E. N. Tsvetkov

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: 10. An improved method for synthesizing oligo(ethylene glycol) bis[2-(diphenylphosphinoyl)ethyl] ethers and their complex-forming properties with respect to alkali-metal-cations in anhydrous acetonitrile

An improved preparative method for the synthesis of oligo(ethylene glycol) bis[2-(diphenylphosphinoyl)ethyl] ethers has been developed. The complex-forming ability of these ligands toward alkali-metal cations has been studied by conductometry in anhydrous MeCN at 25°C. Ligands of this type have been shown to be highly efficient and selective complexing agents with respect to the Li+ cation. The stability series of the complexes M+L has the form Li > Na > K > Rb in all cases. The complexing properties and selectivity displayed by these new monopodands in MeCN have been compared with those in the THF-CHCl3 (4∶1) system studied previously.

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 of chloromethylphosphine oxides

Conclusions1.We have developed a method for the preparation of chloromethylphosphine oxides by substitution of the acetoxy group in acetoxymethylphosphine oxides by chlorine using gaseous HC1 at 180–200°C.2.We have prepared methylbis(chloromethyl)phosphine oxide by reaction of gaseous HC1 with tris(acetoxymethyl)phosphine or tetrakis(hydroxymethyl)phosphonium chloride. In the same way we synthesized dimethylchloromethylphosphine oxide from tris(hydroxymethyl)phosphine methylsulfate.

Synthesis and structure of 1-substituted 1-Oxo-1,2-dihydro-4H-3,1-benzoxaphosphorins

Abstract1-X-1-Oxo-1,2-dihydro-4H-3,1-benzoxaphosphorins (X = CH2Cl, Ph, and OH) were obtained by reacting ortho-(butoxymethoxymethyl)phenylmagnesium bromide with derivatives of chloromethylphosphonic and chloromethylphosphinic acids, followed by intramolecular alkylation. X-Ray diffraction was used to study the molecular and crystalline structure of one of these compounds (with X = OH).

Effect of a catechol segment in a polyether chain on the complexing ability of some phosphonate and quinoline monopodands

The complexing ability of monopodands with o-diethoxyphosphinylmethoxyphenyl and 8-quinoline end groups, containing both ethylene glycol and catechol units in the polyether chain, was studied by conductimetry in tetrahydrofuran-CHCl3. Replacement of ethvlene glycol by catechol changes the efficiency insignificantly, but in a number of cases leads to some increase in K/Li and k/Na selectivity of phosphonate podands, and the K/Li and Na/Li selectivity of quinoline podands.

Molecular and crystal structure of 2H-3,4-dihydro-3-hydroxy-3-oxo-1,5,3-benzodioxaphosphepine

ConclusionsAn x-ray diffraction structural analysis was carried out for 2H-3,4-dihydro-3-hydroxy-3-oxo-1,5,3-benzodioxaphosphepine and the seven-membered heterocycle in this molecule was found to have chair conformation with an axial OH group.

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:

Synthesis of asymmetricP,P-dialkyl-P′,P′-diphenylethylenediphosphine dioxides

AsymmetricP, P-dialkyl-P′,P′-diphenylethylenediphosphine dioxides were synthesized by the addition of dialkylphosphinous acids to diphenylvinylphosphine oxide in toluene without a catalyst and in DMSO in the presence of concentrated aqueous alkali. The method for isolating dipropyl- and dibutylphosphinous acids obtained by reactions of diethylphosphite with the corresponding alkylmagnesium bromides was improved.