GB809494A - Androstene derivatives - Google Patents
Androstene derivativesInfo
- Publication number
- GB809494A GB809494A GB17230/57A GB1723057A GB809494A GB 809494 A GB809494 A GB 809494A GB 17230/57 A GB17230/57 A GB 17230/57A GB 1723057 A GB1723057 A GB 1723057A GB 809494 A GB809494 A GB 809494A
- Authority
- GB
- United Kingdom
- Prior art keywords
- androstene
- hydroxy
- androsten
- dione
- dihydroxy
- 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
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
- C12P33/00—Preparation of steroids
Landscapes
- Organic Chemistry (AREA)
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Zoology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Microbiology (AREA)
- General Chemical & Material Sciences (AREA)
- Biotechnology (AREA)
- Health & Medical Sciences (AREA)
- Biochemistry (AREA)
- Bioinformatics & Cheminformatics (AREA)
- General Engineering & Computer Science (AREA)
- General Health & Medical Sciences (AREA)
- Genetics & Genomics (AREA)
- Steroid Compounds (AREA)
Abstract
The invention comprises 1a -hydroxy androstene derivatives of the formula <FORM:0809494/IV (b)/1> wherein the carbon in the 5-position is attached by a double bond to either the carbon in the 4-position or to the carbon in the 6-position, X is a carbonyl, hydroxymethylene or esterified hydroxymethylene group, Y is an hydroxy or esterified hydroxy group, and Z is a carbonyl, hydroxymethylene, esterified hydroxymethylene or =C(OH) (lower alkyl) group, the alkyl group containing at most eight carbon atoms. The hydroxyl groups may be esterified with alkanoic acids, e.g. formic, acetic, propionic, butyric, valeric, hexanoic, heptanoic and octanoic acids, their branched-chain isomers and cyclic analogues, or with alkane sulphonic acids, e.g. methane, ethane and propane sulphonic acids, forming mono-, di-, tri-esters including mixed esters. The 1a -hydroxy steroids are prepared from the corresponding 1-unsubstituted steroids or their D 1-analogues by subjecting them to the action of enzymes of Penicillium sp. ATCC 12,556 cultivated aerobically. The steroid may be added to a culture medium of the organism or treated with the separated oxygenating enzymes according to known procedures. Subsequent transformations may then be carried out, e.g. reduction of a 17-keto group with an alkali metal hydride, or reaction with an organometallic reagent to yield a 17a -alkyl-17b -ol compound, selective or complete esterification of the hydroxyl groups present, conversion to the 1b -hydroxy isomers by oxidation and then reduction of the resulting 1-oxo compound, or oxidation (Oppenauer) to a D 1,6-3-keto steroid, or direct conversion to estrone by pyrolysis. In examples: (1) D 6-androstene-3,17-dione in ethanol is added to a medium containing aerobically cultivated Penicillium ATCC 12,556 and after 40 hours the mixture is extracted with methylene chloride and chromatographed on silica, whereupon elution with ethyl acetate-benzene gives 2b -hydroxy - D 6 - androstene - 3,17 - dione and then 1a - hydroxy - D 6 - androstene - 3,17 - dione, which is converted (2) to the acetate and (3) to the butyrate; (4) 1,4-androstadiene-3,17-dione treated as in (1) yields 1a -hydroxy-4-androstene-3,17-dione; whilst (5) dehydroisoandrosterone gives mainly 1a ,3b -dihydroxy-5-androsten-17-one, which (6) to (9), is converted into its 3-monoacetate, 1,3-diacetate, 1,3-dimesylate, 1,3-di-ethanesulphonate and 1-mesylate-3-acetate; (10) reduction of 1a ,3b -dihydroxy-5-androsten-17-one with LiAlH4 gives 5-androstene-1a ,3b ,17b -triol and subsequently (11), its triacetate and tripropionate; (12) and (13), 1a ,3b -dihydroxy-5-androsten-17-one is treated with methyl or ethyl magnesium bromide yielding the corresponding 17-methyl or 17-ethyl-5-androstene - 1a ,3b ,17b - triol; (14) oxidation of 1a - hydroxy - 3b - acetoxy - 5 - androsten - 17 - one with CrO3-pyridine, and LiAlH4 reduction of the resulting 3b -acetoxy-5-androstene-1,17-dione gives 5-androstene - 1b ,3b ,17b - triol, which (15) is acetylated to the triacetate; (16) 1a ,3b - dihydroxy - 5 - androsten - 17 - one after protection of the keto group and selective acetylation of the 3-hydroxyl similarly yields 1b ,3b - dihydroxy - 5 - androsten - 17 - one and its 1-monoacetate and 1,3-diacetate.
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US809494XA | 1956-06-06 | 1956-06-06 |
Publications (1)
Publication Number | Publication Date |
---|---|
GB809494A true GB809494A (en) | 1959-02-25 |
Family
ID=22160698
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
GB17230/57A Expired GB809494A (en) | 1956-06-06 | 1957-05-30 | Androstene derivatives |
Country Status (1)
Country | Link |
---|---|
GB (1) | GB809494A (en) |
-
1957
- 1957-05-30 GB GB17230/57A patent/GB809494A/en not_active Expired
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