Urea/thiourea: efficient, inexpensive and reusable catalysts for the synthesis of pyrazole derivatives with 2-iminothiazolidin-4-one and 2,4-thiazolidinediones under solvent-free conditions.

An efficient and green synthesis of pyrazolyl-2,4-thiazolidinediones/pyrazolyl-2-iminothiazolidine-4-ones 7(a-j) has been developed using urea/thiourea as catalyst. Two methods (A and B) have been introduced for the synthesis of these compounds. Method A performed well for the condensation of pyrazole-4-carboxaldehydes 4(a-e) with 2-iminothiazolidin-4-one 5a and with 2,4-thiazolidinedione 5b at 110 [Formula: see text] for 16-20 min to furnish (Z)-5-((1,3-diphenyl-1H-pyrazol-4-yl)methylene)thiazolidine-2,4-diones 7(a-j) in excellent yields. In method B, the pyrazole-4-carboxaldehydes 4(a-e) were condensed with urea/thiourea at 110 [Formula: see text] for 10 min to give key intermediates 6(a-j) which were later condensed with 5a and 5b to afford 7(a-j) via the elimination of urea/thiourea rather than the formation of a Biginelli product. These two protocols are inexpensive, eco-friendly and high yielding to provide the final products. The synthesis of compound 7f.