Rate constants for the decarboxylation of the t ‐butoxicarbonyl radical and concurring radical terminations directly obtained by kinetic ESR
1986; Wiley; Volume: 18; Issue: 2 Linguagem: Inglês
10.1002/kin.550180202
ISSN1097-4601
Autores Tópico(s)Free Radicals and Antioxidants
ResumoAbstract Rate constants of various simultaneous reactions of t ‐butoxicarbonyl and t ‐butyl radicals generated by photolysis of t ‐butylpivalate in n ‐heptane are directly determined by kinetic electron spin resonance. The temperature dependence of the decarboxylation reaction t ‐BuOĊO → t ‐Bu . + CO 2 obeys log ) K /S −1 ( = 13.8−49.0/θ where θ = 2.303 RT /kJ . mol −1 . The self‐ and cross‐termination of the radicals are diffusion limited.
Referência(s)