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.
Synthesis of Seven-Membered Cyclic Enol Ether Derivatives from the Reaction of a Cyclic Phosphonium Ylide with α,β-Unsaturated Esters
Fujimoto, Tetsuya,Kodama, Yoh-Ichi,Yamamoto, Iwao,Kakehi, Akikazu
, p. 6627 - 6630 (1997)
The tandem Michael-intramolecular Wittig reactions of a five-membered cyclic phosphonium ylide (2) with α,β-unsaturated esters afforded seven-membered cyclic enol ether derivatives 4a-e in 37-73% yield. The reaction proceeded via a rigid phosphabicyclic intermediate and supplied the enol ether derivatives with high stereoselectivity. On the other hand, the reaction using ethyl acrylate as a substrate gave the 1:3 adduct 15 of the ylide and the enoate via the repetition of the Michael-type addition and regeneration of the ylide followed by the intramolecular Wittig reaction.
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.
Microwave assisted P–C coupling reactions without directly added P-ligands
Henyecz, Réka,Huszár, Bianka,Keglevich, Gy?rgy,Mucsi, Zoltán
, (2021/12/24)
Our group introduced a green protocol for the Pd(OAc)2- or NiCl2-catalyzed P–C coupling reaction of aryl halides and various > P(O)H-compounds under MW conditions without directly added P-ligands. The reactivity of a few aryl derivatives in the Pd(OAc)2-catalyzed Hirao reaction was also studied. An induction period was observed in the reaction of bromobenzene and diphenylphosphine oxide. Finally, the less known copper(I)-promoted P–C coupling reactions were investigated experimentally. The mechanism was explored by quantum chemical calculations.
High performance liquid phase continuous automatic production and co-production technology of organic phosphine compound
-
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.
METHOD FOR PRODUCING PHOSPHOESTER COMPOUND
-
Paragraph 0023; 0029-0034, (2021/09/27)
PROBLEM TO BE SOLVED: To provide a method whereby, a phosphate compound selected from the group consisting of orthophosphoric acid, phosphonic acid, phosphinic acid, and anhydrides of them is used as raw material and, by one stage reaction, a corresponding phosphoester compound is produced. SOLUTION: To an aqueous solution of a phosphate compound, added is an organic silane or siloxane compound having an alkoxy group or an aryloxy group, and the mixture is subjected to a heating reaction, thereby producing a corresponding phosphoester compound without requiring a catalyst. SELECTED DRAWING: None COPYRIGHT: (C)2021,JPOandINPIT
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.
Application of heteropolyacid in catalytic synthesis of material compound
-
Paragraph 0050-0055; 0064-0065, (2021/04/14)
The invention provides an application of heteropolyacid in catalytic synthesis of a diarylphosphonate compound. The method is characterized by comprising the following steps: in a protective gas atmosphere, taking diarylphosphonic acid and halogenated alkane as raw materials, heteropolyacid as a catalyst and an organic solvent as a solvent, and performing reacting to obtain the diarylphosphonate compound. According to the preparation method disclosed by the invention, only an extremely small amount of catalyst is needed, the reaction temperature is relatively mild, the reaction time can be obviously shortened, the yield and purity are relatively high, and an unexpected technical effect is achieved.
Regio- And stereoselective electrochemical synthesis of sulfonylated enethers from alkynes and sulfonyl hydrazides
Du, Wu-Bo,Wang, Ning-Ning,Pan, Chao,Ni, Shao-Fei,Wen, Li-Rong,Li, Ming,Zhang, Lin-Bao
supporting information, p. 2420 - 2426 (2021/04/07)
An electrooxidative direct difunctionalization of internal alkynes with sulfonyl hydrazides has been developed for the construction of sulfonated enethers. In this transformation, metal catalysts or stoichiometric amount of oxidants are not required and molecular nitrogen and hydrogen are the sole byproducts, providing a simple and green approach for preparing various sulfonyl tetrasubstituted alkenes. Notably, the protocol could be efficiently scaled up and the follow-up procedures of the corresponding functionalized alkenes demonstrate the practicality of the electrochemical synthesis.
