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Updated: Apr 29, 2026

Protocol for the Synthesis of Ortho-trifluoromethoxylated Aniline Derivatives
Published on: January 19, 2016
Synthesis and reactivity of new functionalized perfluoroalkylfluorophosphates
Nadine Allefeld1, Beate Neumann, Hans-Georg Stammler
1Centrum für Molekulare Materialien, Fakultät für Chemie, Anorganische Chemie, Universität Bielefeld, Universitätsstrasse 25, 33615 Bielefeld (Germany).
Abstract:
A new efficient synthesis of functionalized perfluoroalkyl fluorophosphates by oxidative addition of Me2NCH2F to the electron-deficient phosphanes (C2F5)(n)PF(3-n) (n=0-3) is reported. The initially formed zwitterionic, hexacoordinated phosphates [(C2F5)(n)F(5-n)P(CH2NMe2-CH2NMe2)] are converted into the corresponding phosphonium salts [(Me3PCH2NMe2](+)[(C2F5)(n)F(5-n)P(CH2NMe2)](-) by treatment with PMe3. In addition [(C2F5)3F2P(CH2NMe2-CH2NMe2)] can undergo a 1,3-methyl shift from the internal to the terminal nitrogen--a structural characterization was achieved from the CF3 analogue. Reaction of [(C2F5)3F2P(CH2NMe-CH2NMe3)] and PMe3 gave rise to the formation of the zwitterionic phosphonium phosphate [(C2F5)3F2P(CH2NMe-CH2PMe3)], which was fully characterized by X-ray diffraction analysis. Moreover, an efficient one-pot synthesis of Cs(+)[(C2F5)3F2P(CH2NMe2)](-) was pursued. This salt turned out to be a useful nucleophile in several alkylation reactions.
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