C(5)H(7)O(2)(+) ions: the correlation between their thermochemistry in acidic solution and their chemistry in the gas phase

Abstract

Each of a series of C(5)H(6)O(2) isomeric carboxylic acid and unsaturated lactones (1-7) was protonated in both concentrated sulfuric acid and trifluoromethanesulfonic acid. The thermally induced transformations of the protonated species were then studied over a temperature range of -30 to +160 degrees C. In the case of alpha,beta-unsaturated lactones, protonation took place on the carbonyl oxygen and gave the corresponding stable O-protonated species. Conversely, unconjugated lactones and acetylenic acid 7 were converted even at low temperature into the diprotonated ketoacid 8H(2)()o(+2)() by the acid-catalyzed addition of water to the C-protonated precursor. Upon being heated at 160 degrees C, this acid gave protonated 1,3-cyclopentanedione. In the absence of water, decarbonylation followed by polymerization was observed in lactones 4 and 5. The CIMS spectra of compounds 1-7 were recorded using methane, ammonia, and moist air as reagent gases to determine the correlation between the fragmentation routes in the gas phase and the transformations observed in solution. Ammonia and moist air enabled us to determine the different proton affinities of these compounds. The data obtained in strong acids were used to assign reasonable structures to the gas-phase ions.