Fluorinated phosphorus compounds: Part 11. The reactions of some fluorinated amines with dialkyl and bis(fluoroalkyl) phosphorochloridates

Dimethyl phosphorochloridate reacted with RFCH2NH2 in ether in the presence of Et3N to afford (MeO)2P(O)NHCH2RF, where RF = CF3 and C2F5, in 39 and 47% yield, respectively. Similar reactions with di-n-propyl and diisopropyl phosphorochloridates could be effected only with H2NCH2CF3 when 4-dimethylaminopyridine catalyst was added and (n-PrO)2P(O)NHCH2CF3 and (i-PrO)2P(O)NHCH2CF3 were isolated in 49 and 25% yield, respectively. Treatment of POCl3 with one molar equivalent each of H2NCH2CF3 and Et3N permitted the synthesis of Cl2P(O)NHCH2CF3 in 43% yield. Bis(fluoroalkyl) phosphorochloridates (RFO)2P(O)Cl, where RF = C2F5CH2, C3F7CH2 and (CF3)2CH, reacted with 2,2,2-trifluoroethylamine and 2,2,3,3,3-pentafluoropropylamine to furnish phosphoramidates (RFO)2P(O)NHCH2R, where R = CF3 or C2F5, in yields of 32–67%.