1066-51-9Relevant articles and documents
A Bispidol Chelator with a Phosphonate Pendant Arm: Synthesis, Cu(II) Complexation, and 64Cu Labeling
Gillet, Rapha?l,Roux, Amandine,Brandel, Jérémy,Huclier-Markai, Sandrine,Camerel, Franck,Jeannin, Olivier,Nonat, Aline M.,Charbonnière, Lo?c J.
, p. 11738 - 11752 (2017)
Here we present the synthesis and characterization of a new bispidine (3,7-diazabicyclo[3.3.1]nonane) ligand with N-methanephosphonate substituents (L2). Its physicochemical properties in water, as well as those of the corresponding Cu(II) and Zn(II) complexes, have been evaluated by using UV-visible absorption spectroscopy, potentiometry, 1H and 31P NMR, and cyclic voltammetry. Radiolabeling experiments with 64CuII have been carried out, showing excellent radiolabeling properties. Quantitative complexation was achieved within 60 min under stoichiometric conditions, at room temperature and in the nanomolar concentration range. It was also demonstrated that the complexation occurred below pH 2. Properties have been compared to those of the analogue bispidol bearing a N-methanecarboxylate substituent (L1). Although both systems meet the required criteria to be used as new chelator for 64/67Cu in terms of the kinetics of formation, thermodynamic stability, selectivity for Cu(II), and kinetic inertness regarding redox- or acid-assisted decomplexation processes, substitution of the carboxylic acid function by the phosphonic moiety is responsible for a significant increase in the thermodynamic stability of the Cu(II) complex (+2 log units for pCu) and also leads to an increase in the radiochemical yields with 64CuII which is quantitative for L2.
1-(N-Acylamino)alkylphosphonic acids—Deacylation in aqueous solutions
Cypryk, Marek,Drabowicz, Jozef,Gostynski, Bartlomiej,Kudzin, Marcin H.,Kudzin, Zbigniew H.,Urbaniak, Pawel
, p. 651 - 658 (2017)
The 1-(N-acylamino)alkylphosphonic acids (AC)-AAP belong to the interesting and potentially of pharmacological importance group of 1-aminoalkylphosphonic acids derivatives. Since susceptibility of (AC)-AAP on hydrolytic deacylation can form important factor influencing their biological activity, we have undertaken deacylation investigations of these compounds in aqueous media. In this article, we present our results on deacylation of various types of 1-(N-acylamino)alkylphosphonic acids (AC)-AAP, including 1-(N-acetylamino)alkyl-phosphonic Ac-AAP, 1-(N-chloroacetylamino)alkylphosphonic acids Mca-AAP, 1-(N-trifluoroacetylamino)alkylphosphonic acids TFA-AAP, and 1-(N-benzoylamino)-alkylphosphonic Bz-AAP, derived from representative 1-aminoalkylphosphonic acids AAP (GlyP, AlaP, ValP, PglP, and PheP) in neutral and 2?M HCl solutions.
1-(Acylamino)alkylphosphonic acids—alkaline deacylation
Cypryk, Marek,Drabowicz, Jozef,Gostynski, Bartlomiej,Kudzin, Marcin H.,Kudzin, Zbigniew H,Urbaniak, Pawel
, (2018)
The alkaline deacylation of a representative series of 1-(acylamino)alkylphosphonic acids [(AC)-AAP: (AC) = Ac, TFA, Bz; AAP = GlyP, AlaP, ValP, PglP and PheP] in an aqueous solution of KOH (2M) was investigated. The results suggested a two-stage reaction mechanism with a quick interaction of the hydroxyl ion on the carbonyl function of the amide R-C(O)-N(H)- group in the first stage, which leads to instant formation of the intermediary acyl-hydroxyl adducts of R-C(O?)2-N(H)-, visible in the 31P NMR spectra. In the second stage, these intermediates decompose slowly by splitting of the RC(O?)2-N(H)- function with the subsequent formation of 1-aminoalkylphosphonate and carboxylate ions.
Effect of the nature of carbon catalysts on glyphosate synthesis
Pinel, Catherine,Landrivon, Emmanuel,Lini, Hedi,Gallezot, Pierre
, p. 515 - 519 (1999)
Aqueous solutions of PMIDA (N-phosphonomethyliminodiacetic acid) were oxidized, using air, to obtain glyphosate (N-(phosphonomethyl)glycine) an active herbicide. The oxidative decarboxylation reaction was catalyzed selectively by active carbons obtained from different precursors and modified by specific thermal treatments. The activities were highly dependent upon the functional groups present on the carbon surface. Nitrogen-containing functional groups greatly enhanced the oxidation rates; these groups were either issued from the carbon precursors or introduced by thermal treatment under NH3 of active carbons. The highest rates of PMIDA oxidation were obtained using nonactivated carbons treated with NH3 at 900°C. Activities were also enhanced by thermal treatments at 900°C under N2 which eliminated the acidic sites from the carbon surface, and possibly created active basic sites.
Comments on the Synthesis of Aminomethylphosphonic Acid
Soroka, Miroslaw
, p. 547 - 548 (1989)
Two simple methods for the synthesis of aminomethylphosphonic acid from phosphorus(III) chloride and 1,3,5-triacylhexahydro-1,3,5-triazine or N-(hydroxymethyl)benzamide are described.
