24257-90-7Relevant articles and documents
Kinetics and Mechanism of the Reaction of Substituted Phenylhydrazones with Thallium(III) Acetate. Reactions of Mercury(II) Acetate with Nitrogen Compounds. Part 8
Butler, Richard N.,Morris, Gerard J.,O'Donohue, Anne M.
, p. 1243 - 1246 (2007/10/02)
The reaction of substituted phenylhydrazones with thallium(III) acetate in acetic acid involved an electrophilic attack at the hydrazone amino-NH moiety giving an intermediate which is attacked by solvent at the methine carbon.The Hammett ρ values for substituents in the methine and the N-phenyl rings were -1.05 and -3.6, respectively.Activation thermodynamic parameters ΔEa 17.9, ΔHa 17.2 kcal mol-1, and ΔSa -14.65 cal K-1 mol-1 were measured for p-chlorobenzaldehyde p-nitrophenylhydrazone.The main products from aromatic aldehyde arylhydrazones were N'-acetyl-N-aroyl-N'-arylhydrazines (5).The main products from ketone arylhydrazones were α-acetoxy-α-phenylazo-derivatives of the ketone (4).The unexpected divergence of reactivity of phenylhydrazones with the acatates of Hg(II), Tl(III), and Pb(IV) is discussed.
