Oleg I. Artyushin

Synthesis of Fluorine-Containing Cyclic α-Amino Acid and α-Amino Phosphonate Derivatives by Alkene Metathesis

The electrophilic imino esters XF2CC(=NPG)CO2Me and imino phosphonates CF3CC(=NPG)P(O)(OR)2 (PG = SO2Ph, Cbz, Boc) were transformed by nucleophilic and then electrophilic additions into fluorine-containing amino esters and amino phosphonates with two pendent alkene chains (XF2C)(CH2=CH(CH2)nC(NPG)(Z)(CH2)mCH=CH2 [Z = CO2Me, P(O)(OR)2]. The ring-closing metathesis was performed on the α-amino ester dienes with Ru=CHPh(Cl)2(PCy3)2 catalyst and afforded five-, six-, and seven-membered cyclic amino esters, whereas the α-aminophosphonate dienes were transformed with RCM catalyst [Ru=C=C=CPh2(Cl)(PCy3)(p-cymene)]OTf to give six- and seven-membered cyclic α-amino-α-(trifluoromethyl)phosphonates.

Extraction of Lanthanides(III) from HClO4 Solutions with Bis(diphenylphosphorylmethylcarbamoyl)alkanes

Abstract Novel polyfunctional neutral organophosphorus compounds, namely bis(diphenylphosphoryl-methylcarbamoyl)alkanes of general formula [Ph2P(O)CH2C(O)NH]2(CH2)n (I-III; n = 3, 5, 8), were synthesized and studied as extractants for La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, and Y from perchloric acid solutions. The influence of both of HClO4 concentration in the aqueous phase and that of the extractant in the organic phase on the extraction of metal ions is considered. The stoichiometry of the extracted complexes has been determined. Bis(diphenylphosphorylmethylcarbamoyl)alkanes II and III possess a higher extraction efficiency towards Ln(III) than their monoanalogue Ph2P(O)CH2C(O)NHC9H19. The potentialities of polymeric resin impregnated with bis(diphenylphosphorylmethylcarbamoyl)pentane II for the preconcentration of lanthanides(III) from perchloric acid solutions are demonstrated.

Synthesis and physiological activity of new organophosphorus pesticides of 1,3,2-oxazaphosphorinane series

Methods for the synthesis of 2-aryloxy(arylthio)- and 2-alkoxy(alkylthio)-2-thio(oxo)-1,3,2-oxazaphosphorinanes and theirN-substituted derivatives based on the reactions of the corresponding dichlorophosphates, dichlorothio-, and dithiophosphates with 3-aminopropan-1-ol or its substituted derivatives in the presence of Et3N or aqueous alkali under phase transfer catalysis conditions, as well as by the reaction of the tetramethylammonium salt of 2-hydroxy-2-thio-1,3,2-oxazaphosphorinane with alkyl- and acyl halides, by that of 2-chloro-2-thio-1,3,2-oxazaphosphorinane with sodium thiolates, and by other methods, were developed. The compounds obtained exhibit high nematocide activity but low toxicity for mammals. Some active synergists for permethrine were found among these compounds.

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.

Bis(carbamoylmethylphosphine oxide) ligands fixed on the arene core via 1,2,3-triazole linkers: novel effective extractants for palladium, lanthanides and actinides

Novel polydentate neutral organophosphorus ligands containing two diphenyl-(diethylcarbamoylmethyl)phosphine oxide moieties fixed on the arene platform via methylene-1,2,3-triazole linkers (Ar-CMPO) were synthesized by the method of “click” chemistry and studied as an extractant for Pd(II), U(VI), Th(IV) and lanthanide(III) ions from HNO3 solutions. The influence of aqueous and organic phases on the extraction efficiency was elucidated and the stoichiometry of the complexes extracted was determined. The introduction of a 1,2,3-triazole fragment into the methylene bridge of a CMPO molecule resulted in a considerable increase in the efficiency of Pd(II) extraction. This modification of a CMPO molecule does not essentially change the extraction efficiency towards U(VI) and Ln(III) but drastically decreases the Th(IV) extraction and changes the order in the extractability of U(VI) and Th(IV) from HNO3 solutions. Bis-CMPO ligands containing two 1,2,3-triazole moieties (Ar-CMPO) were found to possess a higher extraction efficiency towards Pd(II), U(VI), Th(IV) and lanthanide(III) ions than their mono analog 2-(diphenylphosphoryl)-N,N-diethyl-3-(1-phenyl-1H-1,2,3-triazol-4-yl)propanamide.

