Protonation Sites in Pyrimidine and Pyrimidinamines in the Gas Phase

Abstract

Protonation sites in gaseous pyrimidine (1), 2-pyrimidinamine (2), and 4-pyrimidinamine (3) were elucidated by neutralization−reionization mass spectrometry and MP2/6-311G(2d,p) ab initio calculations. Pyrimidine was protonated with NH4+ and t-C4H9+ exclusively at the nitrogen atoms whose proton affinity (PA) was calculated at 879 kJ mol-1 in excellent agreement with the experimental datum. The C-2 and C-5 positions in 1 had PA = 573 and 645 kJ mol-1, respectively. 2 was protonated with t-C4H9+ at N-1 and/or N-3 and the amine group in a statistical 2:1 ratio, consistent with the calculated PA = 909 and 864 kJ mol-1, respectively. 3 was protonated at N-1, N-3, and the amine group, which had PA = 943, 905, and 835 kJ mol-1, respectively. The C-5 positions in 2 and 3 were less basic, PA = 807 and 781 kJ mol-1, respectively, and were not attacked by the gas-phase acids used. The thermodynamic proton affinities of gaseous 1, 2, and 3 followed the order of their basicities in solution. The substituent electroni...