Selective Monophosphorylation of Aliphatic Diamines

This article describes an improved method to synthesize phosphoramidic acid aminoalkyl esters from diamines by the adaptation of industrial patents. Four mono-phosphorylated products having amino sites were obtained in good a yield. Such compounds have potential coordination properties with transition metals and also potential biological activity.     

Monophosphorylation of 1,4:3,6-dianhydro-D-mannitol

Efficient procedures were developed for the synthesis of monophosphorylated derivatives of 1,4:3,6-dianhydro-D-mannitol. The latter are of interest as compounds bearing different phosphorus-containing fragments on a three-dimensional matrix having an inner chiral cavity.     

水杨酰腙与磷酰二氯的缩合反应

一些水杨酸的衍生物具有生物活性早有报道.本文研究水杨酰腙与硫代磷酰二氯或磷酰二氯缩合时可能发生的不同关环方式,并通过对反应产物的生物活性测定寻找有效的杀菌剂. 我们发现,在三乙胺存在下水杨酰腙1与硫代磷酰二氯2在四氢呋喃中反应主要以酮式关环生成3类化合物,而与磷酰二氯反应则主要以烯醇式关环生成4类化合物.     

The reaction of trifluoromethanesulphonicanhydride with phosphoryl compounds

Hexamethylphosphortriamide and triphenylphosphine oxide react with trifluoromethanesulphonic anhydride to give diphosphonium salts.     

Thermodynamics of the Solvation and phase distributions of ethylenediamine in acetonitrile-dimethylsulfoxide-hexane systems

The enthalpies of dissolution and solvation of ethylenediamine over the range of compositions of a mixed acetonitrile-dimethylsulfoxide solvent at 298 K are determined calorimetrically. It is found that with an increase in the acetonitrile concentration, the solvation exothermicity of ethylenediamine declines, owing to the resolvation of amino groups. The Gibbs energies of transfer of ethylenediamine from dimethylsulfoxide into its mixtures with acetonitrile are determined from the distribution of a substance between immiscible phases. It is found that increasing the acetonitrile concentration in a binary solvent improves the stability of the ethylenediamine solvatocomplex, owing to a change in the entropy component of the Gibbs energy.     

Acid-base properties of phosphoryl compounds 14. Hydrogen-bond polarity in complex phosphoryl compounds

Conclusions Dipole moments have been measured for phosphoryl compound complexes with alcohols and substituted phenols. A scheme for calculating the H-bond polarity (_h) in these systems is discussed; the value of _H can be described in terms of a charge transfer model.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 10, pp. 2288–2292, October, 1978.The authors wish to thank B. A. Kvasov for his help with the measurements on the NMR spectra.     

Regioselective Monophosphorylation of Primary OH Groups in the Presence of Secondary OH Groups

With various model hydroxy compounds as examples, efficient procedures were developed for regioselective monophosphorylation of primary hydroxy groups in the presence of unprotected secondary hydroxy groups.     

Synthesis of alpha-P-modified nucleoside diphosphates with ethylenediamine

This report describes a one-pot synthesis of alpha-P-borano-, alpha-P-thio-, and alpha-P-seleno-modified nucleoside diphosphate analogues that are otherwise difficult to obtain. The key step involves the intramolecular nucleophilic attack by an amino group in 5 to remove the gamma-phosphate. The absolute configurations of P-diastereomers were confirmed by analysis of their 1H NMR. Affinity studies revealed that the nucleoside boranodiphosphates are potentially useful in antiviral research.     

Catalytic synthesis of phosphoryl isocyanates

A general efficient method for the synthesis of phosphoryl isocyanates was developed. The method involves reactions of phosphoryl chlorides with sodium cyanate in the presence of anhydrous magnesium chloride as a catalyst. Dedicated to the Corresponding Member of the Russian Academy of Sciences T. A. Mastryukova. For the preliminary report, see Ref. 1. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 2543–2545, November, 2005.     

