22006-44-6Relevant academic research and scientific papers
AROMATIC POLYFLUORO-COMPOUNDS. PART LVIII. THE REACTION OF n-BUTYLLITHIUM WITH METHYL-, FLUOROMETHYL-, AND DIFLUOROMETHYL-PENTAFLUOROBENZENE
Coe, Paul L.,Oldfield, David,Tatlow, John Colin
, p. 341 - 348 (1985)
No metallation of the benzylic C-H bonds was detected when n-butyllithium reacted at -78 deg C with methyl-, fluoromethyl- and difluoromethyl-penta-fluorobenzene.The isolated product, in each case, was the parasubstituted butyl toluene; respectively,1-n-b
The preparation, stability and reactivity of perfluorobenzyl-cadmium and -copper reagents
Burton, Donald J.,Yang, Zhen-Yu,Platonov, V.
, p. 23 - 24 (1994)
Perfluorobenzyl bromide reacts readily with acid-washed cadmium powder in DMF at room temperature to give the F-benzylcadmium reagent.Metathesis of the F-benzylcadmium reagent with Cu(I)Br at -40 deg C to -35 deg C in DMF affords the F-benzylcopper reagen
Oxygen replacement by fluorine in carbonyl derivatives of perfluoroaromatic compounds and isomerization of perfluoroindan-1,3-dione to perfluoro-3-methylenephthalide under the action of HF/SbF5
Zonov, Yaroslav V.,Karpov, Victor M.,Platonov, Vyacheslav E.,Rybalova, Tatjana V.,Gatilov, Yuri V.
, p. 1574 - 1583 (2008/09/18)
When acted upon by HF/SbF5 at 95 °C, carbonyl groups of perfluorinated acetophenone (10), 3,4-dihydronaphthalen-1(2H)-one (8), 2,3-dihydronaphthalene-1,4-dione (9), benzocyclobutenone (6), benzocyclobutenedione (7) and indan-1-one (1) are converted into difluoromethylene groups to give the corresponding perfluoroaromatic products. Perfluoroindan-2-one (5), under the same conditions, is transformed to bis(perfluoroindan-2-yl) ether (21). On heating with HF/SbF5, perfluoroindan-1,3-dione (2) isomerizes into perfluoro-3-methylenephthalide (4) at 95 °C, and gives 4,5,6,7-tetrafluoro-3-trifluoromethyl-phthalide (14) at 130 °C. Compound 4 in the absence of a solvent dimerizes giving perfluorodispiro[phthalide-3,1′-cyclobutane-2′,3″-phthalide] (18), and when heated with SbF5 at 130 °C, it is converted into perfluoro-3-methylphthalide (3). When acted upon by HF/SbF5 at 95 °C, perfluorinated benzoic acid (12) and phthalic anhydride (13) give the corresponding products with trifluoromethyl groups.
Reductive transformations of organofluorine compounds: II. Hydrodechlorination of chloropolyfluoroarenes by the action of zinc
Krasnov,Platonov
, p. 1488 - 1499 (2007/10/03)
Polyfluoroarenes containing chlorine atoms in the aromatic ring and/or in the benzylic position undergo hydrodechlorination by the action of zinc in aqueous dimethylformamide. The use of Zn/Cu and addition of salts (NaCl, Na2SO4, NH4Cl) favor reductive dechlorination of the Carom - Cl bond. Polyfluorobenzotrichlorides react with excess zinc to give the corresponding CH3-substituted derivatives, otherwise CH2Cl- and CHCl2-containing compounds are formed. The reduction of C6F5CCl3 and C6F5CH2Cl with zinc in the presence of copper provides lower yields of the hydrodechlorination products and leads to formation of 1,2-bis(pentafluorophenyl)ethane.
FLUORINATIONS WITH COMPLEX METAL FLUORIDES. PART 9. FLUORINATIONS OF TOLUENE AND XYLENE DERIVATIVES BY MEANS OF CAESIUM TETRAFLUOROCOBALTATE(III)
Bailey, John,Plevey, Raymond G.,Tatlow, John Colin
, p. 1 - 14 (2007/10/02)
Benzotrifluoride at 320 deg C afforded some m-fluorobenzotrifluoride and octafluorotoluene (III), together with perfluoromethylcyclohexane (I), and also traces of 2H-heptafluorotoluene and 1-trifluoromethylnonafluorocyclohex-1-ene.Toluene itself gave (difluoromethyl)benzene, fluoro- and difluoro-methylpentafluorobenzene, difluoromethylundecafluorocyclohexane and (I); also traces of di- and tri-fluoromethylnonafluorocyclohex-1-ene: no benzotrifluoride or (III) were detected. 1,3-Bis(trifluoromethyl)benzene at 420 deg C gave 4,5,6-trifluoro-1,3-bis(trifluoromethyl)benzene, decafluoro-1,3-dimethylbenzene, and perfluoro-1,3-dimethylcyclohexane.Para-xylene at 350 deg C afforded 1,4-bis(difluoromethyl)tetrafluorobenzene, 1-difluoromethyl-4-trifluoromethyltetrafluorobenzene, decafluoro-1,4-dimethylbenzene (XIX), and perfluoro-1,4-dimethylcyclohexane (XVIII).Defluorination occurred to a significant extent on passage of the saturated cyclic fluorocarbons (I) and (XVIII) over the fully spent fluorinating agent (presumably caesium trifluorocobaltate) at ca. 400 deg C; the fluorocarbon arenes, (III) and (XIX) respectively, were obtained.
REACTION OF POLYFLUORINATED DERIVATIVES OF BENZENE CONTAINING HYDROGEN ATOMS IN THE SIDE CHAIN WITH VANADIUM PENTAFLUORIDE
Avramenko, A. A.,Bardin, V. V.,Karelin, A. I.,Krasil'nikov, V. A.,Tushin, P. P.,et al.
, p. 2318 - 2323 (2007/10/02)
The treatment of C6F5R (R=CH3, CH2F, CHF2) compounds with vanadium pentafluoride at -25 to -30 deg C leads to a 1-R-heptafluoro-1,4-cyclohexadienes, 1-R-nonafluorocyclohexenes, and products form fluorination of the side chain.Fluorination of the anisole derivatives C6F5OCH3 and C6F5OCHF2 only takes place in the aromatic ring.
