C(10)-C(19) bond cleavage reaction of 19-oxygenated androst-4-ene-3,6-dione steroids under various conditions.
C(10)-C(19) bond cleavage reaction of 19-hydroxy- and 19-oxoandrost-4-ene-3,6,17-triones (5, 6) was explored under various conditions. Treatment of steroids 5 and 6 with KOH in MeOH gave the A-ring aromatized product 6-oxoestrone (11) in a fair yield, respectively, in contrast, the treatment with a weak base yielded 4-methyl steroid 17 (20%) in the case of 19-alcohol 5 or 19-nor-Delta(5(10))-steroid 9 (12-67%) along with compound 11 (6-27%) in the case of 19-aldehyde 6. Reaction of compound 6 with HCl in MeOH produced 3-methyl ethers of 6-oxoestrone and Delta(6)-estrone, compounds 12 and 14 (ca. 20% each). Thus, 6-oxosteroids 5 and 6 showed unique C(10)-C(19) bond cleavage reactions with a base or acid.
Tohoku Pharmaceutical University, Sendai, Japan.
Masao
M
Nagaoka
Mitsuteru
M
Numazawa
D000447:Aldehydes / Q000737:chemistry; D000735:Androstenedione / Q000031:analogs & derivatives* / Q000737:chemistry* / Q000378:metabolism; D001141:Aromatase / Q000378:metabolism; D002244:Carbon / Q000737:chemistry*; D004970:Estrone / Q000737:chemistry; D006851:Hydrochloric Acid / Q000737:chemistry; D006878:Hydroxides / Q000737:chemistry; D015394:Molecular Structure; D017680:Potassium Compounds / Q000737:chemistry
D000447:Aldehydes; D006878:Hydroxides; D017680:Potassium Compounds; D004970:Estrone; D000735:Androstenedione; D002244:Carbon; C014142:19-oxo-delta(4) androstene-3,17-dione; D001141:Aromatase; D006851:Hydrochloric Acid; C029943:potassium hydroxide