432-16-6

Upstream product

• 377-10-6 2H-decafluoro-1-trifluoromethyl-cyclohexane 
• 92-52-4 biphenyl 
• 98-08-8 α,α,α-trifluorotoluene 
• 355-02-2 perfluoro(methylcyclohexane) 
• 103-82-2 phenylacetic acid 
• 31665-17-5 1-Trifluoromethylheptafluorocyclohexa-1,4-diene 
• 434-64-0 perfluorotoluene 
• 108-88-3 toluene 
• 14100-81-3 cis 4H-1-trifluoromethyl/-decafluorocyclohexane 
• 355-75-9 decafluorocyclohex-1-ene 
• 374-75-4 decafluoro-1-iodo-2-trifluoromethyl-cyclohexane 
• 14100-80-2 trans 4H-1-trifluoromethyldecafluorocyclohexane 

Downstream Products

• 1551-37-7 1-amino-3-imino-2-trifluoromethylhexafluorocyclohex-1-ene 
• 85577-98-6 1-methoxy-2-trifluoromethyloctafluorocyclohex-1-ene 
• 434-64-0 perfluorotoluene 
• 424-33-9 dianilinium hexafluoroglutarate 
• 85578-01-4 trans-1-Methoxy-2-trifluoromethyldecafluorocyclohexane 
• 85578-01-4 cis-1-Methoxy-2-trifluoromethyldecafluorocyclohexane 
• 130503-86-5 2-Trifluoromethylnonafluorocyclohexanone 
• 130482-36-9 1H,2H-2-Trifluoromethyloctafluorocyclohexanol 

Relevant academic research and scientific papers

Interaction of perfluorocarbons with carbon

Activated carbon is an effective stoichiometric fluorine acceptor which defluorinates perfluoroalkanes with the partial structure (Rf)2CFCF(Rf)2 to alkenes and perfluoroalkenes to dienes.Carbon catalyzes double-bond shifts, as well as cis/trans and ring-chain perfluoro-olefin isomerizations.Carbon effectively catalyzes TFE and HFP dimerizations.Less effecively, carbon catalyzes further oligomerization of TFE to give low yields of linear, internal olefins.Free radicals may be the key surface intermediates.

Functionalization of saturated fluorocarbons

A method is described for transforming perfluoroalkanes and perfluorocycloalkanes bearing tertiary fluorine into perfluoroenolates, which can be variously derivatized.

FLUORINATIONS WITH POTASSIUM TETRAFLUOROCOBALTATE. PART VIII. FLUORINATIONS OF TOLUENE AND OF PHENYLACETIC ACID

At 340 deg C, toluene gave five 1-trifluoromethyl-substituted compounds: -2H,4H,5H-tetrafluorocyclohexa-1,4-diene (IX); -2H-4H/5H-hexafluorocyclohex-1-ene (X); -2H-octafluorocyclohex-1-ene (IV); -nonafluorocyclohex-1-ene (III); also perfluoromethylcyclohexane (II): traces of perfluorocyclohexane (I) were found.The 1-difluoromethyl-substituted analogues of these five were also obtained: - compounds XII, XV, VIII, VI, and V, respectively.A further five 1-difluoromethyl-substituted derivatives were found : -nonafluorocyclohex-3-ene (VII); an inseparable mixture of the -2H,4H- and -2H,5H-heptafluorocyclohex-1-enes (XI); -2H-3H/4H-hexafluorocyclohex-1-ene (probably) (XIV); and (difluoromethyl)benzene (XIII). Structures of the unknown products were established by analysis and by nmr and ir spectroscopy.Further, the key intermediate (XII) was oxidized to difluoromalonic acid, whilst compound IV was dehydrofluorinated, to give 2H-(difluoromethyl)tetrafluorobenzene (XXI), together with an inseparable mixture of 2H,4H- and 2H,5H-1-(difluoromethyl)pentafluorocyclohexa-1,4-diene (XX).Dehydrofluorination of mixed heptafluoro-enes XI afforded 2H-1-(difluoromethyl)hexafluorocyclohexa-1,4-diene (XVIII), and mixed 2H-1- and 1H-2-(difluoromethyl)hexafluorocyclohexa-1,3-diene (XIX). Difluoromethylundecafluorocyclohexane (V) did not dehydrofluorinate.Phenylacetic acid was fluorinated likewise, and gave a similar range of products, but also one (originally an acid fluoride?) which was converted to the methyl ester of tridecafluoro(cyclohexylacetic) acid (XVII).The probable pathway of the fluorination process could be worked out.

