Nitrogen fluorides reduction

All the reactants were premixed in a 3.8-liter reservoir and pressurized to 103 MPa, using nitrogen fluoride as an initiator. The monomer mixture was bled through a heated and agitated pressure vessel. Flow of the gas was maintained through the system by stagewise reduction in the pressure. Pressure was reduced to 96.5 MPa in the reactor and to atmospheric pressure in the product collector. The product was discharged in the form of a foam with the unreacted monomers. 

Fluorinated -alkenes and -cycloalkenes have a special relationship with their hydrocarbon analogues, usually exhibiting a chemistry that is complementary. For example, the fluorinated systems are frequently susceptible to nucleophilic attack, in some cases dramatically so, and therefore reactions of nucleophiles with fluorinated alkenes often reveal unique new chemistry. This chapter covers electrochemical reduction, principles governing orientation and reactivity of fluorinated alkenes towards nucleophiles, fluoride ion as a nucleophile and the mirror-image relationship of this chemistry with that of proton-induced reactions, reactions with nitrogen-, oxygen-, carbon- centred nucleophiles etc., and, finally, chemistry of some oligomers of fluorinated -alkenes and -cycloalkenes. 

Cinnolines may be formed by the cyclization of 2-hydrazone or 2-hydrazonophosphorane derivatives of 3-(2-fluoro- or chlorophenyl)-3-oxopropionates (Scheme 87), which are prepared from the oxopropionates via reaction with /i-toluenesulfonyl azide and treatment of the diazo derivatives with phosphines. Simple hydrazones undergo cyclization by displacement of fluoride under thermal or basic conditions, and reaction of chloro compounds is successful under basic conditions, though Wolff-Kishner reduction may compete in the absence of a methyl group on the terminal nitrogen. The diazo compounds cyclize, via tri- -butylphosphazines, more readily than do the hydrazones and base catalysis is not required it may be that cyclization proceeds via a phosphonium salt, with subsequent hydration and elimination of tri- -butylphosphine oxide. The triphenylphosphazines do not cyclize, but are labile intermediates to the hydrazones <88Cpbi321>. 

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