7067-73-4Relevant academic research and scientific papers
Calcium-mediated hydrophosphorylation of organic isocyanates with diphenylphosphane oxide
Haerling, Stephan,Greiser, Julia,Al-Shboul, Tareq M. A.,Goerls, Helmar,Krieck, Sven,Westerhausen, Matthias
, p. 1264 - 1273 (2013/10/22)
The calcium-mediated addition of diphenylphosphane oxide to organic isocyanates and isothiocyanates yields N-alkyl and N-aryl substituted diphenylphosphorylformamides (E≤O, R≤iPr, tBu, cHex, Ph, C6H4-4-Br, C6H2-2,4,6-Me3, and Naph) and -thioformamides (E≤S, R≤iPr, cHex, Ph, and C6H4-4-Me), respectively, of the type Ph2P(O)-C(E)-N(H)R. All derivatives were characterized by IR and NMR spectroscopy as well as X-ray diffraction experiments. The wavenumbers of the N-H stretching modes are smaller for the thio analogues and N-aryl substituents. In the solid state all formamides and thioformamides form dimers by N-HO-P hydrogen bridges. The P-CCE bonds are significantly elongated compared with the P-CPh distances.
Ambident reactivity of chloro(dialkylamino)-(diphenylphosphinoyl)methanes
Morgalyuk, Vasilii Petrovich,Strelkova, Tat'Yana Vladimirovna,Nifant'Ev, Eduard Eugenievich
, p. 93 - 100 (2012/03/07)
The chemical properties of chloro(dialkylamino)(diphenylphosphinoyl) methanes have been studied using the simplest compound of this series, chloro(dimethylamino)(diphenylphosphinoyl)methane, as an example. Chloro- (dimethylamino)(diphenylphosphinoyl)methane shows ambident reactivity when reacting with electrophiles and nucleophiles depending on coreactant nature, it behaves as either electrophilic substrate or phosphorus nucleophile. This fact can be explained by its dissociation in solutions with both C-Cl bond cleavage to give (dimethylamino)- (diphenylphosphinoyl)methyl cation and Cl- anion and C-P bond cleavage to form chloro(dimethylamino)methyl cation and diphenylphosphinite anion. The capability of chloro(dimethylamino) (diphenylphosphinoyl)methane to produce spontaneously Ph2PO-anion allows us to recommend application in organic and organophosphorus synthesis as a synthetic equivalent (synthon) of diphenylphosphinite anion.
Synthesis of polyfunctionalized methylphosphine oxides
Morgalyuk,Strelkova,Nifant'Ev
, p. 380 - 385 (2013/06/05)
N,N-Dialkylamino(diphenylphosphoryl)chloromethanes, a new type of organophosphorus compounds, were synthesized. On dissolving in polar and low polar solvents, N,N-dialkylamino(diphenylphosphoryl)chloromethanes dissociate spontaneously with the P - C bond cleavage to form the diphenylphosphinite anion Ph2PO-. This was confirmed by the reaction of N,N-dimethylamino(diphenylphosphoryl)chloromethane with electrophilic substrates to form the corresponding addition or substitution products of Ph 2PO-. The capability of spontaneous generating the diphenylphosphinite anion considers accessible N,N- dimethylamino(diphenylphosphoryl)chloromethane as a synthetic equivalent of the diphenylphosphinite anion.
