- ELECTROCHEMICAL FLUORINATION OF N-CHLOROALKYL-SUBSTITUTED CYCLIC AMINES
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The electrochemical fluorination of such N-chloroalkyl substituted cyclic amines as N-chloromethylpyrrolidine (1), N-(3-chloropropyl)pyrrolidine (2), N-chloromethylpiperidine (3), N-(2-chloroethyl)piperidine (4), N-(3-chloropropyl)piperidine (5), N-chloromethylmorpholine (6), N-(3-chloropropyl)morpholine (7), N-(2-chloroallyl)morpholine (8) has been conducted.Except in the cases of the N-chloromethyl-substituted ones (1,3 and 6), the corresponding chlorine-retaining-perfluoroamines were obteined in a yield of 5 - 20 percent together with perfluorinated ones (Yield = 20 - 60 percent).Neither chlorine-retaining amines nor perfluorinated amines, both of which having the original skeleton, was produced from fluorinations of 1, 3 and 6 in an appreciable yield.The spectroscopic data and physical properties of newly synthesized perfluoro-N-chloroalkyl-substituted cyclic amines are presented.
- Hayashi, Eiji,Abe, Takashi,Baba, Hajime,Nagase, Shunji
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- Electrochemical fluorination of several methyl and/or ethyl esters of morpholino-substituted carboxylic acids
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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.
- Abe,Baba,Okuhara,Fukaya
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p. 115 - 128
(2007/10/03)
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- The electrochemical fluorination of N-containing carboxylic acids (Part 4). Fluorination of methyl 3-dialkylamino-isobutyrates and methyl 3-dialkylamino-n-butyrates
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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.
- Abe, Takashi,Fukaya, Haruhiko,Hayashi, Eiji,Hayakawa, Yoshio,Nishida, Masakazu,Baba, Hajime
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p. 193 - 202
(2007/10/02)
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