392-56-3 Hexafluorobenzene

Lenzer T, Luther K, Troe J, Gilbert R G and Urn K F 1995 Trajectory simulations of collisional energy transfer in highly excited benzene and hexafluorobenzene J. Chem. Phys. 103 626-41... 

For heavy molecules with very small rotational state spacing, this limit on AJ puts severe upper limits on the amount of energy that can be taken up in the rotations of a heavy molecule during a collision. Despite these limitations, P(E, E ) distributions have been obtained by inverting data of the type described here for values of AE in the range -1500 cm > AE > -8000 cnD for the two donor molecules pyrazine and hexafluorobenzene with carbon dioxide as a bath acceptor molecule [15,16]. Figure C3.3.11 shows these experimentally derived... 

Figure C3.3.11. The energy transfer probability distribution function P(E, E ) (see figure C3.3.2) for two molecules, pyrazine and hexafluorobenzene, excited at 248 nm, arising from collisions with carbon dioxide...

Figure C3.3.12. The energy-transfer-probability-distribution function P(E, E ) (see figure C3.3.2 and figure C3.3.11) for two molecules, pyrazine and hexafluorobenzene, excited at 248 nm, arising from collisions with carbon dioxide molecules. Both collisions that leave the carbon dioxide bath molecule in its ground vibrationless state, OO O, and those that excite the 00 1 vibrational state (2349 cm ), have been included in computing this probability. The spikes in the distribution arise from excitation of the carbon dioxide bath 00 1 vibrational mode.

Morgulis J M, Sapers S S, Steel C and Oref I 1989 Collisional aotivation of oyolobutene by hexafluorobenzene a ohemioal probe for highly energetio oollisions in reaotive systems J. Chem. Rhys. 90 923-9... 

The most common types of aryl halides m nucleophilic aromatic substitutions are those that bear o ox p nitro substituents Among other classes of reactive aryl halides a few merit special consideration One class includes highly fluormated aromatic compounds such as hexafluorobenzene which undergoes substitution of one of its fluorines on reac tion with nucleophiles such as sodium methoxide... 

Write equations describing the addition-elimination mechanism for the reaction of hexafluorobenzene with sodium methoxide clearly showing the structure of the rate determining intermediate j... 

Other aryl halides that give stabilized anions can undergo nucleophilic aromatic substitution by the addition-elimination mechanism Two exam pies are hexafluorobenzene and 2 chloropyridme... 

Pentafluorophenol is readily prepared by heating hexafluorobenzene with potassium hydrox ide in tert butyl alcohol... 

Question. List the symmetry elements of each of the following molecules (a) 1,2,3-trifluorobenzene, (b) 1,2,4-trifluorobenzene, (c) 1,3,5-trifluorobenzene, (d) 1,2,4,5-tetrafluoro-benzene, (e) hexafluorobenzene, (f) l,4-dibromo-2,5-difluorobenzene. 

HEXAFLUOROBENZENE The development of commercial routes to hexafluoroben2ene [392-56-3] included an intensive study of its derivatives. Particularly noteworthy was the development of high temperature lubricants, heat-transfer fluids, and radiation-resistant polymers (248). 

Hexafluorobenzene. Hexafluoroben2ene [392-56-3] C F, is a colorless Hquid with a sweet odor. Hexafluoroben2ene (perfluoroben2ene) has... 

An alternative hexafluorobenzene process features exchange fluorination (KF) of hexachlorobenzene in the presence of polar solvents (226,249) or under solvent-free conditions (450—540°C, autoclave) (250). Intermediates such as chloropentafluorobenzene can be further fluorinated to hexafluorobenzene (42—51% yield) by cesium fluoride in sulfolane (226,249). 

Pyrolytic routes to hexafluorobenzene have also attracted attention but have not been commercialized. Pyrolysis of tribromofluoromethane [353-54-8] CBr F, at 630—640°C in a platinum tube gives hexafluorobenzene in 55% yield (251—253). The principal disadvantage of this process is the low weight yield of product 90% of the costly CBr F that is charged is lost as bromine. Of economic potential is the related copyrolysis of dichlorofluoromethane [754-34-0] and chlorofluoromethane [593-70-4] (254,255). 

Hexafluorobenzene [392-56-3] M 186.1, m 5.1°, b 79-80°, d 1.61, n 1.378. Main impurities are incompletely fluorinated benzenes. Purified by standing in contact with oleum for 4h at room temperature, repeating until the oleum does not become coloured. Washed several times with water, then dried with P2O5. Final purification was by repeated fractional crystn. 

An interesting variant in which nucleophilic aromatic substitution is carried out on the crown nucleus rather than using the crown as nucleophile was reported by Haines . In this approach, hexafluorobenzene was stirred in 1,2-dimethoxyethane at room temperature with pentaethylene glycol and sodium hydride. A double nucleophilic aromatic substitution occurred affording 2, 3, 4 ,5 -tetrafluorobenzo-15-crown-5 as an oil in 38% yield. The reaction is illustrated below. 

Reactions of the halogen iluorides with other unsaturated functional groups are generally reported only with highly fluorinated substrates Hexafluorobenzene and denvatives [118] and octaflvoronaphthalene [119] react with mixtures of bromine and bromine trifluoride by 1,4 addition of fluorine followed by addition of bromine fluoride across a reniatning double bond (equation 22)... 

Oxidative reactions of dienes are accomphshed under similar conditions as those of alkenes. Abicydic diene synthesized from hexafluorobenzene and 1,2-di-chloroethylene is monoepoxidized by triflnoroperoxyacetic acid [43] (equation 35). 

In an unusual example of displacement of fluonne by hydroxyl, hydroxyl radicals attack fluorinated benzenes Hexafluorobenzene is the least reactive The hydroxyl radical generates the pentafluorocyclohexadienonyl radical from it [13] (equation 13) These unstable species are detected spectroscopically Their disap-... 

A mixture of nitromethane and hexafluorobenzene, when thermolyzed at 550 °C, yields pentafluorotoluene and pentafluorophenol as major products- The formation of nitrosyl and mtryl fluondes is probably a dnving force in this transfor-madon [705] A potential general preparative route to various perfluorovmyl amines is pyrolytic decarboxylation of potassium salts of perfluoro-2-(dialky-... 

In 1966, a photochemical rearrangement by ultraviolet (UV) irradiation of hexafluorobenzene to hexafluorobicyclo[2 2 0]hexa-2,5-diene was achieved Since then, many reactions analogous to the valence tautomerism of benzene and bicy clo[2 2 0]hexadiene (1 e, Dewar benzene), as well as of fluonnated benzvalene and... 

UV irradiation of a mixture of hexafluorobenzene in the presence of oxygen gives Dewar benzene oxide also as a minor product, which undergoes thermal transformation to hexafluorocyclohexa-2,4-dienone [J46] (equation 36)... 

UV irradiation of hexafluorobenzene with indene or cycloalkenes gives high yields of 2+2 adducts, which undergo further intramolecular cycloaddition to form hexafluoropolycycloalkanes [754] (equation 38) Photolysis of fluormated deriva tives of vinylbenzenes afford benzocyclobutenes, whereas allyl benzenes yield Dewar benzene-type products [755]... 

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