Reaction of 1,1,2-trifluoro-2-hexafluoro-2′-(heptafluoropropoxy)-propoxyethylene with amines or alcohols

摘要: Abstract Reaction between 1,1,2-trifluoro-2-hexafluoro-2′-(heptafluoropropoxy)-propoxyethylene and secondary amines (dimethylamine, diethylamine, dibutylamine, pyrrolidine, piperidine, morpholine) leads either to perfluoro-2-propoxy-3(1H′)-ethoxy-2″-alkoxypropanes — the addition products double bond or an N,N-dialkylamide of α-substituted fluoroacetic acid depending on solvent used following work-up crude product. With primary (propylamine, butylamine, monoethanolamine), fluorine-containing imines N-alkylamides (as a mixture diastereomers) were obtained. The use diethanolamine produces 2-{fluoro-2[hexafluoro-2′-(heptafluoropropoxy)-propoxy]-methyl}-4,5,7,8-tetrahydro-[1.6.3]dioxasozine. 1,1,2-trifluoro-2′-hexafluoro-2′-(heptafluoropropoxy)-propoxyethylene with alcohols (methanol, ethanol, β,β,β-trifluoroethanol, 2-methoxyethanol, 2-ethoxyethanol, iso-propanol, butanol pentafluorophenol) in presence KOH tetrahydrofuran (sulfolane, DMSO, acetonitrile) sodium alkoxide alcoholic medium yields only corresponding ethers as diastereomers. Treatment ethyleneglycol, glycerine, pentaerythritol, triethanolamine, 2-(2-hydroxyethylsulphanyl) 4-(2-hydroxyethyl) phenol 1,1,2-trifluoro-2′-(heptafluoropropoxy)-2-hexafluoropropoxyethylene provides all OH groups if reaction is carried out sulfolane acetonitrile. However, THF formation together ethers. initial perfluoro(propoxypropoxy) olefin can be hydrolyzed alkaline media give fluoro-[hexafluoro-2-(heptafluoropropoxy)propoxy]acetic acid.