Steroids 49. Investigations on the dehydration of 17 alpha-ethynyl-17 beta-hydroxysteroids.
The acidic dehydration of 17 alpha-ethynyl-17 beta-hydroxysteroids (1-3) was investigated. On reaction with thionyl chloride, phosphorus oxychloride, and formic acid, the desired dehydration was accompanied by chlorination, Wagner-Meerwein rearrangement, and D-homoaromatic rearrangement. The structure of the product from the transformation of 17 beta-hydroxypregn-20-yne derivative (3) on reaction with formic acid was misjudged. It was regarded as a pregn-16-en-20-yne (10) instead of the actually rearranged D-homoaromatic compound (11). As a consequence, physical data corresponding to this latter structure have been cited in the literature as those of pregn-16-en-20-yne derivative (10). This confusion prompted us to prepare compounds of both types (4, 9, 10, and 11), the characterization of which is here described.
Vincze
I
I
Department of Organic Chemistry, Attila József University, Szeged, Hungary.
Lökös
M
M
Bakos
T
T
Dancsi
A
A
Mák
M
M
D005003:Ethisterone / Q000737:chemistry*; D005561:Formates / Q000737:chemistry; D007202:Indicators and Reagents; D009682:Magnetic Resonance Spectroscopy; D008656:Mestranol / Q000737:chemistry*; D015394:Molecular Structure; D009640:Norethindrone / Q000737:chemistry*; D010758:Phosphorus / Q000737:chemistry; D017553:Phosphorus Compounds; D013461:Sulfur Oxides / Q000737:chemistry; D014867:Water / Q000737:chemistry*
D005561:Formates; D007202:Indicators and Reagents; D017553:Phosphorus Compounds; D013461:Sulfur Oxides; D014867:Water; C030544:formic acid; D010758:Phosphorus; C023589:thionyl chloride; C013196:phosphoryl chloride; D008656:Mestranol; D005003:Ethisterone; D009640:Norethindrone