2787-79-3Relevant articles and documents
Mechanism of Oxidative Activation of Fluorinated Aromatic Compounds by N-Bridged Diiron-Phthalocyanine: What Determines the Reactivity?
Colomban, Cédric,Tobing, Anthonio H.,Mukherjee, Gourab,Sastri, Chivukula V.,Sorokin, Alexander B.,de Visser, Sam P.
supporting information, p. 14320 - 14331 (2019/11/03)
The biodegradation of compounds with C?F bonds is challenging due to the fact that these bonds are stronger than the C?H bond in methane. In this work, results on the unprecedented reactivity of a biomimetic model complex that contains an N-bridged diiron-phthalocyanine are presented; this model complex is shown to react with perfluorinated arenes under addition of H2O2 effectively. To get mechanistic insight into this unusual reactivity, detailed density functional theory calculations on the mechanism of C6F6 activation by an iron(IV)-oxo active species of the N-bridged diiron phthalocyanine system were performed. Our studies show that the reaction proceeds through a rate-determining electrophilic C?O addition reaction followed by a 1,2-fluoride shift to give the ketone product, which can further rearrange to the phenol. A thermochemical analysis shows that the weakest C?F bond is the aliphatic C?F bond in the ketone intermediate. The oxidative defluorination of perfluoroaromatics is demonstrated to proceed through a completely different mechanism compared to that of aromatic C?H hydroxylation by iron(IV)-oxo intermediates such as cytochrome P450 Compound I.
Pyrolysis reactions of 4-phenyl-2,3,5,6-tetrafluorophenyl prop-2-enyl ether and 4-trifluoromethyl-2,3,5,6-tetrafluorophenyl prop-2-enyl ether: Remarkable rearrangement reactions of intramolecular Diels-Alder products.: Mechanistic implications of a new thermal retro-Diels-Alder reaction to cyclohexa-2,4-dienylmethyl fluoroketenes and recyclisations
Allen, David M.,Batsanov, Andrei S.,Brooke, Gerald M.,Lockett, Stephen J.
, p. 57 - 67 (2007/10/03)
The pyrolyses of 4-phenyl-2,3,5,6-tetrafluorophenyl prop-2-enyl ether (26) under flash vapour phase (FVP) conditions at 350°C and of 4-trifluoromethyl-2,3,5,6-tetrafluorophenyl prop-2-enyl ether (27) on heating in vacuo at 169°C give mixtures of products which include 3-phenyl-2,4,5,7-tetrafluorotricyclo[3.3.1.02,7]non-3-ene-6-one (28), and 3-trifluoromethyl-2,4,5,7-tetrafluorotricyclo[3.3.1.0 2,7]non-3-ene-6-one (31), respectively, the products of one of the two possible intramolecular Diels-Alder reactions of the Claisen rearrangement intermediates 2. FVP of 26 at 430°C and 27 at 450°C give the bicyclic compounds 7-phenyl-2,5β,6,7aβ-tetrafluoro-3aβ,4,5,7a-tetrahydroinden-1-one (34) and 7-trifluoromethyl-2,5β,6,7aβ-tetrafluoro-3aβ,4,5,7a- tetrahydroinden-1-one (37), respectively. It is proposed that these latter two compounds are formed via two possible intermediates produced by recyclisations of the tethered 2,4,5-trifluoro-3-(substituent)-2,4-cyclohexadienylmethyl fluoroketene (23), itself formed via new retro-cyclisation reactions of 28 and 31, respectively. Also formed from 27 via 31 is 1,2,4β,5,7-tetrafluoro-3-(trifluoromethyl)bicyclo[3.3.1]nona-2,6-dien-8-one (39).