Irradiation of dienol acetates derived from testosterone and 4-methyltestosterone with a low pressure mercury lamp is described. The irradiation involves acetyl rearrangement from oxygen at C-3 to the carbon at C-4 and C-6. Thus androsta-3,5-diene-3,17β-diol diacetate (1) resulted in 2 and 8; 4α-methylandrosta-3,5-diene-3,17β-diol diacetate (13) yielded the corresponding 4-methyl homologs 14 and 15. The chemistry and stereochemistry of the isolated products support the previously postulated cage mechanism and stereoelectronic control for this photochemical reaction. 1b The stability relations of the 6-acetyltestosterone epimers are discussed and compared with those of the corresponding epimeric saturated derivatives. The unusual stability of the 6β-acetyl-testosterone is explained by electronic factors.
|Number of pages||6|
|Journal||Journal of the American Chemical Society|
|State||Published - 1 Dec 1964|
ASJC Scopus subject areas
- Chemistry (all)
- Colloid and Surface Chemistry