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 D_Ln 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     

Synthesis and Tautomerism of 1,3,2-Azathiaphosphacyclanes

1,3,2-Azathiaphosphacyclanes were prepared by intramolecular alkylation of N-( y -haloalkyl)amidophosphates and phosphonates.     

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.     

Acylation of Phosphorus Substituted Ch-Acids Under Phase Transfer Catalysis Conditions

Abstract.

Acylation of phosphoryl- and thiophosphoryl acetonitriles under phase transfer catalysis (PTC) conditions leads in high yields to C-acylated products existing as Z-isomers of the corresponding enol forms. They are stabilized by strong intramolecular H-bonds. On the contrary, acylation of phosphorylacetone proceeds mainly at the oxygene atom and gives Z and E enolacetate. Phosphorus trichloride was used as an acylating agent under PTC conditions. S-Alkyldichlorophosphites were obtained by the reaction with mercaptanes. Alcohols react with PCl₃ in the presence of sodium carbonate to result in dialkylphosphites.     

Synthesis and Structure of New <Emphasis Type="Italic">gem</Emphasis>-Diols with 1,2,3-Triazole Fragment

α-(1,2,3-Triazole)-substituted acetals were obtained using the click procedure. Under acid hydrolysis conditions these acetals were converted into earlier unknown stable gem-diols containing a triazole ring.     

Synthesis of Phosphorus-Containing Podands―Analogs of Diglycolamide Based on Diphenyl- and Dibutylphosphorylmethanol under Phase Transfer Catalysis Conditions

A convenient method for preparation of phosphorus-containing podands R₂P(O)CH₂OCH₂X, where X = C(O)NBu₂; P(O)R′₂, R = R′ = Ph, Bu, R = Ph, R′ = Bu via OH-alkylation of phosphorylmethanols under the phase transfer conditions in the presence of Cs₂CO₃ was developed. Carbamoyl-substituted dimethyl ethers were synthesized via transformation of phosphorylmethanols to phosphorylmethoxyacetic acids, followed by amidation. Symmetrical bisphosphoryl substituted dimethyl ethers were obtained by reaction of phosphorylmethanols with tosyl chloride in the presence of Cs₂CO₃. The synthesis of unsymmetrical substituted ether in the presence of Cs₂CO₃ was complicated by transesterification of phosphorylmethyl tosylate resulting in the formation of symmetrical dimethyl ethers as byproducts.     

Regioselective functionalization of gem-bis(trifluoromethylated) alkanols

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Acylation of phosphoryl- and thiophosphorylacetonitriles under phase transfer catalysis conditions and the keto-enol tautomerism of phosphorus-substituted acylacetonitriles

A procedure was developed for acylation of phosphoryl- and thiophosphorylacetonitriles under phase transfer catalysis conditions. The reaction in the solid KOH/MeCN system affordedC-acylation products in high yields. In the individual state and in aprotic solvents, these products exist in the enol form (Z isomers) stabilizedvia a strong intramolecular hydrogen bond. In hydroxyl-containing media and in aprotic bipolar solvents, these compounds exist as a mixture of two geometric isomers (E andZ) of the corresponding enols. In this case, theZ isomer exists in two forms, namely, in the cyclic form with an intramolecular hydrogen bond and in the open form stabilized by intermolecular hydrogen bonds with the solvent. The results of X-ray diffraction analysis of both forms ofZ isomers of the compounds containing the phosphoryl and thiophosphoryl groups are discussed. Deceased. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 1687–1694, September, 1998.