Quaternary ammonium ionic liquids containing fluorous ponytails: Competitive alkylation and elimination reactions of I(CH2)_nR_f (n = 2,3) with tertiary amines

摘要

The formation of quaternary ammonium iodides possessing a fluorine-containing chain has been investigated. Reactions of tertiary amines, such as i-PrMe2N and n-BuMe2N with i(CH2)_n(CF2)_m(CF3), (n = 2, m = 5 and 7) do not cleanly yield the anticipated quaternary ammonium halide salt, instead elimination occurs and [RMe2NH]1 (R = i-Pr, n-Bu) and CH2=CH(CF2)_m(CF3) are formed. This is confirmed by the crystallographic characterisation of [n-BuMe2NH]I which is found to adopt a micellar-type arrangement in the solid state. Increasing the spacer chain-length to n = 3 does result in the desired quaternary ammonium halide salts, [RMe2N(CH2)3(CF2)_(m)(CF3)]I, (m = 3, 7). Quaternisation of MeBuN((CH2)3CgF_(17)) with 1-iodooctane gave the asymmetric quaternary ammonium salt possessing a fluorinated alkyl chain, [n-BuMeOctN((CH2)3C8F_(17))]l. Unlike in previously studied perprotio systems, low symmetry ammonium systems possessing long fluorinated chains do not result in room temperature ionic liquids.