92610-64-5Relevant academic research and scientific papers
On the Stereoelectronic Requirements of 1,2-Rearrangements of Vinyl Cations
Collins, Clair J.,Martinez, Antonio Garcia,Alvarez, Roberto Martinez,Aguirre, Juan Arranz
, p. 2815 - 2824 (2007/10/02)
The triflates 8,9,12,17,19, and 23 have been synthesized to investigate their solvolysis products in absol. 2,2,2-trifluoroethanol (TFE) (Table 1).The kinetics of the solvolysis in 50percent ethanol have been measured as well.The rate constants give a straight correlation line when we apply an approximate Taft's equation, from which we deduce that the solvolyses take place by a kc mechanism; one exception is 12, as it reacts with S-O bond cleavage.We also deduce that the value of ρ* does not depend on steric factors.Relations between structure and rearrangement of vinyl cations are discussed.Mechanisms for the formation of reaction products are proposed.
VINYL CATIONS. 40. pi - AND sigma -ROUTES TO VINYL CATIONS. SOLVOLYSES OF 2-METHYLCYCLOHEXENYL, CYCLOPENTYLIDENEETHYL, HEX-5-YN-1-YL, AND RELATED TRIFLATES.
Hanack,Fuchs,Collins
, p. 4008 - 4017 (2007/10/12)
Three triflates were solvolyzed at various temperatures in water-alcohol mixtures, in TFE-water mixtures, in TFA, in TFIP, in HFIP, and in 100% TFE in the presence of various buffers and the resulting products were determined. The three reactants were also solvolyzed in a standard mixture (1:100:100 equals triflate:TFE:Na//2CO//3) at various temperatures, and the yields of products were compared. The solvolysis products were shown to be under kinetic control.
