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Rearrangements of 3H-Pyrazoles—Adducts of Dimethyl Acetylenedicarboxylate with Diphenyldiazomethane and 9-Diazofluorene

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Abstract

Structurally related 3H-pyrazoles resulting from 1,3-dipolar cycloaddition of diphenyldiazomethane and 9-diazofluorene to dimethyl acetylenedicarboxylate undergo van Alphen–Hüttel rearrangement on heating in a polar solvent (methanol, ethanol, acetic acid). In the first case, the rearrangement involves strictly regioselective 1,5-phenyl migration toward the carbon atom with the formation of relatively stable 4H-pyrazole. Post-rearrangement of the product on heating at 180°C in toluene gives a mixture of methyl 1H-pyrazole-1-carboxylates via successive migrations of the CO2Me group. In the second case, the aryl substituent concurrently migrates both to nitrogen atom with the formation of 1H-pyrazole structure (phenanthridine derivative) and to carbon atom with subsequent rearrangement of unstable 4H-pyrazole to 3H-pyrazole fused to phenanthrene fragment. Heating of dimethyl acetylenedicarboxylate adducts (3H-pyrazoles) in an aprotic solvent (benzene, toluene) leads to the corresponding denitrogenation products. This process is especially facile for the spirocyclic 3H-pyrazole derived from 9-diazofluorene, and it yields cyclopropene derivative. Some previous errors in the structure determination of the rearrangement products have been corrected.

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Authors and Affiliations

  1. Ogarev Mordovian State University, ul. Bol’shevistskaya 68, Saransk, 430005, Russia

    V. A. Vasin, E. V. Bezrukova & Yu. A. Popkova

  2. St. Petersburg State University, Universitetskii pr. 26, St. Petersburg, 198504, Russia

    V. V. Razin

  3. Lobachevskii Nizhny Novgorod State University, pr. Gagarina 23, Nizhny Novgorod, 603950, Russia

    N. V. Somov

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  1. V. A. Vasin
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  2. V. V. Razin
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  3. E. V. Bezrukova
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  4. Yu. A. Popkova
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  5. N. V. Somov
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Correspondence to E. V. Bezrukova.

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Original Russian Text © V.A. Vasin, V.V. Razin, E.V. Bezrukova, Yu.A. Popkova, N.V. Somov, 2018, published in Zhurnal Organicheskoi Khimii, 2018, Vol. 54, No. 6, pp. 890–897.

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Vasin, V.A., Razin, V.V., Bezrukova, E.V. et al. Rearrangements of 3H-Pyrazoles—Adducts of Dimethyl Acetylenedicarboxylate with Diphenyldiazomethane and 9-Diazofluorene. Russ J Org Chem 54, 892–900 (2018). https://doi.org/10.1134/S1070428018060118

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  • DOI: https://doi.org/10.1134/S1070428018060118

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