O. I. Artyushin

N-Tris[(2-aminoethyl)-2-(diphenylphosphoryl) acetamide)] - novel CMPO tripodand: synthesis, extraction studies and luminescent properties of lanthanide complexes

A ligand system containing three carbamoylmethylphosphine oxide (CMPO) moieties attached to a tripodal platform with a central nitrogen atom has been synthesized for metal complexation and extraction from neutral and nitric acid solutions. Liquid-liquid extractions performed for Ln(III), both from neutral and acidic media, show excellent extraction properties which exceeded those for the known mono- and di-CMPO derivatives as well as the related tripodands. A considerable enhancement of the DLn values was observed in the presence of IL ([bmim][Tf2N]) in the organic phase towards lanthanide ions from 3M HNO3 solutions. The protonation of the central amine nitrogen atom of the ligand 1 in the acidic media provides also the effective extraction of the perrhenate anionic complexes. The europium complexes formed by mono- and tris-CMPO ligands in the solid state, as well as Eu(III) and Tb(III) complexes generated in solutions, possess intensive luminescence at 300K

Functionalized mercaptoacetic and propionic acid amides: synthesis, cyclopalladation features, and catalytic activity of metal complexes

Upon treatment with thiophenol or neomenthyl mercaptane, chloroacetand propionamides with an additional Nor S-donor substituent in the amine part gave new multidentate ligands readily undergoing direct cyclopalladation in the reaction with PdCl2(NCPh)2. The realization of κ3-X, N, S-coordination (X = N, S) in the complexes obtained was confirmed by IR and NMR spectroscopy and, in some cases, by single-crystal X-ray crystallography. The evaluation of catalytic activity of the palladocycles in the Suzuki cross-coupling of aryl bromides with PhB(OH)2 allowed us to establish the principal structure—activity correlations.

Synthesis of some acyclic quaternary ammonium compounds. Alkylation of secondary and tertiary amines in a two-phase system

A series of acyclic symmetrical and asymmetrical quaternary ammonium chlorides of the general formula R1R2R3N+AR4Cl– (R1 = Me, Bu; R2 = n-C12H25, PhCH2, CnH2n+1(OCH2CH2)m, n = 9 and 12, m = 1 and 2; R3 = n-C12H25, PhCH2, HOCH2CH2,–OOCCH2; R4 = n-C12H25, PhCH2; A = (CH2CH2O)1,2, CH2C(O)O) was synthesized by the alkylation of tertiary amines in a two-phase system containing water. A convenient method for the synthesis of the initial symmetrical and asymmetrical tertiary amines of the general formula MeNR1R2 (R1 = Me, Bu; R2 = n-C12H25, PhCH2, CnH2n+1(OCH2CH2)m, n = 9 and 12, m = 1 and 2) in an organic phase-aqueous phase heterogeneous system, which allows the use of aqueous solutions of alkali and amines, was developed. The improved method for the preparation of intermediate ethylene glycol and diethylene glycol monoethers is monoalkylation of glycols in dioxane using solid KOH in a two-phase system.

Synthesis and complexing properties of phosphorylated imines of 8-formyl-7-hydroxycoumarin

Condensation of o-(diphenylthiophosphoryl)aniline with 8-formyl-7-hydroxy-4-methylcoumarin yields the Schiff base capable of acting as a tridentate monoanionic ligand upon coordination with the ReI and PdII ions. The corresponding palladium complex shows high catalytic activity in the Suzuki cross-couplings of aryl bromides with phenylboronic acid. The analogous P(O)-substituted ligand was not isolated in the pure form; however, using template-assisted method, its κ3-O,N,O-zinc complex was synthesized; this complex is luminescent in the MeCN solution at 20 ℃.

Phosphorylation of cytisine using azide—alkyne click chemistry

Abstract4-Cytisine-substituted 1-phosphorylated 1,2,3-triazoles possessing potential biological activity were first synthesized by the click reaction of N-propargyl cytisine with azido-γ-alkyl phosphates and phosphonates.

