3467-85-4Relevant articles and documents
An efficient approach to the synthesis of 2,3,4,5-tetrafluorophenol
Maksimov, A. M.,Mezhenkova, T. V.,Nikul’shin, P. V.,Tretyakov, E. V.
, p. 995 - 998 (2021)
A new method for the preparation of 2,3,4,5-tetrafluorophenol from 2-[(2,3,4,5,6-pentafluorophenyl)thio]acetic acid has been proposed. It included the intramolecular cyclization of the salt of this acid in the presence of K2CO3 with the substitution of the ortho fluorine atom and the formation of a lactone, which under the reaction conditions underwent the ring-opening with the formation of the potassium salt of 2-[6-hydroxy(2,3,4,5-tetrafluorophenyl)-thio]acetic acid. The resulting salt was converted into methyl ester and desulfurized with Raney nickel to 2,3,4,5-tetrafluorophenol. The proposed method is a simple and efficient way to obtain poorly available 2,3,4,5-tetrafluorophenol in ~58% total yield based on 2-[(2,3,4,5,6-pentafluorophenyl)thio]acetic acid.
Catalytic defluorination of perfluorinated aromatics under oxidative conditions using N-bridged diiron phthalocyanine
Colomban, Cédric,Kudrik, Evgenij V.,Afanasiev, Pavel,Sorokin, Alexander B.
supporting information, p. 11321 - 11330 (2014/11/07)
Carbon-fluorine bonds are the strongest single bonds in organic chemistry, making activation and cleavage usually associated with organometallic and reductive approaches particularly difficult. We describe here an efficient defluorination of poly- and perfluorinated aromatics under oxidative conditions catalyzed by the μ-nitrido diiron phthalocyanine complex [(Pc)Fe III(μ-N)FeIV(Pc)] under mild conditions (hydrogen peroxide as the oxidant, near-ambient temperatures). The reaction proceeds via the formation of a high-valent diiron phthalocyanine radical cation complex with fluoride axial ligands, [(Pc)(F)FeIV(μ-N)FeIV(F) (Pc+?)], which was isolated and characterized by UV-vis, EPR, 19F NMR, Fe K-edge EXAFS, XANES, and Kβ X-ray emission spectroscopy, ESI-MS, and electrochemical techniques. A wide range of per- and polyfluorinated aromatics (21 examples), including C6F6, C6F5CF3, C6F5CN, and C6F5NO2, were defluorinated with high conversions and high turnover numbers. [(Pc)FeIII(μ-N)Fe IV(Pc)] immobilized on a carbon support showed increased catalytic activity in heterogeneous defluorination in water, providing up to 4825 C-F cleavages per catalyst molecule. The μ-nitrido diiron structure is essential for the oxidative defluorination. Intramolecular competitive reactions using C6F3Cl3 and C6F3H 3 probes indicated preferential transformation of C-F bonds with respect to C-Cl and C-H bonds. On the basis of the available data, mechanistic issues of this unusual reactivity are discussed and a tentative mechanism of defluorination under oxidative conditions is proposed.
Benzene derivatives and a liquid-crystalline medium
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, (2008/06/13)
The invention relates to novel benzene derivatives of the formula I STR1 in which n is 0, 1, 2, 3, 4, 5, 6 or 7, Q is --O--, --CH=CH-- or a single bond, r is 0, 1, 2, 3, 4 or 5, s is 0, 1 or 2, X is F, Cl, OCHF2 or CF3, L is H or F, and A is STR2 Z, Z-Ar, Ar-Z, Z-Cyc in which Z is a single bond, --(CH2)2 -- or --(CH2)4 --, Ar is 1,4-phenylene or biphenyl-4,4'-diyl and Cyc is trans-1,4-cyclohexylene.