy or acyloxy) - 5 - enes by conventional conversions (many being described) at the 20- and 21-positions followed, where appropriate, by conversion of a 3- (hydroxy or acyloxy)-5-ene group to a 3-oxo-4- ene group, and, when required, by #<SP>6</SP>-dehydrogenation. In addition, 19-nor-pregnenes of Formula I may be prepared from 3-acyloxy-16α- alkyl - pregn - 5 - en - 20 - ones by successively introducing 5α- halo - 6,19 - epoxy and 21- acyloxy groupings and then converting the former grouping to produce a #<SP>4</SP>-3-oxo-19-norpregnene. Compounds of Formula I are said to possess strong progestative, ovulation-inhibiting and pregnancy-maintaining properties. 16α- Ethyl - 21,21 - diiodo - pregn - 4 - ene- 3,20-dione is prepared from 16α-ethyl-progesterone with iodine and calcium chloride (Example 16α- Ethyl - 21 - iodopregn - 4 - ene - 3,20- dione is prepared from 16α-ethyl-21-hydroxypregn - 4 - - ene - 3,20 - dione via the 21 - mesylate of the latter (Example 5). 16α- Ethyl - 21 - iodo - 19 - norpregn - 4 - ene- 3,20-dione is prepared from 16α-ethyl-21-hydroxy - 19 - norpregn - 4 - ene - 3,20 - dione via the 21-mesylate of the latter (Example 7). 3,20 - Dioxo - 16α- ethyl - 21 - acetoxy - pregn- 4-en-19-al (III) is prepared from 3#-acetoxy- 16α- ethyl - pregn - 5 - en - 20 - one (II) by the sequence : II # 3# - acetoxy - 5 - bromo - 6#- hydroxy - 16α- ethyl - 5α- pregnan - 20 - one # 3# - acetoxy - 5 - bromo - 6#,19 - epoxy - 16α- ethyl - 5α- pregnan 20 - one # 3# - hydroxy- 5 - bromo - 6#,19 - epoxy - 16αethyl - 5α- pregnan - 20 - one # 3# - hydroxy - 5,21- dibromo - 6#,19 - epoxy - 16α- ethyl - 5α- pregnan- 20 - one # 3# - hpdroxy - 5 - bromo - 6#,19- epoxy - 16α- ethyl - 21 - acetoxy - 5α- - pregnan- 20 - one # 6#,19 - epoxy - 16α- ethyl - 21- acetoxypregn - 4 - ene - 3,20 - dione # 16α- ethyl 19 - hydroxy - 21 - acetoxypregn - 4 - ene- 3,20-dione # III (Example 6). 3 - Ethoxy - 16α- ethyl - 19 norpregna - 3,5- diene-20,21-diol is prepared from 16α-ethyl-21- hydroxy - 19 - norpregn - 4 - ene - 3,20 - dione via 3 - ethoxy - 16α- ethyl - 21 - hydroxy - 19- norpregna-3,5-dien-20-one (Example 8). |
