1083-98-3Relevant academic research and scientific papers
Functionalised phosphonate ester supported lanthanide (Ln = La, Nd, Dy, Er) complexes
Koehne, Ingo,Lik, Artur,Gerstel, Miriam,Bruhn, Clemens,Reithmaier, Johann Peter,Benyoucef, Mohamed,Pietschnig, Rudolf
, p. 16683 - 16692 (2020)
A series of phosphonate ester supported lanthanide complexes bearing functionalities for subsequent immobilisation on semiconductor surfaces are prepared. Six phosphonate ester ligands (L1-L6) with varying aromatic residues are synthesised. Subsequent com
Visible-light-mediated phosphonylation reaction: formation of phosphonates from alkyl/arylhydrazines and trialkylphosphites using zinc phthalocyanine
Hosseini-Sarvari, Mona,Koohgard, Mehdi
, p. 5905 - 5911 (2021/07/12)
In this work, we developed a ligand- and base-free visible-light-mediated protocol for the photoredox syntheses of arylphosphonates and, for the first time, alkyl phosphonates. Zinc phthalocyanine-photocatalyzed Csp2-P and Csp3-P bond formations were efficiently achieved by reacting aryl/alkylhydrazines with trialkylphosphites in the presence of air serving as an abundant oxidant. The reaction conditions tolerated a wide variety of functional groups.
Palladium-catalyzed phosphorylation of benzyl ammonium triflates with P(O)H compounds
Chen, Tieqiao,Huang, Tianzeng,Liu, Long,Wang, Wenqi,Wang, Yuan,Xu, Hanshuang,Xu, Kaiqiang
, (2020/03/03)
A palladium-catalyzed phosphorylation of benzyl ammonium triflates with P(O)H compounds has been developed. Various benzylphosphorus compounds were produced in good to excellent yields with high functional group tolerance. All the three kinds of hydrogen phosphoryl compounds, i.e. H-phosphonates, H-phosphinates and secondary phosphine oxides, were applicable to this reaction. The successful scale-up experiment and one-pot synthetic operation also well demonstrated its practicality.
Utilization of 1,3-Dioxolanes in the Synthesis of α-branched Alkyl and Aryl 9-[2-(Phosphonomethoxy)Ethyl]Purines and Study of the Influence of α-branched Substitution for Potential Biological Activity
Pomeisl, Karel,Pohl, Radek,Snoeck, Robert,Andrei, Graciela,Kre?merová, Marcela
, p. 119 - 156 (2019/01/04)
Syntheses of α-branched alkyl and aryl substituted 9-[2-(phosphonomethoxy)ethyl]purines from substituted 1,3-dioxolanes have been developed. Key synthetic precursors, α-substituted dialkyl [(2-hydroxyethoxy)methyl]phosphonates were prepared via Lewis acid mediated cleavage of 1,3-dioxolanes followed by reaction with dialkyl or trialkyl phosphites. The best preparative yields were achieved under conditions utilizing tin tetrachloride as Lewis acid and triisopropyl phosphite. Attachment of purine bases to dialkyl [(2-hydroxyethoxy)methyl]phosphonates was performed by Mitsunobu reaction. Final α-branched 9-[2-(phosphonomethoxy)ethyl]purines were tested for antiviral, cytostatic and antiparasitic activity, the latter one determined as inhibitory activity towards Plasmodium falciparum enzyme hypoxanthine-guanine-xanthine phosphoribosyltransfesase. In most cases biological activity was only marginal.
Preparation method of aryl methyl phosphine acylate
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Paragraph 0037, (2019/10/01)
The invention discloses a preparation method of aryl methyl phosphine acylate. The method uses (hetero) aryl acetic acid as the starting material, and the raw materials are easily available and have agreat variety. The product obtained by the method provided by the invention has various types and wide uses. The aryl methyl phosphine acylate can be easily converted into a bis (hetero)arylethene derivative, and the compound can be used for preparation of dyes, fluorescent agents, whiteners, light-emitting diodes and other devices. In addition, the method disclosed by the invention has the advantages of easily available, stable and low toxicity raw materials, mild reaction conditions, high yield of target product, low pollution, simple reaction operation and post-treatment process, and is suitable for industrial production.
Alcohol-based Michaelis-Arbuzov reaction: An efficient and environmentally-benign method for C-P(O) bond formation
Ma, Xiantao,Xu, Qing,Li, Huan,Su, Chenliang,Yu, Lei,Zhang, Xu,Cao, Hongen,Han, Li-Biao
supporting information, p. 3408 - 3413 (2018/08/06)
The famous Michaelis-Arbuzov reaction is extensively used both in the laboratory and industry to manufacture tons of widely-used organophosphoryl compounds every year. However, this method and the modified Michaelis-Arbuzov reactions developed recently still have some limitations. We now report a new alcohol-version of the Michaelis-Arbuzov reaction that can provide an efficient and environmentally-benign method to address the problems of the known Michaelis-Arbuzov reactions. That is, a wide range of alcohols can readily react with phosphites, phosphonites, and phosphinites to give all the three kinds of phosphoryl compounds (phosphonates, phosphinates, and phosphine oxides) using an n-Bu4NI-catalyzed efficient C-P(O) bond formation reaction. This general method can also be easily scaled up and used for further synthetic transformations in one pot.
