Hexafluoropropene reaction with

Hexafluoropropene is converted to its 1,2-epoxide in 55% yield by bubbling through a solution of chromium tnoxide in fluorosulfonic acid [8], the analogous reaction with a mixture of chromium trioxide and dichromium tnoxide gives pentafluoroacetonyl fluorosulfate [.5] (equation 6)... 

Hexadiene-3-ol, hydrogenation, 30 361 Hexadiene, reaction with HCN, 33 19-20 Hexafluoropropene oxide oligomers, 42 497 Hexahydronaphthalenes, intermediates of naphthalene hydrogenation, 18 32, 33... 

R.G. Watts, C.G. Allison, K.P. Barthold, P. Tarrant, Reaction of hexafluoropropene oxide with Grignard reagents, J. Fluor. Chem. 3 (1973) 7-15. 

Reactions with hexafluoropropene oxide (61) provide a good route to perfluo-rinated ketones [51, 52] and trapping with acid fluorides directly also gives ketones [53] (Scheme 26). 

Hexafluoropropene dimers and trimers can give a variety of products if a pre-equilibrium is established with fluoride ion before reaction with the nucleo-... 

Recently a study of the use of various a, ta-diiodo telomers led to an interesting, selective 1 1 addition reaction with hexafluoropropene [208,209]. 

The reaction of hexafluoropropene (15) with antimony(V) fluoride in liquid sulfur dioxide yields a mixture of octafluoropropane and perfluoro(4-methylpent-2-ene). ... 

The reaction of hexafluoropropene dimers with cesium fluoride and sulfur monochloride leads to bis[perfluoro(l,l-dimethylbutyl)] trisulfide (7, n = 3) as the main product. - ... 

It was noted that for the perfluorobutanoic acid salts of the alkaline earth metals the yield of perfluoroalkene increased with increasing weight of the metal cation (vide supra). Decomposition of the barium salt gave hexafluoropropene in 78% yield while the reaction with the magnesium salt gave > 5 % of the same product. An exception was ammonium per-fluorobutanoate (4) which formed no alkene, but instead gave an almost quantitative yield of... 

Systems with perfluoroalkyl groups directly attached to the double bond are particularly unreactive towards electrophiles but reaction of hexafluoropropene (HFP) with SbFs leads to a perfluoroallyl cation, which then reacts with another molecule of HFP to give a dimer, probably by an electrophilic process [168] (Figure 7.51) that is analogous to that described earlier for 1,1,1-trifluoropropene [169], (Chapter 4, Section VIB). Similar addition and isomerisation reactions, which proceed via carbocationic intermediates, are given in Figure 7.52 [170-172]. 

So far, the only case where attack occurs at the CF2 position in hexafluoropropene oxide involves reaction with butyl lithium [156] (Figure 8.61). 

Perfluorinated olefins have been found to give both vinyl azides and the saturated fluoroazides on reaction with triethylammonium azide apparently the intermediate carbanion tends to abstract a proton in this case. Reaction of hexafluoropropene (28) with sodium azide in DMF leads stereospecifically to the trans azide 29. 

Phosgene reacts, sometimes violently, with a large number of common inorganic (Chapter 9) and organic (Chapter 10) substances. Hazardous reactions with lithium, sodium, potassium, aluminium, lithium amide, hexa-2,4-diyn-l, 6-diol, propan-2-ol, and hexafluoropropene have been mentioned specifically [1787]. Mixtures of potassium and phosgene are reported to explode when subjected to shock [1913a]. In addition, phosgene... 

PERCLENE (127-18-4) or PERCLOROETILENO (Spanish) (127-18-4) see perchloroethylene. PERFLUROETHYLENE (116-14-3) FjC=CFj Highly reactive, thermally unstable, flammable gas (flash point <32°F/<0°C). Explodes underpressure. Able to form unstable peroxides in air. If inhibitor (usually limolene) is not present in adequate concentrations, explosive polymerization may occur above 2025 mm Hg/2.66 bars at normal tenqjerature. Inhibited monomer will explode on contact with iodine pentafluoride and other substances, or in elevated tenperatures. Violent reaction with chloro-peroxytrifluoromethane, difluoromethylene dihypofluorite dioxygen difluoride, halogens, oxidizers, oxygen, sulfur trioxide, triboron pentafluoride. Incompatible with ethylene, hexafluoropropene forms an explosive peroxide. Normal gases date containers when opened and discard after 12 months. 

Reactions of perfluorinated alkenes, such as hexafluoropropene, with fluoride ion give perfluoroalkylcarbanions which can act as nucleophiles in S Ar reactions with perfluoroheteroaromatic systems (Fig. 8.13). These reactions are another example of mirror-image chemistry and reflect well-known Friedel-Crafts reactions of hydrocarbon systems that proceed by reaction of the corresponding electrophile and carbocationic intermediates. Poly substitution processes are possible and, indeed, all five fluorine atoms may be replaced upon reaction with an excess of tetrafluoroethylene and fluoride ion. ... 

Garbon-fluorine bonds of fluoroalkenes can be cleaved by reaction with metal hydrides to give HF and vinyl complexes. Thus, the rhodium compound [Rh (Z)-GF=GF(GF3) (PEt3)3] can be synthesized by regioselective G-F bond activation of hexafluoropropene at [RhH(PEt3)3] in the presence of Et3N/Gs2G03 (Scheme 10 left). ... 

Fluoroalkylquinolines can also be obtained from iV-arylfluoroalkylketenimines generated by treating hexafluoropropene dimer with primary arylamines indeed, the intermediate ketenimines can be isolated only if the aryl group possesses no available o-hydrogens (see Scheme 20). The extension of this reaction to heterocyclic synthesis is discussed in detail elsewhere (see p. 464). 

---