Substituent Effects in the Oxythallation of Alkenes

Abstract

<jats:p>The rate constants for oxythallation of alkenes have been correlated with their experimental and calculated ionization potentials respectively. A good correlation between the rate constants and the ionization potentials of alkenes was found. It was found that inductive effects were the most important in the oxythallation of RCH=CH<jats:sub>2</jats:sub> and R<jats:sup>1</jats:sup>R<jats:sup>2</jats:sup>C=CH<jats:sub>2</jats:sub> alkenes</jats:p>

Comparative reactions of nitrogen compounds with the isoelectronic series mercury(II), thallium(III), and lead(IV) acetates. Principles of oxidation reactions

“…Orbital control of Hg2A attack on carbon nucleophiles has been suggested with pyridine iV-oxide where mercuration occurs at the softer 2-position giving compound 7.71b Correlations of the 7 8 reaction rates of Hg2A, TTA, and LTA with ionization potentials of alkenes and with the inverse of the HOMO-LUMO gap have been noted suggesting significant orbital control. 72 In this context it is of interest that the reaction of Hg2A with phenylhydrazones gave the products 8 in a regiospecific reaction73 which is quite different from those of TTA and LTA. However, it is relevant that metallo intermediates can sometimes be isolated from Hg2A reactions with nitrogen compounds and in these the mercury is generally bonded to the harder site.…”

“…(71) with LTA in benzene under reflux gave the rearranged products73 and 74 (Scheme XVII) 121. The relative migratory aptitudes for p-Y-C6H4 and Ph varied from 0.39 for p-N02 to 152 for p-MeO and a pathway(72) involving a concerted electron deficient migration of the aryl group with elimination of lead diacetate and acetate ion from an TV-lead intermediate has been…”