New synthesis ofγ-aminopropylphosphonic acid

Conclusions -Aminopropylphosphonic acid was synthesized by the hydrolysis of O,O-diethyl -aminopropylphosphonate, which was obtained by the condensation of O,O-diethyl vinylphosphonate with nitromethane in the presence of sodium ethylate, and subsequent reduction.Translated from Izvestiya Academii Nauk SSSR, Seriya Khimicheskaya, No. 6, pp. 1353–1354, June, 1971.     

An NMR study of optical isomers in solution

NMR ³¹P-{¹H} spectra of stereoisomeric N - [S - (methylethoxyphosphinyl) - thioglycolyl]valines in solution to reveal association of the molecules, and interaction of the chiral centres. Under fast inter-associate exchange in achiral media, these interactions lead to the following: (i) The chemical shift of the racemic mixture of enantiomers deviates from the shift of the individual species; (ii) the spectra of non-racemic mixtures are doublets; (iii) there are 2ⁿ lines in the spectrum of a mixture containing unequal concentrations of stereoisomers with n asymmetric centres. The integrated intensity ratio is equal to the concentration ratio in all cases. The concept of statistically controlled associate diastereomerism (SCAD) is introduced and the respective formalism is given to describe the spectral effects accompanying variations of temperature and concentration. It is also shown applicable to more complicated cases involving ion exchange of chiral fragments between stereoisomers.     

Experience of σπ-correlations of carbanion reactions with electrophilic reagents

The problem of the possibility of applying ap-correlation analysis by the three sigmas' system to carbanion reactions with electrophilic reagents was considered. In particular the alkylation as well as Wittig and Homer olefination reactions were discussed. It was shown that the condition for the application of correlation analysis to such reactions is the constancy of the Brönsted's parameter connected with steric and reorganization factors of the substrates and solvents. Perfect correlations were observed when this condition was met.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 3, pp. 634–639, March, 1996.     

Synthesis of novel O,O"-dialkyl α-aminoalkylphosphonothioates

O,O"-Dialkyl -amino(cyclohexyl)phosphonothioates were synthesized by the reactions of O,O"-dialkyl phosphonothioites with [2-(N-cyclohexylideneamino)ethyl] vinyl ether.     

IR and <Superscript>31</Superscript>P NMR spectroscopic study of complexation of carbamoyl methyl phosphinates with U<Superscript>VI</Superscript> and Th<Superscript>IV</Superscript> in nitric acid solutions

The composition of complexes formed upon the extraction of U^VI and Th^IV nitrates with O-n-nonyl(N,N-dibutylcarbamoylmethyl) methyl phosphinate (L) from solutions of nitric acid without additional solvent was determined by ³¹P NMR spectroscopy. The structures of the complexes formed were studied by IR spectroscopy. Uranium(VI) is extracted from 3 and 5 M solutions of HNO₃ as the [UO₂(L)₂(NO₃)₂] complex, while thorium(IV) is extracted from 5 M HNO₃ as the [Th(L)₃(NO₃)₃]⁺·NO ₃ ⁻ complex. In both cases, ligand L has bidentate coordination. Ligand L contacts with 3 and 5 M nitric acid to form adducts L·HNO₃ and L· (HNO₃)₂, respectively. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 2460–2464, November, 2005.