Synthesis And Characterization Of New Highly Fluorinated Phosphoramidates

A one-pot synthesis of new bis(polyfluoroalkyl)dialkylaminophosphoramidates (R-F(CH2)(2)O)(2)P(O)NR2 (1-6) (R-F = C6F13, NR2 = NC5H10 (1), NC4H8 (2), NEt2 (3); R-F = C8F17, NR2 = NC5H10 (4), NC4H8 (5), NEt2 (6)) and polyfluoroalkyl bis(dialkylamino)phosphoramidates R-F(CH2)(2)OP(O)(NR2)(2) (9-14) (R-F = C6F13, NR2 = NC5H10 (9), NC4H8 (10), NEt2 (11); R-F = C8F17, NR2 = NC5H10 (12), NC4H8 (13), NEt2 (14)) was performed through phosphorylation of corresponding highly fluorinated alcohols with P(O)Cl-3 in dry diethyl ether followed by aminolysis. However, the former phosphoramidates (1-6) and corresponding morpholinyl derivatives 7 and 8 were alternatively prepared in better yields from phosphoramidation reaction of bis(fluoroalkyl)phosphites with amines in the presence of I-2 and H2O2 in dichloromethane. All these phosphoramidates were obtained in good yields and characterized by multinuclear (H-1, C-13, P-31 and F-19) NMR, IR spectroscopy and HRMS.