GB841870A - Improvements in or relating to 6-methyl steroids - Google Patents
Improvements in or relating to 6-methyl steroidsInfo
- Publication number
- GB841870A GB841870A GB1414157A GB1414157A GB841870A GB 841870 A GB841870 A GB 841870A GB 1414157 A GB1414157 A GB 1414157A GB 1414157 A GB1414157 A GB 1414157A GB 841870 A GB841870 A GB 841870A
- Authority
- GB
- United Kingdom
- Prior art keywords
- methyl
- give
- ene
- hydroxy
- acid
- 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
- C07—ORGANIC CHEMISTRY
- C07J—STEROIDS
- C07J71/00—Steroids in which the cyclopenta(a)hydrophenanthrene skeleton is condensed with a heterocyclic ring
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07J—STEROIDS
- C07J1/00—Normal steroids containing carbon, hydrogen, halogen or oxygen, not substituted in position 17 beta by a carbon atom, e.g. estrane, androstane
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07J—STEROIDS
- C07J53/00—Steroids in which the cyclopenta(a)hydrophenanthrene skeleton has been modified by condensation with a carbocyclic rings or by formation of an additional ring by means of a direct link between two ring carbon atoms, including carboxyclic rings fused to the cyclopenta(a)hydrophenanthrene skeleton are included in this class
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07J—STEROIDS
- C07J75/00—Processes 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 6-methyl-25D-spirost-5-en-3 b -ol and the 3b -acyloxy derivatives thereof; 6 - methylandrost - 5 - ene - 3b :17b - diol; 17 a - ethynyl - 6 - methylandrost - 5 - ene - 3b : 17b - diol; 17b - acetoxy - 6#x - methyl - 3:5-cycloandrostan-6#x-ol; 17 a -ethynyl-6#x-methyl-3:5-cycloandrostane-6#x:17b -dioland 6#x-hydroxyl-6#x - methyl - 3:5 - cyclopregnan - 20 - one; and a method for the preparation of a 3b - hydroxy - 6 - methyl - D 5 - steroid of the androstane, pregnane or spirostane series by oxidizing the corresponding 6b -hydroxy- or 6b -acyloxy-3:5-cyclo-steroid to a 6-oxo-3:5-cyclo-steroid, treating this with a methyl organometallic reagent to give a 6#x-hydroxy-6#x-methyl-3:5-cyclosteroid and rearranging this with an acid. The oxidation of the 6b -hydroxy-steroid is advantageously effected with chromium trioxide, sodium dichromate, N-bromoacetamide or pyridine/chromic acid, while the 6b -acyloxysteroid may be directly oxidized with chromic acid. Grignard reagents are the preferred organometallic reagents, and the rearrangement may be effected either by treatment with a source of hydrogen ions e.g. sulphuric acid, in an aliphatic acid containing at most 5 carbon atoms to give the 3b -acyloxy-6-methyl- D 5-steroid which is subsequently hydrolysed with aqueous ethanolic alkali, or by use of the source of hydrogen ions in an aqueous organic solvent to give the 3b -hydroxy compound direct. The 3b -acetoxy compounds may alternatively be obtained by the use of a Lewis acid such as boron trifluoride in acetics-anhydride. Primary or secondary hydroxyl groups are protected prior to the oxidation stage e.g. by acylation, and oxo groups are protected by ketal formation or reduction, with subsequent regeneration. In examples (1) 3b -hydroxy-25D-spirost-5-ene and toluene-p-sulphonic acid in pyridine give 3b -toluene-p-sulphonyloxy-25D-spirost-5-ene, this is refluxed with potassuim acetate in water to give 3:5-cyclo-25D-spirostan-6b -ol and this is treated according to the process of the invention to give successively, the 6-one, the 6#x-methyl-6#x-ol, 3b -acetoxy-6-methyl-25D-spirost-5-ene and, finally, the corresponding 3b -ol; (2) 6b :17b -diacetoxy-3:5-cycloandrostane gives by the process of the invention, the 6-one, the 6#x-methyl-6#x-ol (after acetylation of the initially obtained 17b -ol), 3b -17b - diacetoxy - 6 - methylandrost 5-ene and finally the corresponding 3b :17b -diol; (3) 3:5 - cyclo - 17a - ethynyl - androstane - 6b -17b - diol gives, by the process of the invention, the 6-one (2:4 - dinitrophenylhydrazone described), the 6#x-methyl-6#x-ol, 3b -acetoxy-17 a - ethynyl - 6 - methylandrost - 5 - ene-17b -ol and, finally, the corresponding 3b -ol; and (4) 6b -hydroxy-3:5-cyclopregnan-20-one is reduced and acetylated to give 6b :20#x-diacetoxy-3:5-cyclopregnane, this is oxidized, the product converted to its semicarbazone and then decomposed with pyruvic acid and acetic acid to give 20#x-acetoxy-3:5-cyclopregnan-6-one, this with a Grignard reagent gives 6#x-methyl-3:5-cyclopregnane-6#x:20#x-diol, this is oxidized to the corresponding 20-one and this is treated according to the last stage of the process of the invention to give 3b -acetoxy-6-methylpregn-5-en-20-one In the Provisional Specification reference is also made to other 17 a -alkynyl-17b -hydroxy3:5-cycloandrostan-6b -ols and their conversion to the corresponding 17 a -alkynyl-6-methyl-androst-5-ene-3b :17b -diols by the process of the invention.
Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GB1414157A GB841870A (en) | 1957-05-03 | 1957-05-03 | Improvements in or relating to 6-methyl steroids |
CH5908058A CH366533A (en) | 1957-05-03 | 1958-05-03 | Process for the preparation of 3ss-oxy-6-methyl-5-steroids |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GB1414157A GB841870A (en) | 1957-05-03 | 1957-05-03 | Improvements in or relating to 6-methyl steroids |
Publications (1)
Publication Number | Publication Date |
---|---|
GB841870A true GB841870A (en) | 1960-07-20 |
Family
ID=10035755
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
GB1414157A Expired GB841870A (en) | 1957-05-03 | 1957-05-03 | Improvements in or relating to 6-methyl steroids |
Country Status (1)
Country | Link |
---|---|
GB (1) | GB841870A (en) |
-
1957
- 1957-05-03 GB GB1414157A patent/GB841870A/en not_active Expired
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