Fluoroethylene reaction

Hutton, H. M., Schaefer, T. Solvent Effects on the Proton Chemical Shift and H—H, H-F Coupling Constants in 1-Chloro-l-fluoroethylene. Reaction Field and Dispersion Interactions. Can. J. Chem. 45, 1111 (1967). 

Antimony pentafluoride was also reported to catalyze condensation of CFC-113 with fluoroethylenes. Reaction proceeds under mild conditions, producing the corresponding butanes in high yield [7] ... 

Perfluorinated benzocycloalkanes also react with fluoroethylenes. Reaction proceeds under mild conditions in the presence of SbF5 catalyst, producing a mixture of 1 1 and 1 2 adducts [158] ... 

The UPS of the early stages of thermal degradation of a polymer to gaseous products was reported by Betteridge and coworkers130. PTFE (i.e. several of the commercial homopolymers, copolymers and y-irradiated samples) was used and the tetra-fluoroethylene reaction product was monitored by PES. The reaction was found to be first order for homopolymers. The copolymers and y-irradiated samples showed differences of both products and rates. 

Preliminary work on the mercury-photosensitized reaction of trimethylsilane with vinylidene fluoride has indicated that hydrogen is produced with the quantum yield to be expected by analogy with the trimethylsilane-tetra-fluoroethylene reaction, and that hexamethyldisilane is not formed, so that initiation is proceeding as before to give trimethylsilyl radicals, which add to the olefin. Since no appreciable yields of 1 1 or 1 2 adduct were obtained, however, it appears that the MesSi-CHs CFj- radicals which are produced react by termination rather than by hydrogen abstraction. 

Tropolone has been made from 1,2-cycloheptanedione by bromination and reduction, and by reaction with A -bromosuccinimide from cyolo-heptanone by bromination, hydrolysis, and reduction from diethyl pimelate by acyloin condensation and bromination from cyclo-heptatriene by permanganate oxidation from 3,5-dihydroxybenzoic acid by a multistep synthesis from 2,3-dimethoxybenzoic acid by a multistep synthesis from tropone by chlorination and hydrolysis, by amination with hydrazine and hydrolysis, or by photooxidation followed by reduction with thiourea from cyclopentadiene and tetra-fluoroethylene and from cyclopentadiene and dichloroketene. - ... 

Ihrig 6S> studied a series of rigid bicyclic compounds (5-8) obtained from the Diels-Alder reaction of hexachlorocyclopentadiene with fluoroethylenes. In... 

Teflon. See in Vol 8, P35l -L to P352-R under Polytetrafluoroethylene and the following Addnl Ref D.M. Cavagnaro, Ed, Poiytetra-fluoroethylene (Teflon) , Vol 2, NTIS/PS-78/0269 (1978) [A bibliography in which worldwide citations of engrg research in the reactions, properties, performance and manuf of Teflon are presented]... 

Kiyama, R., J. Osugi and S. Kusuhara Studies on explosive reactions of tetra-fluoroethylene and acetylene with oxygen or air. Rev. Phys. Chem. Jap. 27, 22-41 (1957). 

The reactions between 1,1 -dicyano-2-p-dimethy laminophenyl-2-fluoroethylene (76) and p-toluidine or phenylenediamines in acetonitrile157 form the substitution products (77) as shown in Scheme 35. The reaction is of the second order in amine when ArNH2 is p-toluidine and it is catalysed by substituted pyridines (and quinolines) in accordance with the presence on the reaction pathway of the zwitterionic complex 78, which is in equilibrium (see equation 14) with the anionic form 79. 

The first member of this family - vinylidene fluoride - readily adds fluoro-sulfonic acid, even in the absence of the catalyst, and it is nitrofluorinated by a HNO3/HF mixture six times faster than CFH=CF2 [15] however, HF/HS03F superacid does not react at ambient temperature with C1CF=CF2 or CF2=CF2. These two olefins show a similar reactivity in electrophilic reactions. Interaction of polyfluorinated propylenes CF2=CXCF3 (X=H,F) with trifluoro- and tetra-fluoroethylenes proceeds at room temperature in the presence of a Lewis acid catalyst to give the corresponding polyfluoropentenes-2 ... 

On the other hand, most reactions of chlorotrifluoro- and bromotri-fluoroethylenes are not regioselective and usually proceed with the formation of approximately equal amounts of both isomers. This is exemplified by the the mixture obtained from the reaction of CF3CH3 with CFC1=CF2 [48] and by cycloaddition of hexafluoroacetone (HFA) to CFBr=CF2 catalyzed by AlClxFy [49] ... 

