Yu. A. Ignat'ev

Anodic synthesis and molecular structure of dodecaethylhexaamidobisphosphonium diperchlorate

AbstractThe electrochemical oxidation of hexaethyl triamidophosphite in the absence of nucleophiles specially introduced into the electrolyte was studied by anodic voltamperometry and preparative electrolysis. The reversible one-electron oxidation of the triamidophosphite molecule gives an unstable radical-cation, which reacts with a molecule of the starting compound to give a dimeric radical-cation, whose subsequent oxidation leads to dodecaethylhexaamidobisphosphonium diperchlorate. This product is the first example of an acyclic, doubly charged bisphosphonium cation with a

Electrochemically induced processes in the formation of phosphorus acid derivatives. 2. The role of polymerization processes in the electrosynthesis of the esters of phosphorus acids from white phosphorus

\mathop P\limits^ + - \mathop P\limits^ +

Tetraalkyl Pyrophosphites in Anodic Substitution Reactions.

. The crystal structure of this compound was obtained by x-ray diffraction structure analysis.

Electrochemical synthesis of difluorophosphoranes

The products of electrolysis in dipolar aprotic solvents on the background of tetraethylammonium iodide in the presence of white phosphorus are trialkyl phosphite (the primary product after splitting of all the P-P bonds in the phosphoric oligomers) and triaryl phosphate. It was found that the formation of triaryl phosphate from white phosphorus proceeds by way of electrochemical reduction of pentaaroxyphosphorane — an intermediate product of the reaction of triaryl phosphite with iodine and phenol. A strong dependence of the yields and distribution of the products on the composition of the electrolyte has been observed.

ELECTROCHEMICAL FLUORINATION OF MONOAMIDOPHOSPHITES

The mechanism of the electrosynthesis of phosphate esters from white phosphorus was investigated. It was shown that the reaction takes place by two paths, i.e., monomeric (with the participation of dissolved phosphorus) and polymeric (with the participation of phosphorus on the surface of an emulsion drop). It was established that in an alcohol solution of tetraethylammonium iodide the main part of the final product is formed through an intermediate polymeric compound. It was noticed that by studying the dynamics of the accumulation of the dissolved product during electrolysis it is possible to trace the mechanism of reaction of the phosphorus at the individual stages of the process.

Electrochemically Induced Formation of Phosphoric Acid Derivatives. Part 4. Synthesis of Triaryl Phosphates (II) from White Phosphorus.

It has been established that the process of splitting of the P-P bonds of the white phosphorus molecules is initiated by cathode-generated nucleophiles (HO−, RO−), while functionalization of the P-H bond formed in phosphoric oligomers occurs under the action only of alcohol. The primary product after splitting of all the P-P bonds in phosphoric oligomers is dialkylphosphite (in alcohol-water media), or trialkylphosphite (in absolute alcohol), in the course of electrolysis being transformed into trialkylphosphate. Formation of esters of pyrophosphoric acid with reduced protogenic character of the medium was examined. It is proposed that under these conditions nucleophilic reagents of the type (〉P)c-O− form and participate in splitting of the P-P bonds.

Electrochemical Synthesis of Esters of Phosphorus(III) and Phosphorus(V) Acids on the Basis of Elemental Phosphorus.

Anodic oxidation of the title compounds (I) in the presence of aromatic hydrocarbons (II) under conditions previously published gives the phosphonates (III).

Electrocatalyzed phosphorylation of olefins

We have studied the electrochemical oxidation of tertiary phosphines, R3P, on a platinum electrode in acetonitrile in the presence of nonhygroscopic n-amylammonium fluoride, CsHIINH3F. The electrolysis was carried out with a Teflon partition in a ggl~anostatic mode and a current density from 3.3 to 6.7 mA/cm 2. The base electrolyte was Et4NBF 4. The reaction proceeds with the transfer of two electrons per tertiary phosphine molecule. A trialkylor triaryldifluorophosphorane, R3PF2, is formed in all cases. Apparently, the anodic oxidatien may be represented by the following equation: R3P 2e + 2CsHIINH3F R3PF 2 + 2CsHIINH3.