Synthesis and physiological activity of new organophosphorus pesticides of 1,3,2-oxazaphosphorinane series

Methods for the synthesis of 2-aryloxy(arylthio)- and 2-alkoxy(alkylthio)-2-thio(oxo)-1,3,2-oxazaphosphorinanes and theirN-substituted derivatives based on the reactions of the corresponding dichlorophosphates, dichlorothio-, and dithiophosphates with 3-aminopropan-1-ol or its substituted derivatives in the presence of Et₃N or aqueous alkali under phase transfer catalysis conditions, as well as by the reaction of the tetramethylammonium salt of 2-hydroxy-2-thio-1,3,2-oxazaphosphorinane with alkyl- and acyl halides, by that of 2-chloro-2-thio-1,3,2-oxazaphosphorinane with sodium thiolates, and by other methods, were developed. The compounds obtained exhibit high nematocide activity but low toxicity for mammals. Some active synergists for permethrine were found among these compounds.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 2241–2249, November, 1995.This study was financially supported in part by the International Science Foundation (Grant Nos. NDO 000 and NDO 300) and by the Russian Foundation for Basic Research (Grant No. 93-03-0451). The authors are grateful for this support.     

Induced Silver Ion Transfer across the Aqueous Solution/Organic Phase Interface in the Presence of Sulfur-Containing Ionophores: Conceptual Models and Analytical Applications

The voltammetric behavior of silver at the water/nitrobenzene and water/1,2-dichloroethane interfaces was studied in the presence of diphenylthiourea and O,O-dihexyl dithiophosphates. The composition of the complexes and the standard potentials of their transfer were determined, and the standard energies and stability constants of the complexes in the membrane phase were calculated. The selectivity and sensitivity of voltammetric methods of analysis at the interface of immiscible electrolytes were discussed.     

Mono and bis[N-aryl(benzyl)]amides of phosphorylacetic acids. One-pot synthesis and extraction of actinides from nitric acid solutions

A one-pot synthetic route to phosphorylacetic acid N-aryl(alkylaryl)amides, including those containing two phosphorylmethylcarbamoyl moieties attached to the arene framework, has been developed. The method is based on reactions of amines with the corresponding acid chlorides generated in situ with the use of phosphorus trichloride as a mild chlorinating agent. The compositions and structures of the compounds obtained and their extraction ability toward Am^III were determined. Suggestions were made about the compositions of the extracted complexes with phosphorylacetic acid N-aryl(alkylaryl)amides. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1387–1394, August, 2006.     

The complexation of (N,N-diethylcarbamoylmethyl)diphenylphosphine sulfide with silver nitrate

The crystalline complex [Ag(L ¹)NO₃]₂ (A) was isolated by the interaction of (N,N-diethylcaibamoylmethyl)diphenylphosphine sulfide Ph₂P(S)CH₂C(O)NEt₂ (L ¹) with AgNO₃ in different solvents at the ratios of metal:ligand = 11 and 12. According to the X-ray data, complexA is a center-symmetric dimer with bridge sulfur atoms. The cations of the metal are in a tetrahedral environment formed by two S atoms and the O atoms of CO and NO₃ groups. The interaction ofL ¹ with AgNO₃ was studied in solution by IR spectroscopy, and the structures of the complexes formed are discussed.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 4, pp. 708–713, April, 1994.The authors are grateful to B. V. Lokshin and his coworkers for help in measurement of the Raman spectra and for useful discussion.The present investigation was financially supported by the Russian Foundation for Basic Research (Project 93-03-4351).     

Study of Tautomerism in Some β-Keto Phosphoryl Prototropic Pentad Systems

Abstract

By the reaction of phosphoryl substituted acylmethylenetriphe-nylphosphoranes (I, II) with hydrogen halides prototropic pentad tautomeric systems (III, IV) have been obtained.     

Prototropic Tautomerism in Phosphoryl-Hydroxyylide and Thiophosphoryl-Mercaptoylide Systems

Abstract

Two new types of tautomerism are discussed: phosphoryl-hydroxyylide and thiophosphoryl-mercaptoylide tautomerism.     

Synthesis of nitro- and aminoalkylphosphonates

Conclusions Some new O, O-dialkyl nitroalkylphosphonates were synthesized by the addition of dialkyl phosphites and thiophosphites to nitroolefins. The corresponding aminophosphonates were obtained from them by reduction. The hydrolysis of the latter gave the corresponding aminoalkylphosphonic acids.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 5, pp. 1164–1168, May, 1972.     

Complexes of (ω-diphenylphosphinoalkyl)diphenylphosphine sulfides with silver nitrate in pyridine

The behavior of the phosphine-phosphine sulfide complexes of silver, [Ph₂P(S)(CH₂) _n PPh₂] _m ·AgNO₃ (n=2 or 4;m=1 or 2), in pyridine was studied. Dissolution of the 1:1 complexes in pyridine leads to destruction of their dimeric structures Ag₂[Ph₂P(S)(CH₂) _n PPh₂]₂(NO₃)₂ (A) to form the complexes Agp_y ⁺−P(Ph₂)(CH₂) _n Ph₂P=S and Agp_y ⁺−S=PPh₂(CH₂) _n PPh₂. The solid complexes isolated from pyridine restore dimeric structure A. According to the data of X-ray diffraction analysis, the 1:2 complex isolated from pyridine has the structure [S=P(Ph₂)(CH₂)₂(Ph₂)P−(NO₃)Ag(Py)−P(Ph₂) (CH₂)₂(Ph₂)P=S]Py. According to the data of IR spectroscopy, dissolution of this complex in chloroform leads to the formation of the dimeric structure Ag₂Ph₂P(S)(CH₂)₂PPh₂]₄(NO₃)₂. Deceased. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 1751–1758, September, 1998.     

Intramolecular cyclization of ω‐haloalkylsubstituted thiophosphorylacetonitriles: Synthesis and stereochemistry of 3‐cyano‐2‐oxo‐1,2‐thiaphosphacyclanes

Intramolecular S‐alkylation in a series of ω‐haloalkyl‐substituted thiophosphorylacetonitriles 5–7 presents an effective synthetic route to the hitherto unknown 3‐cyano‐2‐oxo‐1,2‐thiaphospholanes 14 and thiaphosphinanes 15 . The compounds were obtained as a mixture of cis‐ and trans‐isomers that were resolved to individual stereoisomers in most cases. For some of them, X‐ray diffraction analysis has been performed. It was shown that ³¹P NMR spectroscopy can be used to assign the stereochemistry of 3‐cyano‐2‐oxo‐1,2‐thiaphosphacyclanes. © 2002 John Wiley & Sons, Inc. Heteroatom Chem 13:1–21, 2002; DOI 10.1002/hc.1101     

Synthesis and biological activity of some 1,3,2-diheteraphosphorinanes and their acyclic analogs

Methods were developed for the synthesis of 2-butylthio-2-oxo-1,3,2-oxazaphosphorinane, 2-butylthio-2-thioxo-1,3,2-dioxaphosphorinane, and 2-butylthio-2-thioxo-1,3,2-diazaphosphorinane, as well as of acyclicS-butylO-ethyl (diethylamido)phosphorothioates and-dithioates andS-butyl bis(diethylamido)phosphorodithioate. These compounds can serve as models of possible metabolites of cyclic compounds. Based on the data obtained in studies of the antiesterase activity of the resulting compounds and their synergistic activity in mixtures with permethrine, a possible mechanism ofin vitro andin vivo biological action of diheteraphosphorinanes was proposed.