ChemInform Abstract: ISOMERISIERUNGEN CYCLISCHER N‐ISOALKYL‐AMINE BEI DER ELEKTROCHEMISCHEN FLUORIERUNG

Free radical and isomerisation processes during the electrochemical fluorination of n-butyryl chloride, i-butyryl chloride and pivaloyl chloride in anhydrous hydrogen fluoride

“…(1) in Scheme 2) can undergo additional chemical transformations such as cyclisation and isomerisation mentioned above. Systematic analysis of a variety of small and large reactants using mainly NMR data of partially as well as perfluorinated samples were found to be in agreement with free radical pathway [2][3][4][5][6][7]. There is also reasonable consensus towards this pathway in recent times [8][9][10][11][12][13][14][15][16].…”

“…The product distribution between PFIBA and PFNBA is found to be around 45:55 (experiment nos. [1][2][3][4]. Increase in cell temperature leads to slightly higher levels of cleavage products (experiment no.…”

The Chemistry of Highly Fluorinated Carbocations

“…Reaction of aluminum chloride with F - N -amylpiperidine ( 206 ) was reported in the 1960s to cause ring opening with concomitant Cl/F exchange. , Reaction proceeds at 60−70 °C in CCl 4 as solvent and leads to a mixture of small amounts of trichloropentane 207 and cyclic imine 208 along with two isomeric products of ring opening, imidoyl chlorides 209a , b , isolated in 65−70% yield. The ring-opening reaction of perfluorinated N -alkylpiperidines and -pyrrolidines , by AlCl 3 followed by alkaline hydrolysis of the imidoyl chlorides was used to determine the structure of cyclic amines obtained from electrochemical fluorinations.

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