1,3-Bis[(diphenylphosphorylacetamido)methyl]benzene as reagent for extraction and sorption preconcentration of REE(III), U(VI), and Th(IV) from nitric acid solutions

The extraction of microamounts of REE(III), U(VI), and Th(IV) from HNO3 solutions in the form of complexes with a polyfunctional neutral organophosphorus compound, 1,3-bis[(diphenylphosphorylacetamido)-methyl]benzene, was studied. The influence exerted by the structure of the bridge binding two carbamoylmethyl-phosphine oxide fragments on the efficiency of the extraction of REE(III), U(VI), and Th(IV) and on the stoichiometry of the extractable complexes was analyzed. The possibility of recovering and concentrating REE(III), U(VI), and Th(IV) from nitric acid solutions with a complexing sorbent prepared by noncovalent immobilization of 1,3-bis[(diphenylphosphorylacetamido)methyl]benzene on the surface of carbon nanotubes was examined.

Extraction and sorption preconcentration of U(VI) and Th(IV) from nitric acid solutions using bis(diphenylphosphorylmethylcarbonylamino)alkanes

Extraction of microamounts of U(VI) and Th(IV) from HNO3 solutions in the form of complexes with polyfunctional neutral organophosphorus compounds, bis(diphenylphosphorylmethylcarbonylamino)alkanes [Ph2P(O)CH2C(O)NH]2(CH2)n (n = 3, 5, 8), was studied. The influence of the extractant structure on the efficiency and selectivity of the extraction of U(VI) and Th(IV) was examined, and the stoichiometry of the extractable complexes was determined. The examined compounds exhibit higher extraction ability and selectivity to metal ions in HNO3 solutions, compared to the alkylamide Ph2P(O)CH2C(O)NHC9H19. The possibility of selective recovery and preconcentration of U(VI) and Th(IV) from nitric acid solutions with a complexing sorbent prepared by noncovalent immobilization of bis(diphenylphosphorylmethylcarbonylamino)pentane on a macroporous polymeric matrix was demonstrated.

Structures and NMR spectra of N -(ω-alkoxyethyl) N -(2-hydroxyethyl)- N , N -dimethylammonium chlorides

Homoand heteronuclear NMR experiments (COSY, HSQC, and HMBC) were used for the attribution of the proton and carbon atom signals in the 1H and 13C NMR spectra of N-(ωalkoxyethyl)-N-(2-hydroxyethyl-)N, N-dimethylammonium chlorides Me2(HOCH2CH2)N+(CH2CH2O)nRCl– (n = 1, R = C9H19, C12H25; n = 2, R = C6H13, C12H25; n = 3, R = C3H7) bearing either one, two or three ethylene glycol units in 12-, 15-, and 18-membered substituents at the nitrogen atom. Performed experiments unambiguously confirmed the structures of the ammonium chloride studied.

Synthesis of acyclic quaternary ammonium compounds containing ω-alkoxyethyl and 2-hydroxyethyl substituents at the nitrogen atom

A series of acyclic symmetric quaternary ammonium chlorides Me2(HOCH2CH2)N+(CH2CH2O)nR Cl– (n = 1, R = n-C9H19; n = 2, R = n-C6H13; n = 3, R = n-C3H7) was synthesized by alkylation of the corresponding tertiary amines Me2N(CH2CH2O)nR with ethylene chlorohydrin in a two-phase system, using water as a solvent. The tertiary amines were synthesized in a heterogeneous system organic phase—aqueous phase, using an aqueous solution of Me2NH and a solid alkali. The intermediate monoethers of ethylene, diand triethylene glycol were obtained in high yield via a phase-transfer alkylation in dioxane, using solid KOH. The proton and carbon atom signals in the NMR spectra of the synthesized amines and ammonium chlorides were assigned based on the data of heteronuclear correlations (1H, 13C).

Alkyl (N,N-dibutylcarbamoylmethyl)methylphosphinates as new reagents for extraction and sorption of f-elements and technetium(VII) from acidic solutions

Liquid-phase extraction and sorption (solid-phase extraction) of AmIII, EuIII, UVI, and TcVII with alkyl (N,N-dibutylcarbamoylmethyl)methylphosphinates (ADM) from nitric acid solution were studied. The solvate numbers of extracted UVI, AmIII, EuIII, and TcVII complexes and the separation factors for AmIII/EuIII (fAm/Eu), TcVII/EuIII (fTc/Eu), and UVI/TcVII (fU/Tc) pairs were determined. It was shown for the extraction of AmIII and sorption of PuIV that various ADM derivatives are most efficient for the extraction and sorption concentration of actinides: the heptyl derivative (C7) is efficient for extraction and the decyl derivative (C10) is most efficient for sorption.