Part 3

Absolute Rate Constants for Some Intermolecular Reactions of α-Aminoalkylperoxyl Radicals. Comparison with Alkylperoxyls

“… a 2 k t for the bimolecular self-reaction of TEAOO • . b In di- tert -butylperoxide/acetonitrile (30%/70%) containing 1 M water. c Reference , based on the TEMPO-retarded oxidation of TEA at 313 K, a problematical procedure to judge by rate constants as low as 0.2 × 10 4 M −1 s −1 reported for almost identical reactions; see ref . d Reference , ROO • = (OOCH 2 CHPh) n OO • , 303 K. e ROO • = cholesteryl pelargonate peroxyl, in chlorobenzene at 348 K; see: Aivazyan, T. M.; Vardanyan, R. L. Kinet. Katal .…”

“… c Reference , based on the TEMPO-retarded oxidation of TEA at 313 K, a problematical procedure to judge by rate constants as low as 0.2 × 10 4 M −1 s −1 reported for almost identical reactions; see ref . …”

Molecule-Induced Homolysis versus “Concerted Oxenoid Oxygen Insertion” in the Oxidation of Organic Compounds by Dimethyldioxirane

“…Reaction 12 appears to be >500 times faster than reaction 15; thus, the induced homolysis of DMD by Me • is very fast, >10 6 M -1 s -1 . If we consider that the β-scission of alkoxyl radicals 23,24 (for cumyloxyl radical, rate constants ranging from 2.6 × 10 5 to 1.9 × 10 6 s -1 at 30 °C has been reported 24 for the β-scission in several solvents) and the hydrogen abstraction by alkoxyl radicals from C-H bonds are also fast processes (for cyclohexane a rate constant of 1.0 × 10 6 M -1 s -1 has been reported), 24 the kinetic length of the radical chain of eqs 12-16 must be rather high. This means that a large quantity of DMD is consumed by small amounts of chaininitiating radicals.…”