Aminomethylphosphonic Acids Research Articles

Homochiral Dysprosium Phosphonate Nanowires: Morphology Control and Magnetic Dynamics.

Controllable synthesis of uniformly distributed nanowires of coordination polymers with inherent physical functions is highly desirable but challenging. In particular, the combination of chirality and magnetism into nanowires has potential applications in multifunctional materials and spintronic devices. Herein, we report four pairs of enantiopure coordination polymers with formulae S-, R-Dy(cyampH)3 ⋅ CH3 COOH ⋅ 2H2 O (S-1, R-1), S-, R-Dy(cyampH)3 ⋅ 3H2 O (S-2, R-2), S-, R-Dy(cyampH)2 (C2 H5 COO) ⋅ 3H2 O (S-3, R-3) and S-, R-Dy(cyampH)3 ⋅ 0.5C2 H5 COOH ⋅ 2H2 O (S-4, R-4) [cyampH2 =S-, R-(1-cyclohexylethyl)aminomethylphosphonic acids], which were obtained depending on the pH of the reaction mixtures and the specific carboxylic acid used as pH regulator. Interestingly, compounds 3 were obtained as superlong nanowires, showing 1D neutral chain structure which contains both phosphonate and propionate anion ligands. While compounds 1, 2 and 4 appeared as block-like crystals, superhelices and nanorods, respectively, and exhibited similar neutral chain structures containing only phosphonate ligand. Slow magnetization relaxation characteristic of single-molecule magnet (SMM) behavior was observed for compounds S-1 and S-3. Theoretical calculations were performed to rationalize the magneto-structural relationships.

Phosphonomethylated derivatives of dinitroanilines

A number of dinitroanilines derivatives previously unknown has been synthesized. The alkylamino groups and aminomethylphosphonic groups have been introduced as acids and esters in their structure. The synthesis has been carried out by Kabachnik-Fields reaction and its modification – Moedritzer-Irani reaction, in which formaldehyde and phosphonic acids are used in a highly acidic medium. However, we have not found any other examples of successful application of this reaction to aniline derivatives in the literature. Thus, the possibility to use Moedritzer-Irani reaction to dinitrosubstituted anilines has been found. Obviously, the fact that two nitrogroups reactivate the aromatic ring of aniline is enough to fully avoid adverse polymerization associated with the interaction of formaldehyde with the benzene ring in this case. This polymerization makes it impossible to use Moedritzer-Irani reaction for other compounds with the aniline moiety. Benzylaminophosphonic acids esters have been also synthesized based on dialkyl phosphites and Schiff bases using Kabachnik-Fields reaction with subsequent hydrolyzation to the acids. The required aminosubstituted dinitroanilines with aliphatic aminogroups have been synthesized by the reaction of aliphatic diamines with dinitrochlorbenzenes. The structure of the compounds obtained has been confirmed by the methods of 1H and 31P NMR spectroscopy and elemental analysis. As a result, the application of Moedritzer-Irani reaction has been expanded, and due to it aminomethylphosphonic acids that are previously unknown and structurally similar to the known herbicides have been synthesized.

Reaction of diethyl 5-hydrazino-2-(4-methylphenyl)-1,3-oxazol-4-ylphosphonate with acyl isothiocyanates

The reactions of diethyl 5-hydrazino-2-(4-methylphenyl)-1,3-oxazol-4-ylphosphonate with acetyl, benzoyl, and ethoxycarbonyl isothiocyanates result in the previously unknown (1,3,4-thiadiazol-2-yl)-substituted aminomethylphosphonic acids.

Addition of Di(trimethylsilyl) Phosphite to Schiff Bases of 2,5-Diformylfuran

A series of 2,5-Furanyl-bis-(aminomethylphosphonic Acids) has been synthesized by the addition of di(trimethylsilyl) phosphite to azomethine bond of achiral Schiff bases derved from 2,5-diformylfuran. The stereochemical aspect of this reaction has been studied and compared with the behaviour of achiral terephthalic Schiff bases in similar reaction. Whereas, addition to achiral terephthalic Schiff bases was found to be highly stereoselective, the analogous reaction with achiral 2,5-diformylfuran Schiff bases was stereoselective exclusively in the case when the substituent is benzyl.

