Bis(dialkylamino)phosphines

Article abstract of DOI:10.1021/jo00184a022

Reactions of LiAlH4 with sufficiently sterically hindered (R2N)2PCl derivatives (R = isopropyl and ethyl but not methyl) in diethylether give the corresponding (R2N)2PH derivatives as air-sensitive, vacuum-destillable liquids.Analogous reactions of LiAlH4 with sufficiently sterically hindered heterocycles (CH2)n(NR)2PCl (R = tert-butyl, n = 2 and 3; R not methyl, n not 2) give the corresponding heterocyclic PH derivatives (CH2)n(NR)2PH.The dialkylamino groups in (R2N)2PH undergo successive alcoholysis with the alcohols R'OH (R' = methyl, ethyl, isopropyl, andtert-butyl) to form (R2N)(R'O)PH and (R'O)2PH derivatives, which are identified by their phosphorus-31 NMR spectra.The derivatives (R2N)(R'O)PH (R = isopropyl; R'= methyl, ethyl, isopropyl, and tert-butyl) can be isolated by vacuum distillation as air-sensitive liquids, but the derivatives (R'O)2PH generally decompose upon attempted vacuum distillation.The (R2N)2PH derivatives undergo base-catalyzed addition to (R2N)2PCH=CH2 to give the corresponding diphosphines (R2N)2PCH2CH2P(NR2)2, provided that the R2N groups are not too bulky .The mass spectra and NMR spectra of the new organophosphorus compounds are described.