Comparative Study of Tris (trifluoromethyl) phosphine Oxide, Tris(nonafluorobutyl)phosphine Oxide, and Fluorobis(nonafluorobutyl)phosphine Oxide with Ammonia and Amines

Abstract

Under identical reaction conditions, the behavior of (Rf)3PO (Rf = CF3, C4F9) or (Rf)2P(O)F (Rf = C4F9) with ammonia or amines is different, e.g., (CF3)3PO with NH3, CH3NH2, or (CH3)2NH gives (CF3)3P(NH2)2, (CF3)2P(O)(NHCH3) or (CF3)P(O)(NHCH3)2 (excess (CH3)2NH), or (CF3)2P(O)N(CH3)2, respectively. However, with the same reactants, (C4F9)3PO forms (C4F9)2P(O)(NH-)NH4+ or C4F9P(O)(NH2)2 (excess NH3), C4F9P(O)(NHCH3)2 (excess CH3NH2), or (C4F9)3P(OH)[N(CH3)2], (C4F9)3P[N(CH3)2]2, and (C4F9)2P(O)N(CH3)2. Similar products are found with (C4F9)2P(O)F except with (CH3)2NH where (C4F9)PF(O) [N(CH3)2] is the major product. In addition, new routes to (C4F9)3PO, (C4F9)2PF3, and (C4F9)2P(O)F are described. These products and conditions are compared with those for analogous hydrolysis reactions. © 1988, American Chemical Society. All rights reserved.