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Thermal and acid-catalyzed transformations of 3H-pyrazoles obtained from diphenyldiazomethane and methyl phenylpropiolate

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Abstract

Reaction of diphenyldiazomethane with methyl phenylpropiolate in diethyl ether alongside the expected methyl triphenyl-3H-pyrazole-4-and-5-carboxylates (I and II) (38 and 24%) gave rise also to 8% of methyl 3,5-diphenyl-1-(1-ethoxyethyl)-1H-pyrazole-4-carboxylate. The main thermolysis product obtained from 4-methoxy-carbonyl derivative I was methyl 1,3,5-triphenyl-1H-pyrazole-4-carboxylate, whereas from regioisomer II formed predominantly methyl 4,4,5-triphenyl-4H-pyrazole-3-carboxylate and 1-methoxycarbonyl-2,3,3-triphenylcyclopropene that was a minor product of 3H-pyrazole I thermolysis. Addition of concn. H2SO4 to the solutions of methyl triphenyl-3H-pyrazole-4-and-5-carboxylates in AcOH resulted in fast regioselective isomerization of the 3H-pyrazole derivatives into the corresponding 4H-pyrazoles.

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Authors and Affiliations

  1. St. Petersburg State University, St. Petersburg, 19850, Russia

    A. A. Fedorov, Sh. E. Duisenbaev, V. V. Razin & M. A. Kuznetsov

  2. Institut fur Organische Chemie, Universitat Zurich, Winterthurerstrasse 190, CH-8057, Zurich, Switzerland

    E. Linden

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  1. A. A. Fedorov
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  2. Sh. E. Duisenbaev
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  3. V. V. Razin
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  4. M. A. Kuznetsov
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Original Russian Text © A.A. Fedorov, Sh.E. Duisenbaev, V.V. Razin, M.A. Kuznetsov, E. Linden, 2007, published in Zhurnal Organicheskoi Khimii, 2007, Vol. 43, No. 2, pp. 239–248.

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Fedorov, A.A., Duisenbaev, S.E., Razin, V.V. et al. Thermal and acid-catalyzed transformations of 3H-pyrazoles obtained from diphenyldiazomethane and methyl phenylpropiolate. Russ J Org Chem 43, 231–240 (2007). https://doi.org/10.1134/S1070428007020145

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  • DOI: https://doi.org/10.1134/S1070428007020145

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