2344-10-7

Upstream product

• 110-86-1 pyridine 
• 109-06-8 α-picoline 
• 22041-21-0 methyl 3-(pyrrolidin-1-yl)propanoate 
• 22041-18-5 methyl 2-(pyrrolidin-1-yl)acetate 
• 372-48-5 2-fluoropyridine 
• 2955-88-6 1-pyrrolidineethanol 

Downstream Products

• 377-38-8 tetrafluorosuccinic acid 

Relevant academic research and scientific papers

Electrochemical fluorination of (N,N-dialkylamino)alcohols

Series of amino alcohols including 2-(N,N-dialkylamino)ethanols, 3-(N,N-dimethylamino)propanol and 4-(N,N-dimethylamino)butanol were subjected to electrochemical fluorination. In the case of 2-(N,N-dialkylamino)ethanols, the F-(2-N,N-dialkylamino)acetyl fluorides were obtained in fair to good yields. Yields of each target compound were strongly dependent on the kind of the dialkylamino group. Cyclic amines having an N-(2-hydroxylethyl) group afforded the corresponding F-[N-(c-alkylamino)-substituted acetyl fluorides]. Their yields were generally better than those of acyclic analogs. Several 2-(N,N-dialkylamino)ethanols and 3-(N,N-dimethylamino)propanol were converted into the corresponding trimethylsilylethers, aminoalkyl methyl carbonates and bis-aminoalkyl carbonate, respectively, and they were subjected to fluorination for a comparison of the yield with that obtained from that of the parent aminoalcohol.

Investigations on the product distribution pattern during the electrochemical fluorination of 2-fluoropyridine and pyridine

By using 2-fluoropyridine instead of pyridine as the starting material, a 19% conversion yield of perfluoropiperidine was obtained during the electrochemical fluorination process. At least ten products including perfluoropiperidine were characterised using repeated fractional distillation followed by GC and NMR analysis.

The electrochemical fluorination of nitrogen-containing carboxylic acids. Fluorination of methyl esters of 3-dialkylamino propionic acids

Six methyl esters of 3-dialkylamino-substituted propionic acids were subjected to electrochemical fluorination to give the corresponding perfluoroacid fluorides.The following dialkylamino substituents were investigated: diethylamino, di-n-propylamino, di-n-butylamino, pyrrolidino, morpholino and piperidino groups.These perfluoroacid fluorides, which were obtained in fair yields, are considered to be prospective key precursors for preparing soft-type (degradable) fluorochemicals.The salts show a considerable lowering of surface tension in aqueous solution.Thephysical properties of all the perfluoroacid fluorides obtained are reported, together with their spectroscopic data (19F NMR, mass and IR spectra).

THE ELECTROCHEMICAL FLUORINATION OF NITROGEN-CONTAINING CARBOXYLIC ACIDS. FLUORINATION OF METHYL ESTERS OF CYCLIC AMINOGROUP SUBSTITUTED CARBOXYLIC ACIDS

Nine methyl esters of cyclic amino-group substituted carboxylic acids related to glycine, alanine or β-alanine were subjected to electrochemical fluorination.This afforded the corresponding perfluoroacid fluorides together with cleavage products in fair yields.As cyclic amino-substituents, pyrrolidino-, morpholino-, piperidino-, hexamethyleneimino- and N'-methylpiperazinyl-groups were investigated.The formation of cyclized by-products was not observed, which contrasts with the fluorination of aliphatic dialkylamino-substituted carboxylic acids.From such methyl 2-cyclic amino-propionates (cyclic amino-group: a pyrrolidino, a morpholino or a piperidino-group), the perfluorinated methyl esters were obtained together with the corresponding perfluoroacid fluorides in yields of 1-2percent and 14-29percent, respectively.The formation of the former compounds is ascribed to the blocking effect of the bulky cyclic amino-groups.The physical properties of the new compounds obtained are reported together with their spectral (19F NMR, Mass and IR) data.

FLUORINATIONS WITH COMPLEX METAL FLUORIDES. PART 7. FLUORINATIONS OF THE METHYL PYRIDINES WITH CAESIUM TETRAFLUOROCOBALTATE

4-Methylpyridine passed over caesium tetrafluorocobaltate at 330-340 deg gave tridecafluoro(1,3-dimethylpyrrolidine) (1) and its 3-difluoromethyl analogue (2), together with a range of polyfluoro-4-picolines (4-10) with -CF3, -CHF2 or -CH2F groups in the 4-position. 3-Methylpyridine similarly gave 1 and its 1,2-isomer (11) together with several polyfluoro-3-picolines (14-18). 2-Methylpyridine at 270 deg gave tridecafluoro(1-ethylpyrrolidine) (13), a trace of 11 and 2-trifluoromethyl- (22), 2-difluoromethyl- (23) and 2-fluoromethyl-tetrafluoropyridine (24); there were also products arising by loss of methyl.Other unidentified fluoroalkylpyridines besides those isolated were present in each case.

FLUORINATIONS WITH COMPLEX METAL FLUORIDES. PART 6. FLUORINATION OF PYRIDINE AND RELATED COMPOUNDS WITH CAESIUM TETRAFLUOROCOBALTATE(III)

Pyridine has been fluorinated over caesium tetrafluorocobaltate(III) (CsCo(III)F4) at 300-400 deg C to give a mixture of undecafluoro-N-methyl-pyrrolidine, bis(trifluoromethyl)amine, pentafluoropyridine and several polyfluoropyridines; the product composition depend to some extent on the geometry of the reactor.The fluorinations of pentafluoropyridine, piperidine and undecafluoropiperidine were also investigated.