The reaction of 4-alkylpyrimidines with propyl nitrite under acidic conditions followed by deoximation of the resulting ketoximes gave alkyl pyrimidinyl ketones in satisfactory yields. As compared with the direct oxidation of the alkylpyrimidines with selenium dioxide, the nitrosation followed by deoximation has some advantages for the synthesis of alkyl 4-pyrimidinyl ketones.