Electrochemical Oxidation of Metal Dialkyl Phosphites and Their Reaction with Halogens

Electrochemical oxidation of sodium dialkyl phosphites with alkyl radicals of normal structure leads to formation of tetraalkyl pyrophosphites as the main products, while electrochemical oxidation of litium dialkyl phosphites and sodium salts with branched alkyl radicals yields tetraalkyl hypophosphates. The reaction of metal dialkyl phosphites with halogens leads to analogous results

Electrosynthesis and chemical properties of hexaalkyldiphosphonium salts

Electrochemical oxidation of trialkylphosphines on the background of sodium perchlorate or tetraethylammonium tetrafluoroborate allows synthesis of a new class of organophosphorus compounds, hexaalkyldiphosphonium salts. A mechanism of the electrosynthesis is proposed, which includes generation of radical cations R3P+• on the anode, their reaction with the starting phosphine to give a dimeric radical cation whose oxidation leads to the final product. The synthesized hexaalkyldiphosphonium salts readily react with compounds containing an active hydrogen atom, as well as with dialkyldisulfides, but do not react with aromatic or unsaturated compounds under normal conditions. © 1996 MAEe cyrillic signK Hayκa/Interperiodica Publishing

Reactions of trialkylphosphine radical cations with cycloalkenes

Electrochemical oxidation of tertiary aliphatic phosphines in the presence of cyclohexene or cyclopentene yields isomeric cycloalkenylphosphonium salts with different positions of the double bond in the cycloalkenyl substituent relative to the phosphonium group

Radical Cations of Phosphorous Amides in Reactions with Alkenes

Electrochemical oxidation of diethyl diethylphosphoramidite and ethyl tetraethylphosphorodiamidite in the presence of alkenes results in formation of amido(1-alkenyl)- and amido(2-alkenyl)phosphonates. Under the same conditions, hexaethylphosphorous triamide forms a dodecaethylhexaaminodiphosphonium salt. Electrochemical oxidation of the above phosphoramidites and -diamidites in the presence of diethyl hydrogen phosphite or O,O-dibutyl hydrogen thiophosphite and an alkene involves addition of (RO)2P(O,S)H at the multiple bond and yields a different ratio of isomeric mono- and diamidoalkenylphosphonates

Electrochemical and Catalytic Initiation of Triethyl Phosphite Addition to Cyclohexanone

Electrochemical oxidation of triethyl phosphite in the presence of cyclohexanone results in a mixture of three products: diethyl(1-ethoxycyclohexyl)phosphonate, diethyl phosphonate, and 2-(1-cyclohexenyl)cylcyclohexanone. These products are formed through the stage on the anode synthesis of quasiphosphonium salts, which initiate addition of triethyl phosphite to cyclohexanone and condensation of cyclohexanone. The fact that quasiphosphonium salts catalyze addition of the phosphite to the ketone was proved by independent experiment

Reaction of Olefins with Anodically Generated Radical Cations of Trialkyl Phosphites and Dialkyl Trimethylsilyl Phosphites

Electrochemical oxidation of trialkyl phosphites and dialkyl trimethylsilyl phosphites in the presence of olefins yields mixtures of isomeric dialkyl alkenyl(cycloalkenyl)phosphonates with predominating [alken(cycloalken)-2-yl]phosphonates. A scheme of the process was proposed, which involves attack of the alkene double bond by anodically generated radical cations of phosphites, followed by a second electron transfer, deprotonation, and elimination of cationic species: alkyl cation in the case of trialkyl phosphites and trimethylsilyl cation in the case trimethylsilyl phosphites

Mechanism of Electrochemical Synthesis of Phosphonium and Quasiphosphonium Salts

The radical cations generated on the anode in the course of electrochemical oxidation of tripropylphosphine in the presence of toluene and water are established to react with the aromatic compound and initial phosphine rather than with water molecules. The experimental findings made it possible to propose a new method of electrochemical synthesis of arylphosphonium salts. The electrochemical synthesis of quasiphosphonium salts, performed by electrochemical oxidation of tertiary phosphines in the presence of alcohols, amines, phenols, thiols, and disulfides, is assumed to involve a diphosphonium intermediate, while the synthesis of arylphosphonium cations proceeds by the mechanism of free-radical aromatic substitution

High energy hadrons in EAS at mountain altitude

An extensive simulation has been carried out to estimate the physical interpretation of dynamical factors such as , in terms of high energy interaction features, concentrated in the present analysis on the average transverse momentum. It appears that the large enhancement observed for versus primary energy, suggesting in earliest analysis a significant rise of with energy, is only the result of the limited resolution of the detectors and remains in agreement with a wide range of models used in simulations.Comment: 13 pages, 6 PostScript figures, LaTeX Subm. to JPhys

Free-Radical Phosphorylation of Olefins Initiated by Anodic Oxidation

Electrochemical oxidation of lithium and sodium dialkyl phosphites generates dialkyl phosphonyl radicals, which initiate chain free-radical addition of dialkyl phosphites across the alkene multiple bond to form alkyl(cycloalkyl)phosphonates. Alkyl(cycloalkyl)phosphonates are formed simultaneously owing to anodic oxidation of adsorbed primary radical adducts of phosphonyl radical and alkene molecule to give the carbenium cation, followed by deprotonation of the latter