567-74-8Relevant articles and documents
The scope and limitations of the reaction of Δ5-steroids with mercury(II) trifluoroacetate
Ruddock, Peter L.D.,Williams, David J.,Reese, Paul B.
, p. 650 - 664 (2007/10/03)
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. 3β-Acyloxyandrost-5-en-17-ones gave 3β-acyloxy-6β- hydroxyandrost-4-en-17-ones accompanied by 3β-acyloxy-6- chloromercuriandrost-5-en-17-ones. 3β-Acetoxy-6β-trifluoroacetoxyandrost- 4-en-17-one and 3β-acetoxy-4β-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 3α-acetoxyandrost-5-en-17-one as substrate, a complete reversal in the product distribution was observed. 3β-Haloandrost-5-en-17- ones gave mainly products that reflected S(N)1 substitution of the halide. 3β-Hydroxy- and 3β-trifluoroacetoxyandrost-5-en-17-ones were formed. 3β- Methoxyandrost-5-en-17-one afforded in nearly identical yields androst-4- ene-3,17-dione, 3β-methoxy-6β-hydroxyandrost-4-en-17-one, 3β-methoxy-6- chloromercuriandrost-5-en-17-one and 6β-hydroxyandrost-4-ene-3,17-dione while androst-5-en-17-one yielded 3β,6β-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. 3β-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.
