L. I. Livantsova

Synthesis of (aminomethylene)bisphosphonic acid derivatives

Amino derivatives of methylenebisphosphonic acids were synthesized by phosphorylation of formamide, nitriles or hydrochlorides of alkyl imidates with H3PO3—PCl3—(Me3Si)2NH.

Syntheses of N-phenylaminomethylenediphosphonic and -diphosphinic acids and their derivatives

Substituted aminomethylene diphosphorus-containing compounds are of interest as prmising ligands and biologically active substances [1]. Some of compounds of this type can be obtained by suitable methods using dialkylformamide dialkylacetals [2]. Aiming to synthesize new N-aminomethylenediphosphorus compounds we examined a reaction of some of trimethylsilyl phosphites and hypophosphites taken in excess with the corresponding ethoxymethyleneimine I and formamidine IV obtained similarly to the earlier described procedures [3]. Thus, ethoxymethyleneimine I reacts with a mixture of diethyl(trimethylsilyl)phosphate and diethylphosphite and also with a mixture of tris(trimethylsilyl)phosphate and bis(trimethylsilyl)phosphate at 140–160oС to form diphosphonates II and III. In the zinc chloride catalyst is required for the preparation of compound III (cf. [4]). DOI: 10.1134/S1070363209090230

Synthesis of phosphorus derivatives of 2,6 -Di -tert -butyl -4 -methylphenol

Convenient procedures for the synthesis of 2,6-di-tert-butyl-4-methylphenol (ionol) mono-, di-and triphosphorus derivatives, starting from the readily accessible 3,5-di-tert-butyl-4-hydroxybenzaldehyde, are proposed, and some properties of the obtained compounds are presented.

Synthesis of new types of aminomethylenediphosphorus-containing acids and their derivatives

Convenient methods for synthesis of various aminomethylenediphosphorus-containing acids and their derivatives starting from available trimethylsilyl esters of hypophosphorous and phosphorous acids, ethoxymethyleneimine hydrochlorides, and N-substituted formamides have been proposed. Selected properties of the obtained compounds have been examined.

Addition of tris(trimethylsilyl) phosphite to N-substituted 4-piperidone

Convenient methods for the synthesis of functionalized phosphonic acids containing piperidine moieties via the reaction of tris(trimethylsilyl) phosphite with N-substituted 4-piperidone derivatives have been developed.

Synthesis of new aryl-substituted methylphosphonic and methylenediphosphonic acids and their derivatives

Simple and versatile synthetic procedures towards new aryl-substituted hydroxymethylphosphonic and methylenediphosphonic acids via reactions of either aromatic aldehydes or their derivatives with phosphites were elaborated.

New functionalized derivatives of mono- and diphosphonic acids substituted with five-membered nitrogen heterocycles

New types of (hydroxymethyl)phosphonic and (methylene)diphosphonic acids bearing heterocyclic fragments were synthesized by addition of tris(trimethylsilyl) phosphite to N-formyl derivatives of five-membered nitrogen heterocycles.

Synthesis of mono-and diphosphorus-substituted proline derivatives containing P–C–N fragments

Convenient methods for the synthesis of new types of mono-and diphosphorus-substituted proline derivatives containing P–C–N fragments were developed based on special pre-prepared proline-containing synthons. The corresponding organophosphorus acids including a proline fragment were also synthesized.

Synthesis of Aminomethylenediphosphonates and Their Derivatives Containing PCNH 2 Fragments

Aminomethylenediphosphonic acids containing free amino group are of interest as promising ligands and biologically active substances with diverse properties [1]. We recently developed several convenient methods for the synthesis of N-substituted aminomethylenediphosphonates starting from Nsubstituted formamides and imines [2]. For the synthesis of new trimethylsilyl-containing aminomethylenediphosphonates and their derivatives with PCNH2 fragments we studied the interaction of tris(trimethylsilyl)phosphate with easily accessible hydrochlorides of substituted ethoxymethyleneimines A [3] in the presence of trimethylsilyl trifluoromethanesulfonate as a catalyst. Thus, substituted ethoxymethyleneimines hydrochlorides A reacted with an excess of tris(trimethylsilyl)phosphite in methylene chloride under mild conditions to form diphosphonates I–III with good yields. DOI: 10.1134/S1070363214030347

Synthesis of N-substituted aminomethylenediphosphonites and their derivatives

Substituted aminomethylenediphosphonites are of interest as the key materials in the synthesis of functionalized aminomethylenediphosphorus-containing compounds, which are analogs of natural organophosphorus pyrophosphates and amino acids, promising ligands and biologically active substances with diverse properties [1]. Recently, we have prepared two types of the compounds by reacting bis(trimethylsiloxy) phosphine with substituted methyleneimines [2]. To synthesize new types of N-substituted aminomethylenediphosphonites we studied the direct interaction of bis(trimethylsiloxy) phosphine A with available Nsubstituted formamides. Note that the phosphine A can be easily attached to the carbonyl groups of various aldehydes and ketones [3], but the analogous reaction with formamide is not described. The reaction of an excess of bis(trimethylsiloxy)phosphine A with Nsubstituted formamides proceeds readily in methylene chloride only in the presence of a catalyst (trimethylsilyl trifluoromethanesulfonate) to give the intermediate diphosphonites B. The latter react with bis(trimethylsilyl)amine under reflux in the presence of trimethylchlorosilane to afford diphosphonites I–III with good yields (cf. [4]). DOI: 10.1134/S1070363213060340