1733-55-7Relevant articles and documents
CATALYSIS BY METALLOPORPHYRINS OF OXIDATIVE DESULPHURISATION AT PENTACOVALENT PHOSPHORUS BY CUMYL HYDROPEROXIDE
Davidson, R Stephen,Walker, Martin D
, p. 1827 - 1828 (1988)
Cumyl hydroperoxide causes oxidative desulphurisation at pentacovalent phosphorus with retention of configuration in the presence of various manganese (iii) and iron (ii) mesotetraphenylporphyrins provided imidazole is present, the yields of oxidised phosphorus compounds being influenced by the rate of destruction of the hydroperoxide by parasitic side reactions.
Alteration of the course of the Michaelis-Arbuzov reaction in imidazolium ionic liquids
Matveeva, Ekaterina V.,Kozlov, Vladimir A.,Odinets, Irina L.
, p. 145 - 147 (2010)
Room-temperature imidazolium ionic liquids [Rmim][X] (X = Br, BF 4, NTf2) as a reaction medium change the reaction course of phosphorus(III) acid esters with primary alkyl halides, aryl bromides, and propargyl bromide to afford hydrophosphoryl compounds, products of oxidation of the starting phosphorus substrates, and 2,3-bis(phosphoryl)prop-1-enes, respectively.
Experimental and theoretical study on the "2,2′-bipiridyl-Ni-catalyzed"hirao reaction of > P(O)H reagents and halobenzenes: A Ni(0) → Ni(II) or a Ni(II) → Ni(IV) mechanism?
Keglevich, Gy?rgy,Henyecz, Réka,Mucsi, Zoltán
, p. 14486 - 14495 (2020)
It was found by us that the P.C coupling reaction of >P(O)H reagents with PhX (X = I and Br) in the presence of NiCl2/Zn as the precursors for the assumed Ni(0) complexant together with 2,2′-bipyridine as the ligand took place only with PhI at 50/70 °C. M06-2X/6-31G(d,p)//PCM(MeCN) calculations for the reaction of Ph2P(O)H and PhX revealed a favorable energetics only for the loss of iodide following the oxidative addition of PhI on the Ni(0) atom. However, the assumed transition states with Ni(II) formed after P-ligand uptake and deprotonation could not undergo reductive elimination meaning a "dead-end route". Hence, it was assumed that the initial complexation of the remaining Ni2+ ions with 2,2′-bipyridine may move the P-C coupling forward via a Ni(II) → Ni(IV) transition. This route was also confirmed by calculations, and this mechanism was justified by preparative experiments carried out using NiCl2/bipyridine in the absence of Zn. Hence, the generally accepted Ni(0) → Ni(II) route was refuted by us, confirming the generality of the Ni(II) → N(IV) protocol, either in the presence of bipyridine, or using the excess of the >P(O)H reagent as the P-ligand. The results of the calculations on the complex forming ability of Ni(0) and Ni(II) with 2,2′-bipyridine or the P-reagents were in accord with our mechanistic proposition.
High performance liquid phase continuous automatic production and co-production technology of organic phosphine compound
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Paragraph 0070-0074, (2021/05/12)
The invention relates to the field of photocuring functional new material chemicals, and discloses a high performance liquid phase streamline type continuous automatic production technology of an acylphosphine oxide organic phosphine compound for the first time, which not only can produce a single specific target product, but also can co-produce a product mixture of two or more than two of the products of the type. The process technology has outstanding low-cost economic competitiveness and environment-friendly characteristics for large-scale manufacturing of target products. The target product comprises sym-trimethylbenzoyl diphenyl phosphine oxide (also known as 2, 4, 6-trimethylbenzoyl diphenyl phosphine oxide, trade name TPO), sym-trimethylbenzoyl phenyl ethyl phosphonate (trade name TPO-L) and structural analogues thereof, and a mixture of the sym-trimethylbenzoyl diphenyl phosphine oxide and the sym-trimethylbenzoyl phenyl ethyl phosphonate. The organic phosphine compound is an olefinic bond-containing (C=C) unsaturated radiation polymerization system photoinitiator and/or flame retardant and the like with wide application.
Selective hydrolysis of phosphorus(v) compounds to form organophosphorus monoacids
Ash, Jeffrey,Cordero, Paula,Huang, Hai,Kang, Jun Yong
, p. 6007 - 6014 (2021/07/21)
An azide and transition metal-free method for the synthesis of elusive phosphonic, phosphinic, and phosphoric monoacids has been developed. Inert pentavalent P(v)-compounds (phosphonate, phosphinate, and phosphate) are activated by triflate anhydride (Tf2O)/pyridine system to form a highly reactive phosphoryl pyridinium intermediate that undergoes nucleophilic substitution with H2O to selectively deprotect one alkoxy group and form organophosphorus monoacids.