29949-68-6Relevant academic research and scientific papers
The reactivity of arylphosphorus acid amides under Birch reduction conditions
Stankevic, Marek,Wlodarczyk, Adam,Nieckarz, Damian
, p. 4351 - 4371 (2013/07/26)
Several classes of arylphosphorus acid amides have been tested in reactions with alkali metal solutions in liquid ammonia. The outcomes of such reactions depend on the structures of the starting materials. Generally, two processes-Birch reduction or cleavage of the P-aryl bond-can be operative. Diarylphosphinic amides tend to undergo double Birch reduction to afford bis(cyclohexadienyl)phosphinic amides. Copyright
THE REACTION OF DIBENZYLMERCURY WITH SECONDARY PHOSPHINES: PHOSPHORUS-PHOSPHORUS BOND FORMATION VERSUS BENZYL SUBSTITUTION
Yeh, Jesse T.,Avens, Larry R.,Mills, Jerry L.
, p. 319 - 323 (2007/10/02)
In an attempt to find a simple, high yield synthetic method to create a phosphorus-phosphorus bond from phosphorus-hydrogen bonds, we have investigated the reaction of dibenzylmerury DBM with secondary phosphines.The overall reaction is: DBM + R2PH -> toluene + Hg + R2P-PR2.Thus reaction of diphenylphosphine with DBM produces the desired coupled product tetraphenyl diphosphine in 85-90percent yield.In contrast, the reaction of DBM with 1,3-bis(phenylphosphino)propane Ph(H)P-(CH2)3-P(H)Ph produces the benzyl-substituted product rather than the expected cyclic compound 1,2-diphenyl-1,2-diphospholane PhP-(CH2)3-PPh.The dioxide or disulfide of Ph(H)P-(CH2)3P(H)Ph undergoes no reaction with DBM.The bulky 2,4,6-tris(tert-butyl)phenylphosphine ArPH2 with DBM yields diastereomers of the coupled disecondary diphosphine Ar(H)P-P(H)Ar.The reaction of DBM with diphenylchlorophosphine results in a high yield of tetraphenyl diphosphine, but with phenyldichlorophosphine produces the benzyl-substituted product phenylbenzylchlorophosphine.
Synthesis and Properties of Mixed Substituted (Chloroacetyl)organylphenylphosphanes
Lindner, Ekkehard,Merkle, Ralf Dieter,Mayer, Hermann August
, p. 645 - 658 (2007/10/02)
The mono-, di- and trichloroacetylorganylphenylphosphanes X1X2CClC(O)PPhR (3av-cz) are obtained by reaction of Me3SiPPhR (2v-z) with the azid chlorides X1X2CClC(O)Cl (1a-c).Increasing content of chlorine results in a shift of the >C=O band and the 31P signal to higher wavelengths and fields, respectively, in the IR and 31P NMR spectra of 3av-cz.Due to the centre of chirality at the phosphorus atom in the 1H NMR spectra one observes diastereotopic protons in the chloroacetyl moiety of 3av-az and of the P-adjacent CH2 protons of 3aw-cw and 3ay-cy.The magnetic inequivalence of both methyl substituents in the isopropyl groups of 3ax-cx is observable also in the 13C and 1H NMR spectra.Because of steric reasons the free rotation about the P-isopropyl axis is hindered up to 355 K.From the coalescence temperature the free activation energy ΔG* is calculated to give 74.7 kJ/mole.The degradation of the thermolabile compounds 3av-cz results in the formation of the chlorophosphanes 5v-z.Individual investigations on 3bv, 3bw and 3by indicate the formation of mono- and dichloroacetyl chloride.The appearance of ClCH2C(O)Cl proceeds via the chloroketene 4b.
SYNTHESE DIRECTE DE PHOSPHINES TERTIARIES RACEMIQUES ET DE CHLOROPHOSPHINES DISSYMETRIQUES
Chodkiewicz, W.,Guillerm, D.,Jore, D.,Mathieu, E.,Wodzki, W.
, p. 107 - 114 (2007/10/02)
Racemic tertiary phosphines are obtained from dichlorophenylphosphine by a "one pot" synthesis in two steps: (1) condensation of one equivalent of an organocadmium, and (2) substitution of the second chlorine by another organometallic compound.The phosphines liberated from the resulting complexes can be stabilised by direct complexation with cuprous salts.The monochlorophosphines can be isolated in the first stage when their cadmium complexes are submitted to ligand exchange with pyridine.
