caa a22 4500 605528799 CHVBK 20210128100815.0 cr unu---uuuuu 210128e20150601xx s 000 0 eng 10.1134/S107042801506010X doi (NATIONALLICENCE)springer-10.1134/S107042801506010X Synthesis of 3 H -pyrazoles by reaction of methyl and p -tolyl phenylethynyl sulfones with diphenyldiazomethane and their thermal and acid-catalyzed transformations [Elektronische Daten] [V. Vasin, Yu. Masterova, E. Bezrukova, V. Razin, N. Somov] 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-1H-pyrazoles. Pleiades Publishing, Ltd., 2015 Vasin V. Ogarev Mordovian State University, ul. Bol'shevistskaya 68, 430005, Saransk, Russia aut Masterova Yu Ogarev Mordovian State University, ul. Bol'shevistskaya 68, 430005, Saransk, Russia aut Bezrukova E. Ogarev Mordovian State University, ul. Bol'shevistskaya 68, 430005, Saransk, Russia aut Razin V. St. Petersburg State University, Universitetskii pr. 26, 198504, St. Petersburg, Russia aut Somov N. Lobachevsky State University of Nizhni Novgorod, pr. Gagarina 23, 603950, Nizhni Novgorod, Russia aut Russian Journal of Organic Chemistry Pleiades Publishing 51/6(2015-06-01), 874-883 1070-4280 51:6<874 2015 51 11178 https://doi.org/10.1134/S107042801506010X text/html Onlinezugriff via DOI BK010053 XK010053 XK010000 Metadata rights reserved Springer special CC-BY-NC licence nationallicence 1 research-article jats NATIONALLICENCE NATIONALLICENCE NL-springer NATIONALLICENCE 856 40 https://doi.org/10.1134/S107042801506010X text/html Onlinezugriff via DOI NATIONALLICENCE 700 1- Vasin V. Ogarev Mordovian State University, ul. Bol'shevistskaya 68, 430005, Saransk, Russia aut NATIONALLICENCE 700 1- Masterova Yu Ogarev Mordovian State University, ul. Bol'shevistskaya 68, 430005, Saransk, Russia aut NATIONALLICENCE 700 1- Bezrukova E. Ogarev Mordovian State University, ul. Bol'shevistskaya 68, 430005, Saransk, Russia aut NATIONALLICENCE 700 1- Razin V. St. Petersburg State University, Universitetskii pr. 26, 198504, St. Petersburg, Russia aut NATIONALLICENCE 700 1- Somov N. Lobachevsky State University of Nizhni Novgorod, pr. Gagarina 23, 603950, Nizhni Novgorod, Russia aut NATIONALLICENCE 773 0- Russian Journal of Organic Chemistry Pleiades Publishing 51/6(2015-06-01), 874-883 1070-4280 51:6<874 2015 51 11178