Extraction of U(VI), Th(IV), and Lanthanides(III) from Nitric Acid Solutions with CMPO-Functionalized Ionic Liquid in Molecular Diluents

The extraction of microquantities of U(VI), Th(IV), and lanthanides(III) from nitric acid solutions with CMPO-functionalized ionic liquid 1-[3[[(diphenylphosphinyl)acetyl]amino]propyl]-3-tetradecyl-1H-imidazol-3-ium hexafluorophosphate, CMPO-FIL(I) in molecular organic diluents has been studied. The effect of HNO3 concentration in the aqueous phase and that of extractant concentration in the organic phase on the extraction of metal ions is considered. The stoichiometry of the extracted complexes was determined. CMPO-FIL(I) demonstrates greater extraction ability towards Ln(III) than its neutral CMPO analog, diphenylphosphorylacetic acid N-nonylamide. This inner synergistic effect increases with a decreasing organic diluent polarity. The partition of CMPO-FIL(I) between the equilibrium organic and aqueous phases is the dominant factor governing the extractability of Ln(III) ions in the extraction system.

Extraction Properties of 1,2,3-Triazole Modified Carbamoylmethylphosphine Oxide in Nitric Acid Media

A novel polyfunctional neutral organophosphorus compound, 2-(diphenylphosphoryl)-N,N-diethyl-3-(1-phenyl-1H-1,2,3-triazol-4-yl)propanamide (I), was synthesized and studied as an extractant for Pd(II), Ln(III), U(VI), and Th(IV) from HNO3 solutions. The influence of aqueous and organic phases on the extraction efficiency was elucidated and stoichiometry of the complexes extracted was determined. The introduction of a 1,2,3-triazole fragment into the methylene bridge of diphenyl(diethylcarbamoylmethyl)phosphine oxide resulted in a considerable increase of the efficiency of Pd(II) extraction. The potentialities of carbon nanotubes impregnated with compound I for the preconcentration of Pd(II) from nitric acid solutions are demonstrated. The introduction of a 1,2,3-triazole fragment into the methylene bridge of a CMPO molecule does not essentially change the extraction efficiency of compound I towards U(VI) and Ln(III) but drastically decreases the Th(IV) extraction and change the order in the extractactability of U(VI) and Th(IV) with this compound from HNO3 solutions.

Effective Modular Assembling of Novel Ligands Starting from (Thio)Phosphorylated Anilines

Abstract A series of novel oligodentate ligands has been designed by the modular assembly of ortho-(thio)phosphorylated anilines with a range of commercially available carbonyl compounds. The new ligands readily form complexes with a series of metal ions (Pd(II), Cu(II), Ni(II), and Re(I)) both in neutral and deprotonated forms, providing OO, SN, ONO, SNO, SNS, SNN, and ONN donor sets. The structure and composition of the resulting complexes depend on the nature and mutual disposition of the donating groups as well as on the reaction conditions. GRAPHICAL ABSTRACT

Extraction Properties of P(O)-Modified N-Aryl-Carbamoylmethylphosphine Oxides in Nitric Acid Media

Novel polyfunctional neutral organophosphorus compounds, P(O)-modified N-aryl- carbamoylmethylphosphine oxides, Ph2P(O)CH2C(O)NH-(o-C6H4)(CH2)n-P(O)Ph2 and Ph2P(O)CH2C(O)NH-(m-C6H4)(CH2)n-P(O)Ph2 (n = 1,2), were synthesized and studied as extractants for U(VI), Th(IV) and Ln(III) from HNO3 solutions. The influence of aqueous and organic phases on the extraction efficiency was elucidated and stoichiometry of the complexes extracted was determined. Introduction of an additional phosphoryl group into the phenyl substitutent at the nitrogen atom of diphenyl(N-phenylcarbamoylmethyl)phosphine oxide resulted in an increase of the efficiency of U(VI), Th(IV), Ln(III), and Re(VII) extraction.

Advantages of Organophosphorus Synthesis in Ionic Liquids: “Green” Approaches to Useful Phosphorus-Substituted Building Blocks

Novel examples concerning the application of ionic liquids as a promoting reaction media in organophosphorus chemistry are discussed. Imidazolium ionic liquids were found to accelerate the Michaelis-Arbuzov reaction allowing to perform it under very mild conditions. Both phosphonium and imidazolium ILs give the possibility to perform easily direct amidation of phosphoryl acetic acids by various amines. Nucleophilic displacement reactionin a series of bromoalkylphosphonates was carried out in quantitative yield to afford azidoalkylphosphonates using the [bmim][PF6]/H2O system.