GB764323A - Preparation of steroid compounds - Google Patents

Preparation of steroid compounds

Info

Publication number
GB764323A
GB764323A GB30250/52A GB3025052A GB764323A GB 764323 A GB764323 A GB 764323A GB 30250/52 A GB30250/52 A GB 30250/52A GB 3025052 A GB3025052 A GB 3025052A GB 764323 A GB764323 A GB 764323A
Authority
GB
United Kingdom
Prior art keywords
keto
hydroxy
acid
diketo
ergostene
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
GB30250/52A
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.)
Merck and Co Inc
Original Assignee
Merck and Co Inc
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 Merck and Co Inc filed Critical Merck and Co Inc
Publication of GB764323A publication Critical patent/GB764323A/en
Expired legal-status Critical Current

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07JSTEROIDS
    • C07J9/00Normal steroids containing carbon, hydrogen, halogen or oxygen substituted in position 17 beta by a chain of more than two carbon atoms, e.g. cholane, cholestane, coprostane
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07JSTEROIDS
    • C07J75/00Processes for the preparation of steroids in general

Landscapes

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

Abstract

The invention comprises D 22-3-acetoxy-11-hydroxy - ergostene, D 22 - 3,11 - dihydroxy - ergostene, D 22 - 3,11 - diketo - ergostene and a process for the preparation of a cyclopentanoperhydrophenanthrene compound having at rings B and C the formula <FORM:0764323/IV(b)/1> wherein R represents a hydroxy or keto radical by reducing with a metal and a liquid medium which reacts with the metal to form hydrogen (liquids which react violently with the metal are excluded, e.g. water must not be used with sodium or potassium) a D 8(9)-cyclopentanopolyhydrophenanthrene compound having at rings B and C the structure <FORM:0764323/IV(b)/2> When R represents a hydroxy radical, the resulting compound can be oxidized to an 11-keto - cyclopentanoperhydrophenanthrene compound, e.g. with chromic acid-preferably using acetone or glacial acetic acid as the liquid medium for the oxidation reaction. Suitable metallic reducing agents for the above reduction are alkali metals such as sodium, potassium or lithium, a mercury amalgam of an alkali metal, an alkaline-earth metal such as calcium, and zinc. The 11-keto-cyclopentanoperhydrophenanthrene compounds are obtained from D 8(9)-11 keto reactants when the reduction is effected with an alkali metal in a medium consisting of a lower alkanol such as methanol, ethanol, propanol, isopropanol, butanol or amyl alcohol, or liquid ammonia. The lower alkanol can be used in admixture with liquid ammonia to form 11-hydroxy - cyclopentanoperhydrophenanthrene compounds. The lower alkanol may also be used with an inert solvent, e.g. a hydrocarbon solvent such as benzene, toluene or petroleum ether, or an ether solvent such as diethyl ether. Liquid ammonia can be used admixed with ether. It is preferred to use a liquid medium comprising a lower alkanol with a concentrated aqueous solution of a mineral acid such as concentrated hydrochloric acid when zinc is used as the metallic reducing agent. Mercury amalgam can also be used in a liquid medium comprising a lower alkanol or admixed with a hydrocarbon solvent and/or ether. The above reduction process may be modified in that the D 8(9) - cyclopentanopolyhydrophenanthrene reactant is prepared by the action of boron trifluoride on a monoepoxide of a D 7,9(11)-cyclopentanopolyhydrophenanthrene compound which may be prepared by the process claimed in Specification 764,321. The preferred D 8(9)-11-keto reactants are those having a sterol side chain attached to the carbon atom in the 17-position of the molecule such as D 8(9),22-11-keto - ergostadiene, D 8(9),22 - 3 - acyloxy - 11 - keto - ergostadiene, e.g. D 8(9),22 - 3 - acetoxy - 11 - keto - ergostadiene, D 8(9) - 3 - acyloxy - 11 - keto - cholestene, e.g. D 8(9) - 3 - acetoxy - 11 - keto - cholestene, D 8(9) - 3 - hydroxy - 11 - keto - cholestene, D 8(9)22 - 3 - acyloxy - 11 - keto - stigmastadiene, e.g. D 8(9),22-3-acetoxy-11-keto-stigmastadiene, D 8(9),22 - 3 - hydroxy - 11 - keto-stigmastadiene, D 8(9) - 3 - acyloxy - 11 - keto - cholenic acid. e.g. D 8(9)-3-acetoxy-11-keto-cholenic acid, D 8(9)-3-hydroxy-11-keto-cholenic acid, D 8(9) - 3 - acyloxy - 11 - keto - bisnorallocholenic acid, e.g. D 8(9)-3-acetoxy-11-keto-bisnorallocholenic acid, D 8(9)-3-hydroxy-11-keto-bisnorallocholenic acid, D 8(9)-3-acyloxy-11,20-diketo - allopregnene, e.g. D 8(9) - 3 - acetoxy - 11,20-diketo-allopregnene, D 8(9)-3-hydroxy-11,20 - diketo - allopregnene, D 8(9) - 11 - keto-dehydrotigogenin acylate, e.g. D 8(9)-11-keto-dehydrotigogenin acetate, and D 8(9)-11-keto-dehydrotigogenin. In the examples the following compounds are prepared:-D 22-3-hydroxy-11-keto - ergostene, D 22 - 3,11 - dihydroxy - ergostene, D 22-3,11-diketo-ergostene (two isomers believed to be the 11a - and 11b -hydroxy compounds), D 22 - 3 - acetoxy - 11 - keto - ergostene (the 3-acetoxy group may be hydrolysed with alcoholic sodium hydroxide to form a 3-hydroxy group), 11-keto-tigogenin and 11-hydroxy-tigogenin. The following compounds may also be prepared by the above reduction procedure:-D 22 - 11 - hydroxy - ergostene, D 22 - 11 - keto - ergostene, 3,11 - dihydroxy - cholestane, 3 - hydroxy - 11 - keto - cholestane, D 22-3,11 - dihydroxy - stigmastene, D 22 - 3 - hydroxy - 11 - keto - stigmastene, 3,11 - dihydroxy - cholanic acid, 3 - hydroxy - 11 - keto - cholanic acid, 3,11 - dihydroxy - bisnorallocholanic acid, 3 - hydroxy - 11 - keto - bisnorallocholanic acid, 3,11,20 - trihydroxy - allopregnane and 3 - hydroxy - 11,20 - diketo - allopregnane. The following compounds may be obtained from the optional additional oxidation step:-D 22-11-keto - ergostene, D 22 - 3,11 - diketo - ergostene, 3,11 - diketo - cholestane, D 22 - 3,11 - diketo - stigmastene, 3,11 - diketo - cholanic acid, 3,11-diketo - bisnorallocholanic acid, 3,11,20 - triketo-allopregnane and 3,11-diketo-tigogenin.
GB30250/52A 1951-12-26 1952-11-28 Preparation of steroid compounds Expired GB764323A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US764323XA 1951-12-26 1951-12-26

