Hexafluoropropene oxide

Many perfluoroaUphatic ethers and tertiary amines have been prepared by electrochemical fluorination (1 6), direct fluorination using elemental fluorine (7—9), or, in a few cases, by fluorination using cobalt trifluoride (10). Examples of lower molecular weight materials are shown in Table 1. In addition to these, there are three commercial classes of perfluoropolyethers prepared by anionic polymerization of hexafluoropropene oxide [428-59-1] (11,12), photooxidation of hexafluoropropene [116-15-4] or tetrafluoroethene [116-14-3] (13,14), or by anionic ring-opening polymeriza tion of tetrafluorooxetane [765-63-9] followed by direct fluorination (15). 

The alkoxide formed by attack of the carbonyl group of perfluorobutyrolactone opens the oxirane ring of hexafluoropropene oxide at the central carbon atom [37] (equation 33). A fluorinated sultone reacts with halogenoalkanes in the presence of metal fluoride [3S] (equation 34). 

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... 

The reaction of hexafluoropropene oxide (HFPO) (90) with excess Grignard reagents formed alkylated a,/ -unsaturated ketones (91) (Scheme 33) [80]. 

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 oxide reacts with enamines to give pentafluorinated 1,3-diketones228. 

Perfluoro-w-alkanes Perfluoro-cycloalkanes Perfluoro-w-alkanes Perfluorinated cyclic ethers Perfluorotrialkylamines Perfluoro-w-alkanes Perfluorinated cyclic ethers Perfluorotrialkylamines Homopolymers of hexafluoropropene oxide Photooxidation products of hexafluoropropene or tetrafluoroethene Homopolymers of tetrafluorooxetane... 

Fluorinated epoxides are very important synthetically. Perfluoroalkenes can be oxidized by numerous means to the corresponding epoxides. The most commonly encormtered epoxide is hexafluoropropene oxide (HFPO), which is made from hexafluoropropene and is used in the synthesis of oligomers and as a source of difluorocarbene. HFPO is a colorless, nonflammable gas, boiling at -27.4 °C it can be ring-opened easily by nncleophiles or electrophiles imder a variety of conditions. HFPO can be rearranged by flnoride ion to perfluoropropionyl flnoride and by Lewis acids snch as UO2 to hexafluoroacetone (HFA). Nncleophiles typically attack the most substituted carbon of the epoxide, freeing the oxyanion to lose fluoride or act as a nucleophile itself Some examples of HFPO reactivity are shown in Scheme 3. 

Hexafluoropropene oxide (HFPO) [67] fragments exclusively by a reversible process at high temperature to give trifluoroacetyl fluoride and difluorocarbene only [68] (Figure 6.47). 

Examples of fluoride-ion-initiated reactions involving perfluorinated epoxides are shown in Figure 8.47 [155-158]. Hexafluoropropene oxide (HFPO) and tetrafluoroethene oxide will polymerise under certain conditions in the presence of fluoride ion. The process involves an extending alkoxide and it is terminated by elimination of fluoride ion to give... 

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

Conversely, cleavage with a Lewis acid catalyst gives a ketone [191, 192] (Figure 8.63). These are interesting reactions because they involve a 1,2-fluorine shift to a positive centre (Figure 8.64), a process that is, of course, very well known for hydride shifts. The conversion of hexafluoropropene oxide to hexafluoroacetone is probably the... 

SYNS HEXAFLUOROEPOXYPROPANE HEXAFLUORO-1,2-EPOXYPROPANE HEXAFLUOROPROPENE OXIDE HEXAFLUORO-... 

HEXAFLUOROPROPENE see HDFOOO HEXAFLUOROPROPENE EPOXIDE see HDF050 HEXAFLUOROPROPENE OXIDE see HDF050 HEXAFLUOROPROPYLENE (DOT) see HDFOOO HEXAFLUOROPROPYLENE OXIDE (DOT) see HDF050... 

Fluorination of high molecular weight polyethers with elemental fluorine (diluted with helium) at room temperature gave fluorinated polyethers, which were depolymerized by further treatment with flowing F -He at 55-210 "C to produce carbonyl difluoride, amongst the decomposition products [1197c]. COFj is also formed in the oxidative thermal degradation of polyethers derived from hexafluoropropene oxide [1582]. Polymeric C F Oj decomposes, at an unspecified temperature, into carbonyl difluoride [760], The presence of... 

