부산대학교 도서관

Thermal van Alphen-Hüttel rearrangement of methyl 3,3-diphenyl-3 H-pyrazole-4-carboxylate, 3,3-diphenyl-3 H-pyrazole-4-carbonitrile, and methyl 5-methyl-3,3-diphenyl-3 H-pyrazole-4-carboxylate involves completely regioselective migration of one phenyl group from the 3-position to N with formation of aromatic 1 H-pyrazole system. Thermal rearrangement of methyl 3,3-diphenyl-3 H-pyrazole-5-carboxylate leads to the formation of methyl 4,5-diphenyl-1 H-pyrazole-3-carboxylate as a result of migration of the 3-phenyl group exclusively to the C atom and subsequent prototropic isomerization. Under analogous conditions, methyl 4-methyl-3,3-diphenyl-3 H-pyrazole-5-carboxylate, methyl 5-(methanesulfonyl)-3,3-diphenyl-3 H-pyrazole-4-carboxylate, methyl 5-(benzenesulfonyl)-3,3-diphenyl-3 H-pyrazole-4-carboxylate, and dimethyl 3,3-diphenyl-3 H-pyrazole-4,5-dicarboxylate have been regioselectively converted into the corresponding 4 H-pyrazoles. Thermolysis of 5-(4-methylbenzenesulfonyl)-3,3-diphenyl-3 H-pyrazole-4-carbonitrile gives rise to a mixture of 1 H- and 4 H-pyrazoles, the former considerably prevailing, whereas the corresponding 1 H-pyrazoles are formed as the only product from 5-(methanesulfonyl)- and 5-(benzenesulfonyl)-3,3-diphenyl-3 H-pyrazole-4-carbonitriles. [ABSTRACT FROM AUTHOR]