Zbigniew H. Kudzin

Aminophosphonic Acids - Phosphorus Analogues of Natural Amino Acids.Part 1: Syntheses of α-Aminophosphonic Acids

This review presents a comprehensive account of methods which are commonly applied for the synthesis of alpha- aminophosphonic acids. In the following order, protocols based on the methodologies listed below are discussed: a) simultaneous formation of P-C-N systems; b) nucleophilic substitution with phosphoroorganic nucleophiles; c) additions of the P-H functions to multiple C-N bonds; d) alpha-amination of phosphonates and functionalized alkylphosphonates; e) modifications of the side chain of aminoalkylphosphonates; f) modifications of phosphorus functions and h) modifications of functions containing nitrogen.

Novel approach for the simultaneous analysis of glyphosate and its metabolites

A novel approach for the simultaneous analysis of glyphosate (PMG), and aminomethylphosphonic (AMPA, GlyP), N-methylaminomethylphosphonic (MAMPA. SarP) and methylphosphonic (MPA) acids is presented. This includes a preliminary 31P NMR analysis of mixtures of PMG, MPA, AMPA and MAMPA, their further derivatization to volatile phosphonates by means of the trifluoroacetic acid-trifluoroacetic anhydride-trimethyl orthoacetate reagent and subsequent MS [chemical ionization (CI) MS, GC-CI-MS, GC-electron impact ionization MS] and/or GC-flame ionization detection (FID) analysis of the products of derivatization. The detection limits of PMG, AMPA, MAMPA and MPA by means of GC-CI-MS and GC-FID were determined. The calibration graphs (GC-FID) for these derivatives were in the range 0.1 to 100 nmol linear and sufficiently reproducible for quantitative determinations. The applicability of the method was demonstrated during the analysis of water samples fortified with PMG, AMPA and MAMPA, characterized by recoveries of >95%.

Simultaneous analysis of biologically active aminoalkanephosphonic acids

A new approach for simultaneous analysis of biologically active aminoalkanephosphonic acids, namely glyphosate, phosphonoglycine, phosphonosarcosine, phosphonoalanine, phosphono-beta-alanine, phosphonohomoalanine, phosphono-gamma-homoalanine and glufosinate, is presented. This includes a preliminary 31p NMR analysis of these amino acids, their further derivatization to volatile phosphonates (phosphinates) by means of trifluoroacetic acid-trifluoroacetic anhydride-trimethyl orthoacetate reagent and subsequent analysis of derivatization products using MS and/or GC-MS (chemical ionization and/or electron impact ionization).

1-Aminoalkanediphosphonic acids. Synthesis and acidic properties

Abstract The syntheses of 1-aminoalkane-1, n -diphosphonic acids ( n = 2–4) by the thioureidoalkanephosphonate method are described. The acidities of these amino acids were determined potentiometrically.

Application of the iodine-azide reagent for selective detection of thiophosphoryl compounds in thin-layer chromatography☆

Abstract The application of the iodine-azide-induced reaction for the detection of thiophosphoryl compounds in thin-layer chromatographic systems is described. The detection limits of the derivatives tested were found to be at the nanomole level and depend on the nature of the P(S) n function, particularly on the degree of polarity of the PS bond and the number of sulphur atoms in the molecule. A comparison of the iodine-azide test reaction with other procedures used for thiophosphoryl compounds is presented. A procedure for the differentiation of thiophosphoryl compounds and sulphur compounds based on the combined molybdate procedure preceded by a preoxidation stage is demonstrated.

A new method for the iodometric determination of sulphoxides

A method is described for determination of sulphoxides through their reaction with iodide in a trifluoroacetic acid/acetone medium to produce iodine, which is then titrated with thiosulphate.

Organothiophosphorus compounds as inductors of the iodine-azide reaction. Analytical application.

Thiophosphoryl compounds were found to exhibit strong induction activity in the iodine-azide reaction. On this basis three procedures for their determination: titrimetric (0.15-1 mumol), coulometric (1-20 nmol) and spectrophotometric (0.5-5 nmol) have been developed. RSD in all applied methods (techniques) have been found at the 1-7% level. The induction coefficients were dependent on the type of compound applied and on the reaction condition and varied from 90 to 450.

Orthoformates as reagents for derivatization of aminoalkanephosphonic acids for characterization by gas chromatography-mass spectrometry

Studies of the derivatization of aminoalkanephosphonic acids by trialkyl orthoformates are reported. Gas chromatographic retention data and low-resolution electron impact mass spectra for the derivatives are presented.

Thiophosphoryl compounds as novel inducing agents in the iodine–azide reaction

The application of organophosphorus compounds as inducing agents in the iodine–azide reaction was investigated. The induction activity was exhibited by thiophosphoryl compounds; their induction coefficients were dependent on the number and nature of sulphur atoms in the P(S)n function. These relationships can be used for the group differentiation of organophosphorus compounds, for example phosphates, thiophosphates and dithiophosphates. On the basis of their induction activity the microdetermination of thiophosphoryl inductors on a nmol scale was elucidated.

LONG CHAIN 1-AMINOTHIAALKANE-PHOSPHONATES, THEIR SULPHINYL AND SULPHONYL DERIVATIVES. A NEW TYPE OF COMPLEXANE TYPE SURFACTANTS

Abstract Several long chain 1-aminothiaalkanephosphonic acids 1 were prepared and selectively oxidized to the corresponding sulphinyl 2 and sulphonyl 3 derivatives. For all compounds synthesized surface tension properties were determined. These measurements indicate that the surface activities of compounds 1–3 are comparable with that of typical phosphonate detergents.