Fluorine-containing catalysts

Recently it has been reported (5,66) that ethylene oxide leads to a mixture of cyclic oligomers of D. P. 3,4, 5,6,7,8 and 9 (7 4 6 6 2 1), unaccompanied by open-chain oligomers and polymers, when treated with fluorine-containing catalysts such as antimony pentafluoride or a 1 1 mixture of borontrifluoride and hydrogen fluoride. 

Further improvement in initiation rates could be achieved via the introduction of fluorine substitution onto the NHC s Af-aryl groups. A comparison of fluorine-containing catalysts (22-25) is shown in Chart 9.6 [25,26]. Additional data have... 

The heterobimetallic asymmetric catalyst, Sm-Li-(/ )-BINOL, catalyzes the nitro-aldol reaction of ot,ot-difluoroaldehydes with nitromethane in a good enantioselective manner, as shown in Eq. 3.78. In general, catalytic asymmetric syntheses of fluorine containing compounds have been rather difficult. The S configuration of the nitro-aldol adduct of Eq. 3.78 shows that the nitronate reacts preferentially on the Si face of aldehydes in the presence of (R)-LLB. In general, (R)-LLB causes attack on the Re face. Thus, enantiotopic face selection for a,a-difluoroaldehydes is opposite to that for nonfluorinated aldehydes. The stereoselectivity for a,a-difluoroaldehydes is identical to that of (3-alkoxyaldehydes, as shown in Scheme 3.19, suggesting that the fluorine atoms at the a-position have a great influence on enantioface selection. 

The anion plays a crucial role. BArF and other bulky fluorinated tetra-arylbo-rates or tetraalkoxyaluminates are the most suitable anions. Hexafluorophos-phate-containing catalysts display high reactivity in the initial phase of the reaction, but suffer deactivation before the reaction reaches completion. Tetrafluoro-borate, triflate or other more strongly coordinating anions inhibit the catalyst. 

Fluorinated polymers, especially polytetrafluoroethylene (PTFE) and copolymers of tetrafluoroethylene (TFE) with hexafluoropropylene (HFP) and perfluorinated alkyl vinyl ethers (PFAVE) as well as other fluorine-containing polymers are well known as materials with unique inertness. However, fluorinated polymers with functional groups are of much more interest because they combine the merits of pefluorinated materials and functional polymers (the terms functional monomer/ polymer will be used in this chapter to mean monomer/polymer containing functional groups, respectively). Such materials can be used, e.g., as ion exchange membranes for chlorine-alkali and fuel cells, gas separation membranes, solid polymeric superacid catalysts and polymeric reagents for various organic reactions, and chemical sensors. Of course, fully fluorinated materials are exceptionally inert, but at the same time are the most complicated to produce. 

Bromofluoromenthane has been prepared in high yield using a one-step reaction with bromine, hydrogen fluoride and methane in the presence of an aluminum trifluoride fluidized bed or fluorinated aluminum catalysts optionally containing cobalt or nickel between 450 and 500°C.20... 

Y.C. Jang and H.K. Sung, Method for preparing a homo-and co-poly-mers by polymerization of cyclic olefin compounds using fluorine-containing aromatic hydrocarbon compound as catalyst activator, US Patent 6998450, assigned to Korea Kumho Petrochemical Co., Ltd. (Seoul, KR), February 14,2006. 

Hydrosilylations of fluorine-containing alkenes are free radical reactions initiated by UV light or organic peroxides The direction of addition is the same as with fluonnated alkyl halides However, the reaction between hydrosilanes and fluorine-containing olefins catalyzed by platinum group metal complexes may result in bidirectional addition and/or formation of a vinylic silane, the latter by de hydrogenative silylation[/] The natures of both the silane and the catalyst affect the outcome of the reaction[7] A random selection of some typical new reactions of silanes are shown in Table 1 [1, 2, 3 4]... 

This fluorine-containing, oxidation-resistant alcohol is best oxidized by the Pfitzner-Moffatt reaction, using dichloroacetic acid as catalyst. Observe the use of toluene, instead of carcinogenic benzene, as solvent. A Swern oxidation was not reproducible, and caused substantial epimerization of the isobutyl side chain. Collins oxidation was successful, but ... 

Another advantage was conferred by introducing 6,6 -substituents to BINOL. In general, catalytic asymmetric syntheses of fluorine-containing compounds are rather difficult.42 However, an effective asymmetric nitroaldol reaction of the rather unreactive a,ct-difluoro aldehydes proceeded satisfactorily when using the heterobimetallic asymmetric catalysts generated from 6,6 -bis[(triethylsilyl)-ethynyl]BINOL, as shown in Table 5 43 The -configuration of the nitroaldol adduct 71 showed that the nitronate reacted preferentially on the Si face of the... 

In the presence of alkaline metal fluorides or tertiary amines, perfluoro-olefins react with fluorine-containing keteneimines to form azetidines 25 in mild conditions (76IZV1813). The role of the catalyst seems to be the transformation of the electrophilic keteneimine into the nucleophilic mesomeric anion capable of adding at the multiple bond of the perfluoro-olefin. The addition is accompanied by cyclization generating a catalyst. 

Direct evidence for a combination of catalytic fluorination and chlorination [4] was obtained from radiotracer studies in which fluorinated chromia catalysts were labelled with the short-lived (t /2 = 110 min) / + emitting isotope fluorine-18 [11]. Using this isotope it was possible to probe the interactions between HF and various fluorinated chromia catalysts more directly than had been possible hitherto. Three types of surface F-containing species were differentiated, weakly adsorbed HF which was easily removed by an inert gas flow, non-labile F, believed to be bound directly to surface Crin, and catalytically active F which could be incorporated into the organic products [12]. The controversy between dismutation (concerted F-for-Cl and Cl-for-F transfers) and non-concerted halogen exchange processes has been resolved more recently and the evidence is described later in the chapter. What is clear from this early work however, is the importance of aluminium and chromium(III) oxides as catalyst precursors. Fluorination of the surfaces of these oxides is slow (cf [12]) and although there are many references to alu-... 

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