- AROMATIC POLYFLUORO-COMPOUNDS. PART LVIII. THE REACTION OF n-BUTYLLITHIUM WITH METHYL-, FLUOROMETHYL-, AND DIFLUOROMETHYL-PENTAFLUOROBENZENE
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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
- Coe, Paul L.,Oldfield, David,Tatlow, John Colin
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- The preparation, stability and reactivity of perfluorobenzyl-cadmium and -copper reagents
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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
- Burton, Donald J.,Yang, Zhen-Yu,Platonov, V.
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- 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
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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.
- Zonov, Yaroslav V.,Karpov, Victor M.,Platonov, Vyacheslav E.,Rybalova, Tatjana V.,Gatilov, Yuri V.
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p. 1574 - 1583
(2008/09/18)
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- Reductive transformations of organofluorine compounds: II. Hydrodechlorination of chloropolyfluoroarenes by the action of zinc
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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.
- Krasnov,Platonov
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p. 1488 - 1499
(2007/10/03)
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- FLUORINATIONS WITH COMPLEX METAL FLUORIDES. PART 9. FLUORINATIONS OF TOLUENE AND XYLENE DERIVATIVES BY MEANS OF CAESIUM TETRAFLUOROCOBALTATE(III)
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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.
- Bailey, John,Plevey, Raymond G.,Tatlow, John Colin
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- REACTION OF POLYFLUORINATED DERIVATIVES OF BENZENE CONTAINING HYDROGEN ATOMS IN THE SIDE CHAIN WITH VANADIUM PENTAFLUORIDE
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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.
- Avramenko, A. A.,Bardin, V. V.,Karelin, A. I.,Krasil'nikov, V. A.,Tushin, P. P.,et al.
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p. 2318 - 2323
(2007/10/02)
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