ACTION OF VANADIUM AND ANTIMONY PENTAFLUORIDES ON POLYFLUORINATED DERIVATIVES OF CYCLOHEXADIENE

Polyfluorinated 1,3- and 1,4-cyclohexadienes are fluorinated by vanadium fluoride at -25 to 25 deg C.The olefinic fragments of perfluoro-1,3- and perfluoro-1,4-cyclohexadienes are close to each other in reactivity.Under the influence of vanadium pentafluoride the fluorine atoms add to 1-R-heptafluoro-1,4-cyclohexadienes preferentially at the multiple bond containing the less electron-withdrawing substituent.At -80 to 20 deg C antimony pentafluoride leads to isomerization of the polyfluorinated derivatives of cyclohexadiene.

FLUORINATIONS WITH COMPLEX METAL FLUORIDES. PART 9. FLUORINATIONS OF TOLUENE AND XYLENE DERIVATIVES BY MEANS OF CAESIUM TETRAFLUOROCOBALTATE(III)

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.

FLUORINATION OF POLYFLUOROAROMATIC COMPOUNDS WITH VANADIUM PENTAFLUORIDE

Fluorination of polyfluoro-derivatives of benzene and diphenyl with vanadium pentafluoride at -25 to -10 deg C afforded fluorinated cyclohexadienes and cyclohexenes.Octafluoronaphthalene was converted under these conditions to perfluoro-1,4-dihydronaphthalene, perfluorotetralin, perfluoro-1,4,5,8-tetrahydronaphthalene and perfluoro-1,2,3,4,5,8-hexahydronaphthalene.

AROMATIC FLUORINE DERIVATIVES. XCVII. OXIDATIVE FLUORINATION OF PERFLUORINATED AROMATIC COMPOUNDS WITH VANADIUM PENTAFLUORIDE

Perfluorinated aromatic compounds are converted by the action of vanadium pentafluoride at -25 to -15 deg C into perfluorinated derivatives of cyclohexadiene and cyclohexene.The rate of addition of the two fluorine atoms to the perfluorinated derivatives of 1,3- and 1,4-cyclohexadiene under conditions of competing fluorination depends on the nature of the substituent at the carbon-carbon double bond.

FLUOROCYCLOHEXANES. PART XVI. THE SIX H-TRIFLUOROMETHYLDECAFLUORO- AND TWO OF THE 2H,4H-TRIFLUOROMETHYLNONAFLUORO-CYCLOHEXANES

Fluorination of benzotrifluoride by cobaltic fluoride at 260-280 deg gave, besides the fluorocarbon, the six possible tridecafluoromethylcyclohexane isomers, and two 2H,4H-dodecafluorides.Of the C7HF13 compounds, only the cis-2H-, and the cis- and trans-4H-isomers could be isolated pure.The two 3H-isomers were made by pyrolysis of perfluoro(1-methyl-3-isopropylcyclohexane) in the presence of toluene.The trans-2H-isomer was made by further fluorination of one of the 2H,4H-dodecafluorides.Aqueous potash and the cis-2H-tridecafluoride gave 1-trifluoromethylnonafluorocyclohex-1-ene, which with stronger alkali hydrolysed to 1-carboxynonafluorocyclohex-1-ene.The cis- and trans- 2H and 4H-tridecafluorides were dehydrofluorinated by sodium fluoride at 320-380 deg (the cis-isomer of each pair reacted faster than the trans-: axial versus equatorial hydrogen) to give, respectively, the 1-trifluoromethylnonafluoro-ene and the 4-trifluoromethyl-isomer.The latter was isomerised to the former by sodium fluoride at 500-600 deg.The 1-CF3-ene gave hexafluoroglutaric acid on oxidation with alkaline potassium permanganate.