where an exothermic reaction occurred. After 1 h at 25 "C, all volatile materials were evacuated to leave a white solid, CF3CH,0Li (20 mmol, Preparation of 2,2,2-Trifluoroethyl Dichlorophosphinite, CF3CH20P-CI2. Onto CF,CH,OLi (20 mmol, 2.1 g) in a 1000-mL round-bottomed Pyrex flask at -196 OC, was condensed PCI, (20 mmol, 2.75 g). This flask was warmed to and held at 25 OC for 10 h. Trap-to-trap distillation gave CF,CH,OPCI, (13 mmol, 2.6 g, 65% yield) in a trap at -45 OC, PCI3 in a trap at -120 OC, and a mixture of (CF,CH20),PC1 and (C-F,CH,O),P in a trap at -30 "C.
Preparation of Bis(polyfluoroalky1) Chlorophosphonites, (R,O),PCI, or Tris(polyfluoroalkyl) Phosphites, (R@),P. This preparation can be carried out as described above for polyfluoroalkyl dichlorophosphinites, except the stoichiometry of the reaction is 2:l of RQLi to PC1, or 3:l of R P L i to PC13.
Preparation of (R,O)P(O)CI,, (R,O),P(O)CI, and (R,O),PO. The compound, RQPCI, or (RQ),PCI (5 mmol), was transferred into a 100-mL flask equipped with a Teflon stopcock. Stoichiometric amounts of N204 were condensed at -196 OC onto the compound. The oxidation was complete at low temperatures from -50 to -20 OC. The trap-to-trap distillation gave the products in their respective traps. For (RQ),P, the starting material was transferred to the 100-mL flask under an inert atmosphere. After the flask was evacuated at -196 OC, the stoichiometric amount of N,O, was transferred and the temperature was raised from -196 to +25 OC slowly. After 1 h the volatile materials, including NO, were removed, leaving behind a very slightly volatile liquid or solid.
Preparation of (R,O),P(O)CI from (R@),P + CI,. The tris(po1yfluoroalkyl) phosphites (5 mmol) were transferred into a 100-mL round-bottomed flask under an inert atmosphere. After the flask was evacuated at -196 OC, C1, (5 mmol) was condensed in. The temperature was raised to 25 OC slowly and left there for a few hours. The trap-totrap distillation gave the (RQ),P(O)CI compounds in their respective traps as described earlier.
Hydrolysis of Polyfluoroalkyl Dichlorophosphinates (R@P(O)CI,), Bis(polytluoroalkyl) Chlorophosphonates ((R@),P(O)CI), and (R@),PO. The hydrolysis of these phosphates to form acid phosphates, (RP),P-(O)OH, was carried out by condensing distilled water onto the dichlorophosphinates, chlorophosphonates, or tris(polyfluoroalkyl) phosphates. The reaction proceeded smoothly for the dichlorophosphinates at room temperature, whereas the reaction between (RQ),P(O)CI and H,O took place in the range of 50-64 OC. The reaction was also smooth between [(CF,),CHO],PO and water at ambient temperature, and for [CF,(CH,)CHO],PO and H 2 0 at 68 OC. Freeze-drying gave the acid phosphates R@P(O)(OH), and (RQ),P(O)OH.
Preparation of CF,CH,OP(O) (p-0),P(0)OCH2CF3. CF,CH,OPCI, (1.0 g, 5 mmol) was transferred into a 1000-mL round-bottomed flask equipped with a Teflon stopcock at -196 OC. Then N204 (1.12 g, 12 mmol) was condensed onto the CF,CH,OPCl,. The reaction mixture 2.1 g, -100%).
Notes
was warmed to and left at 25 "C overnight. The trap-to-trap distillation gave NOCl in a trap at -196 OC, N 2 0 3 at -140 O C , and in a trap at -25 OC in -100% yield. This compound was characterized by its IH, I9F and IIP NMR spectra as well as by its mass spectrum.