382-28-5Relevant articles and documents
ELECTROCHEMICAL PRODUCTION OF PARTIALLY FLUORINATED ORGANIC COMPOUNDS: N-METHYLMORPHOLINE FLUORINATION
Gambaretto, G. P.,Napoli, M.,Fraccaro, C.,Conte, L.
, p. 427 - 436 (1982)
The usual electrochemical fluorination of organic compounds in anhydrous HF produces completely fluorinated materials.In order to obtain partially fluorinated compounds, electrofluorination has been conducted under various conditions, including the use of solvents.None of the solvents lead to satisfactory results.Experiments have also been carried out with high concentrations of N-methylmorpholine in anhydrous HF and they have provided information about the selectivity and the mechanism of the reaction.Various partially fluorinated derivatives of N-methylmorpholine have been identified, and some of them separated from the reaction mixture.
Electrochemical fluorination: State of the art and future tendences
Conte, Lino,Gambaretto, Gian Paolo
, p. 139 - 144 (2004)
A brief survey of the ECF process for the preparation of perfluorinated organo-compounds is given. The yield of perfluorinated products depends on the experimental conditions and on the nature of the starting material. Some useful rules are reported in order to optimise the ECF process. An improved operational technique allowed to obtain high yield of perfluorodimorpholinepropane (PFDMP) by simultaneous fluorination of dimorpholinepropane and N -methylmorpholine.
Electrochemical fluorination of several methyl and/or ethyl esters of morpholino-substituted carboxylic acids
Abe,Baba,Okuhara,Fukaya
, p. 115 - 128 (2007/10/03)
Seven methyl and/or ethyl esters of carboxylic acids (-CH2CH2C(O)OEt, -CH2CH2CH2C(O)OMe, -CH2CH2CH2C(O)OEt, -CH(C2H5)C(O)OMe, -CH(n-C3H7)C(O)OMe, -CH2CH2CH2CH2C(O)OEt and -CH2CH2CH2CH2CH2C(O) OEt) having a morpholino group were subjected to electrochemical fluorination (ECF). On ECF, the corresponding perfluoroacid fluorides bearing a perfluoromorpholino group were obtained in fair to good yields. Yields of the targeted perfluoromorpholino-containing perfluoroacid fluorides were influenced by the α-bond cleavage of the carboxylic acid and also by the kind of alkyl group of the carboxylic acid (the latter offering the possibility of cyclization side reactions). Perfluorooxolanes were formed as a major cyclization by-product from the ECF of morpholino-substituted carboxylic acids when the chain length of the alkyl group of the carboxylic acids had a carbon number of three or more and the structure of the alkyl group was branched in such a way as to allow cyclization. Perfluorodioxolanes were obtained in only small yields as the specific cyclization products when the ethyl esters of carboxylic acids were subjected to ECF. Spectroscopic data, as well as physicochemical properties, are described for the new perfluoroheterocyclic compounds with a perfluoromorpholino group that were produced.
Electrochemical fluorination of di- and tri-(2-hydroxyethyl)-substituted alkylamines
Abe, Takashi,Soloshonok, Irina,Baba, Hajime,Sekiya, Akira
, p. 51 - 57 (2007/10/03)
Several 2-(hydroxyethyl)-substituted alkylamines like 1,4-bis(2-hydroxyethyl)piperazine, N,N-bis(2-hydroxyethyl)methylamine, N,N-bis(2-hydroxyethyl)ethylamine, and N,N,N-tris(2-hydroxyethyl)amine as well as their derivatives (HCl salts, a borate and trimethylsilylethers) were subjected to electrochemical fluorination. From 1,4-bis(2-hydroxyethyl)piperazine, F-[1,4-bis(fluorocarbonylmethyl)piperazine] was obtained in low yield. In the fluorination of N,N-bis(2-hydroxyethyl)alkylamines and N,N,N-tris(2-hydroxyethyl)amine, cyclization occurred extensively, affording large quantities of F-morpholine derivatives. However, F-N,N-bis(fluorocarbonylmethyl)methylamine was obtained from the former in low, isolated yield.
