GB893450A - New í~-steroids - Google Patents

New í~-steroids

Info

Publication number
GB893450A
GB893450A GB37504/60A GB3750460A GB893450A GB 893450 A GB893450 A GB 893450A GB 37504/60 A GB37504/60 A GB 37504/60A GB 3750460 A GB3750460 A GB 3750460A GB 893450 A GB893450 A GB 893450A
Authority
GB
United Kingdom
Prior art keywords
hydroxy
methyl
androstane
diketo
give
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired
Application number
GB37504/60A
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Organon Laboratories Ltd
Original Assignee
Organon Laboratories Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Organon Laboratories Ltd filed Critical Organon Laboratories Ltd
Publication of GB893450A publication Critical patent/GB893450A/en
Expired legal-status Critical Current

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07JSTEROIDS
    • C07J1/00Normal steroids containing carbon, hydrogen, halogen or oxygen, not substituted in position 17 beta by a carbon atom, e.g. estrane, androstane
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07JSTEROIDS
    • C07J75/00Processes for the preparation of steroids in general

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Steroid Compounds (AREA)

Abstract

The invention comprises (1) a process for the preparation of a D 5(10)-3 : 6-diketo-oestrene compound which comprises either treating a D 4-3 : 6-diketo-19-nor-steroid with an acid in an aprotonic solvent or treating a 3 : 6-diketo-5-hydroxy-19-nor-steroid with a dehydrating agent and subsequently, if required, with an acid in the presence of an aprotonic solvent, and (2) D 5(10)-3 : 6-diketo-oestrenes of the formula <FORM:0893450/IV (b)/1> (wherein R1 is hydroxy or acyloxy and R2 is hydrogen or a saturated or unsaturated hydrocarbon radical of at most 4 carbon atoms, or R1 and R2 together form a keto group). Suitable aprotonic solvents include hydrocarbons, such as benzene and toluene and halogenated hydrocarbons, such as chloroform, carbon tetrachloride and chlorobenzene. Inorganic or organic acids may be used, and as dehydrating agents mineral acids, formic acid or oxalic acid are prepared. In Examples (1)17a -methyl-19-nor-testosterone and acetic anhydride in presence of dinitro benzene sulphonic acid give D 3,5-3 : 17-diacetoxy - 17a - methyl - 19 - nor - androstadiene, this is reduced with sodium borohydride to give D 5 - 3 - hydroxy - 17 - acetoxy - 17a - methyl - 19 - nor-androstene, this with acetic anhydride gives the 3 : 17-diacetate, this with formic acid and hydrogen peroxide gives 3 : 5 : 6 : 17-tetrahydroxy - 17a - methyl - 19 - nor - androstane 3 : 17-diacetate-6-formate, this with Na2CO3 gives the corresponding 6-ol, this is oxidised to 3 : 5 : 17-trihydroxy-6-keto-17a -methyl-19-norandrostane 3 : 17-diacetate, this is hydrolysed and then oxidised to give 3 : 6-diketo-5-hydroxy-17 - acetoxy - 17a - methyl - 19 - nor - androstane, and this is treated with hydrogen chloride in chloroform to give D 5(10)-3 : 6-diketo-17b -acetoxy-17a -methyl-19-nor-androstene; (2) the intermediate tetrol diacetate of (1) is hydrogenolised with lithium aluminium hydride to 3:5:6:17-tetrahydroxy - 17a - methyl - 19 - nor - androstane, and this is then converted by the methods of (1) to the D 5(10)-3 : 6-diketone, which is subsequently converted to various 17-esters; the 17a -propyl, 17a -allyl and 17a -(3-butenyl) compounds are prepared similarly; (3) the 3-enol acetate of 19-nor-testosterone acetate is reacted with perphthalic acid to give D 4-3-keto-6 : 17-dihydroxy-19-nor-androstene 17-acetate, this is oxidised to the corresponding 6-keto compound and this is treated as in (1) to give the D 5(10)-3:6-diketone, which is subsequently hydrolysed to the free 17-ol and converted to various other 17 esters; (4) D 5(10)- 3: 6-diketo-17b -hydroxy-17a -ethynyl-19-nor-androstene is prepared by the method of (1) via 3 : 17-diacetoxy-5-hydroxy-6-formyloxy-17a -ethynyl-19-nor-androstane, and is then reduced to the corresponding 17a -vinyl and -ethyl compounds, from the first of which various 17-esters are subsequently prepared; (5) 3 : 17-diacetoxy - 5 - hydroxy - 6 - formyloxy - 19 - nor - androstane is prepared as in (1), hydrolysed to the corresponding 6-ol, this is oxidised to the corresponding 6-ketone, this is saponified to 3 : 5 : 17-trihydroxy-6-keto-19-nor-androstane, this is oxidised to 3 : 6 : 17-triketo-5-hydroxy-19-nor-androstane and this is converted as in (1) to D 5(10)-3 : 6 : 17-triketo-19-nor-androstene. The preparation of starting materials for the process of the invention by the above methods is also referred to in more general terms, and an extensive list of esterifying acids is provided.
GB37504/60A 1959-11-12 1960-11-01 New í~-steroids Expired GB893450A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
NL893450X 1959-11-12

Publications (1)

Publication Number Publication Date
GB893450A true GB893450A (en) 1962-04-11

Family

ID=19856009

Family Applications (1)

Application Number Title Priority Date Filing Date
GB37504/60A Expired GB893450A (en) 1959-11-12 1960-11-01 New í~-steroids

Country Status (1)

Country Link
GB (1) GB893450A (en)

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