Perfluoropropene oxide

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. 

Trifluoro-5-trifluoromethyl-l,3,2-dioxathiolane 2,2-dioxide (96) was obtained among other products by reaction of perfluoropropene oxide with sulfur trioxide at 150°C (73IZV2725). Perfluorobutadiene reacted with sulfur trioxide to give the cyclic sulfate (31)... 

When the dihalocarbene is generated thermally or photochemically the product of cheletropic addition to the alkyne is usually isolable in adequate yield. For example, pyrolysis of (trichloromethyl)trifluorosilane at 140°C and 6.5 atm in the presence of perfluorobut-2-yne provides " 3,3-dichloro-l,2-bis(trifluoromethyl)cyclopropene in 93 % yield. The corresponding perfluorocyclopropene is available from addition of di-fluorocarbene which can be generated by thermolysis of perfluoropropene oxide ... 

Perfluorovinylmagnesium bromide, which has been used in studies on the reaction of perfluoropropene oxide with Cirignard reagents (see p. 130),i also featui in the above investigations of the exchange route (see p. 268). 4JT-Decafluorobi(yclo-[2,2,1 ]hept-l-ylmagnesium iodide has found employment in the synthesis of bis-(4 -decafluorobicyclo [2,2,1 ]hept-l-yl)mercury (1) (see below). ... 

Tetrafluoroethylene oxide features, with perfluoropropene oxide, in recent Russian work on fluoride-initiated reactions of perfluorodicarboxylic acid fluorides (perfluoromalonyl and perfluoroadipoyl difluoride) with peifluoro-oxirans,... 

Free-radical homo- and co-polymerisation (with tetrafluoroethyiene) of diiluoroketrai dimethyl acetal, CFj C(OMe>2, has been described in the patent literature. The monomer was prepared by decarboxylative defluorination of the salt CF3 C(0Me)2 C02K, prepared in a multi-stage process from perfluoropropene oxide (c/. ref 103). The synthesis of the first acetal of bis(tri-... 

Information already available on the preparation of perfluoropyruvyl fluoride or its dimer, perfluoro-(2-fluorocarbonyl-2,5-dimethyl-4-oxo-l,3-dioxolane), by treating perfluoropropene oxide with hot benzophenone has been more or less duplicated in the patent literature, as well as details... 

The development of a new high-performance fluoro-elastomer based on perfluoromethyl perfluorovinyl ether has already been mentioned (see ref. 305 and p. 26). Preparation of the ether involves ring-opening of perfluoro-propene oxide with trifluoromethoxide ion generated in situ from carbonyl fluoride. Similarly, perfluorobut-3-enyl perfluorovinyl ether (58) can be synthesized from perfluoropropene oxide and perfluoroglutaryl difluoride > ... 

Perfluoropropene oxide is a convenient, volatile, thermal source of difluoro-carbene, and its use in the preparation of fluorocyclopropanes has been further exemplified, perfluorinated, polyfluorinated, and hydrocarbon olefins being employed as substrates (see also p. 17) it has also been employed to convert perfluorobut-2-yne into 3,3-difluoro-l,2-bis(trifluoromethyl)cyclo-propene. Qose examination of the reaction between the epoxide and a mixture of cis- and rra .r-l-chloro-l,2-difluoroethylene at ca. 200°C has revealed that stereospecific addition of difluorocarbene takes place, but that loss of configuration can subsequently result from slow thermal isomerization of the cyclopropane product. Thermal decomposition of perfluoropropene oxide at 200 "C in the absence of a trap yields mainly perfiuorocyclo-propane and trifluoroacetyl fluoride together with tetrafluoroethylene, perfluoroisobutene oxide, perfluorobut-l-ene, and poly(difluoromethylene). 

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... 

This big influence of temperature on the equilibrium is a consequence of the large change in translational entropy in going from reactants to products [15]. Agf+iv) is also able to oxidize perfluoroolefins such as perfluoropropene the ionization potential of which is much lower (7= 10.62 eV) [29] than those of xenon or oxygen. The observed formation of perfluoropropane (quantitatively) is in accord with the cation being attacked by F, followed by a second one-electron oxidation and F attack. The hierarchy of powerful oxidizers could be written as follows (see also Sections 4.2.2.5 and 4.2.2.6). 

Preparation of nitronitroso dimers from a variety of straight chain alkenes has been patented. " The reactions of nitric oxide with alkenes are extremely complex (e.g. isobutylene) and are rarely usefiil. Perfluoroalkenes add nitric oxide at room temperature in the da tetraflucMoethylene gives ONCF2CF2NO (68%) the reaction with perfluoropropene is more complex. ... 

Also, intermediate peroxides are formed in the oxidation of perfluorinated alkenes, e.g. in the photo-oxidation of perfluoroethene and perfluoropropene for the formation of Fomblin (Ausimont Co.) perfluoro-polyether fluids [198, 199]. 

Since the ionization potentials of perfluoro-olefins such as perfluoropropene, C,Felectron-oxidized by Ag sJ,. The observed quantitative oxidation of CjFs to QFg therefore probably involves two sequences of electron oxidation followed by F attack on the radical cations, as follows ... 

Banks, R.E. Haszeldine, R.N. Rohinson, J.M. Reactions of pyridine 1-oxides, 5-methylpyrimidine 1-oxide, and quinoline 1-oxide with perfluoropropene and perfluoro (2-methylpent-2-ene) synthesis of 2-(l,2,2,2-tetrafluoroethyl)pyridines or -pyrimidines and their A-oxides and of 2,2,3-trifluoro-2,3-dihydro-3-trifluoromethylfuro[3,2-h] pyridine. J. Chem. Soc., Perkin Trans. 1 1976, (11), 1226-1230. 

Similarly produced trifluoromethyl carbanion, as well as perfluoroisopropyl carbanion generated by addition of fluoride anion to perfluoropropene, is able to add to a variety of iV-(4-methoxy-benzyl) pyridinium and quinolinium salts. The obtained dihydroazines can easily be transformed into 2-perfluoroalkyl azines through oxidative dealkylation-aromatization with CAN or DDQ (Scheme 31) [110, 111],... 

Bis(trifluoromethyl)-l,2,4,5-tetrazine (1111) and its homologue 1112 are extremely reactive hetero-dienes towards Diels - Alder reaction. Compounds 1111 and 1112 were prepared by reaction of oxadiazole 1114 [675] or perfluoropropene 1116 [676], respectively, with hydrazine, followed by oxidation (Scheme 237). 

The kinetics of the thermal decomposition of 1,1,1-trifluoroacetone have been studied, both in the presence and absence of foreign gases (e.g., nitric oxide, propene, perfluoropropene). The following reactions were written to account for the predominant products from pyrolysis of the ketone alone at 547 °C and initial pressure 106 mmHg ... 

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