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Absolute Rate Constants for Alkoxycarbonyl Radical Reactions
journal contribution
posted on 1998-01-30, 00:00 authored by Pavel A. Simakov, Felix N. Martinez, John H. Horner, Martin NewcombPTOC oxalates (anhydrides of an oxalic acid monoester and
N-hydroxypyridine-2-thione) were used
in laser flash photolysis (LFP) kinetic studies. Irradiation of
the PTOC oxalates gave the following
alkoxycarbonyl radicals ROC(·)O: 2a, R =
PhCH2; 2b, R =
(trans-2-phenylcyclopropyl)methyl;
2c, R = (2,2-diphenylcyclopropyl)methyl. Rate
constants for decarboxylation of radical 2a
measured
by LFP were in agreement with those obtained previously by indirect
kinetic methods. Rate
constants for decarboxylation of radical 2c were measured by
LFP over the temperature range
3−48 °C; the reaction is described by log k =
12.2−9.6/2.3RT (kcal/mol). Reactions of
Bu3SnH
with radical 2c produced from the corresponding phenylseleno
carbonate gave inconsistent kinetic
results apparently due to the production of small amounts of PhSeH that
reacted rapidly with 2c.
An approximate rate constant at 2 °C for reaction of
Bu3SnH with 2c produced from the
PTOC
oxalate was obtained. Tin hydride reacts with the alkoxycarbonyl
radical approximately 1 order
of magnitude less rapidly than it reacts with alkyl radicals. Rate
constants for 5-exo cyclizations
of simple alkoxycarbonyl radicals were estimated from previous results
and the approximate rate
constant for tin hydride trapping; the cyclizations are slightly faster
than 5-exo cyclizations of
structurally related alkyl radicals.