Unsaturated Phosphonic Acids Research Articles

Interaction of O- and P- nucleophiles with perfluorinated olefins: Novel synthetic route to fluorinated phosphorus-containing monomers

A novel synthetic method for the preparation of partially fluorinated unsaturated diethyl phosphonates and phosphonic acids is presented involving the deprotonation of the starting α-hydroxymethyl diethylphosphonate or diethylphosphite with a strong base, followed by in situ addition of an O- or P-nucleophile to the terminal double bond of the perfluorinated olefin. Subsequent elimination of the corresponding leaving groups and restoring of the double bond leads to the target bifunctional perfluorinated olefins. Reaction of the diethyl phosphonate group with trimethylsilyl bromide (TMS-Br) and subsequent hydrolysis/methanolysis gave the corresponding unsaturated phosphonic acids. In the case of using α-hydroxymethyl diethylphosphonate, the reaction may be accompanied by an addition of a second equivalent of an O-nucleophile to form bis-functional internal olefins. The reaction conditions, factors affecting the reactivity, stereo- and regioselectivity of the process, the choice of reagent as well as the course of competitive reactions are discussed, too.

Quantum-chemical calculations of chemical shifts in NMR spectra of organic molecules: V. Stereochemical structure of unsaturated phosphonic acids dichlorides from 31P NMR spectral data

The stereochemical structure of unsaturated phosphonic acids dichlorides containing fragments C=C-POCl2 and C=N-POCl2 was investigated by 31P NMR spectroscopy and quantum chemistry. Starting from the experimental measurement and theoretical calculation of 31P NMR chemical shifts configurations were assigned and the conformational composition of compounds under study was determined.

An Efficient Route to 4-Halophosphaisocoumarins via CuX2-Mediated Direct Halocyclization of 2-(1-Alkynyl)phenylphosphonic Acid Diesters

A series of 4-halophosphaisocoumarins were synthesized via CuX2 (X = Br, Cl) -mediated direct halocyclization of 2-(1-alkynyl)phenylphosphonic acid diesters in dichloroethane with the addition of n-Bu4NX or/and AgI in good to excellent yields. This reaction provides an efficient route to 4-halophosphaisocoumarins and represents the first example of bromo- and chlorocyclization of unsaturated phosphonic acid diesters.

ChemInform Abstract: Synthesis of trans‐1,2‐Difluoroethenediylbis(phosphonic acid) and Other Unsaturated Phosphonic Acids.

AbstractThe title bis(phosphonic acid) (V), and the phosphonic acids (XI) and (XIII) are prepared according to the scheme.

Synthesis of trans-1,2-difluoroethenediylbis(phosphonic acid) and other unsaturated phosphonic acids

Synthese de tetrafluoro-3,3,4,4 cyclobutene-1 (ou hexafluoro-3,3,4,4,5,5 cyclopentene-1 ou octafluoro cyclohexene-1) de phosphonique-1,2 acide et de difluoro-1,2 ethylenediphosphonique-1,2 acide a partir de la reaction de [bromo diethoxyphosphoryl fluoro] methyl sulfinate avec HO°. Le difluoro-1,2 ethylenediphosphonique-1,2 acide reagit avec de la poudre de zinc et donne le complexe [Zn(H 2 O) 6 ] + [O(HO)P(O)CF=CFP(O)(OH)O] 2− qui est etudie par diffraction RX

Reactions of Unsaturated Phosphonic Acids with 2-Aminopyridine

Abstract Different unsaturated phosphonic acids of the general formula (R=C1, OCH3, OH, NMe2, C6H5; R′=C1, OCH3, H, NMe2) have been prepared starting from propargyl alcohol. Reaction of chlorophosphonic acids with 2-amino-pyridine yields phosphoramidates, which in the next step undergo a base-catalyzed cyclization by addition of the ring nitrogen across the unsaturated bond, leading to the unstable derivative 1. In the case of the allenic phosphonic acid in which R=R′=NMe2, the NH2 group of 2-aminopyridine adds first to the allenic system yielding an enamine, which on heating cyclizes to give a new phosphorus-nitrogen heterocyclic system 2.

