1809-19-4Relevant articles and documents
Trialkyl Phosphite Addition to the Bis(benzene)-iron(II) and -ruthenium(II) Dications: Catalysed Hydrolysis to Dialkyl Phosphites
Sweigart, Dwight A.
, p. 1159 - 1160 (1980)
Phosphite addition to 2+ (M = Fe,Ru) yields cyclohexadienyl phosphonium and phosphonate adducts that catalyse the conversion of excess of phosphite into HP(O)(OR)2 and RP(O)(OR)2.
Stability of phosphite coordinated to ruthenium(II) in aqueous media
Truzzi, Daniela R.,Franco, Douglas W.
, p. 238 - 244 (2014)
Changes in the reactivity of phosphorus(III) esters, which are promoted by coordination to the ruthenium(II) metal centre, were the focus of this study. Nuclear magnetic resonance data, which were acquired as a function of time, suggest that the phosphite coordination to the ruthenium(II) centre stabilises these molecules in terms of hydrolysis. This stabilisation is greater when the coordination occurs to the trans-[Ru(H2O)(NH3) 4]2+ rather than to the trans-[Ru(NO)(NH3) 4]3+ fragment, and these results are interpreted considering the 4dπ(RuII) → 3dπ(P(III)) back-bonding interactions. The correlation between the data on alkyl phosphite hydrolysis constants in trans-[Ru(NO)(NH3)4P(III)]n + (P(III) = P(OEt)3, P(O)(OEt)2, P(O iPr)3 and P(OBu)3) complexes and the δ13C data show that the hydrolysis of phosphites that are coordinated to Ru(II) preferably occurs via the Michaelis-Arbuzov mechanism. Only the nitrosyl complex, where P(III) = P(OMe)3, did not exhibit this correlation, which suggests that the hydrolysis likely occurs via the Aksnes mechanism in this case.
Synthesis and characterization of new symmetrical bisphosphonates
Marques Rodrigues, Janaina,DaCosta, Joao Batista Neves
, p. 137 - 149 (2002)
In order to search for new chelating agents, widely employed methodologies in the chemistry of organophosphorus compounds such as the Michaelis-Arbuzov and Michaelis-Becker reactions were used to synthesize new bisphosphonates in high yields. The importance of the synthesis of these compounds resides in their potential capability of complexing different metals, all the more so because bisphosphonates have been widely employed in the diagnosis and therapy of several bone diseases, such as osteoporosis and hypercalcemia, as extracting agents for alkaline, alkaline earth, and transition metals, and also as reaction catalysts. All bisphosphonates synthesized were characterized by IR, 1H-NMR, 13C-NMR, 31P-NMR, and mass spectroscopy.
Method for preparing phosphite diester by transesterification
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Paragraph 0023, (2020/01/25)
The invention discloses a method for preparing phosphite diester by transesterification. Dimethyl phosphite and monohydric alcohol which are used as raw materials are stirred, reacted and rectified under the action of a basic catalyst to prepare the phosphite diester, so the problems of high deice requirements and large amount of acid-containing three wastes in the process of producing the phosphite diester by reacting phosphorus trichloride with alcohol are avoided. The method has the advantages of low raw material toxicity, simple process, mild reaction conditions, low device requirements, low pollution, high raw material conversion rate, high product selectivity, stable supply of the raw materials, provision of the phosphite diester used for fine chemical engineering or medical intermediates by dimethyl phosphite production enterprises, high added values of the product, and provision of a new way for the synthesis of the phosphite diester.
