Japanese Patent JPS4911696

B1

1,255,950. 18-Methylene steroids. CIBAGEIGY A.G. 20 Dec., 1968 [22 Dec., 1967; 25 Nov., 1968], No. 60763/68. Heading C2U. 18-Methylene steroids are prepared (1) by heating N-oxides of tertiary 18-aminomethyl steroids; or (2) by splitting 18-sulphonic acid esters of 18,20-dihydroxy-18a, 20-cyclo-18- homo-pregnene compounds with a strong base (the products being 18-methylene-20-oxo-pregnane compounds); or (3) by reacting 18-oxosteroids with a reactive methylene phosphorane. Products of the androstane and 19-nor-androstane series and those of the formulµ wherein X is H or CH 3 and R is H or a free or esterified OH group, and in which in Formula (I) the A6 and, in 10-methyl compounds, the #1 double bonds are optional, and in Formula (III) Y 1 is H(OH) or free or ketalized oxo and Y 2 is free or ketalized oxo and which contain a #4 or a #5-double bond, excluding 18-methyleneprogesterone, are novel. In the above processes functional groups may be protected and subsequently released, and in the products hydroxyl and oxo groups may be interconverted, the former may be esterified, a 17-oxo group may be converted to a 17α-hydrocarbyl- 17#-hydroxy group, and double bonds may be introduced. N-oxides of tertiary 18-aminomethyl steroids are prepared by alkylation and oxidation of 18-aminomethyl steroids (prepared by reduction of 18-cyano-steroids). 1 8-Sulphonic esters of 18,20-dihydroxy- 1 8a,20- cyclo- 18-homopregnane compounds are prepared by the following process (where R is alkyl or aryl). #5 - 3 - # acetoxy - 18 - cyano - 20,20 - ethylenedioxypregnene is prepared by ketalizing 18- cyanopregnerolone acetate. #5(10)-3,3,20,20- bismethylenedioxy - 18 - oxo - 19 - norpregnene is prepared from 3#-acetoxy-5α-chloro-6#,20#. dihydroxypregnane-18-acid (prepared by addition of HOCl to the corresponding #5-compound) via the 18,20-lactone of 3#-acetoxy-5α.-chloro- 6#,19 - oxido - 20# - hydroxypregnane 18 - acid, the corresponding 3#-ol, the corresponding 3-one, the lactone of #4-3-oxo-6#19-oxido-20#-hydrozy pregnane-18-acid, the 18,20-lactone of #4-3-oxo- 19,20# - dihydroxy - pregnene - 18 - acid, the 18,20 - lactone of #5(10)- 3 - oxo - 20# - hydroxy- 19 - norpregnene - 18 - acid, the 18,20 - lactone of #5(10)- 3,3 - ethylenedioxy - 20# - hydroxy- 19 -norpregnene - 18 - acid and the methyl ester of #5(10)- 3,3 - ethylenedioxy - 20 - oxo - 19 - norpregnene-18-acid and other un-named intermediates. 3# - Benzoyloxy - 17,17 - ethylenedioxy - 18 - oxo - 5α - androstane is prepared from 3# - benzoyloxy - 18,20# oxido - 5α - pregnane via 3# - benzoyloxy - 18 - acetoxy - 20α - bromo- 5α - pregeane and 3# - benzoyloxy - 18 - acetoxy- 17 - oxo - 5α - androstane, and other unnamed intermediates. The 18-methylene steroids of the invention variously have gestagenic, anti-ovulatory, androgenic and anabolic activity, and they may be made up into pharmaceutical and veterinary compositions with suitable carriers.

ANNER G
KALVODA J

JP2752072A

March 19, 1974

March 21, 1972

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CIBA GEIGY AG (CH)

A23K1/165; A61K31/568; A61K31/57; C07J1/00; C07J7/00; C07J31/00; C07J41/00; C07J75/00; C12P33/02; B05B3/00; (IPC1-7): C07C169/34

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