Die Reaktion der Zweikomponentensysteme P(OR)3 − x(NR2)x (x = 0–3)/CCl4 und P4/CCl4 mit HF-Donatoren

Reaction of the Two-component Systems P(OR)_{3 ? x}(NR₂)_x (x = 0–3)/CCl₄ and P₄/CCl₄ with HF-Donators The combination of organylammonium fluorides and carbon tetrachloride is a good agent for oxidative fluorination of trivalent phosphorus compounds. As oxidation products [(RO)PF₅]^? and (RO)₂P(O)F are obtained from P(OR)₃, (Et₂N)₂P(O)F and (Et₂N)₂(EtO)PF₂ from P(OEt)(NEt₂)₂ as well as (Et₂N)₃PF₂ and [(Et₂N)₃PF]⁺ from P(NEt₂)₃. In the system R₂NH/CCl₄/Et₃N · n HF P₄ is fast oxidized forming [HPF₅]^?, R₂NH · PF₅ and (R₂N)₂P(O)F. In the case of simultaneous addition of alcohols [(RO)PF₅]^?, (RO)₃PO and (R₂N)₂P(O)F are formed. The reactions are controlled by the nucleophilic power and the concentration of fluoride, the acidity of the system, and the temperature.