The scope and limitations of the reaction of delta 5-steroids with mercury(II) trifluoroacetate.
The effect of the C-3 substituent on the reaction of androst-5-enes with mercury(II) trifluoroacetate in dichloromethane (modified Treibs oxidation) was investigated. 3 beta-Acyloxyandrost-5-en-17-ones gave 3 beta-acyloxy-6 beta-hydroxyandrost-4-en-17-ones accompanied by 3 beta-acyloxy-6-chloromercuriandrost-5-en-17-ones. 3 beta-Acetoxy-6 beta-trifluoroacetoxyandrost-4-en-17-one and 3 beta-acetoxy-4 beta-trifluoroacetoxyandrost-5-en-17-one were revealed to be intermediates in the reaction. The formation of the chloromercury steroids indicated participation in the reaction by the solvent. With 3 alpha-acetoxyandrost-5-en-17-one as substrate, a complete reversal in the product distribution was observed. 3 beta-Haloandrost-5-en-17-ones gave mainly products that reflected SN1 substitution of the halide. 3 beta-Hydroxy- and 3 beta-trifluoroacetoxyandrost-5-en-17-ones were formed. 3 beta-Methoxyandrost-5-en-17-one afforded in nearly identical yields androst-4-ene-3,17-dione, 3 beta-methoxy-6 beta-hydroxyandrost-4-en-17-one, 3 beta-methoxy-6-chloromercuriandrost-5-en-17-one and 6 beta-hydroxyandrost-4-ene-3,17-dione while androst-5-en-17-one yielded 3 beta,6 beta-dihydroxyandrost-4-en-17-one, androst-5-ene-7,17-dione and androst-4-ene-3,17-dione. The effects of solvent and other mercury salts on the reaction were also studied. Treibs oxidation was successful in chloroform, carbon tetrachloride, and dibromomethane, but not in other solvents tested. 3 beta-Acetoxy-6-bromomercuriandrost-5-en-17-one was obtained in dibromomethane. Replacement of the reagent by mercury(II) trichloroacetate altered the intermediates formed but not the products. Mercury(II) tribromoacetate was unreactive, however.
Ruddock
P L
PL
Chemistry Department, University of the West Indies, Mona, Kingston, Jamaica.
Williams
D J
DJ
Reese
P B
PB
D000736:Androstenes / Q000737:chemistry*; D007202:Indicators and Reagents; D009682:Magnetic Resonance Spectroscopy; D017669:Mercury Compounds / Q000737:chemistry; D015394:Molecular Structure; D010084:Oxidation-Reduction; D013055:Spectrophotometry, Infrared; D014269:Trifluoroacetic Acid / Q000737:chemistry*
D000736:Androstenes; D007202:Indicators and Reagents; D017669:Mercury Compounds; D014269:Trifluoroacetic Acid