Electron ionisation induced fragmentation of ethyl 5(1H)-oxo- and 7(1H)-oxo-1-aryl-2,3-dihydroimidazo[1,2-a]-pyrimidine-6-carboxylates: evidence for an unusually regioselective rearrangement of M(+*) ions.
The 70-eV electron ionisation (EI) mass spectra of the title compounds show clear differences between the 5-oxo and 7-oxo isomers due to regioselective fragmentations involving the ester function. Exceptionally abundant metastable peaks due to molecular ions fragmenting to [M -CO2](+.) were observed exclusively for the 7-oxo isomers, suggesting that the sufficiently long-lived molecular ions undergo a slow rearrangement preceding this fragmentation reaction. The results are contrasted to the available literature data on the ester group fragmentations involving the loss of CO2 and the EI mass spectrometry of pyrimidone beta-oxo esters. A reaction mechanism is proposed for the elimination of CO2 following ethyl group migration to the pyrimidone carbonyl oxygen.
Ovcharenko
V V
VV
Department of Chemistry, University of Turku, FIN-20014 Turku, Finland.
Pihlaja
K
K
Matosiuk
D
D
D000478:Alkylation; D002245:Carbon Dioxide / Q000737:chemistry; D004952:Esters; D007536:Isomerism; D011743:Pyrimidines / Q000737:chemistry*; D011744:Pyrimidinones / Q000737:chemistry; D021241:Spectrometry, Mass, Electrospray Ionization
D004952:Esters; D011743:Pyrimidines; D011744:Pyrimidinones; D002245:Carbon Dioxide