Thiamin hydrochloride was thermally degraded in phosphate buffer (pH 6.5) at 110 degrees C for 2 h. A major decomposition product was isolated by column chromatography and structurally identified by spectrometric techniques ((1)H NMR, (13)C NMR, 2D NMR, and MS) as 2-methyl-4-amino-5-(2-methyl-3-furylthiomethyl)pyrimidine (MAMP). The possible formation pathway of MAMP was studied using two model systems. It is proposed that MAMP is formed by nucleophilic attack of 2-methyl-3-furanthiol on the thiamin.