Homogeneous catalysts for selective molecular oxygen driven oxidative decarboxylations
Riley, Dennis P.,Fields, Donald L.,Rivers, Willie
, p. 3371 - 3378 (1991)
Cobalt(II) ion has been found to catalyze the molecular oxygen driven oxidation of N-(phosphonomethyl)iminodiacetic acid (PMIDA) to N-(phosphonomethyl)glycine (PMG) in aqueous solution.1 This homogeneous catalytic conversion is novel and represents, in effect, an oxidative dealkylation of one carboxymethyl moiety yielding the N-substituted glycine. The reaction is selective to the desired product PMG when carried out at the natural pH of the free acid substrate (～ 1-2) and when carried out at substrate loadings less than 5% by weight. In addition, the catalytic system is selective for the PMIDA substrate; i.e., other closely related ligands show no reactivity, e.g., NTA, EDTA, etc. The results of kinetic and mechanistic studies on dilute systems are presented and discussed with special emphasis on how an understanding of the mechanism can make it possible to generate a catalyst system that gives high yields even with high substrate loadings. The reactions are first-order in substrate and [Co]t. The oxygen pressure dependence exhibits saturation kinetics, while the selectivity increases as oxygen pressure increases. The rate is also inversely proportional to [H+]. The high selectivity of the oxidation and the unique selectivity of the cobalt catalytic system for the PMIDA substrate are discussed in terms of the magnitude of the metal ligand binding constant at the low pH of the reaction.
Chemical and Mutagenic Analysis of Aminomethylphosphonate Biodegradation
Avila, L. Z.,Loo, S. H.,Frost, J. W.
, p. 6758 - 6764 (1987)
Utilization of aminomethyl-, N-methylaminomethyl-, N,N-dimethylaminomethyl-, and N-acetylaminomethylphosphonate by Escherichia coli as a sole source of phosphorus during growth resulted in the extracellular generation of N-methylacetamide, N,N-dimethylacetamide, trimethylamine, and N-methylacetamide, respectively.Product identification relied on synthesis of (13)C-enriched aminomethylphosphonates followed by (1)H NMR analysis of products isolated from the biodegradation of the labeled and unlabeled phosphorus sources.To circumvent the requirement of an intact cell for carbon to phosphorus bond degradation, transposon mutagenesis was exploited as a complement to the chemical analysis.E. coli K-12 were infected with λTn5.Colonies resistant to kanamycin were selected and then screened for loss of the ability to use ethylphosphonate as a sole source of phosphorus.The mutant identified, E. coli SL724, was also unable to degrade aminomethylphosphonates.This combination of chemical and mutagenic analysis points toward a shared mechanism between alkyl- and aminomethylphosphonate biodegradation.
PROCESS FOR OXIDATION OF N-(PHOSPHONOMETHYL)IMINODIACETIC ACID
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Paragraph 0104, (2015/11/10)
An oxidation catalyst is prepared by pyrolyzing a source of iron and a source of nitrogen on a carbon support. Preferably, a noble metal is deposited over the modified support which comprises iron and nitrogen bound to the carbon support. The catalyst is effective for oxidation reactions such as the oxidative cleavage of tertiary amines to produce secondary amines, especially the oxidation of N-(phosphonomethyl)iminodiacetic acid to N-(phosphonomethyl)-glycine.
METHOD FOR THE SYNTHESIS OF AMINOALKYLENEPHOSPHONIC ACID
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Paragraph 0073, (2014/02/15)
The present invention is related to a method for the synthesis of an aminoalkylenephosphonic acid or its phosphonate esters comprising the following steps: a) forming, in the presence of an aldehyde or ketone and an acid catalyst, a reaction mixture by mixing a compound comprising at least one HNR1R2 moiety or a salt thereof, with a compound having one or more P-O-P anhydride moieties, said moieties comprising one P atom at the oxidation state (+III) and one P atom at the oxidation state (+III) or (+V), wherein the ratio of moles of aldehyde or ketone to N-H moieties is 1 or more and wherein the ratio of N-H moieties to P-O-P anhydride moieties is 0.3 or more and, b) recovering the resulting aminoalkylenephosphonic acid comprising compound or its phosphonate esters.
METHOD FOR THE SYNTHESIS OF ALPHA-AMINOALKYLENEPHOSPHONIC ACID
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Page/Page column 23, (2014/02/15)
The present invention is related to a new method for the synthesis of alpha-aminoalkylenephosphonic acid or its phosphonate esters comprising the steps of forming a reaction mixture by mixing a P-O-P anhydride moiety comprising compound, having one P-atom at the oxidation state (+111) and the other P-atom at the oxidation state (+111) or (+V), an aminoalkanecarboxylic acid and an acid catalyst, wherein said reaction mixture comprises an equivalent ratio of alpha-aminoalkylene carboxylic acid to P-O-P anhydride moieties of at least 0.2, and recovering the resulting alpha-aminoalkylene phosphonic acid compound or an ester thereof from the reaction mixture.
