Ambident nucleophiles : V. Mercury(II) derivatives of diethyl malonate, ethyl acetoacetate, ethyl cyanoacetate, and malononitrile

Abstract

Mercury(II) oxide reacts with diethyl malonate, ethyl acetoacetate and ethyl cyanoacetate, but not with malononitrile to give the mercurycarbon bonded derivatives Hg[CH(COOEt)R] 2 (R = COOEt, COMe and CN, respectively). Mercury(II) bromide and mercury(II) acetate, as well as mercury(II) chloride, react with diethyl malonate, ethyl acetoacetate, adn acetylacetone to yield the gem-disubstituted species (XHg) 2C(COR 1)COR 2 (X = Cl, Br, MeCOO; R 1, R 2 = Me, OEt): ethyl cyanoacetate and malononitrile react with the chloride and acetate, but not the bromide, or mercury(II), to yield the gem-disubstituted species (XHg) 2C(CN)R (X = Cl, MeCOO; R = COOEt, CN).