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Reaction of hydrazones derived from active methylene compounds with Vilsmeier–Haack reagent

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Abstract

Reaction of hydrazones derived from active methylene compounds with the Vilsmeier–Haack reagent was studied. Compounds with sulfone, ester, nitrile, triphenylphosphonium, and phthalimide moieties were evaluated. It was found that electron-withdrawing and steric effects provided by the substituent at α position strongly influenced the regioselectivity of the reaction. Increasing mesomeric electron-withdrawing effect of this group favors the formation of functionalized 1,3,4-trisubstituted pyrazoles as compared to 1,3-disubstituted pyrazole-4-carbaldehydes. On the contrary, enhanced steric hindrance and lowered electron-withdrawing effect shift the balance toward 1,3-disubstituted pyrazole-4-carbaldehydes. Other factors such as substituent at the nitrogen atom of the hydrazone, as well as reagent ratio, can affect the outcome of the reaction dramatically, so that in certain cases acyclic products are obtained.

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Notes

  1. In addition to compounds 8a–8i, we have also attempted to study hydrazones of general formula 8 with R 2 = Ph, EWG = C(O)Me (8j), CONMe2 (8k), and NO2 (8l). We could not obtain hydrazone 8j due to its fast cyclization into the pyrazole derivative. Although hydrazone 8k was formed, its purification failed in our hands. Compound 8l was obtained, but it gave a complex mixture of unidentified products upon reaction with Vilsmeier–Haack reagent.

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Authors and Affiliations

  1. National Taras Shevchenko University of Kyiv, Volodymyrska Street, 64, Kiev, 01601, Ukraine

    Oleksandr O. Grygorenko

  2. Institute of Organic Chemistry, National Academy of Sciences of Ukraine, Murmanska Street 5, Kiev, 02660, Ukraine

    Sergey P. Ivonin, Bohdan B. Kurpil’ & Dmitry M. Volochnyuk

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  1. Sergey P. Ivonin
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  2. Bohdan B. Kurpil’
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  3. Oleksandr O. Grygorenko
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  4. Dmitry M. Volochnyuk
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Correspondence to Oleksandr O. Grygorenko.

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Ivonin, S.P., Kurpil’, B.B., Grygorenko, O.O. et al. Reaction of hydrazones derived from active methylene compounds with Vilsmeier–Haack reagent. Monatsh Chem 145, 2011–2017 (2014). https://doi.org/10.1007/s00706-014-1293-7

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  • DOI: https://doi.org/10.1007/s00706-014-1293-7

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