摘要 |
<p>A new organic synthesis useful for perfluoro-alkylation, comprises contacting a material RfH and a base (or base generator) with a substrate having at least one electrophilic function in a polar medium, with the condition that when the substrate is base-sensitive and is not added last to the medium: either (a) to effect the addition, then optionally to follow the reaction after addition so that (i) at least 90% of the addition of the last reagent is carried out and (ii) the reaction mixture is maintained for at least 0.5 hours (including addition time) at a temperature no more than -20 (preferably-30) deg C.; or (b) to comply with at least one, preferably both, of the following conditions: (i) the water content is no more than 200 ppm (2 significant figures), preferably 100 ppm (2 significant figures) and more preferably 50 ppm (1 significant figure); and (ii) the amount of base is no more than 1.3 times the stoichiometric amount relative to the substrate at a temperature no greater than 0 deg C, or 1.1 times the stoichiometric amount at a temperature no more than 20 deg C. Also claimed are: (1) the reactant (RfH and base) used in the process, where RfH is of formula H-(CX2)p-GEA; and (2) a compound of formula R11R12N-C(R13)(Rf)-O<->M<+> (IV). X = F, CnF2n+1 or Cl; n <= 5, (preferably 2); p = <= 2; GEA = electro-attracting group whose optional functional groups are inert in the reaction conditions, preferably F or Cn'F2n'+1; n' <= 8, preferably 5; M<+> = monovalent cation, esp. alkali or quaternary phosphonium (pref. <= 40C, esp. <= 24C); and R11-R13 = hydrocarbon chains, such as aryl including alkylaryl, or alkyl including aralkyl and cycloalkyl, which may be linked to each other to form one or more rings.</p> |