Aminophosphonic Acids Research Articles

Mutual separation of indium(III), gallium(III) and zinc(II) with alkylated aminophosphonic acids with different basicities of amine moiety

Abstract New aminophosphonic acid extractants, α-(4- n -octylanilino)benzylphosphonic acid monobutyl ester (OABPM) and α-dodecylaminobenzylphosphonic acid monobutyl ester (DABPM) with different amino moiety basicities were synthesized to examine the effect of the basicity on their extraction selectivities for In(III), Ga(III), Zn(II), Cu(II), Se(IV) and Se(VI). The extraction order for metals using OABPM was In(III) > Ga(III) > Cu(II) > Zn(II), while Se(IV) and Se(VI) were not extracted. On the other hand, DABPM exhibited the reverse extraction order for Cu(II) and Zn(II). The mutual separation ability of DABPM for these metals was higher than that of OABPM as is determined by the basicity of the amino moiety of their extractants. The extraction equilibria for Ga(III) and Zn(II) with OABPM and DABPM were discussed using slope analysis. It was observed that only Ga(III)- and Zn(II)-DABPM complexes contained nitrate ions, because the phosphonic acid moiety of DABPM was hard to participate in the metal extraction.

ChemInform Abstract: Stereoselective Cyclopropanation as a Way to 1‐Aminocyclopropane‐1‐phosphonic Acids: Rationale for Phosphoryl Group Migration.

AbstractAsymmetric cyclopropanation of vinyl phoshonates such as (I), (V), and (VII) with the methylide (II) affords isomeric products whose methylation (with retention or inversion) leads to intermediates of rigid aminophosphonic acids.

Removal of iron from sythetic copper leach solution using a hydroxy-oxime chelating resin

Iron removal is a common procedure in hydrometallurgy of non-ferrous metallic ores. Chemical precipitation and solvent extraction are currently the main methods employed for separation of iron from copper leach solution. However, chemical precipitation methods have the problem of producing large amounts of iron precipitates, and/or requiring high temperature and high pressure conditions for precipitation. The precipitates are difficult to separate from the solution. Emulsification is a general problem for solvent extraction, which causes loss of extractants and contamination of the electrolyte. A common problem for solvent extraction and chelating ion exchange processes is the difficult iron stripping process. Therefore, finding an efficient and environmentally friendly method for iron removal is of great significance. In this paper, new processes of using ion exchange resins to remove iron from copper leach solution have been investigated.Salicylic acid, amino carboxylic acid, amino phosphonic acid and hydroxy-oxime resins were employed to adsorb iron from a synthetic copper leach solution containing 40g/L of Cu2+ and 36g/L of Fe3+. It was found that a hydroxy-oxime resin, named Z-Fe, has excellent adsorption selectivity on Fe3+. Desorption behavior of the resin was studied by two step elutions using dilute H2SO4 and oxalic acid solution, respectively. After optimizing the adsorption-elution processes, the extent of removal of iron from the simulated copper leach solution using resin Z-Fe was 89.83%, while copper recovery could reach 100% in closed circuit processing.

Stereoselective Cyclopropanation as a Way to 1‐Aminocyclopropane‐1‐phosphonic Acids: Rationale for Phosphoryl Group Migration

AbstractAsymmetric cyclopropanation of vinylphosphonates by using (S)‐dimethylsulfonium(p‐tolylsulfinyl)methylide and subsequent highly stereoselective methylation provided substituted cyclopropylphosphonates, which are useful intermediates in the synthesis of rigid aminophosphonic acids. However, in some examples desulfinylation by iPrMgCl led to 1,2‐migration of the phosphoryl group. The scope of this transformation was investigated by changing the temperature, electronegativity of the substituent α to phosphoryl group, and the configuration of the cyclopropylphosphonates. It was found that a cis relationship between the phosphoryl and sulfinyl groups led exclusively to the product of migration. It was proposed that the rearrangement occurred as an internal process in a concerted manner. The feasibility of an intramolecular mechanism was supported by DFT calculations. The products of desulfinylation with retained structure were used for the synthesis of enantiomerically pure 1‐aminocyclopropane‐1‐phosphonic acids.

Resolution of fluorinated aminophosphonic acid enantiomers by precolumn derivatization with following reverse phase liquid chromatography

GRAPHICAL ABSTRACT

Image analysis of phenylisothiocyanate derivatised and charge-couple device-detected glyphosate and glufosinate in food samples separated by thin-layer chromatography

ABSTRACTThe paper presents the application of pre-chromatographic derivatisation reaction of aminophosphonic acids (glyphosate and glufosinate) with phenylisothiocyanate in thin-layer chromatography (TLC). Silica gel as stationary phase and a mixture of methanol–water–diethyl ether (2:1:1, v/v/v) and ethanol–water–diethyl ether (4:1:2, v/v/v) were used as the mobile phase, respectively. Detection was performed by spraying TLC plates with a freshly prepared mixture of sodium azide (1%), starch solution (1% for glyphosate and 2% for glufosinate), and potassium iodide (1.0 × 10–2 mol L−1) adjusted to pH 6.0 and exposed to iodine vapour for 15 s. Both glyphosate and glufosinate as phenylthiocarbamates (PTC-derivatives) were visible as white spots against a violet background which were converted into chromatograms using TLSee software. The calibration curves for glyphosate and glufosinate were within the ranges of 8.45–84.5 ng and 1.98–79.2 ng per spot, respectively. The limits of detection and quantification for glyphosate were at a level of 4 and 8.45 ng per spot, and for glufosinate were 0.99 and 1.78 ng per spot, respectively. The proposed method was successfully used in the determination of aminophosphonic acids in spiked plants samples.

