1201-02-1Relevant articles and documents
Disubstitution on hexafluorobenzene with N-methylformamides
Koppang, R.,Grace, D.
, p. 27 - 30 (1994)
Nucleophilic attack on hexafluorobenzene by N-methylformamide, treated with different bases, gave N-methyl-2,3,4,5,6-pentafluoroformanilide, N-formyl-N,N'-dimethyl-2,3,5,6-tetrafluorophenylene-1,4-diamine and N,N'-diformyl-N,N'-dimethyl-2,3,5,6-tetrafluorophenylene-1,4-diamine.The substituted benzenes could be hydrolyzed to N-methyl-2,3,4,5,6-pentafluoroaniline and N,N'-dimethyl-2,3,5,6-tetrafluorophenylene-1,4-diamine.
Anilinic N-oxides support cytochrome P450-mediated N-dealkylation through hydrogen-atom transfer
Roberts, Kenneth M.,Jones, Jeffery P.
experimental part, p. 8096 - 8107 (2010/09/11)
The mechanism of N-dealkylation mediated by cytochrome P450 (P450) has long been studied and argued as either a single electron transfer (SET) or a hydrogen atom transfer (HAT) from the amine to the oxidant of the P450, the reputed iron-oxene. In our study, tertiary anilinic N-oxides were used as oxygen surrogates to directly generate a P450-mediated oxidant that is capable of N-dealkylating the dimethylaniline derived from oxygen donation. These surrogates were employed to probe the generated reactive oxygen species and the subsequent mechanism of N-dealkylation to distinguish between the HAT and SET mechanisms. In addition to the expected N-demethylation of the product aniline, 2,3,4,5,6-pentafluoro-N,N-dimethylaniline N-oxide (PFDMAO) was found to be capable of N-dealkylating both N,N-dimethylaniline (DMA) and N-cyclopropyl-N-methylaniline (CPMA). Rate comparisons of the N-demethylation of DMA supported by PFDMAO show a 27-fold faster rate than when supported by N,N-dimethylaniline N-oxide (DMAO). Whereas intermolecular kinetic isotope effects were masked, intramolecular measurements showed values reflective of those seen previously in DMAO- and the native NADPH/O2-supported systems (2.33 and 2.8 for the N-demethylation of PFDMA and DMA from the PFDMAO system, respectively). PFDMAO-supported N-dealkylation of CPMA led to the ring-intact product N-cyclopropylaniline (CPA), similar to that seen with the native system. The formation of CPA argues against a SET mechanism in favor of a P450-like HAT mechanism. We suggest that the similarity of KIEs, in addition to the formation of the ring-intact CPA, argues for a similar mechanism of Compound I (Cpd I) formation followed by HAT for N-dealkylation by the native and N-oxide-supported systems and demonstrate the ability of the N-oxide-generated oxidant to act as an accurate mimic of the native P450 oxidant.
Polyfluorinated arylnitramines
Platonov,Haas,Schelvis,Lieb,Dvornikova,Osina,Gatilov, Yu.V.
, p. 131 - 139 (2007/10/03)
N-methyl- and N-butylperfluoroarylamines are transformed by HNO3 into N-nitro-N-methyl- and N-nitro-N-butylperfluoroarylamines. These reactions were used to synthesise N-nitro-N-methylpentafluoroaniline and its p-CF3, -CN, -C6F5 substituted derivatives, N-nitro-N-methylperfluoro-2,4-xylidine, N-nitro-N-methyl-4-aminotetrafluoropyridine, N-nitro-N-methyl-5-aminoperfluoroindane, N-nitro-N-methyl-2-aminoheptafluoronaphthalene, 4,4′-bis(N-nitro-N-methylamino)octafluorobiphenyl from 4,4′-bis(N-methylamino)octafluorobiphenyl, N-nitro-N-n-butylpentafluoroaniline, N-nitro-N-n-butylperfluoro-p-toluidine, N-nitro-N-n-butyl-4-aminotetrafluoropyridine and N-nitro-bis(perfluoro-p-tolyl)amine. Tetrafluoro-p-benzoquinone and heptafluoro-p-toluquinol were obtained from N-methylpentafluoroaniline and N-methylperfluoro-p-toluidine, respectively, under the action of a mixture of HNO3 and H2SO4. The X-ray crystal structure of N-nitro-N-methylperfluoro-p-toluidine was determined.