V. E. Baulin

Ortho-phosphorylated phenols and their methoxymethyl ethers, phosphines, and phosphine oxides

Conclusions1.By reaction of o-methoxymethoxyphenyllithium with P(III) acid chlorides and with phosphinyl chlorides o-methoxymethoxyphenylphosphines and methoxymethyl ethers of o-phosphinyl-substituted phenols were obtained, and by hydrolysis transformed into the corresponding o-phosphinyl-substituted phenols.2.A method for obtaining phenol methoxymethyl ethers was developed by alkylation of phenols with monochlorodimethyl ether in two steps.

Phosphorus-containing podands 7. Complexing properties of ortho-diphenylphosphinyl-substituted diphenyl ethers of oligoethylene glycols with respect to alkali-metal cations

Stability constants of complexes of alkali-metal cations with oligoethylene glycol diethers RO(CH2CH2O)nR (n=1–5), where R=2-Ph2P(O)C6H4 and 2-Ph2(O)-4-t-BuC6H3P, have been determined conductometrically in a tetrahydrofuran-chloroform mixture (4∶1 by volume). The dependence of complexing ability on a number of monopodand donor centers for Li+ and Na+ has multiple extrema. For K+, Rb+, and Cs+ the complexing abilities steadily increase with the length of the ligand polyether chain. Monopodands based on triethylene glycol and its pyrocatechol analog are highly effective (log K=6.7–7.0) with respect to Li+. The synthesis of ligands with a lipophilic tert-butyl substituent in the terminal group is described.

Phosphorus-containing podands 4. Effect of polyether chain length of oligoethylene glycol bis(ortho-diphenylphosphinylmethyl)phenyl ethers on their complex-forming and selective properties with respect to alkali metal cations

Alkylation of o-(diphenylphosphinylmethyl)phenol by oligoethylene glycol ditosylates leads to a series of acyclic polyether complexing agents (podands) with phosphinylmethylphenyl terminal groups. A conductometric method in tetrahydrofuranchloroform (4∶1 by volume) has been used to determine the stability constants of the podands with alkali metal 2,4-dinitrophenoxides. Several of the prepared ligands exhibited a high Li/Na, Na/K, and Li/K selectivity. For lithium and sodium cations, the curve of complex-forming ability against the overall number of donor centers in the structure of the podand has a maximum for the case of tetraethylene glycol bis(o-diphenylphosphinylmethyl)phenyl ether. For lithium cations, this compound surpasses the crown ethers in terms of its effectiveness and is the most powerful of the phosphoryl-containing complexing agents. For potassium, rubidium, and cesium cations, the complex-forming ability increases with increase in the number of oxygen donor centers in the polyether chain of the ligand.

Synthesis and study of the antiinflammatory and analgesic activity of some phosphinic acid esters

As is known, 1,1-dimethyl-3-oxobutylphosphonic acid dimethyl ester (dimephosphon) exhibits antiinflammatory properties, although the mechanism of its action differs from that known in classical nonsteroidal drugs [1]. Recently we have demonstrated that some alkyldiphenylphosphin oxides possess antiinflananatory and/or analgesic properties [2]. The most active of these compounds, isoamyldiphenylphosphin oxide, has rather low toxicity and is comparable in its activity with acetylsalicylic acid. In contrast to the latter acid, this oxide produces no ulcerogenic effect even at a dose of 1/3 LD50. Therefore, it was of interest to continue the search for new antiinflammatory and analgesic agents in the series of phosphoryl-containing compounds. The purpose of this work was to study the antiinflammatory and analgesic properties and the acute toxicity of some alkyl and acryl esters of diphenylphosphinic ( I XVII) and dibutylphosphinic (XVIII) acids. Most of the esters of diphenyl-and dibutylphosphinic acids were obtained by interactions of their chloroanhydrides with the corresponding alcohols or phenols in the presence of bases (triethylamine or pyridine) in a benzene medium:

PHOSPHORUS-CONTAINING PODANDS. 8. A STUDY OF METAL--LIGAND INTERACTION BY FOURIER TRANSFORM INFRARED SPECTROSCOPY IN ANHYDROUS ACETONITRILE

The interaction of phosphorus-containing monopodands with Li+, Na+, and K+ cations in anhydrous CH3CN has been studied by FTIR spectroscopy. It has been shown that phosphoryl groups of the ligands take part in the formation of complexes with the alkali metal cation. The IR results obtained do not permit a clear conclusion as to whether or not the ether oxygen atoms of the ligand polyether chain participate in the complexation. It is suggested that in CH3CN the formation of 1:1 complexes is not accompanied by conformational reorganization of the monopodand.

Phosphorus-containing podands. 6. Calorimetric study of complexation of 1,17-bis (diphenylphosphinyl)-3,6,9,12,15-pentaoxaheptadecane with alkali and alkaline-earth metal salts in acetonitrile

Abstract1, 17-bis-(Diphenylphosphinyl-3, 6, 9, 12, 15-pentaoxaheptadecane in MeCN forms complexes of 1∶1 and 1∶2 composition (M∶L) with alkali and alkaline-earth metal salts, complexes of 1∶1 and 2∶1 composition were found for Li salts. The BaL2+ complex is the most stable complex, and the complexes NH4L+ and CaL2+ are the least stable. The selectivity for Li is significantly higher for the podand studied than for crown ethers.

Phosphorus-containing podands. 4. Complexation of calcium chloride in alcohol at 298 K by solution calorimetry

Conclusions1.Solution calorimetry showed that podands with rigid o-(diphenylphosphinyl)phenyl terminal groups form complexes with CaCl2 with 1∶1 and 1∶2 composition in alcohol.2.The values of the stepwise stability constants for the 1∶2 complexes as a rule exceed the stability constants for the 1∶1 complexes.3.The high values of the stepwise stability constants are explained mainly by the enthalpic contribution for complexes of 1∶1 composition and the entropic contribution for the 1∶2 complexes.