Vinyl fluonde

The followmg types of studies will not be presented individually but may have contnbuted supportmg data to coverage by compound type conformational analyses [23 24, 25, 26 27], fluoropolymers [28, 29, 30 31, 32], solid-state NMR [ii], and solvent effects [34 35, 36, 37] Many excellent articles with m-depth NMR interpretation of one specific compound or of a small, structurally related group of compounds can be found in the chemical hterature A few of these, not incorporated elsewhere in this secUon are referenced here carbonyl fluondes [JS 39 40], fluoropropanes [41 42, 43], fluorocyclopropanes [44, 45 46], fluorobutanes [47], perfluorocyclobutanone [48], fluorohexanes [49], and vinyl fluondes [50, 51 52, 53, 54]... 

Poly(vinyl fluonde) is a linear semicrystalhne polymer of the following general structure... 

A number of publications have appeared revealing that catalytic processes which are unsuccessful with vinylic fluondes can be applied effectively to fluoro-alkyl- and fluoioarylethylenes Hydroformylation [56] and related reactions such as amidocarbonylation [571 will proceed in high yield and regioselectivity The choice of the catalyst system, especially of rhodium and cobalt catalysts, allows either regioselective reaction to proceed A few of the large number of syntheuc variants are given in equation 45... 

When vinyl silicon tnfluonde is treated with two equivalents of potassium fluonde, a new reagent, a dipotassium organopentafluorosilicate, is formed [101] This intermediate has found application as a component in an efficient stereoselective copper chlonde-promoted coupling reaction (equation 81)... 

Vinyl and phenyl tnfluoromethyl groups are reactive m the presence of aluminum chloride [10 Replacement of fluorine by chlorine often occurs Polyfluori-nated tnfluoromethylbenzenes form reactive a,a-difluorobenzyl cations in antimony pentafluoride [77] 1 Phenylperfluoropropene cyclizes in aluminum chlonde to afford 1,1,3-trichloro 2 fluoromdene [10] (equation 10) The reaction IS hypothesized to proceed via an allylic carbocation, whose fluonde atoms undergo halogen exchange... 

Dehydrochlorination of bis(tnfluoromethyUhio)acetyl chloride with calcium oxide gives bis(tnfluoromethylthio)ketene [5] (equation 6) Elimination of hydrogen chlonde or hydrogen bromide by means of tetrabutylammonium or potassium fluoride from vinylic chlorides or bromides leads to acetylenes or allenes [d] (equation 7) Addition of dicyclohexyl-18-crown-6 ether raises the yields of potassium fluonde-promoted elimination of hydrogen bromide from (Z)-P-bromo-p-ni-trostyrene m acctonitnle from 0 to 53-71 % In dimethyl formamide, yields increase from 28-35% to 58-68%... 

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