Sorption and separation of platinum and palladium from aqueous solution by aminophosphonic acid functionalized silica

Sorption and separation of platinum and palladium from aqueous solution by aminophosphonic acid functionalized silica

Reactivity of aminophosphonic acids. Oxidative dephosphonylation of 1-aminoalkylphosphonic acids by aqueous halogens.

The reactions of 1-aminoalkylphosphonic acids with bromine-water, chlorine-water and iodine-water were investigated. The formation of phosphoric(v) acid, as a result of a halogen-promoted cleavage of the Cα-P bond, accompanied by nitrogen release, was observed. The dephosphonylation of 1-aminoalkylphosphonic acids was found to occur quantitatively. In the reactions of 1-aminoalkylphosphonic acids with other halogen-water reagents investigated by (31)P NMR, scission of the Cα-P bond was also observed, the reaction rates being comparable for bromine and chlorine, but much slower for iodine.

Synthesis of activated carbon-based amino phosphonic acid chelating resin and its adsorption properties for Ce(III) removal

This work aims to investigate the adsorption of Ce(III) onto chelating resin based on activated carbon (CRAC). The CRAC adsorbent was prepared from activated carbon (AC) followed by oxidation, silane coupling, ammoniation and phosphorylation, and characterized by Fourier transform-infrared spectrometry, nitrogen adsorption measurements and scanning electron microscopy. The effects of solution pH, adsorbent dosage and contact time were studied by batch technique. Langmuir and Freundlich isotherms were used to describe the adsorption behaviour of Ce(III) by CRAC, and the results showed that the adsorption behaviour well fitted the Langmuir model. The maximum uptake capacity (qmax) calculated by using the Langmuir equation for cerium ions was found to be 94.34 mg/g. A comparison of the kinetic models and the overall experimental data was best fitted with the type 1 pseudo second-order kinetic model. The calculated thermodynamic parameters (ΔG°, ΔH° and ΔS°) showed that the adsorption for Ce(III) was feasible, spontaneous and exothermic at 25–45 °C. The CRAC showed an excellent adsorptive selectivity towards Ce(III). Moreover, more than 82% of Ce(III) adsorbed onto CRAC could be desorbed with HCl and could be used several times.

Molecular insight into the mode-of-action of phosphonate monolayers as active functions of hybrid metal oxide adsorbents. Case study in sequestration of rare earth elements

Organic–inorganic hybrid adsorbents for separation of rare earth elements were prepared by grafting of amino phosphonic acid ligands onto mesoporous TiO2. Their structure and capacity were elucidated using X-ray studies of molecular model compounds.

Термохимические методы изучения состава органокремнеземов с иммобилизованными аминофосфоновыми кислотами

Термохимические методы изучения состава органокремнеземов с иммобилизованными аминофосфоновыми кислотами

Fungal platform for direct chiral phosphonic building blocks production. Closer look on conversion pathway.

The application of Rhodospirillum toruloides strain allowed resolving the chemically synthesized racemic mixtures of following chiral aminophosphonic acids: 1-aminoethylphosphonic acid (1), 1-amino-1-iso-propyl-1-phosphonic acid (2), 1-amino-1-phenylmethylphosphonic acid (4) and 1-amino-2-phenylethylphosphonic acid (3). The applied protocols resulted in obtaining pure (R)-1-aminoethylphosphonic acid (100 % of e.e.) and enantiomerically enriched mixtures of other phosphonates (73 % e.e. of (S)-1-amino-1-phenylmethylphosphonic acid, 51 % e.e. of (R)-1-amino-2-phenylethylphosphonic acid and 40 % e.e. of (S)-1-amino-2-methylpropylphosphonic acid). Products are valuable chiral building blocks and serve as aminophosphonic acids platform for further applications. Performed experiments allowed to define the path of xenobiotics bioconversion.

Sylilation of poly(alkylene H-phosphonate)s – Rapid and efficient method for obtaining poly(alkylene trisilylmethylphosphite)s

Well-defined poly(alkylene trimethylsilylphosphite)s (P+3) were obtained for the first time via silylation of poly(oxyethylene H-phosphonate)s (P+5) with N,O-bis(trimethylsilyl)acetamide or trimethylsilyl chloride. The reaction with both silylating agents proceeds at room temperature in quantitative conversion. It has been followed by 1H and 31P NMR spectroscopy. Poly(alkylene trimethylsilylphosphite)s represent important precursors for the preparation of polymeric aminophosphonic acids, α-hydroxyphosphonates, as well as in a Staudinger-polyphosphite reaction with azides yielding polyphosphoramides.

