7342-45-2Relevant academic research and scientific papers
SUBSTITUTION AT SATURATED CARBON. PART 25. THE IODODEMETALLATION OF BENZYLTRIALKYLTINS IN METHANOL
Abraham, Michael H.,Andonian-Haftvan, Jenik
, p. 819 - 830 (2007/10/02)
The action of I2/I- in methanol on compounds PhCH2SnR3 leads only to cleavage of the benzyl group (as PhCH2I) when R=Et, Prn or Bun.With PhCH2SnMe3, both benzyl and methyl groups are removed.Rate constants are reported for the iododemetallation of all four PhCH2SnR3 compounds, R=Me, Et, Prn and Bun.The present results and previous literature data show that with a constant SnR3 leaving group, the sequence of alkyl-tin reactivity is Ph>PhCH2>Me>Et>Prn, with the benzyl-tin bond being broken 3-4 times as rapidly as the methyl-tin bond and about 40 times as rapidly as the ethyl-tin bond.The effect of added anions, Cl-, Br-, I- and ClO4- on the rate constants (and products) are reported, and it is shown that both kinetic studies and product analyses lead to the conclusion that foreign anions do not participate in the reaction mechanism.These are, however, specific kinetic salt effects in the order NaBrNaClNaClO4NaI.