Synthetic method for alkyl group phosphorous acid diester compounds or alkyl group phosphinic acid ester compounds
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Paragraph 0086; 0087; 0088; 0089, (2017/04/26)
The invention discloses a synthetic method for alkyl group phosphorous acid diester compounds or alkyl group phosphinic acid ester compounds. According to the synthetic method, alcohols which are cheap, easy to get, wide in source, stable and low in toxicity serve as alkylating reagents, iodine salt which is cheap and easy to get serves as catalysts, no solvent is needed, and the alkyl group phosphorous acid diester compounds can be selectively directly obtained after a reaction. The reaction method is simple, the condition is mild, no organic solvent is needed and operation is simple. According to the method, the requirements for reaction conditions are low, various types of alcohols such as a benzyl group type, an allyl type and a fat type can be utilized as the alkylate reagents to implement the synthesis of different types of substituted alkyl group phosphorous acid diester, and the method can be further expanded to the synthesis of the alkyl group phosphinic acid ester compounds through the reaction between the substituted phosphonous acid diester and the alcohols.
Investigation of reactive intermediates and reaction pathways in the coupling agent mediated phosphonamidation reaction
Fredriksen, Kim Alex,Amedjkouh, Mohamed
supporting information, p. 474 - 482 (2016/02/18)
The preparation of carboxamides through the coupling agent mediated reaction of carboxylic acids and amines is one of the most frequently employed reaction types of modern organic synthesis and has largely replaced older methods of amide formation based on reactive acyl chloride intermediates. However, the preparations of analogous phosphonamidates still rely on the use of phosphonochloridate intermediates - a method that is incompatible with sensitive functional groups. Herein, we present a comprehensive study in which different coupling agents are tested in the phosphonamidation reaction. The procedures, parallel to those typically applied to the preparation of carboxamides, were generally unsuccessful with regard to the coupling reactions of monoesters of phosphonic acids and amines, with the exception of those mediated by (benzotriazol-1-yloxy)tripyrrolidinophosphonium hexafluorophosphate (PyBOP). The implementation of a preactivation period in the absence of the amine coupling partner allowed for efficient phosphonamidate formation with coupling agents such as (1-cyano-2-ethyoxy-2-oxoethylideneaminooxy)dimethylamino-morpholino-carbenium hexafluorophosphate (COMU), [ethyl cyano(hydroxyimino)acetato-O2]tri-1-pyrrolidinylphosphonium hexafluorophosphate (PyOxim), dicyclohexyl carbodiimide (DCC), N,N′-diisopropylcarbodiimide (DIC), and N,N,N′,N′-tetramethyl-O-(1H-benzotriazol-1-yl)uronium hexafluorophosphate (HBTU). The reactive intermediates observed by 31P NMR analysis were individually synthesized and examined to understand their influence on the reaction. A phosphonamidation reaction that uses (1-cyano-2-ethyoxy-2-oxoethylideneaminooxy)dimethylamino-morpholino-carbenium hexafluorophosphate (COMU) to mediate the coupling of monoalkyl esters of phosphonic acids and amines was developed. A preactivation period without the amine was needed to obtain the product. Using this step allowed for other coupling agents to be successfully used in the reaction.
Palladium-catalyzed α-arylation of benzylic phosphonates
Montel, Sonia,Raffier, Ludovic,He, Yuying,Walsh, Patrick J.
supporting information, p. 1446 - 1449 (2014/04/03)
A new synthetic route to access diarylmethyl phosphonates is presented. The transformation enables the introduction of aromatic groups on benzylic phosphonates via a deprotonative cross-coupling process (DCCP). The Pd(OAc) 2/CataCXium A-based catalyst afforded a reaction between benzyl diisopropyl phosphonate derivatives and aryl bromides in good to excellent isolated yields (64-92%).
Synthesis of aryl and arylmethyl phosphonates by cross-coupling of aryl or arylmethyl halides (X = I, Br and Cl) with diisopropyl H-phosphonate
Xu, Kai,Hu, Hao,Yang, Fan,Wu, Yangjie
supporting information, p. 319 - 325 (2013/02/25)
An efficient and generally applicable protocol for the palladacycle- catalysed arylation or K2CO3-promoted arylmethylation of diisopropyl H-phosphonate has been developed. The remarkable features of the palladacycle-catalysed arylation reaction include wide substrate scope (aryl iodides, bromides and chlorides), significant shortening of the reaction time (2 or 3 h) and a low catalyst loading of 1 mol-%. Note that with the base K 2CO3 as promoter, arylmethylation could be achieved without any palladium catalyst. Moreover, the first example of a palladium-catalysed phosphonation of inactive electron-rich aryl chlorides with tBuOK as the base has been realized. This result could be considered an important improvement and complement to earlier work of Montchamp and Han, whose catalytic systems are typically compatible with electron-deficient and electron-neutral aryl chlorides.