Synthesis of C-heteryl-substituted aminomethylphosphonic acids derivatives

The available diethyl 5-hydrazino-2-p-tolyl-1,3-oxazol-1-ylphosphonate was readily acylated with chlorides of carboxylic acids of heterocyclic series. On heating in acetic acid it underwent the oxazole ring cleavage, recyclization and diethylation that was used to prepar the substituted 2-p-toluylaminomethylphosphonic acids containing a series of 2-heteryl-1,3,4-oxadiazol-5-yl residues in the α-position relative to the phosponyl group.

Synthesis of Novel Aminophosphonic Derivatives of Benzo‐15‐crown‐5 Ether.

AbstractFor Abstract see ChemInform Abstract in Full Text.

SYNTHESIS OF NOVEL AMINOPHOSPHONIC DERIVATIVES OF BENZO-15-CROWN-5 ETHER

Synthesis of new aminomethylphosphonic acids containing benzo-15-crown-5 ether, is described. These compounds were obtained from the 4′-formylbenzo-15-crown-5 by a sequence of reactions, which afforded 4′-(aminomethylphosphono)-benzo-15-crown-5 and its N-benzyl derivative in high yields.

Acid-Catalyzed Cleavage Of 2-Pyridyl and 4-Pyridyl Derivatives Of Aminomethylphosphonic Acid. Kinetic And Chemical Arguments For A Mechanism With A-SE2 Character

Studies of the acid-catalyzed cleavage of 2-pyridyl and 4-pyridyl(amino)methylphosphonic acids demonstrate that protonation has a profound effect on the cleavage of C-P bonds. In H2SO4, and other strong mineral acids the cleavage of aminophosphonic acids 1 and 4 exhibits a kinetic depedence on Zucker-Hammett acidity function (h o), with rate law, v = k[phosphonate]·h o, and also fulfil the Bunnett approach on acidity function. The measured solvent isotope effect K H/K D is small, and varied from 1.46 for 1b to 1.18 for 4b. The isotope effect shows that protons are involved on the rate-determining step of the cleavage. All of this evidence indicates that the cleavage of 1 or 4 shows A-SE2 character substitution reaction. Calculated activation parameters and some chemical experiments indicate that the protonated phosphonate molecule is split by a dissociative mechanism, combined with formation of a positive-charged phosphorus moiety.

Polymeric aminomethylphosphonic acids - 2. Polychelatogenes for separation of transition metal ions by membrane filtration

Investigations on the complex formation of monomeric and polymeric aminomethylphosphonic acids with several transition metal ions were carried out. These water-soluble complexes were separated from aqueous solution using an ultrafiltration system. The maximal loading capacities of the polymeric chelatogenes with Cu2+, Cd2+, Hg2+, and Pb2+ ions were determined at various pH values. Mixed loading studies were carried out to determine the selectivity of these macromolecular chelating agents for metal ions. Compared with known aminoalkylphosphonic acid groups containing polymers, the polyacryloylaminomethylphosphonic acid in particular exhibits good complexation ability for the transition metal ions Cd2+ and Hg2+. The acid-base equilibria and complexation behavior of these polychelatogenes were investigated. Acid dissociation constants of the chelating agents and the formation constants of the chelates were determined by means of potentiometric titration. Spectrophotometry was used to determine the dependence of the metal ion/ligand ratio of the formed complexes on the pH. The structure of the formed complexes was investigated using IR spectroscopy. Proposals for the structures of the complexes were made on the basis of these measurements.

FORMATION OF AMINOMETHYLPHOSPHONIC ACIDS AND MONOESTERS FROM AMINOMETHYLPHOSPHONATES

Correcting a previous preliminary communication, the reaction between diethyl N-benzoyl α-aminomethylphosphonate and PCl5, is shown to afford the corresponding aminomethylphosphonic acids and monoesters instead of the previous mentioned oxazaphospholene.