Electrochemical fluorination of (N,N-dialkylamino)alcohols
Abe, Takashi,Fukaya, Haruhiko,Hayashi, Eiji,Ono, Taizo,Nishida, Masakazu,Soloshonok, Irina,Okuhara, Kunio
, p. 229 - 237 (2007/10/03)
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.
The electrochemical fluorination of N-containing carboxylic acids (Part 4). Fluorination of methyl 3-dialkylamino-isobutyrates and methyl 3-dialkylamino-n-butyrates
Abe, Takashi,Fukaya, Haruhiko,Hayashi, Eiji,Hayakawa, Yoshio,Nishida, Masakazu,Baba, Hajime
, p. 193 - 202 (2007/10/02)
Several methyl esters of 3-dialkylamino-substituted n- and isobutyric acids have been subjected to electrochemical fluorination to give the corresponding perfluoroacid fluorides.Dimethyl, diethyl, pyrrolidino, morpholino, piperidino and N-methylpiperazino groups were investigated as dialkylamino substituents.The structure/yield relationship was evaluated both in terms of the structure of the acid and the kind of amino group, respectively.Better yields of perfluoroacid fluorides were obtained from methyl esters having isobutyric acid skeletons than those having n-butyric acid groups, and from the acids containing cyclic amino groups than those containing acyclic ones.
The electrochemical fluorination of nitrogen-containing carboxylic acids. Fluorination of methyl esters of 3-dialkylamino propionic acids
Abe, Takashi,Hayashi, Eiji,Fukaya, Haruhiko,Hayakawa, Yoshio,Baba, Hajime,et al.
, p. 101 - 111 (2007/10/02)
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 DIMETHYLAMINO- OR DIETHYLAMINO-SUBSTITUTED CARBOXYLIC ACID DERIVATIVES
Abe, Takashi,Hayashi, Eiji,Baba, Hajime,Fukaya, Haruhiko
, p. 257 - 279 (2007/10/02)
The electrochemical fluorination of six derivatives of dimethylamino- or diethylamino-substituted carboxylic acids has been conducted.As the main fluorination products, cyclized and cleaved products as well as the desired N-containing perfluoroacid fluorides were formed, and their ratios depended on the chain length and the structure of the starting carboxylic acids, and the nature of the dialkylamino group.Through this work, perfluoro(dimethylamino-acetyl fluoride), perfluoro(diethylamino-acetyl fluoride), perfluoro(2-dimethylamino-propionyl fluoride), perfluoro(2-dimethylamino-butyryl fluoride) and perfluoro(3-dimethylamino-propionyl fluoride) were prepared.Except for perfluoro(dimethylamino-acetyl fluoride), these acid fluorides were new compounds.The physical properties of new compounds obtained including these acid fluorides are reported together with their spectral (19F nmr, Mass and IR) data.
THE ELECTROCHEMICAL FLUORINATION OF NITROGEN-CONTAINING CARBOXYLIC ACIDS. FLUORINATION OF METHYL ESTERS OF CYCLIC AMINOGROUP SUBSTITUTED CARBOXYLIC ACIDS
Abe, Takashi,Hayashi, Eiji,Fukaya, Haruhiko,Baba, Hajime
, p. 173 - 196 (2007/10/02)
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.
THE ELECTROCHEMICAL FLUORINATION OF ORGANIC COMPOUNDS: FURTHER DATA IN SUPPORT OF THE ECbECN MECHANISM
Gambaretto, G. P.,Napoli, M.,Conte, L.,Scipioni, A.,Armelli, R.
, p. 149 - 156 (2007/10/02)
Data in support of the four-stage mechanism ECbECN result from the electrochemical fluorination of some acyl halides (benzoyl, n-butyryl and iso-butyryl, benzenesulphonyl and p-toluenesulphonyl chlorides) and amines (tripropylamine and N-methylmorpholine).
