Thiadiazole ring opening in the derivatives of 2-substituted 5-(1,2,3-thiadiazol-4-yl)-3-furoic acid under the action of bases

Resumo

Transformations of the derivatives of 2-substituted 5-(1,2,3-thiadiazol-4-yl)-3-furoic acid under the action of bases has been studied. In the presence of potassium tert-butylate in THF, the studied compounds decompose with the cleavage of the thiadiazole ring, liberation of nitrogen, and formation of labile acetylene thiolates. In the presence of methyl iodide, these salts form stable 2-methylthioethynylfurans. Under the action of sodium ethylate in ethanol, thiadiazole ring of ethyl [2-methyl-5-(1,2,3-thiadiazol-4-yl)]-3-furoate is split to form the corresponding sodium acetylene thiolate. Under the action of ethanol, two molecules of this salt give bis(furyl)dithiafulvene. In the DMF–potassium carbonate system, acetylene thiolates react with primary and secondary amines giving thioamides of (4-ethoxycarbonyl-5-methylfur-2-yl)acetic acid. Treating of ethyl 2-methyland 2-N-morpholinomethyl-5-(1,2,3-thiadiazol-4-yl)-3-furoates with hydrazine hydrate leads to hydrazinolysis of the ester group and cleavage of thiadiazole ring resulting in the formation of hydrazides of 4-hydrazinocarbonylfur-2-ylacetic acid. In the case of ethyl 2-acetoxymethyl- and 2-(4-nitrophenoxy)methyl-5-(1,2,3-thiadiazol-4-yl)-3-furoates, thiadiazole ring is retained and exclusively hydrazinolysis of the ester groups is observed.