Synthesis of Partially Fluorinated Alkyl Triflates by Electrochemical Fluorination (Simons Process).

A scalable straightforward synthesis of monofluoro- and difluoromethyl triflate CF SO OCH F (M ) and CF SO OCHF (M ) through electrochemical fluorination (ECF, Simons process) of methyl triflate M in anhydrous hydrogen fluoride at nickel anodes is presented. The ECF method is also feasible for the preparation of the deuterated analogues CF SO OCD F (M ) and CF SO OCDF (M ). Surprisingly, no H/D exchange occurs during ECF of CF SO OCD (M ); this provides further evidence for a NiF /NiF -mediated ECF mechanism.

Insights into structure-property relationships in ionic liquids using cyclic perfluoroalkylsulfonylimides.

Room temperature ionic liquids of cyclic sulfonimide anions cPFSI (ring size: = 4-6) with the cations [EMIm] (1-ethyl-3-methylimidazolium), [BMIm] (1-butyl-3-methylimidazolium) and [BMPL] (BMPL = 1-butyl-1-methylpyrrolidinium) have been synthesized. Their solid-state structures have been elucidated by single-crystal X-ray diffraction and their physicochemical properties (thermal behaviour and stability, dynamic viscosity and specific conductivity) have been assessed. In addition, the ion diffusion was studied by pulsed field gradient stimulated echo (PFGSTE) NMR spectroscopy.

Hydrogen-bond-induced selectivity of a head-to-head photo-dimerisation of dialkynylanthracene - access to tetradentate Lewis acids.

Using 2-hydroxypropyl-protecting groups, 1,8-dialkynylanthracene photo-dimers were prepared in head-to-head-configuration by UV irradiation on a multi-gram scale. In non-polar solvents, the combination of non-covalent hydrogen bonds and π-π-interactions induces the formation of the -isomer in up to 85% yield. Instead, more polar solvents or irradiation of unprotected 1,8-diethynylanthracene led to formation of the corresponding -isomer in large excess.

Stable and Storable N(CF ) Transfer Reagents.

Fluorinated groups are essential for drug design, agrochemicals, and materials science. The bis(trifluoromethyl)amino group is an example of a stable group that has a high potential. While the number of molecules containing perfluoroalkyl, perfluoroalkoxy, and other fluorinated groups is steadily increasing, examples with the N(CF ) group are rare.