Publications (1)

Publication Number Publication Date
GB764323A true GB764323A (en) 1956-12-28

Family

ID=22131964

Family Applications (1)

Application Number Title Priority Date Filing Date
GB30250/52A Expired GB764323A (en) 1951-12-26 1952-11-28 Preparation of steroid compounds

Country Status (1)

Country Link
GB (1) GB764323A (en)

Similar Documents

Publication Publication Date Title
GB996080A (en) 17-monoesters of 17ª‡,21-dihydroxy steroids and process for the preparation thereof
GB929271A (en) Steroids and their production
GB764323A (en) Preparation of steroid compounds
US3077482A (en) 19-oxygenated steroids and process for their manufacture
US2798082A (en) Delta22-11-oxygenated-steroids and process of preparing them
GB1146992A (en) Improvements in or relating to novel steroids and the manufacture thereof
GB931222A (en) Steroid compounds
US3079407A (en) 16-trihalomethyl steroids
GB996079A (en) 17ª‡,21-substituted methylenedioxy steroids and methods therefor
US3450720A (en) 3-difluoromethylene steroids
GB1148618A (en) (optionally 17-alkylated) 17-oxygenated 7-methyl-5ª‡-androst/estr-2-enes
GB957581A (en) Steroid compounds
GB887815A (en) Steroids
GB805585A (en) Steroid compounds
GB739597A (en) Steroid ketals
US3499014A (en) 17-hydroxyalkynylation process
GB877585A (en) Improvements in or relating to steroids and the manufacture thereof
GB796768A (en) Manufacture of derivatives of 5-pregnene-3,17ª‡-diol-20-ones
GB768648A (en) Cyclopentanopolyhydrophenanthrene compounds
GB991473A (en) New steroid compounds, processes for their production and their conversion into therapeutically-valuable substances
GB1015016A (en) New steroid compounds and processes
GB1014656A (en) New oxido-steroids and a process for their manufacture
GB957542A (en) Cycloalkenyl ethers of 17ª‰-hydroxy androstanes
GB991474A (en) Novel steroid compounds and their preparation
GB811961A (en) New biologically-active steroid compounds and process for the preparation thereof