G. V. Bodrin

POLY-(DIPHENYLPHOSPHINYLMETHYL)ARENES - NEW ORGANOPHOSPHORUS EXTRACTANTS OF TRANS-PLUTONIUM ELEMENTS

The extraction properties of poly-(diphenylphosphinylmethyl)arenes in which the fragments of different methyl substituted aromatic compounds serve as hard bridges connecting the P=O functional groups was studied. The extraction of trivalent transplutonium elements and rare earth elements, uranium(VI), plutonium(IV) by chloroform solutions of these reagents as function of HNO/sub 3/ and ligands concentration was investigated. The selectivity of reagents was found to depend only on mutual arrangement of P=O groups in the bridge regardless of their number. Conformational analysis of the reagents described have been used to establish their structure and cause of their selectivity with respect to one or another element. 8 figures, 2 tables.

New type of 2-alkyl-substituted 1,8-naphthyridine systems containing a phosphoryl group in the side chain

First organophosphorus derivatives of 2-alkyl-and 2,3-alkylene-substituted 1,8-naphthyridines were synthesized by the Friedländer reaction starting from 2-aminonicotinaldehyde and diphenylphosphoryl(cyclo)alkanones, respectively.

A new organophosphorus pyridine complexone — 2,6-bis (dihydroxyphosphorylmethyl)pyridine

Conclusions1.A new organophosphorus complexone, containing a pyridine fragment, was synthesized. The acid-base and complexing properties of alkaline earth and transition metal ions were studied. The composition of the complexes formed was found to be 1:1.2.The introduction of the pyridine fragment into the complexone synthesized leads to an increase in the complexation selectivity.

Aza-Michael reaction as an efficient method for the synthesis of first representatives of β-azahetaryl-β-diphenylphosphorylalkanones

Aza-Michael reaction of (E)-4-(diphenylphosphoryl)but-3-en-2-one (1) with a number of mono-and bicyclic nitrogen heterocycles proceeds regioselectively in the absence of catalysts with the formation of corresponding β-azahetaryl β-diphenylphosphoryl ketones; in the case of imidazole, the presence of chiral organic catalysts allows one to increase the yields of the adducts and to obtain them in enantiomerically enriched form.

Reactions of phosphoryl- and thiophosphorylacetonitriles with poly(bromomethyl)arenes containing closely-spaced bromomethyl groups. New types of phosphorus-substituted fused systems

Reactions of phosphoryl- and thiophosphorylacetonitriles with poly((bromomethyl)arenes containing closely-spaced bromomethyl groups under conditions of phase-transfer catalysis occur as cycloalkylation to form new types of fused systems, in which aromatic rings are annelated with a five-, six-, or seven-membered ring containing the exocyclic phosphorus containing and cyano substituents. The reaction pathway is independent of the reagent ratio. Under the same conditions, the reaction with 1,3,5-tris(bromomethyl)-2,4,6-trimethylbenzene affords products of monoalkylation at all electrophilic groups of the starting substrate. In the resulting compounds, the alkoxy groups at the phosphorus atom are easily transformed into the hydroxy groups via the corresponding silyl ethers to give the corresponding phosphorus acids, whereas the cyano group is chemically inert.

Selective monoalkylation of phosphorus-substituted CH acids with (bromomethyl)- and 1,4-bis(bromomethyl)benzenes

C-Alkylation of phosphorus-substituted CH acids with various substituted (bromomethyl)arenes under phase transfer catalysis conditions (K2CO3/MeCN) proceeds with high selectivity (75—100%) as monoalkylation.

A cyclopendant complexon based on dibenzo-18-crown-6

A derivative of dibenzo-18-crown-6 containing dihydroxyphosphorylmethyl groups in the 4, 5, 4′, and 5′ positions of the benzene ring has been synthesized. Unlike dibenzo-18-crown-6, its phosphorylated derivative does not form stable complexes with cations of alkali and alkaline-earth metals. Complexes with transition metals are water-insoluble in most cases.

PROTONATION OF PHOSPHINYLMETHYLPYRIDINES AND THEIR N-OXIDES IN NITROMETHANE

The protonation of phosphinylmethylpyridines with different structures and their N-oxides differing both in the nature and the number of functional groups (pyridine nitrogen, N → O, and P=O) was studied by potentiometric titration in nitromethane and IR spectroscopy. Regardless of the number of P=O groups, all the investigated phosphinylmethylpyridines were N bases, and their pK values changed in the range 10.4-4.7. In the case of N-oxides of phosphinylmethylpyridines, the oxygen atoms of N → O and P=O groups participated simultaneously in protonation, and the pK values were 6.7-5.0. The structure of the protonation products is discussed.

Phosphorylmethylpyridines and their N-oxides: Synthesis and equilibrium CH-acidity

Certain phosphorylmethylpyridines and their N-oxides were synthesized, which are of interest as extractants and complex-forming agents. Their equilibrium CH-acidity with reference to 9-phenylfluorene (K+ counterion) was studied by the indicator method in dimethyl sulfoxide. The acidifying action of a series of pyridine groupings was characterized by means of σC− values.

Poly(diphenylphosphinylmethyl) arenes, organophosphorus extractants for transplutonium elements

Conclusions1.New diphenylphosphinylmethyl substituted arenes, derivatives of benzene, naphthalene, and dibenzo-18-crown-6 have been synthesized.2.The extraction properties of these ligands having limited conformational mobility have been studied relative to tervalent transplutonium elements, europium, and sexivalent uranium.3.It has been shown that the extraction selectivity is dependent on the relative position of the coordination centers in the aromatic nucleus.