Linear alkyl diamine-uranium-phosphate systems: U(VI) to U(IV) reduction with ethylenediamine

Mild-hydrothermal reactions in acidic medium using 1,3-diaminopropane, 1,4-diaminobutane, and 1,5-diaminopentane as structure directing agents led to three-dimensional (3D) uranyl phosphates (CH?)?(NH?)?{[(UO?)(H?O)][(UO?)(PO?)]?} (C3U5P4), (CH?)?(NH?)?{[(UO?)(H?O)][(UO?)(PO?)]?} (C4U5P4) and (CH?)5(NH?)?{[(UO?)(H?O)][(UO?)(PO?)]?} (C5U5P4). The structures of (C4U5P4) and (C5U5P4) were solved in the space group Cmc2? using single-crystal X-ray diffraction data. The compounds are isostructural to the corresponding uranyl vanadates and contain the same 3D inorganic framework built from uranyl-phosphate layers of uranophane-type anion topology pillared by [UO?(H?O)] pentagonal bipyramids. In neutral or basic medium the alkyl diamines decompose to give ammonium uranyl phosphate trihydrate. In the same conditions by using ethylenediamine, unexpected reduction of uranium(VI) to uranium(IV) occurs leading to the formation of (CH?)?(NH?)?[U(PO?)?] (C2UP2) single crystals. C2UP2 undergoes a reversible phase transition from triclinic to monoclinic symmetry at about 230 °C. The structure of the two forms results from the stacking of inorganic layers (∞)1[U(PO?)?]2?, and organic layers containing ethylene diammonium ions, the two layers being linked by hydrogen bonds. Single crystals of (CH?)?(NH?)?[PO?OH] (C2HP) are formed by evaporation of the solution after filtering of C2UP2 single crystals. The structure of C2HP contains infinite (∞)1[PO?OH]2? chains connected by (CH?)?(NH?)?2? ions through hydrogen bonds.     

Enolization of the phosphoryl group

Enolization of the phosphoryl group has been studied where Y = PPh₃, CN, Ts, COOEt, CONEt₂; R and R′ = Et, Bu, Ph, EtO, BuO, PhO; and X = Cl, Br, ClO₄, BF₄. It has been established that substances with are phosphaenols, but in substances with Y = CONEt₂ the phosphoryl group cannot be enolized under any conditions. Phosphaenolization is favored by a high acidifying ability of the Y group, the ability of the X anion to stabilize the phosphaenolic form due to formation of a hydrogen bond OH…X with the anion, and a low electronegativity of R and R′ groups. To evaluate the acidifying ability of Y, this article defines specific σ⁻ constants dependent on the number of substituents at the α-carbon atom: σ_CH3⁻, σ_CH2⁻ and σ_CH⁻. Their sums characterize the enolization ability of the phosphoryl group. The enolic structure in the solid state is possible if ∑_CHn⁻ > 2. If this sum lies in the range of 2 < ∑_CHn⁻ < 2.6 the phosphoryl–phosphaenol tautomerism can be expected in appropriate solutions. Acidic properties of the investigated compounds in MeNO₂ and EtOH (absolute) have been determined. Calculations of the acidity of the phosphoryl CH forms (A) and of the phosphaenol OH forms (B) have been carried out.     

Template reactions of fluorine-containing 1,3-diketones with ethylenediamine

Depending on the nature of the dicarbonyl fragment, the reaction of fluorinated copper(II) bis(1,3-diketonates) with ethylenediamine and its monoprotonated salts under mild conditions gives N,N-ethylenebis(aminovinyl ketones) and/or 1,4-diazepines. In excess ethylenediamine, copper(II) and nickel(II) N,N-ethylenebis(aminovinyl ketonates) undergo cyclization to 1,4-diazepines.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 9, pp. 2088–2092, September, 1991.     

Extraction of f-elements from nitric acid solutions with phosphoryl ketones

The extraction ability and selectivity of a series of phosphoryl ketones Ph₂P(O)CH₂C(O)Me, and Ph₂P(O)CRR’CH₂C(O)Me (R = H, Me; R’ = H, Me, n-C₅H₁₁, Ph, 2-thienyl, 2-furyl) towards trivalent lanthanides (La^III, Nd^III, Ho^III, Yb^III) and actinides (U^VI, Th^IV) were studied. The efficiency and selectivity of the new ligands in the extraction of f-elements from nitric acid solutions into chloroform were compared to those of model phosphine oxide Ph₂P(O)Bu and known extractants: tributyl phosphate (BuO)₃P(O), trioctylphosphine oxide (C₈H₁₇)₃P(O), and carbamoylmethyl phosphine oxide Ph₂P(O)CH₂C(O)NBu₂.