E. I. Goryunov

Extraction of f-elements from nitric acid solutions with phosphoryl ketones

The extraction ability and selectivity of a series of phosphoryl ketones Ph2P(O)CH2C(O)Me, and Ph2P(O)CRR’CH2C(O)Me (R = H, Me; R’ = H, Me, n-C5H11, Ph, 2-thienyl, 2-furyl) towards trivalent lanthanides (LaIII, NdIII, HoIII, YbIII) and actinides (UVI, ThIV) were studied. The efficiency and selectivity of the new ligands in the extraction of f-elements from nitric acid solutions into chloroform were compared to those of model phosphine oxide Ph2P(O)Bu and known extractants: tributyl phosphate (BuO)3P(O), trioctylphosphine oxide (C8H17)3P(O), and carbamoylmethyl phosphine oxide Ph2P(O)CH2C(O)NBu2.

β-Diphenylphosphorylated alkanones and related compounds: synthesis and structure

The reactions of diphenyl(diisopropyl)chlorophosphine with arylidene(heteroarylidene)-acetones and 3-benzylidenepentane-2,4-dione in the presence of acetic acid proceed at a high rate at room temperature to afford the corresponding β-diorganylphosphorylated alkanones and alkanediones in high yields. The reaction of diphenylchlorophosphine with 4-methoxybut-3-en-2-one and dibenzylideneacetone carried out under similar conditions at the equimolar reagent ratio can serve as a convenient method for the synthesis of unique β-diphenylphosphorylalkenones. The structures of compounds obtained were established by IR, Raman, and NMR spectroscopy and X-ray diffraction.

Synthesis and properties of 10-hydroxy-10-oxo-10H-10λ5-phenoxaphosphine-2,8-dicarboxylic acid and related polybenzoimidazoles

Oxidation of 10-hydroxy-2,8-dimethyl-10H-10λ5-phenoxaphosphine 10-oxide (1) with potassium permanganate in an alkaline medium afforded 10-hydroxy-10-oxo-10H-10λ5-phenoxaphosphine-2,8-dicarboxylic acid (2). The latter exists as a stable crystal hydrate containing two water molecules. With the aim of examining the possibility of performing the synthesis of polybenzoazoles based on acid 2, the model reaction of the latter with o-phenylenediamine in polyphosphoric acid (PPA) was studied. New high-molecular-weight phosphorus-containing polybenzoimidazoles were prepared by the reaction of 2 with various aromatic tetraamines in PPA and Eaton’s reagent.

Extraction of lanthanides(III) by phosphorylated naphthyridine ligands from carbonate solutions

The extraction capacities and selectivities of 1,8-naphthyridine-based neutral organophosphorus reagents in extracting trivalent lanthanides (Ln, Nd, Ho, Yb) from carbonate solutions were studied. The length and nature of the linker between the naphthyridine and phosphoryl moieties were found to have considerable influence on the efficiency and selectivity of lanthanide extraction.

N-(1,5-dimethyl-3-oxo-2-phenyl-1,2-dihydropyrazol-4-yl)-P,P-diphenylamidophosphinate and its complexes with neodymium(III), erbium(III), thorium(IV), and uranyl nitrates: Synthesis and crystal and molecular structure

A new phosphoryl-containing ligand based on 4-aminoantipyrine-N-(1,5-dimethyl-3-oxo-2-phenyl-1,2-dihydropyrazol-4-yl)-P,P-diphenylamidophosphinate (L) was synthesized. In crystals, the L molecules were found to be combined in centrosymmetric dimers through N-H…O=C hydrogen bonds. The complexes of L with neodymium(III), erbium(III), thorium(IV), and uranyl nitrates were obtained, and their structures were determined. The bands of the C=O and P=O groups in the IR spectra of these complexes are shifted toward low frequencies (by 50–65 and 40–70 cm−1, respectively), which is indicative of a bidentate coordination of the organophosphorus ligand. According to the X-ray crystallography data, uranyl is bidentately coordinated by both the L molecule (through the C=O and P=O groups) and two nitrate anions.

Synthesis and Comparative Analysis of the Steric and Supramolecular Structures of Diastereomers of 4,4-Bis(trifluoromethyl)-2-(fluoroalkoxy)-6,7-benzo-1,3,2λ5- dioxaphosphepin-5-one 2-Oxides

Reaction with hexafluoroacetone of 2-fluoroalkoxy-5,6-benzo-1,3,2-dioxophosphorinan-5-ones containing a chiral fluorinated exocyclic substituent on the phosphorus atom, with hexafluoroacetone leads to formation of 4,4-bis(trifluoromethyl)-6,7-benzo-1,4,2-dioxaphosphepines with a high regio- and stereoselectivity. The configuration of all isolated individual diastereomers was established by X-ray diffraction. The molecular and supramolecular structure of the compounds were examined in terms of the proposed model that takes account of the revealed effect of separation of hydrophilic and lipophilic regions in the crystal.

Effect of the nature of substituents at the phosphorus atom on extraction properties of phosphorylketones toward f-elements

Extraction abilities of phosphorylketones with alkyl and cycloalkyl substituents at the phosphorus atom R2P(O)CH2CH2C(O)Me (R = Pri, But) and R2P(O)CHPhCH2C(O)Me (R = Pri, cyclo-C6H11) toward UVI, ThIV, and a series of tervalent lanthanides (LaIII, NdIII, HoIII, YbIII) were studied. The efficiencies and selectivities of recovery of f-elements from nitric acid solutions to chloroform by these ligands were compared with extraction properties of both the model phosphorylketones with phenyl substituents at the phosphorus atom Ph2P(O)CH2CH2C(O)Me and Ph2P(O)CHPhCH2C(O)Me and other known extractants such as tributyl phosphate (BuO)3P(O), trioctylphosphine oxide (C8H17)3P(O), and carbamoylphosphine oxide Ph2P(O)CH2C(O)NBu2.

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.

α- and β-diphenylphosphorylated secondary alkanols: I. general method of synthesis and extraction properties towards f-elements

A simple and effective general method of synthesis of α- and β-diphenylphosphorylated secondary alkanols by the reduction of the corresponding phosphorylalkanones with NaBH4 was developed. The extraction properties of the resulting phosphorylalkanols Ph2P(O)(CR2)nCH2CH(OH)Me (n = 0, 1; R = H, Me) were studied in the recovery of f-elements (LaIII, NdIII, HoIII, YbIII, UVI, ThIV) from nitric acid solutions into chloroform and compared with those of both related phosphorylketones and known extractants (n-BuO)3PO, (n-C8H17)3PO, and Ph2P(O)CH2C(O)N(n-Bu)2.

Specifics of titanium tetrafluoride complexation with Ph2P(O)(CH2)2C(O)NMe2: The remarkable stability of the seven-membered chelate heterocycle TiOPCCCO and its conformational isomerism in solution

The composition and structure of the products of the reaction of titanium tetrafluoride with Ph2P(O)(CH2)2C(O)NМе2 (L), the simplest representative of diphenyl[2-(N,N-dialkylcarbamoyl)ethyl]phosphine oxides, in a СН2Сl2 have been studied by 19F and 31P NMR. It has been shown for the first time that functionalized phosphine oxides form stable seven-membered chelate heterocycles on complexes of d° transition metals. On the basis of NMR data, previously unknown conformational isomerism of the seven-membered TiOPCCCO heterocycle in solution has been proposed. A simple and rather efficient method of synthesis of the ligand (L) from commercially available reagents has been developed.