114362-22-0Relevant academic research and scientific papers
On the Chichibabin Amination of Pyrimidine and N-Alkylpyrimidinium Salts Using Liquid Ammonia/Potassium Permanganate
Buurman, Dick J.,Plas, Henk C. van der
, p. 1377 - 1380 (2007/10/02)
Treatment of the 2-R-pyrimidines (1, R = methyl, ethyl, i-propyl and t-butyl) with potassium amide/liquid ammonia/potassium permanganate leads to amination at C-4(6).The yields of the 4(6)-amino compounds 3 increase in the order 2-methyl (10percent), 2-ethyl (30percent), 2-i-propyl (45percent) and 2-t-butyl (60percent).Treatment of the 2-R-N-methylpyrimidinium salts (4, R = hydrogen, methyl) with liquid ammonia/potassium permanganate leads to a regiospecific imination at C-6, the corresponding 2-R-1,6-dihydro-6-imino-1-methylpyrimidines 6 being obtained in 80-85percent yield.It is proved by 15N-labelling that no ring opening is involved in these imination reactions.Treatment of the imino compounds with base leads to the corresponding 2-R-6-methylaminopyrimidines 8, involving, as proved by 15N-labelling, an ANRORC-mechanism. 2-t-Butyl-1-ethylpyrimidinium tetrafluoroborate (9b) when treated with liquid ammonia/potassium permanganate undergoes N-deethylation, 2-t-butylpyrimidine being exclusively formed.