ChemInform Abstract: Review: Solution Equilibria of Ternary Complexes Formed from Copper(II), Aliphatic Amines, and Bioligands

AbstractReview: 155 refs.

ChemInform Abstract: Chiral Sulfinimines in Asymmetric Synthesis of Enantiomeric Aminophosphonic Acids

AbstractReview: 59 refs.

Chiral Sulfinimines in Asymmetric Synthesis of Enantiomeric Aminophosphonic Acids

Aminophosphonic acids have become important in different fields of chemistry, medicine and agriculture. In this review article, we highlight a new strategy developed in the author's laboratory of asymmetric synthesis of enantiomeric aminophosphonic acid that users chiral sulfinimines as reagents. A key reaction in the synthesis of enantiopure α-, β- and γ-aminophosphonic acids is a highly or fully diastereoselective addition of trivalent phosphorus nucleophiles and α-phosphonate carbanions to enantiopure sulfinimines. The steric course of these addition reactions is rationalized. The usefulness of the sulfinimine methodology is demonstrated by the synthesis of biologically active enantiopure 2-amino-3-phosphonopropanoic acid (AP3), 2-amino-4-phosphonobutanoic acid (AP4) and phosphoemeriamine.

Oxidative Degradation of Amino Acids and Aminophosphonic Acids by 2,2′‐Bipyridine Complexes of Copper(II)

AbstractCopper(II)–amino acid (AA) complexes that contain 2,2′‐bipyridine (bpy) as supporting ligand were investigated. X‐ray structural analysis of three new bpy‐based complexes revealed a bidentate coordination of the AAs on the copper(II) centers similar to that proposed for the substrate on the iron(II) center of the 1‐aminocyclopropane‐1‐carboxylic acid oxidase (ACCO). Similar complexes with two aminophosphonic acids (APAs), 1‐aminocyclopropane‐1‐phosphonic acid (ACP) and (1‐amino‐1‐methyl)ethylphosphonic acid (AMEP), were also investigated, and the latter complex was structurally characterized. This structure reveals the bidentate coordination of α‐aminophosphonate on the copper(II) ion. The oxidation of the bound amino acids (AAs) and aminophosphonates (APAs), which model the reaction catalyzed by ACCO, was investigated. The complexes react with H2O2 and give oxidation products that were identified by gas chromatography. Reduction of CuII to CuI was detected by UV/Vis spectroscopy upon reaction with H2O2 or ascorbate. This reduction is proposed to be the initial step for the peroxide/copper activation prior to the oxidation of the AA and APA ligands by means of a radical mechanism.

Removal of zinc from a base‐metal solution using ion exchange at Rustenburg Base Metal Refiners

AbstractBACKGROUNDChanges to the process flowsheet and increasing zinc content of the feed materials to the Anglo American Platinum Rustenburg Base Metals Refinery circuit resulted in increasing deportment of zinc to the nickel product and necessitated a dedicated zinc‐removal circuit to ensure continued consistent quality of the nickel cathode.RESULTSThe development of an ion‐exchange process for the removal of 0.03 g L−1 Zn from a stream containing 70 g L−1 Ni, 0.2 g L−1 Co is described. Batch testwork compared the di(2‐ethylhexyl)phosphoric acid‐impregnated resin, Lewatit VP OC 1026, with the aminophosphonic acid resin, Purolite S950, and identified the most suitable resin for this application with respect to loading capacity and selectivity. Continuous column testwork then allowed determination of the mass transfer zone length, on which the full‐scale plant design was based.CONCLUSIONA plant treating 15 m3 h–1 was installed for removal of zinc from the selected process stream using Lewatit VP OC 1026. The zinc content of the nickel cathode was reduced by 40% following commissioning of this ion‐exchange plant, allowing the target product specification to be consistently met. © 2014 Society of Chemical Industry.

ChemInform Abstract: Synthetic Methods of Cyclic α‐Aminophosphonic Acids and Their Esters.

This review describes the most synthetic methods of cyclic �-aminophosphonic acids and their mono- or di-esters in which at least two atoms of the PCN system such as linkage of types CP, CN and PCN are part of a heterocyclic system.

Calorimetric Studies of the Interactions between Several Aminophosphonic Acids and Urea in Aqueous Solutions at 298.15 K

The enthalpies of solution of 1-aminobutylphosphonic acid (NvalP), 1-amino-2-methylpropylphosphonic acid (ValP), 1-amino-3-(methylthio)propylphosphonic acid (MetP), N-methyl-1-aminopropylphosphonic acid (Me-HalP), and N,N-dimethyl-1-aminopropylphosphonic acid (Me2-HalP) in water and aqueous urea solutions were measured within the molality range from (0.5 to 4) mol (U)·kg–1 (H2O) at a temperature of 298.15 K. The results obtained were used to determine the standard enthalpies of solution, whose values were then used to calculate the enthalpic heterogeneous pair (phosphonic amino acid–urea) interaction coefficients.