- Synthesis and reactivity of substituted α-carbonylphosphonites and their derivatives
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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.
- Prishchenko, Andrey A.,Livantsov, Mikhail V.,Novikova, Olga P.,Livantsova, Ludmila I.,Petrosyan, Valery S.
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- Synthesis of tervalent phosphorus esters in biphasic system using potassium phosphate as unique solid base
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The synthesis of tervalent phosphorus esters continues to be a significant area of interest, much of it again directed toward the synthesis of phosphite ligands for metal-catalyzed reactions. Typically, they were obtained through esterification of the corresponding phosphorus chlorides with the appropriate alcohols in the presence of an amine. In this paper, we present a new method for the synthesis of tervalent phosphorus esters, not yet mentioned in the literature, when potassium phosphate, as a unique base, is used in liquid-solid system. Symmetrical and unsymmetrical phosphites were obtained with good yields (65%-80%) using this method. The compounds were characterized by 31P NMR spectroscopy.
- Ilia, Gheorghe,Iliescu, Smaranda,Macarie, Lavinia,Popa, Adriana
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- Silver-Catalyzed Regioselective Phosphorylation of para-Quinone Methides with P(III)-Nucleophiles
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A simple and efficient method for the silver-catalyzed regioselective phosphorylation of para-quinone methides (p-QMs) with P(III)-nucleophiles (P(OR)3, ArP(OR)2, Ar2P-OR) has been established via Michaelis-Arbuzov-type reaction. A broad range of P(III)-nucleophiles and para-quinone methides are well tolerated under the mild conditions, giving the expected diarylmethyl-substituted organophosphorus compounds with good to excellent yields. Moreover, a series of corresponding enantiomers can be obtained by employing dialkyl arylphosphonite (ArP(OR)2) as substrates. The control experiments and 31P NMR tracking experiments were also performed to gain insights for the plausible reaction mechanism. This protocol may have significant implications for the formation of C(sp3)-P bonds in Michaelis-Arbuzov-type reactions.
- Liu, Yu,Tang, Ke-Wen,Wong, Wai-Yeung,Xie, Jun,Xiong, Biquan,Xu, Shipan,Xu, Weifeng
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p. 14983 - 15003
(2021/11/12)
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- Electrochemical Oxidation of Metal Dialkyl Phosphites and Their Reaction with Halogens
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Electrochemical oxidation of sodium dialkyl phosphites with alkyl radicals of normal structure leads to formation of tetraalkyl pyrophosphites as the main products, while electrochemical oxidation of litium dialkyl phosphites and sodium salts with branched alkyl radicals yields tetraalkyl hypophosphates. The reaction of metal dialkyl phosphites with halogens leads to analogous results.
- Romakhin,Zagumennov,Nikitin
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p. 1022 - 1026
(2007/10/03)
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- OXIDATIVE ALKOXYLATION OF PHOSPHINE IN ALCOHOLIC SOLUTIONS OF PLATINUM(IV) HALIDE COMPLEXES
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Platinum(IV) halide complexes are shown for the first time to undergo fast reduction in alcohols (MeOH, EtOH, PrOH, BuOH, and i-AmOH) at 298-323 K under the action of PH3 to Pt(II)halide complexes with the highly selective formation of the corresponding trialkyl phosphites.The products of O-phosphorylation of the alcohols are studied by GLC and 31P NMR and IR spectroscopy.The intermediate compounds were studied by x-ray microanalyses and x-ray photoelectron and UV spectroscopy.The reaction is promoted by Pt(II) compounds and retarded by H2O and acids.The complex Pt(IV) chlorides are reduced more slowly than the mixed chloride bromide and especially chloride complexes.The kinetics and mechanism of this new reaction are discussed.
- Dorfman, Ya. A.,Levina, L. V.,Aibasov, E. Zh.
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p. 1847 - 1859
(2007/10/02)
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- Axial ligand substitution reactions of ruthenium(II) dimethylglyoxime complexes
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Kinetics of ligand substitution reactions of six-coordinated Ru(II) macrocyclil complexes of the following type have been investigated: (T)Ru(DMGH)2(L) + X -> (T)Ru(DMGH)2(X) + L where T and L are either both triphenylphosphine ligands or methylimidazole and triphenylphosphine ligands, respectively.The nucleophile X is either MeIm, Im, py, pip, P(OBu)3 or Timc.In all cases, with the exception of Timic as a nucleophile, the reaction mechanism is strictly dissociative (D).The reaction proceeds through the formation of a five-coordinate intermediate which possess little or no ability to discriminate between different nucleophiles.In the case of Tmic, the rate data can be fitted by a dissociative Id or a Associative Ia interchange mechanism.
- Khalifa, Mohamed A.,El-Awady, Abbas A.
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p. 774 - 778
(2007/10/02)
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- Chewing insect toxicant compositions
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This invention relates to chewing insect toxicant compositions comprising (1) a 1-(mono-substituted phenyl)-3-benzoyl urea compound in admixture with (2) an amount sufficient to enhance the chewing insect toxicity of said urea compound of a phosphorous-containing compound. This invention is also directed to chewing insect toxicant compositions comprising an acceptable carrier and as the active toxicant an effective amount of the composition of this invention as well as to a method of controlling insects by subjecting them to an effective amount of the composition of this invention.
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