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The reactions of a variety of electrophiles with the N-silyl-P-trifluoroethoxyphosphoranimine anion Me3Sin°P(Me)(OCH2CF3)CH− 2 (1a), prepared by the deprotonation of the dimethyl precursor Me3SiN[dbnd]P(OCH2CF3)Me2 (1) with n-BuLi in Et2O at-78°C, were studied. Thus, treatment of 1a with alkyl halides, ethyl chloroformate, or bromine afforded the new N-silylphosphoranimine derivatives Me3SiN[dbnd]P(Me)(OCH2CF3)CH2R [2: R = Me, 3: R = CH2Ph, 4: R = CH[sbnd]CH2, 5: R = C(O)OEt, and 6: R = Br]. In another series, when 1a was allowed to react with various carbonyl compounds, 1,2-addition of the anion to the carbonyl group was observed. Quenching with Me3SiCl gave the O-silylated products Me3SiN[dbnd]P(Me)(OCH2CF3)CH2°C(OSiMe3)R1R2 [7: R 1 = R 2 = Me; 8: R 1 = Me, R 2 = Ph; 9: R1 = Me, R 2 = CH[sbnd]CH2; and 10: R 1 = H, R 2 = Ph]. Compounds 2–10 were obtained as distillable, thermally stable liquids and were characterized by NMR spectroscopy (1H, 13C, and 31P) and elemental analysis. |
