Abstract
The e.s.r. spectrum of the t-butoxycarbonyl σ-radical, generated by u.v. irradiation of a liquid mixture of di-t-butyl peroxide and t-butyl formate, has been observed. Decarboxylation of this radical has been monitored by kinetic e.s.r. spectroscopy and the unimolecular rate constant for the reaction But·ĊO → But·+ CO2 is given by log (k/s–1)= 13·4 – 12·1/θ where θ= 2·303 RT/kcal mol–1.These kinetic parameters differ from those reported in an earlier communication because it was assumed that the rate constants for reaction of a t-butyl radical with a t-butyl radical or with a t-butoxycarbonyl radical had the same value. This assumption has been tested experimentally and shown to be incorrect.Abstraction of hydrogen from the alkoxy-groups of alkyl carbonates gives radicals which do not decompose to form alkoxycarbonyl radicals.
Sign-in/Register to access full text options 
Talk to us
Join us for a 30 min session where you can share your feedback and ask us any queries you have
Schedule a callMore From: Journal of the Chemical Society, Perkin Transactions 2
Disclaimer: All third-party content on this website/platform is and will remain the property of their respective owners and is provided on "as is" basis without any warranties, express or implied. Use of third-party content does not indicate any affiliation, sponsorship with or endorsement by them. Any references to third-party content is to identify the corresponding services and shall be considered fair use under The CopyrightLaw.
