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Regioselective synthesis of 5-aminopyrazoles from reactions of amidrazones with activated nitriles: NMR investigation and X-ray structural analysis

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Abstract

N-Arylbenzamidrazones and ethyl 2-cyano-3-ethoxybut-2-enoate reacted together in ethanol and catalyzed by triethylamine (Et3N) to give 5-amino-3-methyl-1-(aryl(phenylimino)methyl)-1H-pyrazole derivatives. Reaction of the target amidrazones with bis-(methylthio)methylidene)malononitrile in EtOH/Et3N/DMF mixture proceeded to give the corresponding 5-aminopyrazoles. The structure of the obtained products was proved by IR, mass, and NMR spectra and elemental analyses. Two-dimensional NMR spectroscopy and X-ray structural analyses were used to differentiate the assigned structures from other possible ring systems and regioisomers. The reaction mechanism is discussed.

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Acknowledgements

We thank the DFG (BR 1750) for its financial support for the stay of Professor Aly at the Karlsruhe Institute of Technology, Institute of Organic Chemistry, Germany. The NMR spectrometer at the Florida Institute of Technology was purchased with the assistance of the U.S. National Science Foundation (CHE 03 42251).

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Correspondence to Ashraf A. Aly.

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Aly, A.A., Ramadan, M., El-Aziz, M.A. et al. Regioselective synthesis of 5-aminopyrazoles from reactions of amidrazones with activated nitriles: NMR investigation and X-ray structural analysis. Chem. Pap. 71, 1409–1417 (2017). https://doi.org/10.1007/s11696-017-0131-x

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