20327-65-5Relevant articles and documents
Isotopomer Distributions of Neutral Products from a Doubly Labeled Cation in the Gas Phase. Interconversion of 1-Fluoro-1-propyl Cation and 1-Fluoroisopropyl Cation on the C3H6F+ Potential Energy Surface
Shaler, Thomas A.,Morton, Thomas Hellman
, p. 6771 - 6779 (2007/10/02)
The title cations CH3CH2CHF+ (3) and CH3CHCH2F+ (4) are formed as transient intermediates in the gas phase.These are labile on the millisecond timescale as free ions but can be intercepted in ion-neutral complexes.When 3 is generated as free cation by reaction of CF3+ with propionaldehyde, it rearranges to (CH3)2CF+ (1), as shown by recovery of 2-fluoropropene as a neutral product from its deprotonation in an EBFlow experiment.The same neutral product is recovered when 1 is produced directly by reaction of acetone with CF3+ in the EBFlow.Neutral productsindicative of 3 and 4 (allyl fluoride and 1-fluoropropene) are recovered when these cations are formed in + PhO.> ion-neutral complexes by electron bombardment of CH3CDFCH2OPh (6).Analysis of the isotopic distribution in the recovered neutrals from EBFlow radiolysis of CH3CDF*CH2OPh (where the asterisked carbon is 13C-labeled) allows an assessment of the primary rearrangement pathways.The distribution of label is assayed by using 19F NMR.Rearrangement of the R+ moiety to form deuterated 1 occurs in about half of the complexes formed.In the remainder, methyl transfer (to form deuterated 3) is 2-3 times faster than fluoride transfer (to form deuterated 4).Scrambling of deuterium in the neutral products provides evidence that 3 and 4 interconvert within the ion-neutral complexes.
Bestimmung der Geschwindigkeitskonstanten der Reaktion von 1CH2 mit Fluor- und Chlorethen
Simon, F. G.,Heydtmann, H.
, p. 543 - 545 (2007/10/02)
The rate constants for the addition of 1CH2 to fluoroethene and chloroethene have been determined using the known rate constant for the reaction of 1CH2 with ketene.The experiments yielded the results k4a(296 K) = (8.2 -/+ 0.6)E13 cm3 mol-1 s-1 k4b(296 K) = (2.9 -/+ 0.4)E13 cm3 mol-1 s-1. - Keywords: Chemical Kinetics / Gases / Photochemistry / Radicals