Galina K. Genkina

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 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.

Arbuzov rearrangement in the 1,3,2-oxazaphosphinane series

Reactions of 2-alkoxy-1,3,2-oxazaphosphinanes (including 3-alkyl derivatives) with methyl and ethyl bromoacetates give two types of Arbuzov rearrangement products (cyclic and acyclic ones). The ratio between their yields is virtually independent of the nature of the substituent in position 3 of the starting reagent, being mainly determined by the nature of the substituent in the phosphorus bound alkoxy group and varying from 96 : 4 to 2 : 98. Acyclic products can be converted into cyclic ones.

Novel Biologically Active 1,3,2-Oxazaphosphinane Derivatives

Abstract The facile synthetic approaches to a wide range of potentially biologically active compounds bearing the cyclic 1,3,2-oxazaphosphinane moiety as a “cell transport” and the residues of formic, acetic, and amino acids or 3,5-bis(benzylidene)piperidone framework have been developed. The methods are based on the Arbuzov reaction of preformed cyclic P(III) esters with chloroacetic or chloroformic acid esters, where the nature of the reactants influences the ratio of cyclic and linear products, cyclizations of susbstituted dichlorophosphoryl compounds with aminopropanols, or amination of P-isothiocyanates.

Synthesis of camphecene derivatives using click chemistry methodology and study of their antiviral activity

A series of seventeen tetrazole derivatives of 1,7,7-trimethyl-[2.2.1]bicycloheptane were synthesized using click chemistry methodology and characterized by spectral data. Studies of cytotoxicity and in vitro antiviral activity against influenza virus A/Puerto Rico/8/34 (H1N1) in MDCK cells of the compounds obtained were performed. The structure-activity relationship analysis suggests that to possess virus-inhibiting activity, the compounds of this group should bear oxygen atom with a short linker (C2-C4), either as a hydroxyl group (18, 19, 29), keto-group (21) or as a part of a heterocycle (24). These compounds demonstrated low cytotoxicity along with high anti-viral activity.

1,3,2-Oxazaphosphinane analogs of phosphorylacetic acid derivatives: synthesis and properties

Reactions of 2-AlkO-1,3,2-oxazaphosphinanes with alkyl N-haloacetylamino or N-chloromethyl-N-methoxycarbonylamino carboxylates mainly give products with retention (Alk = Me) and opening of the ring (Alk = Et). In aqueous solution, cyclic products with the N-isopropyl group are only stable, while the rest undergo hydrolysis with cleavage of the P-N bond of the ring. Oxazaphosphinane analogs of phosphorylacetamide and phosphorylacetohydrazide were synthesized.

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

GRAPHICAL ABSTRACT ABSTRACT Novel polydentate neutral organophosphorus ligands containing two diphenyl-(diethylcarbamoyl-methyl)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 lanthanides(III) ions from HNO3 solutions.

Effect of ionic liquid on the extraction of actinides and lanthanides with 1,2,3-triazole–modified carbamoylmethylphosphine oxide from nitric acid solutions

Abstract Solvent extraction of U(VI), Th(IV), Am(III) and lanthanides(III) from aqueous nitric acid solutions with 1,2,3-triazole–modified carbamoylmethylphosphine oxide (L) and [C4mim][Tf2N] ionic liquid dissolved in 1,2-dichloroethane was studied. A considerable synergistic effect in this system was observed. This effect is associated with the high hydrophobicity of the IL anions which participate in the formation of metal extracted ion species. The influence of aqueous and organic phases on the extraction efficiency was elucidated and stoichiometry of the complexes extracted was determined. The synergistic effect for metal ion extraction from aqueous nitric acid solutions with compound L and [C4mim][Tf2N] in 1,2-dichloroethane becomes weaker when the acidity of the aqueous phase increases. The partition of Tf2N− anions between the organic and aqueous phases is the major factor governing the extractability of metal ions in the L – IL synergistic system. The interaction of L with HTf2N and HNO3 also substantially affects the efficiency of metal ion extraction.

Phosphorylation of natural products—Cytisine, anabasine, and camphor using click chemistry methodology

GRAPHICAL ABSTRACT ABSTRACT Anabasine-, cytisine-, and camphor-containing azides and acetylenes were used as building blocks in copper(I) catalyzed 1,3-dipolar cycloaddition reactions with a series of acetylenes and azides via click chemistry to provide a range of anabasine, cytisine, and camphor conjugates that are substances with potential biological activity.

Interaction of 2-Alkoxy-3-Alkyl-1,3,2-Oxazaphosphinanes with Alkyl Chloroformates

Depending on steric hindnanus at the nitrogen atom interaction of 2-alkoxy-3-alky(aryl)-1,3,2-oxazaphosphinanes with alkyl chloroformates proceeds according to the Arbuzov reaction or with the formation of acyclic chlorofosphites.