Fluonnation with compounds

The presence of a tnalkylsUyl group in a fluonnated organic compound may be useful to direct further transformations of that matenal Yet m some instances it IS the fluonnated substituent that controls the reactions of the tnalkylsdyl group Contrary to predictions, treatment of tert-hnlyX 3-tnfluoromethyl-6-tnmethylsilyl-phenyl carbamate with rert-butyllithium results m metallation of one of the methyl groups attached to silicon rather than that of the aromatic nng [90] (equation 75)... 

A new thermal preparation ot fluorinated species is copyrolysis Copyrolysis of fluorinated compounds like perfluorobenzene, fluorinated aromatic anhydndes, and fluorinated heteroaromatics with tetrafluoroethylene or other fluonnated olefins is a useful method of preparing fluorinated olefins [88 89], functionalized fluoroaromatics [90 91 92, 93, 94, 95], fluonnated benzocycloalkanes [80, 96, 97, 98, 99, 700], fluorinated heterocycles [80, 93, 101, 102, 103], and fluonnated polycyclic compounds [104] (equations 19 and 20)... 

The mass spectrometry of fluonnated organic compounds was reviewed in 1961 [55], and this review should be consulted for information on the applications of mass spectrometry in organofluorine chemistry up to that time With the advent of... 

When there is an o.-hydrogen in the sulfide, the sulfuranes are unstable and cannot be isolated [775]. Sulfoxides [116] and sulfinylfluorides [117] are oxidatively fluonnated with fluorine to give hexavalent sulfur compounds in yields up to 90%. 

Of alicyclic compounds, fluorination of cyclopentane and cyclohexane has been sufficiently investigated in the past. Cycloheptane on fluonnation with cobalt trifluoride gives a mixture of highly fluonnated and perfluorinated cycloheptanes and methylcyclohexanes [/2] (equation 12). 

After a vigorous initial activity, whereby new fluonnated organometallic compounds were first synthesized, much of the research effort has decreased Some activity has been concerned with the reactions of perfluoroaromatic magnesium compounds... 

Only a few reports of unsaturated fluonnated cadmium compounds have appeared The direct reaction of perfluoroalkenyl iodides or bromides with cadmium powder in DMF stereospecifically gives the vinylcadmium compounds [143] (equation 110) Table 5 shows several typical vinylcadmiums prepared by this method. 

Various fluonnated cyclic compounds containing -N=N- bonding can be decomposed by the elimination of nitrogen The photolysis of phenylfluorodiazi-nne results in the formation of the intermediate phenylfiuorocarbene, which can react instantaneously with olefins [76] (equation 45)... 

Mmy fluonnated aromatic compounds are alkylated with alkyl halides under Fnedel-Crafts conditions For example, the intramolecular alkylation of 3-fluoro-A-(chloroace-tyl)amhne with aluminum chlonde gives 6-fluorooxmdole [5] (equation 5) Similarly, 3 -chloro-4-fluoropropiophenone affords 5-fluoroindanone [6] (equation 6)... 

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