2 perfluoropropene

Information on the production levels of the perfluoroethers and perfluorotertiary amines is not disclosed, but the products are available commercially and are marketed, for instance, as part of the Fluorinert Electronic Liquids family by 3M Co. (17). These Hquids have boiling points of 30—215°C with molecular weights of about 300—800. They range in price from 26—88/kg. Perfluoropropene oxide polyethers are marketed by Du Pont with the trade name Krytox (29). The linear perfluoropropene oxide polyethers are marketed by Daikin under the trade name Demnum (28). The perfluoropolyethers derived from photooxidation are marketed by Montefluos under the trade name of Fomblin (30). These three classes of polyethers are priced from about 100—150/kg. 

The same dichotomy was observed with hexafluorodimethylcarbene (228), formed by thermolysis of diazirine (227) at 150 °C. The carbene (228) can stabilize itself either intramolecularly to perfluoropropene (229), or intermolecularly by addition to multiple bonds. Oxirane (230) is formed with hexafluoroacetone, cyclopropene (231) with 2-butyne (66MI50800). 

Iodine monochloride adds unidirectionally to perfluoropropene-2-ol to form a chlorohydrin, which easily dehydrochlonnates to yield lodopentafluoroacetone [/5] (equation 8). 

Sodium nitrite in dimethylformamide acts as a nucleophile and reacts with perfluoropropene to generate a perfluoroalkyl nitrite anion The intermediate carbanion undergoes intramolecular nitrosation with loss of carbonyl difluoride to give tnfluoroacetic acid upon hydrolysis [5] (equation 6)... 

Perfluoroallyl fluorosulfate is prepared by the treatment oiperfluoropropene with sulfur tnoxide m the presence of boron catalysts [2, 3, 4, 5, 6, 7] (equation 2) Perfluoroisopropyl allyl ether reacts similarly to give 58% polyfluoroallyl fluorosulfate in a cis/trans ratio of 6 4 [S] Sultones are the exclusive products without catalyst. Polyfluoroolefins such as 2-hydropentafluoropropylene [9], (2,3-dichloropropyl)tri-fluoroethylene [70], perfluoropropene [2, i], perfluoroisopropyl alkenyl ethers [S], and acyclic polyfluoroallyl ethers [77] undergo sulfur trioxidation to regioselectively produce the corresponding P-sultones in high yield... 

The behavior of strained,/Zuorimiret/ methylenecyelopropanes depends upon the position and level of fluorination [34], l-(Difluoromethylene)cyclopropane is much like tetrafluoroethylene in its preference for [2+2] cycloaddition (equation 37), but Its 2,2-difluoro isomer favors [4+2] cycloadditions (equation 38). Perfluoromethylenecyclopropane is an exceptionally reactive dienophile but does not undergo [2+2] cycloadditions, possibly because of stenc reasons [34, 45] Cycloadditions involving most possible combinations of simple fluoroalkenes and alkenes or alkynes have been tried [85], but kinetic activation enthalpies (A/f j for only the dimerizations of tetrafluoroethylene (22 6-23 5 kcal/mol), chlorotri-fluoroethylene (23 6 kcal/mol), and perfluoropropene (31.6 kcal/mol) and the cycloaddition between chlorotnfluoroethylene and perfluoropropene (25.5 kcal/mol) have been determined accurately [97, 98] Some cycloadditions involving more functionalized alkenes are listed in Table 5 [99. 100, 101, 102, 103]... 

For dienophiles with vinylic fluorine, such as perfluoropropene, the [2+4] reactivity is diminished so that [2-1-2] cycloaddition dominates [71] (equation 64). 

Although hexafluoro-l,3-butadiene is better known for its [2+2] reactions, its Diels-Alder reactions, particularly with electron-deficient alkenes such as acrylonitrile and perfluoropropene, are not unknown [9] The first report of a Diels-Alder reaction is with an acetylenic dienophile Although the major product of Us reaction with phenylacetylene is its [2+2] adduct, a 3 5% yield of products of a Diels-Alder reaction is also observed [123] (equation 103)... 

Perfluoro-l,4-pentadiene and perfluoropropene undergo similar reactions. Atkinson and McKeagen 41 reported two similar reactions ... 

The procedure illustrates a fairly general method for the preparation of -substituted perfiuoroolefins. The method has been applied to the synthesis of 2-cyclohexyl- (70%), 2-benzyl- (61%), and 2-(/>-fluorophenyl)perfluoropropenes (67%), and it is probably applicable to any a-trifluoromethyl ketone. Olefins containing a perfluoroalkyl group other than trifluoromethyl can be prepared by the same procedure by the substitution of lithium chlorodifluoroacetate for sodium chlorodifluoroacetate.7 Other routes to / -substituted perfiuoroolefins are not general or convenient. Routes to perfiuoroolefins generally yield the a-substi-tuted olefin rather than the /3-substituted olefin. 

There are hazards involved both during the preparation and after isolation of these materials. Addition of sodium methoxide powder to perfluoropropene in diglyme at — 60°C led to ignition in some cases, and the products, 1,3,3-trifluoro-2-methoxycyclopropene (very volatile and flammable), or 3,3-difluoro-... 

The decomposition products, up to a temperature of 500°C, are principally the monomer, tetrafluoroethylene, but also include perfluoropropene, other perfluro compounds containing four or five carbon atoms, and an unidentified particulate waxy fume. From 500°C to 800°C, the pyrolysis product is carbonyl fluoride, which can hydrolyze to form HE and CO2. 

Perfluoropropene (1) can be directly oxidized to perfluoro-1,2-epoxypropane (2) by a variety of oxidizing reagents, e.g. oxygen, hydrogen peroxide.50 s2 Pcrfluoro-1,2-epoxypropane (2) can fluorinate carboxylic acids to their corresponding acid fluorides in the presence of tertiary amines.52 55... 

In general, the chemistry of fluoro-l,3,5-triazines resembles that of the chloro derivatives, and therefore will not be discussed in detail. There is evidence that cyanuric fluoride is less reactive than cyanuric chloride in reaction with aniline (76CCC3378). Chambers et al. have reported the isolation of a stable anion cr- complex from the reaction of cyanuric fluoride and cesium fluoride (equation 32) (77JCS(Pl)l605). Such species are believed to be intermediates in the formation of (68) from cyanuric fluoride and perfluoropropene (equation 33). Olah et al. have shown that cyanuric fluoride deoxygenates sulfoxides efficiently (equation 34) (80S221). 

---