Perfluoropropene, reaction

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 ... 

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). 

Further reactions mentioned already and belonging also to this section are those of perfluoropropene (360) (57USP2817662) and the alkynic thioacetate (350) with hydrazine (67RTC907), which afford the dihydrotetrazines (361) and (351), respectively. 

The accessible perfluoroalkyliron(II) tetracarbonyl iodides are also thermally unstable. The reaction path depends on the structure of the starting compound. Thus, perfluoropropyliron(II) tetracarbonyl iodide (11) yields, under a rare /(-elimination, perfluoropropene.147... 

Reaction of perfluoropropene with diethylamine yields (F)-fluoroenaminc 3 and fluoro-alkylamine 4 in a 1 1 or 3 1 mixture (depending on the reaction conditions used). This mixture is known as Ishikawa s reagent and can be used (without separation) for the transformation of alkyl alcohols to fluoroalkanes (see Vol. ElOb/Part 1. p99).218... 

Starting in 1969, D.E. Rice used this method to prepare dicarboxylic oligomers which contained vinylidene fluoride and perfluoropropene. He used the way these fluorinated monomers fit the reaction of chain-termination by recombination but the basic difficulty lay in the preparation of the difunctional initiator [80-83] ... 

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)... 

Under strenuous conditions, hydrogen fluoride adds across the double bond of perfluoropropene to form a single reaction product. What is its structure Hydrogen chloride and hydrogen bromide react similarly. 

What is the product of the reaction between perfluoropropene and potassium fluoride in formamide ... 

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. ... 

Problems of orientation of attack and reactivities of fluorinated alkenes arise in a way that is analogous but entirely complementary to the classical problems of electrophilic attack on alkenes. For example, typical of the results that we must be able to account for is the reaction of methoxide in methanol which occurs specifically at the Cp2= site in perfluoropropene (Figure 7.15). Also, there is a very wide range of reactivity with perfluoroalkenes for example, reactions of tetrafluoroethene usually require base catalysis, whereas perfluoroisobutene reacts with neutral methanol. 

Atkinson et a/. - - have reported that the thermal decomposition of tetra-fluoroethylene can be divided into three temperature phases (see also ref. 454). At temperatures below 550 °C perfluorocyclobutane is the main product above 550 °C the equilibrium mixture of tetrafluoroethylene and perfluorocyclobutane decomposes to form perfluoropropene by a first-order reaction, and perfluoro-propene decomposes in turn by a 1.5-order process to perfluoroisobutene above 700 °C the perfluoroisobutene decomposes by a first-order reaction to perfluoro-ethane and non-volatiles. The observations are shown to be consistent with a reaction scheme involving CFj radicals in Phases 1 and 2, and CFj radicals in Phase 3, as follows... 

Papers on the pyrolytic decomposition of fluorinated hydrocarbons have included those on methyl fluoride , and ethyl fluoride , on polyfluorinated methanes and ethanes - - , on vinyl fluoride - , on per-fluoroethylene and on perfluoropropene . Isomerisation reactions of fluoro-olefins - - - have been discussed. Of related interest have been the reactions of fluorosilanes reported by Haszeldine et a/. 9J.806.8i4.8is ref. 778). 

Formation of azides by nucleophilic attack on alkenes with non-conjugative electron-withdrawing groups is also known. It has been established for example, that Irani-peiiluoropropenyl azide (167) is formed by reaction of perfluoropropene (168) with trimethylam-monium azide at 0°, and the intermediacy of a carbanion (169) has been postulated (Scheme 2) 3n-3i3 formation of such carban-... 

Whereas both tri(t-butyl)phosphine and secondary phosphines react with perfluoropropene to give the perfluorovinylphosphines (91), the corresponding reactions of triethylphosphine (and methylaryl-... 

Reactions of a-methyl-V-ethylnitrone (lOd) are interesting since some olefins form reverse-oriented cycloadducts. For example, lOd and perfluoropropene give a mixture of adducts of type Xt and Xc in a 3 2 ratio.40 Reverse-oriented cycloadducts IVt and IVc are also obtained from lOd and methyl methacrylate.41,42... 

Banks, R.E. Khaffaff, S.N. Fluorocarbon derivatives of nitrogen. Part 18. Synthesis of fluorinated indohzines through reactions of pyridinium ethoxycarbonylmethylide or pyridinium phenacylide with perfluoropropene, perfluorobut-2-3me and 3,3,3-trifluoro-propyne. J. Fluorine Chem. 1991, 51, 407-418, and references therein. 

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. 

Banks, R.E. Mullen, K. Nicholson, W.J. Oppenheim, C. Prakash, A. N-Fluoro compounds. IV. Photochentical and fluoride-initiated reactions between perfluoro-V-fluoropiperidine and perfluoropropene. J. Chem. Soc., Perkin Trans. I 1972, (8), 1098-1103. 

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