Hexafluoropropene oxide as key compound in fluoroorganic synthesis 85AG164. 

Hexafluoropropene oxide is also a good reagent for the nucleophilic formation of the Bi-F bond in triphenylbismuth) V) compounds [99JFC(93)103],... 

Hexafluoropropene oxide is prepared by reaction of hexafluoropropene with alkaline hydrogen peroxide (see Houben-Weyl, Vol. E5, p 17) and used as the crude product without separation from unreacted starting material.26... 

Millauer, H. Schwertfeger, W. Siegemund, G. Hexafluoropropene oxide a key compound in organofluorine chemistry. Angew. Chem., Ini. Ed. Engl. 1985, 24, 161. 

It is worth of mentioning that the cross-coupling of 16 and acid derived from hexafluoropropene oxide trimer leads to clean formation of 18 in relatively high yield (Fig. 9.4). More data on the synthesis of five-membered perfluorinated ethers can be found in Chapter 4. 

Heterocycles containing limited amount of fluorinated substituents (usually 1-3) can be named using trivial names or conventional nomenclature in combination with indication of the position of fluorinated substituents, for example, 2-fluoro-4-tri-fluoromethylpyridine. The situation becomes more complicated in case of poly-fluorinated and completely fluorinated heterocycles. In case of heterocycles with relatively small number of fluorinated substituents and well-defined stmctures, Greek or Latin numeral roots can be used. Names such as hexafluoropropene oxide, 2,2-bis (trifluoromethyl)oxirane, 2,2,3,3-tetrafluorooxetane, tetrakis(trifluoromethyl)furane, pentafluoropyridine, tetrafluoropyridazine, tetrafluoropyrimidine, and heptafluoro-quinoline are unambiguous and commonly accepted (see Fig. 0.1). 

Addition of difluorocarbene, from hexafluoropropene oxide at 185 °C, to 2,3-dichlorotetrafluoropropene yields the expected cyclopropane, easily de-chlorinated by zinc in dioxan to the reactive and highly toxic hexafluoromethylene-cyclopropane, containing some (5%) isomeric hexafluoro-l-methylcyclopropene. This interesting monomer undergoes the reactions shown in Scheme 7, and its... 

The reaction of hexafluoropropene oxide (HFPO) with Grignard reagents RMgX (X = Cl or Br) (1 1 molar ratio) affords the 2-halogenotetrafluoropropionyl fluoride (4), isolated as the methyl or ethyl ester (26—56%) with an excess of Grignard reagent the ketones (5) (ca. 55 %) can be isolated (the proposed reaction pathway is shown in Scheme 4) (see also p. 278). Ketone (5 R = Me) also results... 

Trade Name Synonyms Cyracure UVR-6216 t[Dow http //www.dow.com] 1,2-Epoxy-1,1,2,3,3,3-hexafluoropropane CAS 428-59-1 EINECS/ELINCS 207-050-4 Synonyms Acetone, hexafluoro Hexafluoroepoxypropane Hexafluoro-1,2-epoxypropane Hexafluoropropene epoxide Hexafluoropropene oxide Hexafluoropropylene oxide Oxirane, trifluoro (trifluoromethyl)- Perfluoro (methyloxirane) Perfluoropropylene oxide Propane, 1,2-epoxy-1,1,2,3,3,3-hexafluoro-Propylene oxide hexafluoride ... 

Hexafluoropropene. See Hexafluoropropylene Hexafluoropropene epoxide Hexafluoropropene oxide. See 1,2-Epoxy-1,1,2,3,3,3-hexafluoropropane... 

A low yield of a perfluorobenzodioxin is formed from C6F50 Cs and hexafluoropropene oxide/ The reactions of fluorinated anilines, phenyl-hydrazines, and carboxylic acids with thiolates have been reported. All the fluorine in CeFe is replaced by chlorine under mild conditions, using the reagent BMC (S2CI2-AICI3-SO2CI2). ... 

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