Introduction of nitro and fluorosulfonoxy groups can be carried out by reaction of ionic 02N0S02F with fluoroolefins [8,116-118]. Nitronium fluorosulfa-te is not as active as halogen fluorosulfates addition to CH2=CF2 and CFH=CF2 proceeds only at ambient temperature [117]. Reaction with TFE and chloro-fluoroethylene proceeds at a noticeable rate at temperature above 50 °C, while addition to 2-H-F-propene only at temperatures higher than 120 °C [117] ... 

Reactivity of nitrosonium fluorosulfate and trifluoromethansulfonate 0N0S02X (X=F, CF3) is similar to that of nitronium fluorosulfate, although they are less active than the latter. Reaction, which occurs only with fluoroethylenes and perfluorinated vinyl ethers [ 119 -121 ], is of an electrophilic nature it results in low to moderate yields of nitrosoalkyl compounds when the olefin has a limited contact time with the reaction mixture ... 

As mentioned above, arsenic trifluoride does not react with fluoroolefins in the absence of a catalyst, and due to a convenient boiling point and high polarity it was often used as a solvent for an electrophilic reaction, such as mercuration. Later it was found that in the presence of a Lewis acid, such as SbF5, this compound readily adds to different fluoroethylenes [7,121,122] ... 

Alkylation of fluoroolefins is probably the most studied reaction of that kind. Different aspects of this process, such as reaction with formaldehyde and hexamethylenetetramine in HF [3], or condensation of halomethanes with fluoroethylenes, catalyzed by AlCl3 [27] have been reviewed. A recent development in this field mostly associated with the introduction of new catalysts, such as SbF5 [7] or aluminum chorofluoride AlClxFy [12], was covered in two other review articles. Here a brief description of some of these reactions is given. 

Recently it has been found that ACF is able to activate hexafluoroacetone (HFA) and that reaction of fluoroethylenes proceeds exclusively as electrophilic 2 + 2 cycloaddition with formation of the corresponding oxetanes [49] (see also Eq. 35) ... 

The first example of electrophilic condensation of polyfluorinated olefins with fluoroethylenes was reported in 1975 [150]. Reaction of HFP and TFE in the presence of SbF5 catalyst produces F-pentene-2, mostly the trans-isomer ... 

Reaction of polyfluorinated dienes with TFE resembles the reaction of polyfluoropropynes with fluoroethylenes. Polyfluorinated dienes react with TFE at ambient temperature in the presence of SbF5 catalyst [159].F-Heptadiene-2,4 (65) was obtained in 77% yield in reaction of F-pentadiene-1,3 and TFE along with small amounts of F-nonadiene-3,5. F-Hexadiene-2,4 reacts with TFE at 50 °C to give a mixture of isomeric octadienes 66 a, b ... 

In Table 5 (p. 55) we compared the relative rates of addition of methyl, fluoromethyl, difluoromethyl and trifluoromethyl radicals to ethylene and tetra-fluoroethylene. Figure 3 shows the Arrnehius plots for these competitive reactions. These indicate in a very graphic way the fact that this systematic variation in relative rate can be entirely attributed to variation in the activation energy differences. 

The three routes are not always kinetically distinguishable. Silversmith and Smith (1958), for example, mentioned that the second-order kinetics in the reaction of l,l-diphenyl-2-fluoroethylene with ethoxide ion fits a reaction via a carbanionic intermediate, or the formation of a fluoroether, if the latter is either formed rapidly and decomposed slowly (kikzKk-i + kz ki), or if it formed in a rate-determining step (k1k2l(k-l + k2Xki). 

The reactions of l,l-bis(trifluoromethyl)-2-fluoroethylene with compounds having two nucleophilic centers leads to the formation of five-membered heterocycles (90IZY2583, 88S194). 

Reaction of 1,2-Dichloro-l-fluoroethylene with Butyllithium and Acetone... 

The product ratios observed for additions between allene and chlorotri-fluoroethylene or l,l-dichloro-2,2-difluoroethylene 126>, 85 15 in favor of the 3-chloro isomer and 95 5 for the 3,3-dichloro adduct, can t be interpreted unambiguously. If both adducts in a set stem from a common type of intermediate, then the product ratios indicate how different that intermediate is from the sorts of diradicals implicated in cydoadditions between, say, l,l-dichloro-2,2-difluoroethylene and the 2,4-hexadienes 16J. But the two adducts may arise throu gh completely independent, dissimilar reaction mechanisms. 

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