Synthesis of β-Aminophosphonates and Study of Their Acid-Base Properties and Phase Distribution in Water-Organic Solvent Systems

New and previously known β-aminoethylphosphonates were synthesized by addition of primary and secondary amines to vinylphosphonates, and their IR and NMR spectra were examined. Diethyl 2-diethylaminoethylphosphonate and diethyl 2-morpholinoethylphosphonate were found to be stronger bases than the corresponding aminomethylphosphonates, but all these are weaker bases than their precursors, nonphosphorylated amines. Distribution constants of β-aminophosphonates between water and some organic solvents were determined and compared with those of their α-amino homologs.     

Membrane Transport of Inorganic Acids with α- Aminophosphoryl Compounds

Transport of some inorganic acids (HCl, HBr, HClO₄, HNO₃, H₂SO₄, and H₂PO₄) through hydrophobic impregnated membranes with aminophosphoryl compounds of the general formula R ₂ ¹ P(O)CH₂ ⋅ NR²R³ [R¹ = C₄H₉(C₂H₅)CHCH₂O, R² = C₄H₉, R³ = C₈H₁₇; R¹ = R³ = C₈H₁₇, R² = H; R¹ = C₁₀H₂, R² = R³ = C₂H₅; R¹ = C₁₀H₂₁, R² + R³ = (CH₂)₂O(CH₂)₂; R¹ = C₈H₁₇, R² = H, R³ = 2-quinolyl] and dodecylamine as carriers was studied. The membrane phases were solutions of the carriers in phenylcyclohexane and tridecane. General regularities that correlate the structure of an aminophosphoryl compounds to its transport properties toward inorganic acids were established. The largest flows are characteristic of perchloric, nitric, and hydrobromic acids.__________Translated from Zhurnal Obshchei Khimii, Vol. 75, No. 4, 2005, pp. 575–578.Original Russian Text Copyright © 2005 by Garifzyanov, Shirshova, Cherkasov.     

Partition constants of α-aminophosphonates in two-phase aqueous-organic solvent systems

Two-phase potentiometric titration was used to determine partition constants for a series of -aminophosphonates (RO)₂P(O)CH₂NR¹R² [R = Alk (C₂-C₅), R¹, R² = Me, Et, (CH₂)₅] between water and organic solvents, such as chloroform, carbon tetrachloride, toluene, octane, n-octanol, nitrobenzene, o-xylene, and cyclohexane. Correlations between the partition constants and the number of carbon atoms in substrate molecules were obtained. Solvent effects on partition constants were discussed, and solution parameters of -aminophosphonates were calculated.Translated from Zhurnal Obshchei Khimii, Vol. 74, No. 12, 2004, pp. 1998–2002.Original Russian Text Copyright © 2004 by Garifzyanov, Nuriazdanova, Zakharov, Cherkasov.This revised version was published online in April 2005 with a corrected cover date.     

Synthesis and Acid-Base Properties of α-Aminophosphoryl Compounds

-Aminophosphoryl compounds of the phosphonate, phosphine oxide, and ,-bis(phosphine oxide) series and some of their thiophosphoryl analogs were synthesized. Potentiometric measurements of the pK_a of the conjugate acids revealed an insignificant effect of variation of substituents on the phosphorus, nitrogen, and -carbon atoms on the basicity of the phosphorylated amines. The latter are weak bases. Organophosphorus groups decrease the basicity of the amines by almost 5 pK _a units. The role of the hydrophobic effect and intramolecular H-bonding in the obtained substances was discussed.     

Metastable ionic cubic structure I clathrate hydrate formed with tetra-n-butylammonium bromide

1. Download : Download high-res image (143KB)
2. Download : Download full-size image

     

Liquid–liquid extraction of copper(II) ions with a novel aminophosphoryl extractant, 2-ethylhexyl hydrogen {[bis(2-ethylhexyl)amino]methyl}phosphonate

Russian Journal of General Chemistry -     

Synthesis of the novel β-aminophosphoryl compounds and their acid-base properties and membrane-transport abilities towards carboxylic acids

The highly efficient synthesis of β-aminophosphoryl compounds with one and two ethylphosphoryl groups was performed by the addition of amines to the vinylphosphoryl compounds in water as a solvent. The acid-base properties and membrane-transport abilities of the target compounds towards carboxylic acids were studied. Selectivity towards acetic acid was revealed.     

Diastereotopic splitting in the 13C NMR spectra of sulfur homofullerenes and methanofullerenes with chiral fragments

Using gauge‐invariant atomic orbital PBE/3ζ quantum chemistry approach, ¹³C NMR chemical shifts and diastereotopic splittings of sp² fullerenyl carbons of a number of sulfur homofullerenes and methanofullerenes have been predicted and discussed. An anisochrony of fullerene carbons is caused by a chiral center of attached moieties. Clearly distinguishable diastereotopic pairs (from 8 to 11) of fullerenyl carbons of homofullerenes were observed. Unambiguous assignments of ¹³C NMR chemical shifts were performed, and diastereotopic splittings of methanofullerenes were observed for α, β and γ to a functionalization site. Copyright © 2013 John Wiley & Sons, Ltd.