ChemInform Abstract: REACTION OF α,α,Ω‐TRIHYDROPERFLUOROALKANOLS WITH PHOSPHORUS TRICHLORIDE

Abstract

Die Fluoralkohole (I) reagieren mit Phosphortrichlorid bei Temperaturen unter 80°C zu den Dichlorphosphiten (II), bei Temperaturen über 80°C entstehen die Trialkylphosphite (IV).

Fluoroalkoxy-derivatives of trivalent phosphorus: synthesis and reactivity

“…It becomes the main reaction in the case of 2-fluoroethanol, which affords bis(2-fluoroethyl) phosphites in a high yield on treatment with PCI3. 63 The addition of a catalyst (pyridine) accelerates the reaction significantly and improves the yield of the trialkyl phosphite: 60 R F = CHF 2 (CF 2 ) n CH 2 , n = 1, 3, 5.…”

“…Attention was first turned to the ease of the alcoholysis of RF-alkyl phosphites by more basic alcohols in the studies of Fokin and coworkers. 60 ' 62 Thus the reaction of tris(tetrafluoropropyl) phosphite with Mel, in which MeOH was used as the catalyst, has been described. 62 In the presence of an excess of methanol and under comparatively mild conditions, the complete transesterification of tris(tetrafluoropropyl) phosphite is observed.…”

“…Only diphenyl phosphite, 274 The disproportionation reactions of the RF-derivatives of P(III) proceed more readily than those of the usual phosphites. 60 -62>98 Thus octafluoropentyl dibromophosphite has been obtained by the disproportionation of tris(octafluoropentyl) phosphite in the presence of PBr3 in acetonitrile. 284 Exchange and symmetrisation occur in the interaction of CHF 2 CF 2 CH 2 OPC1 2 with piperylene and epoxyethane.…”

“…284 Exchange and symmetrisation occur in the interaction of CHF 2 CF 2 CH 2 OPC1 2 with piperylene and epoxyethane. 60 …”

“…286 Thus, bis(trifluoroethyl) trichloromethylphosphonite is oxidised by oxygen only under UV radiation. 105 Stronger oxidants -N^, 60 Sulfur adds to tris-and bis-(fluoroalkyl) phosphites with much greater difficulty than to the corresponding alkyl phosphites. The reaction takes place only after prolonged heating in dioxane 61 -62 -164 -292 or pyridine.…”