The formation of phosphorus-containing nitroxyl radicals in the photolysis of 2-methyl-2-nitrosopropane in esters of unsaturated phosphonic acid

1. In the photolysis of 2-methyl-2-nitrosopropane in esters ofα-alkenylphosphonic acids, nitroxyl radicals are formed with a phosphonealkyl group at the nitrogen atom on account of the addition of radical chain carriers to the nitroso compound during the radical polymerization of the phosphonates. 2. The constants of hyperfine interaction with the31p nucleus in the ESR spectra of the nitroxyls studied depend on the degree of polymerization of the radical to be trapped. The mechanism of this interaction is not associated to any appreciable degree with p-d overlapping and may include as the principal element the hyperconjugation of the orbital of the unpaired electron with the P-C bond.

An unsaturated phosphonic acid analogue of phosphatidylethanolamine and its activity in blood‐clotting systems

An unsaturated phosphonolipid analogous to phosphatidylethanolamine,rac-dioleoylglyceryl(2-aminoethyl)phosphonate, was synthesized by a general method introduced by Baer for similar saturated substances. An improvement was made in the preparation of the phthalimidoethyl-phosphonic acid precursor.The phosphonolipid was purified by DEAE cellulose and silicic acid chromatography. It was tested by comparison with synthetic phosphatidyl (dioleoyl) ethanolamine and phosphatidyl(dilinoleoyl) ethanolamine in the Hicks-Pitney test and in a test for prothrombin conversion by using purified blood coagulation factors. In both tests it had more acceleratory activity than the synthetic phosphatidylethanolamines.

The Stereochemistry of Unsaturated Phosphonic Acids1

The Stereochemistry of Unsaturated Phosphonic Acids¹

Derivatives of Unsaturated Phosphonic Acids

Derivatives of Unsaturated Phosphonic Acids

Studies in the field of derivatives of unsaturated phosphonic acids 21. Esters and amides of ?-ethylhexoxyvinylphosphonic acid

β-(β-Ethylhexoxy)-vinylphosphonic dichloride, diethyl, dipropyl, dibutyl, di-isobutyl, di-isoamyl, dihexyl, di-2-ethylhexyl, di-(methoxyethyl) and di(ethoxyethyl) esters of β-(β-ethylhexoxy)-vinylphosphonic acid, tetramethyldiamide, tetraethyldiamide and dipiperidide β -(β-ethylhexoxy)-vinylphosphonic acid were prepared and characterized.

Derivatives of unsaturated phosphonic acids Communication 20. 2-chloro-3-methyl-3-butenyl-and 3-methyl-1,3-butadienyl-phosphonic esters

1. With the aid of the reaction between isoprene and phosphorus pentachloride, 2-chloro-3-methyl-3-butenylphosphonic dichloride was prepared. 2. The methyl, ethyl, propyl, isopropyl, butyl, isobutyl, allyl, hexyl, 2-methoxyethyl, and 2-ethoxyethyl esters of 2-chloro-3-methyl-3-butenylphosphonic and 3-methyl-1,3-butadienylphosphonic acids were prepared and characterized.

Derivatives of unsaturated phosphonic acids

Derivatives of unsaturated phosphonic acids

Derivatives of unsaturated phosphonic acids communication 13. Diester of 2-indenylphosphonic acid

Derivatives of unsaturated phosphonic acids communication 13. Diester of 2-indenylphosphonic acid

Derivatives of unsaturated phosphonic acids communication 17. Derivatives of styrylphosphonic acid

??? N-substituted P-styrylphosphonic diamides, two O,O-diesters of ???-diesters of phosphonothioic acid, and two S,S-diesters of stylrylphosphonodithioic acid were synthesized and characterized.

Derivatives of unsaturated phosphonic acids Communication 7. Diesters of 2-phenoxyvinylphosphonic acid

The dimethyl, diethyl, dipropyl, diisopropyl, dibutyl, diisobutyl, diallyl, dihexyl, bis(2-methoxyethyl), and bis(2-ethoxyethyl) esters of 2-phenoxyvinylphosphonic acid have been prepared by the action of 2-phenoxyvinyl-phosphonic dichloride on alcohols in presence of pyridine. The properties of these esters have been described.

Derivatives of unsaturated phosphonic acids

Derivatives of unsaturated phosphonic acids

Derivatives of unsaturated phosphonic acids

Derivatives of unsaturated phosphonic acids

Derivatives of unsaturated phosphonic acids

Derivatives of unsaturated phosphonic acids

Derivatives of unsaturated phosphonic acids

Derivatives of unsaturated phosphonic acids