Action des hydrazines fluoroalkylées sur les phosphoallènes: synthèse d’hydrazones N-fluoroalkylées β-phosphonatées

Ten phosphorylated β-hydrazones of structure R2P(O)C(NNHRF)CHR2′ were prepared in 54–91% yield by heating the allenes R2P(O)CHCCR2′ with fluorinated hydrazines H2NNHRF in chloroform or methanol [R=Ph, OCH2C(Me)2CH2O or OCH2C(Me)(Pr)CH2O, R′=H or Me and RF=CH2CF3 or C6F5]. Two cyclohexyl derivatives were prepared similarly from R2P(O)CHCCy. The triphenyl derivatives Ph2P(O)CH2C(NNHCH2CF3)Ph and Ph2P(O)CH2C(NNHC6F5)Ph were made in 91 and 68% yield by heating the ketones Ph2P(O)CH2C(O)Ph with an ethanol solution of the corresponding hydrazines. The stereochemistry of the hydrazones was determined by multinuclear NMR experiments. Compounds with C(NNHRF)Me groups exist as a mixture of Z and E isomers, with the Z form predominating (fluorinated group syn to phosphorus). Those with C(NNHRF)CHMe2, C(NNHRF)Cy or C(NNHRF)Ph groups were formed selectively, the Z isomers being the only products. The results are explained by steric hindrance, the bulkier isopropyl, cyclohexyl or phenyl group disfavouring the E configuration. 1H, 13C, 19F, 31P NMR data, coupling constants and IR data are reported.