Patent GB-982921-A (GB)
Title: New oxido-steroids and seco-steroids and process for their manufacture
IPC: C07J75/00
Filed: 1961-03-02
Abstract: The invention comprises (1) 1,11a -oxido-steroids and their preparation by treating 1-unsubstituted 11a -hydroxy-steroids which contain no other free hydroxyl groups with oxidizing metal acylates; and (2) 9,11-seco-11-nor-3-oxosteroids of the pregnane series.  The secosteroids are by-products in the reaction with metal acylates, the starting materials for which may be of the cholane, cholestane, coprostane, spirostane, furostane, cardanolide, pregnane, androstane or 19-nor-androstane series. These compounds may contain esterified or etherified hydroxyl groups (which may subsequently be hydrolysed), free or ketalized oxo groups, esterified or lactonized carboxyl groups, alkyl groups or halogen atoms as substituents in the steroid nucleus or the 17-side chain.  They may also contain double bonds, especially starting from carbon atom 5.  In the oxido products D 5-3-ketals may be reacted with mild acids to give D 5-3-ketones, while in the seco products the more usual D 4-3-ketones are formed by this process.  20-Ketal groups may be hydrolysed during the oxidation process or subsequently. Examples are given and the conversion of 3-oxygenated 18,20 - lactones of 1,11a  - oxido - 20 - hydroxy - pregnane - 18 - acids into the corresponding 1 - dehydro - 18,20 - lactones of 20 - hydroxy - pregnene - 18 - acids is also described. Also referred to is the preparation of 1-dehydro-aldosterone by converting the 18,20-lactone of 3-oxo-11a ,20b -dihydroxy-D 1,4 -pregnadiene-18-acid into the 11b ,18-lactone of 3 - oxo - 11b ,20b - dihydroxy - D 1,4 - pregnadiene -18-acid, oxidizing this to the 20-ketone, introducing a 21-acyloxy group, ketalizing the 20-oxo group, reducing with lithium aluminium hydride, selectively re-oxidizing the 3-hydroxyl group, and hydrolysing the 20-ketal.  The preparation of D 1,3,5(10)-3,11a ,17b -trihydroxy - 17a  - methyl - oestratriene by treatment of D 5 - 3 - oxo - 1a ,11a  - oxido - 17b - hydroxy -17a  - methyl - 19 - nor - androstene with acetic acid and sodium acetate is also described.  D 5 - 3,20 - bisethylenedioxy - 11a  - hydroxypregnene is prepared by ketalizing 11a -hydroxyprogesterone. 3,20 - Bisethylenedioxy - 11a  -hydroxy - 21 - acetoxy - 5b  - pregnane is prepared by ketalizing the corresponding dione. 3,20-Bisethylenedioxy - 11a  - hydroxy - 5a  - and 5b  - pregnanes are obtained from the corresponding 3a - and 3b ,11a -diacetoxy-20-oxo-compounds by partial hydrolysis, oxidation, ketalization and hydrolysis.  D 5 - 3 - Ethylenedioxy - 11a  - hydroxy - 17b  - acetoxy - 17a  - methyl - androstene is prepared by acetylating and ketalizing D 4-3-oxo - 11a ,17b  - dihydroxy - 17a  - methyl - androstene to give D 5 - 3 - ethylenedioxy - 11a ,17b -diacetoxy - 17a  - methyl - androstene and partially hydrolysing this.  The 18,20-lactone of D 5-3-ethylenedioxy - 11 - oxo - 20b  - hydroxy - pregnene-18-acid is obtained as a by-product in the treatment of the corresponding 11a -ol with lead tetra-acetate.  D 5-3-ethylendioxy-11a -hydroxy-17b  - acetoxy - 17a  - methyl - 19 - nor - androstene is prepared from 11a -hydroxy-19-nor-methyl-testosterone. 3,20 - Dioxo - 11a  - hydroxy - 5a  -pregnane is prepared from 3b ,11a  - diacetoxy-20 - oxo - 5a  - pregnane by ketalization, alkaline hydrolysis, oxidation and ketal splitting.  Specification 982,922 is referred to.