Per- and Poly-fluorinated Aliphatic Derivatives of the Main-group Elements

Per- and Poly-fluorinated Aliphatic Derivatives of the Main-group Elements 

As in Vol. 1, no attempt has been made to draw together information on reactions believed to involve transient per- or poly-iluoroaliphatic derivatives of Na, K, Rb, or Cs generated, for example, by proton abstraction from fluorocarbon hydrides or via attack of the corresponding metal fluorides on fluoro-olefins. 

Reagents i, reflux then add H 0 ii, COj, then add HjO iii, MeCHO, reflux then add HjO iv. Me,CO, reflux then add 

Full details of the preparation of alkylmagnesium fluorides are now available (c/.Vol. 1, p. 87), and information on their structure and reactivity is also to hand. At last, phenylmagnesium fluoride has been prepared directly, albeit in poor yield the magnesium must be in the super-active form obtainable by alkali-metal reduction of anhydrous magnesium chloride or bromide in ether solvents.  

Cakhim.— Perfluorobut-2-yne is released in low yield when the glass-like matrix obtained by co-deposition of calcium vapour and perfluorobut-2-ene on a cold (-196 °Q surface, in vacuo, is allowed to warm up. Under similar circumstances, perfluoropropane does not react perfluoro-propene and -cyclobutene give only large amounts of polymer . The butene - butyne defluorination is believed to involve the intermediate CF,-CF C(CF,)-CaF. (See p. 427 for information on atomic Ca-C F reactions.) 

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