Phosphorylthioacetamides in the synthesis of annulated quinoxalines

Diethoxyphosphorylthioacetamide in the reaction with 2,3-dichloroquinoxaline acted as a thionating reagent, giving diethoxyphosphorylacetonitrile and 2-chloro-3-[(3-chloro-2-quinoxalinyl)thio]quinoxaline. Reactions of phosphorylthioacetamides with N-methylquinoxalinium iodide in alcohol media in the presence of a base proceeded stereoselectively to afford cis-3-phosphoryl-1,3,3a,4,9,9a-hexahydro-2H-pyrrolo[2,3-b]quinoxaline-2-thiones. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 5, pp. 1010–1013, May, 2007.     

Simple route to secondary amides of phosphorylacetic acids and their use for extraction and sorption of actinides from nitric acid solutions

An efficient method for the synthesis of secondary alkylamides of phosphorylacetic acids (APA) was proposed. The method involves amidation of ethyl phosphorylacetates with primary aliphatic amines. The scope of reaction was determined. Reactions with ethylenediamine and 1,4-diaminobutane yield the corresponding bisamides; in the case of 1,3-diaminopropane, N-(3-aminopropyl)diphenylphosphorylacetamide or N,N-propylenebis(diphenylphosphorylacetamide) was obtained, depending on the reaction conditions. The extraction of americium(III) complexes and the sorption of uranium(VI) by sorbents with physically sorbed APA from nitric acid solutions were studied. There is no correlation between the partition coefficient of americium(III) and the structure of APA; in the sorption of uranium(VI), the degree of extraction depends on the complexone structure.__________Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 2394–2402, November, 2004.     

Investigation of the phosphinyl analog of α-ketoglutaric acid

It was shown by³¹P and¹³C NMR spectroscopy that methyl(3-carboxy-3-oxopropyl)phosphinic acid (4-methylhydroxyphosphinyl-2-oxobutyric acid) (1) and the amide (2) of the latter exist in keto forms in non-aqueous solutions. In aqueous solutions an equilibrium between the keto,gem-diol, and enol forms has been observed. The proportions of the diol and enol forms increase as the acidity of the media increases. Silylation of acid 1 with hexamethyldisilazane gives the tris(trimethylsilyl) derivative of enol form (3) (Z- andE-isomers).Translated fromIzyestiya Akadetnii Nauk. Seriya Khimicheskaya, No. 1, pp. 125–128, January, 1994.     

The Synthesis of Aminophosphinocarbonic Acids

Abstract

A practical synthesis of racemic phosphinothricin and both of its enantiomers by the Michael addition of Schiff base of glycine to vinylphosphinate in the presence of sodium ethoxide or potassium hydroxide in ethanol was reported (I).     

Non-Racemic Mixtures of 1,3,2-Oxazaphosphacyclanes - Enantiomeric Composition Determination by NMR

Abstract

The enantiomeric ratio in non-racemic mixtures of 2-anilino-2-oxo-1,3,2-oxazaphospho-rinane (I) and 3-(α-rnethylbenzyl)-(I)¹ enantiomers was determined by measurement of the integral intensity ratio of two ³¹P-NMR signals, assigned to enantiomers and differentiated due to the effect of statistically controlled associate-diastereoisomerim (scada), ² when association occurs under conditions of fast exchange.     

Enolization of the Phosphoryl Group

Abstract

The ability of the phosphoryl group to undergo enolization has been studied. The introduction of strongly electronegative substituents at thee α-carbon atom is shown to increase CH- acidity greately and result in the enolization of the P=O group.     

Reversible Phosphorylation of Trimethylsilylisothiocyanate

Abstract

The reaction of trimethylsilylisothiocyanate with phosphorus acids chlorides was demonstrated to be reversible.     

The Effect of Swstituents at the Carbon and Phosphorus on the Tautomeric Equilibrium in the Phosphoryl-Hydroxyylide Systems

Abstract

It has been established that in the phosphoryl-hydroxyylide systems (I-VIII) the increasing acidity of the carbon atom depending on substituent Y (which is characterized by [sgrave]^? _CH value) shifts the equilibrium to the hydroxyylide form (B).