Polymeric aminomethylphosphonic acids - 1. Synthesis and properties in solution

Three water-soluble polyaminomethylphosphonic acids were obtained by radical polymerization in aqueous solution. The corresponding monomers were synthesized by different procedures. A Mannich-type reaction of diallylamine, formaldehyde, and phosphorous acid leads to diallylaminomethylphosphonic acid. Reaction of diallyl formamide and phosphorous acid results in diallylaminomethyldiphosphonic acid. Acryloylaminomethylphosphonic acid was prepared by acylation of aminomethylphosphonic acid. The diallyl compounds polymerize via cyclopolymerization, leading to polymers containing substituted pyrrolidinium rings as units of the macromolecule. Both the monomers and the polymers form zwitterionic structures in aqueous solution within a limited pH range. This was proved by 31 P-, 1H- and 13C-NMR spectroscopy, as well as by FT-IR measurements. The monomers are water-soluble without limitations, but the polymers are insoluble in a pH range near their isoelectric point, which was determined by turbidimetry and viscometry. An improvement of the solubility was achieved after the addition of inorganic salts. As expected, the monomeric and polymeric acryloyl compounds form no zwitterionic structure; both are soluble over the whole pH range investigated.

Phosphoranaloge von Aminosäuren II1. Synthese von α-Aminophosphonsäuren und α-Aminophosphinsäuren, ausgehend von den entsprechendenN-Acylimino-Derivaten

Synthesis of α-Amino Phosphonic Acids and α-Amino Phosphinic Acids via the Corresponding N-Acylimino Derivatives Acyliminomethylphosphonic and acyliminomethylphosphinic esters, usually formed in situ from the corresponding acylamino(bromo)methyl compounds, react with higher order mixed cuprates to yield, after hydrolysis, C-substituted aminomethylphosphonic acids and aminomethylphosphinic acids, respectively.

ChemInform Abstract: Substituted Aminomethylphosphonic Acids and Their Esters.

AbstractDas Bis‐oxazolidinyl‐p‐xylol (I) reagiert mit phosphoriger Säure bzw. Dialkylphosphiten (II) zu der Bis‐phosphonsäure (IIIa) bzw. den Estern (IIIb) und (IIIc), die sich auch durch Aminomethylierung von (II) mit Bis‐(β‐hydroxyethylamino)‐p‐xylol (IV) und Formaldehyd darstellen lassen.

Synthesis and Biological Activity of Aminomethylphosphonic Acids Related to the Herbicide Glyphosate

Several aminomethylphosphonic acids related to the herbicide glyphosate have been synthesised and their post-emergent herbicidal properties studied

Reaction in the system trialkyl phosphite-carboxamide or secondary amine

A study was made of reaction in the system: triethyl phosphite-amide (amine)-paraform(benzaldehyde). The reaction leads to the formation of the corresponding esters of aminomethyl(alkyl)phosphonic acids.

Transamination of Aminoalkylphosphonic Acids with Alpha Ketoglutarate

Dialyzed homogenates prepared from Escherichia coli, Tetrahymena pyriformis, sea anemone (Anthopleura elegantissima), and mouse liver were tested for ability to transaminate 17 aminoalkylphosphonic acids with alpha-ketoglutarate. 2-Aminoethylphosphonic acid (2-AEP), which occurs naturally in Tetrahymena and anemone, was transaminated by these latter organisms more than any of the substances tested, but not by preparations from liver or E. coli. 3-Aminopropylphosphonic acid was transaminated by all preparations, but much less by Tetrahymena or anemone than was 2-AEP. 2-Amino-3-phosphonopropionic acid was transaminated by all preparations. 2-Amino-4-phosphonobutyric acid was transaminated by three of the preparations, but not by liver. Of the other 13 substances tested, the following gave positive results: DL-1,2-diaminoethylphosphonic acid with E. coli, DL-1,2-diaminoethylphosphonic and aminomethylphosphonic acids with Tetrahymena, DL-1-aminopropylphosphonic acid with anemone, and DL-1-aminoethylphosphonic and DL-1-aminobutylphosphonic acids with liver. The significance of these transaminations is discussed.