1887-73-6Relevant academic research and scientific papers
Reductively activated "Polar" nucleophilic aromatic substitution. III - The reactions of polyfluoronitrobenzenes with methanol
Niat, Mohammed,Marquet, Jorge,Gallardo, Iluminada,Cervera, Maria,Mir, Miquel
, p. 9059 - 9062 (1994)
The nucleophilic aromatic substitution reactions of pentafluoronitrobenzene (PFNB) and 2,3,4,5-tetrafluoronitrobenzene with methanol are both reductively activated. However, the first one is sensitive to the presence of radical scavengers but the second i
Reductively Activated "Polar" Nucleophilic Aromatic Substitution of Pentafluoronitrobenzene. The SRN2 Hypothesis Revisited
Marquet, Jorge,Jiang, Ziqi,Gallardo, Iluminada,Batlle, Anna,Cayon, Eduard
, p. 2801 - 2804 (1993)
The reactions between pentafluoronitrobenzene and several nucleophiles, in aqueous media, can be photo- and electro-stimulated (reductively).Our results indicate we are in the presence of a chain reaction type that includes direct attack of the nucleophil
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.
Constructing a catalytic cycle for c-f to c-x (x = o, s, n) bond transformation based on gold-mediated ligand nucleophilic attack
Hu, Ji-Yun,Zhang, Jing,Wang, Gao-Xiang,Sun, Hao-Ling,Zhang, Jun-Long
supporting information, p. 2274 - 2283 (2017/01/16)
A tricoordinated gold(I) chloride complex, tBuXantphosAuCl, supported by a sterically bulky 9,9-dimethyl-4,5-bis(di-Tert-butylphosphino)xanthene ligand (tBuXantphos) was synthesized. This complex features a remarkably longer Au?Cl bond length [2.632(1) ?] than bicoordinated linear gold complexes (2.27-2.30 ?) and tricoordinated XantphosAuCl [2.462(1) ?]. Single-crystal Xray diffraction analysis of a cocrystal of tBuXantphosAuCl and pentafluoronitrobenzene (PFNB) and UV-vis spectroscopic titration experiments revealed the existence of an anion-φ interaction between the Cl anion ligand and PFNB. Stoichiometric reaction between PFNB and tBuXantphosAuOtBu, after replacement of Cl by a more nucleophilic tBuO anion ligand, showed higher reactivity and para selectivity in the transformation of C-F to C-OtBu bond, distinctively different from that when only KOtBu was used (ortho selectivity) under the identical condition. Mechanistic studies including density functional theory calculations suggested a gold-mediated nucleophilic ligand attack of the C?F bond pathway via an SNAr process. On the basis of these results, using trimethylsilyl derivatives TMS-X (X = OMe, SEt, NEt) as the nucleophilic ligand source and the fluorine acceptor, catalytic transformation of the C-F bond of aromatic substrates to the C-X (X = O, S, N) bond was achieved with tBuXantphosAuCl as the catalyst (up to 20 turnover numbers).
Fluorine-containing phenylmaleimide derivative, polymer, chemically amplified resist composition, and method for pattern formation using the composition
-
, (2008/06/13)
A fluorine-containing phenylmaleimide derivative having a specific structure. A polymer obtained by polymerizing monomers containing the derivative. A polymer containing a specific structural unit and having a weight-average molecular weight of 2,000 to 2
The effect of fluorine substitution on the physicochemical properties and the analgesic activity of paracetamol
Barnard,Storr,O'Neill,Park
, p. 736 - 744 (2007/10/02)
The physicochemical properties and analgesic action of six fluorinated analogues of 4-hydroxyacetanilide (paracetamol) have been investigated. Fluorine substitution adjacent to the hydroxyl group increased lipophilicity and oxidation potential whilst substitution adjacent to the amide had little effect on lipophilicity but led to a greater increase in oxidation potential. Lack of coplanarity and conjugation of the amide group and aromatic ring was also apparent with the analogues that had fluorine in the 2 and 6 positions. Introduction of fluorine into the amide group of paracetamol increased the lipophilicity 4-fold and also increased the oxidation potential of paracetamol. ED50 values for analgesic activity in the phenylquinone-induced abdominal constriction test on male Swiss White mice showed that ring substitution by fluorine reduced activity, especially at the 2,6-positions. Introduction of fluorine into the amide group enhanced activity significantly. Correlation of the analgesic activity with the physicochemical properties indicated that conjugation (and planarity) of the amide group with the aromatic ring is essential for activity and that ease of oxidation may also be an important factor.
