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The Smiles Rearrangement of Fluorinated Hydrazonoyl Esters to Unsymmetrical N',N'-Diaryl Acylhydrazines
Adrian Warcholiński1, Katarzyna Urbaniak1, Radomir Jasiński2
1University of Lodz , Faculty of Chemistry, Department of Organic and Applied Chemistry, Tamka 12, Łódź91-403, Poland.
Abstract:
Two-step telescopic synthesis of unsymmetrical diarylhydrazides formally derived from di- and trifluoroacetic acid is reported. The method comprises trapping of the in situ-generated 1,3-dipolar di- and trifluoroacetonitrile imine with phenolate, followed by the Smiles rearrangement of the initially formed hydrazonoyl ester. Mechanistic analysis of the second step using DFT calculations revealed a single-step aryl migration proceeding through a pseudocyclic transition state and exhibiting only a minor influence of the fluoromethyl substituent. The structures of selected CF3- and CHF2-functionalized products were confirmed by X-ray analysis.
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