METHOD FOR PRODUCING ORGANOPHOSPHORUS COMPOUND
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Paragraph 0086; 0094, (2020/05/02)
PROBLEM TO BE SOLVED: To provide a method for producing an organophosphorus compound which has excellent energy efficiency without containing a halogenated alkyl or a by-product derived from a halogenated alkyl. SOLUTION: There is provided a method for producing an organophosphorus compound by reacting a trivalent organophosphorus compound represented by the following general formula (1) in the presence of a super strong acid and/or at least one acid catalyst containing a solid superstrong acid catalyst to generate a pentavalent organophosphorus compound represented by the following general formula. (where Z1 represents OR2 or R2; Z2 represents OR3 or R3; R1, R2 and R3 represent an alkyl group, an alkenyl group or the like; when R2 and R3 are an alkyl group or the like, R2 and R3 may be bonded to each other to form a cyclic structure; and R1 may be a hydrogen atom.) SELECTED DRAWING: None COPYRIGHT: (C)2020,JPOandINPIT
Water determines the products: An unexpected Br?nsted acid-catalyzed PO-R cleavage of P(iii) esters selectively producing P(O)-H and P(O)-R compounds
Li, Chunya,Wang, Qi,Zhang, Jian-Qiu,Ye, Jingjing,Xie, Ju,Xu, Qing,Han, Li-Biao
supporting information, p. 2916 - 2922 (2019/06/18)
Water is found able to determine the selectivity of Br?nsted acid-catalyzed C-O cleavage reactions of trialkyl phosphites: with water, the reaction quickly takes place at room temperature to afford quantitative yields of H-phosphonates; without water, the reaction selectively affords alkylphosphonates in high yields, providing a novel halide-free alternative to the famous Michaelis-Arbuzov reaction. This method is general as it can be readily extended to phosphonites and phosphinites and a large scale reaction with much lower loading of the catalyst, enabling a simple, efficient, and practical preparation of the corresponding organophosphorus compounds. Experimental findings in control reactions and substrate extension as well as preliminary theoretical calculation of the possible transition states all suggest that the monomolecular mechanism is preferred.
Synthesis of phosphonates in a continuous flow manner
Tóth, Nóra,Tajti, ádám,Ladányi-Pára, Katalin,Bálint, Erika,Keglevich, Gy?rgy
, p. 285 - 286 (2019/03/11)
The synthesis of dialkyl H-phosphonates and α-aminophosphonates was studied in a continuous flow microwave reactor. Depending on the conditions, the alcoholysis of dialkyl H-phosphonates could be fine-tuned towards the mixed and the fully transesterified products. The continuous flow synthesis of α-aryl-α-aminophosphonates was elaborated utilizing the aza-Pudovik reaction of imines and dialkyl H-phosphonates, as well as the by the Kabachnik-Fields condensation of primary amines, benzaldehyde and > P(O)H reagents.
Synthesis and extraction behavior of alkyl and cyclic aminophosphonates towards actinides
Das, Dhrubajyoti,Brahmmananda Rao,Sivaraman,Sivaramakrishna, Akella,Vijayakrishna, Kari
supporting information, p. 597 - 604 (2018/07/13)
Alkyl and cyclic substituted aminophosphonates (AmPs) were synthesized and characterized with various spectroscopic techniques. The molecular structures of diphenyl phenyl aminophosphonate (DPhPhAmP) and diphenyl cyclohexyl aminophosphonate (DPhCyAmP) wer
Extraction of actinides by Tri-n-butyl phosphate derivatives: Effect of substituents
Annam, Suresh,Gopakumar, Gopinadhanpillai,Brahmmananda Rao,Sivaraman,Sivaramakrishna, Akella,Vijayakrishna, Kari
, p. 123 - 132 (2017/09/18)
Tri-n-butyl phosphate (TBP) is most extensively used extractant in the nuclear fuel cycle. The present work investigates the effect of substituents and their role in the basicity of organophosphorus extractant on the uptake of actinides. In this connection, we have synthesized six different analogues of TBP by altering one of its butoxy group. The synthesized TBP derivatives were well characterized and evaluated for their solvent extraction behavior towards U(VI), Th(IV), Pu(IV) and Am(III), as well as acid uptake as a function of nitric acid ranging from 0.01 to 6 M and the data provides the comparison of their extraction behavior with that of 30% (1.1 M) tri-n-butyl phosphate under identical conditions. It was observed that distribution coefficient values strongly depend on the nature and size of the substituents. The presence of electron donating groups enhances the uptake of the actinides and the distribution coefficient values were significantly larger as compared to that of TBP. In addition, the effect of sodium nitrate on the extraction of uranium and enthalpy of extraction were also studied and revealed that the extraction process was exothermic.
Remarkable structural effects on the complexation of actinides with H-phosphonates: A combined experimental and quantum chemical study
Chandrasekar, Aditi,Brahmmananda Rao,Sundararajan, Mahesh,Ghanty, Tapan K.,Sivaraman
supporting information, p. 3841 - 3850 (2018/03/21)
The structural effects of the carbon chain on the extraction of actinides by organo-phosphorus extractants have been examined experimentally and by computation. Branched butyl H-phosphonates and their linear chain isomer, n-butyl H-phosphonate (DBHP), wer
