Synthesis of 3H-pyrazoles by reaction of methyl and p-tolyl phenylethynyl sulfones with diphenyldiazomethane and their thermal and acid-catalyzed transformations

Abstract

Methyl and p-tolyl phenylethynyl sulfones reacted with diphenyldiazomethane in diethyl ether at 20°C to give 1,3-dipolar cycloaddition products both according and contrary to the von Auwers rule, sulfonylsubstituted 3H-pyrazoles at a ratio of 1 : 1.5 and 1.3 : 1, respectively. On heating in toluene for 2 h, the Auwers adducts underwent van Alphen-Hüttel rearrangement with 1,5-sigmatropic shift of one phenyl substituent to afford sulfonyl-substituted 4H-pyrazoles. Under analogous conditions, the anti-Auwers adducts rearranged into sulfonyl-substituted N-phenyl-1H-pyrazoles containing a small amount of the denitrogenation product, sulfonyl-substituted cyclopropene. The Auwers adducts, as well as 4H-pyrazoles resulting from their thermal rearrangement, were converted in 5-7 days at 20°C into 3,4,4-triphenyl-1H-pyrazol-5(4H)-one by the action of a catalytic amount of sulfuric acid in acetic acid. Under analogous conditions, the regioisomeric anti-Auwers adducts gave rise to 3,4,5-triphenyl-1H-pyrazole with an impurity of 4-(R-sulfonyl)-1,3,5-triphenyl-1Hpyrazoles.* In the reaction of diphenyldiazomethane with propynal only Auwers 3H-pyrazole was obtained [7], whereas in the reaction with 3-phenylpropynenitrile, only the anti-Auwers adduct was formed [13].