The chemistry of 5-hydroxylated pyrimidines and their preparative methods were brieAy reviewed. A route leading to the synthesis of 5-hydroxypyrimidines was suggested which involves using α-benzyloxy-p-dicarbonyl compounds, keto-esters or related substances as three-carbon components to condense with amidine derivatives and was exemplified in a preparation of various 2-substituted 4,5,6-trihydroxypyrimidines from ethyl benzyloxymalonate.