Abstract
The reaction of N-polyfluorophenylcarbonimidoyl dichlorides with tertiary amines in acetonitrile afforded chloroamidines R2NC(Cl) = NArF and alkyl chloride. The precursor of the products is the corresponding quaternary ammonium salt [R3N+C(Cl) = NArF]-Cl-. The rate of the salt formation is described by a second order equation; however with some amines a saturation effect was observed for the reaction rate with the growing amine concentration. This fact and also the influence of the amine and the substrate structure on the reaction rate suggests that reaction proceeds by addition-elimination mechanism with formation of a tetrahedral intermediate. The latter in the rate-limiting stage undergoes a stereomutation into an intermediate of a configuration favorable for conversion into a quaternary salt.
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Mikhailov, V.A., Savelova, V.A., Popov, A.A. et al. Kinetics and Mechanism of Reaction between N-Polyfluorophenylcarbonimidoyl Dichlorides and Tertiary Amines in Acetonitrile. Russian Journal of Organic Chemistry 39, 1116–1124 (2003). https://doi.org/10.1023/B:RUJO.0000010178.95945.a5
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DOI: https://doi.org/10.1023/B:RUJO.0000010178.95945.a5