4323-64-2Relevant academic research and scientific papers
Ready Approach to Organophosphines from ArCl via Selective Cleavage of C-P Bonds by Sodium
Ye, Jingjing,Zhang, Jian-Qiu,Saga, Yuta,Onozawa, Shunya,Kobayashi, Shu,Sato, Kazuhiko,Fukaya, Norihisa,Han, Li-Biao
supporting information, p. 2682 - 2694 (2020/07/30)
The preparation, application, and reaction mechanism of sodium phosphide R2PNa and other alkali metal phosphides R2PM (M = Li and K) have been studied. R2PNa could be prepared, accurately and selectively, via the reactions of SD (sodium finely dispersed in mineral oil) with phosphinites R2POR′ and chlorophosphines R2PCl. R2PNa could also be prepared from triarylphosphines and diarylphosphines via the selective cleavage of C-P bonds. Na was superior to Li and K for these reactions. R2PNa reacted with a variety of ArCl to efficiently produce R2PAr. ArCl is superior to ArBr and ArI since they only gave low yields of the products. In addition, Ph2PNa is superior to Ph2PLi and Ph2PK since Ph2PLi did not produce the coupling product with PhCl, while Ph2PK only gave a low yield of the product. An electron-withdrawing group on the benzene ring of ArCl greatly accelerated the reactions with R2PNa, while an alkyl group reduced the reactivity. Vinyl chloride and alkyl chlorides RCl also reacted efficiently. While t-BuCl did not produce the corresponding product, admantyl halides could give the corresponding phosphine in high yields. A wide range of phosphines were prepared by this method from the corresponding chlorides. Unsymmetric phosphines could also be conveniently generated in one pot starting from Ph3P. Chiral phosphines were also obtained in good yields from the reactions of menthyl chlorides with R2PNa. Possible mechanistic pathways were given for the reductive cleavage of R3P by sodium generating R2PNa and the substitution reactions of R2PNa with ArCl generating R2PAr.
Synthesis and reactivity of substituted α-carbonylphosphonites and their derivatives
Prishchenko, Andrey A.,Livantsov, Mikhail V.,Novikova, Olga P.,Livantsova, Ludmila I.,Petrosyan, Valery S.
experimental part, p. 352 - 372 (2012/08/28)
Convenient methods for the synthesis of functionalized organophosphorus compounds containing carbonyl groups as well as di- or trialkoxymethyl fragments attached to phosphorus, and their derivatives, starting from the available derivatives of trivalent phosphorus acids, are proposed, and some properties of the new functionalized organophosphorus compounds are presented. So, the alkylation and acylation reaction of (dialkoxymethyl) phosphonites and their analogs have been studied. It is found that the Arbuzov rearrangement of these compounds was accompanied by the phosphorus-carbon bond cleavage with unique retention of the three-coordinate phosphorus.
INVESTIGATION OF THE REACTION BETWEEN DIALKYLPHOSPHINE OXIDES AND CARBONTETRACHLORIDE
Aksnes, Gunnar,Majewski, Piotr
, p. 261 - 274 (2007/10/02)
The time dependent formation of intermediates and end products in the reaction between Et2P(O)H and CCl4 is analysed using (31)P-NMR technique.The various reaction steps are studied separately in order to elucidate the overall mechanism.A key step is the disproportionation of Et2P(O)H catalysed by Et2PCl and Et2P(O)Cl, in a cyclic process, the latter being produced initially by the reaction between Et2P(O)H and CCl4.The diethylphosphine formed during disproportionation reacts immediately with CCl4, driving the reaction through the intermediates, Et2PCl and Et2PCCl3which react with Et2P(O)OH producing Et2P(O)Cl, (Et2PO)2O, and Et2P(O)CHCl2, as end products.The influence of the substituents on rate and product yields was studied with n-propyl, n-butyl, n-octyl, and allyl as substituents in the dialkylphosphine oxide.
