137252-02-9Relevant articles and documents
Thermolysis of α-hydroperoxyalkyl diazenes. Spin trapping of radical intermediates and spin trapping kinetics
Mathew, Lukose,Osei-Twum, Emmanuel Y.,Warkentin, John
, p. 1398 - 1402 (2007/10/02)
α-Hydroperoxyalkyl diazenes (Me2C(OOH)N=NR, 1, R = CH2CF3, CH2CH2OMe, CH(Me)2, CMe3, CH2Ph, Ph, CH2CH2OPh, and c-C3H5CD2) decompose in benzene, at 50 deg C or less, by a mechanism involving free radical (R*) intermediates.The radicals were trapped with 1-methyl-4-nitroso-3,5-diphenylpyrazole, 2, to afford spin adducts (nitroxyls) that were observed by ESR spectroscopy.When the solvent was ethyl vinyl ether, radicals from 1 (R = CH2CH2OPh) were trapped by the solvent and the adduct radicals so formed were spin trapped by 2.These observations support free radical mechanisms for thermolysis of 1 and for the hydroxyalkylations that occur when 1 are decomposed in solutions containing enol ethers or other unsaturated substrates.The ring-opening of cyclopropylmethyl radicals (cpm) to 3-butenyl radicals was used to estimate the rate constant for radical trapping by 2.For cpm the rate constant is given by log kcpm = (10.7 +/- 0.4) - (3.9 +/- 0.5)/Θ where Θ = 2.3 RT kcal mol-1.At 25 deg C, the spin trapping rate constant has the value 6.9 x 107 M-1 s-1. Key words: hydroperoxyalkyl diazenes; radicals, spin trapping; spin trapping, rate constant.