Methyl Trifluoropyruvate Diethoxyphosphorylimine

The first example of trifluoropyruvate phosphorylimines was prepared, and its capability for O- and S-amidoalkylation of water, alcohols, and compounds with the SH function was shown. Phenol and 4-methoxyphenol are O-alkylated, while 3-dimethylaminophenol and indole undergo regiospecific C-alkylation at the site of the highest -electron density.     

Sigmatropic isomerizations in azaallyl systems: XX. <Emphasis Type="Italic">N</Emphasis>-Alkylbenzimidoylphosphonates

Synthetic approaches are developed to benzimidoylphosphoryl derivatives containing electronically and sterically diverse alkyl substituents on the nitrogen atom, as well as their prototropic isomers. Regularities in prototropic transitions in the phosphorylated C=N-C triad were revealed and applied in the synthesis of -aminophosphonic acid derivatives.Translated from Zhurnal Obshchei Khimii, Vol. 74, No. 9, 2004, pp. 1447–1455.Original Russian Text Copyright © 2004 by Onysko, Kim, Rassukanaya, Kiseleva, Sinitsa.For communication XIX, see [1].This revised version was published online in April 2005 with a corrected cover date.     

N-sulfonyl-and N-phosphorylbenzimidoylphosphonates

A procedure for preparing N-sulfonyl-and N-phosphorylbenzimidoylphosphonates by oxidation of the corresponding α-(sulfonylamino)-and α-(phosphorylamino)benzylphosphonates was developed. The σ constants of imidoylphosphonate groups were evaluated by ¹⁹F NMR spectroscopy, and specific features of their electronic effects were considered. The reactions of the imidoylphosphonates obtained with O-, S-, P-, and N-nucleophiles were studied. The phosphonate-phosphoramidate rearrangement of α-aminobenzylidene-bisphosphonates was found.     

Reaction of N-(Trichloroacetyl)trichloroacetimidoyl Chloride with Phosphites

N-(Trichloroacetyl)trichloroacetylimidoyl chloride reacts with trialkyl phosphites with substitution of the imidoyl chlorine atom and formation of C-phosphorylated heterodienes. The reaction with triphenyl phosphite or o-phenylene diethylphosphoroamidite proceeds as [4+1]-cycloaddition to give mono- or spirocyclic oxazaphospholines with the five-coordinate phosphorus atom. Dialkyl or diphenyl hydrogen phosphites add across the C = N bond of imidoyl chloride to give labile N-(-phosphorylated) trichloroacetamides.     

N-aryltrifluoroacetimidoylphosphonates

By reaction of N-aryltrifluoroacetimidoyl chlorides with trialkyl phosphites the corresponding N-aryltrifluoroacetimidoylphosphonates CF₃C(=NAr)P(O)(OR)₂ existing as dynamic equilibrium mixture of Z,Eisomers [Z/E ～ (7–12):1] were prepared. By ¹⁹F NMR spectroscopy kinetic and activation parameters of Z-E isomerization were evaluated. Reaction of imidoylphosphonates with O-or S-centered nucleophiles leads to the products of addition to C=N bond whereas cycloaddition with of nitrile oxide gives previously unknown phosphorylated oxadiazolines.     

α-Hydroxy- and (α-acyloxyimino)benzylphosphonates

N-Hydroxyfluorobenzimidoylphosphonates and their O-acyl derivatives are synthesized. Reaction of phosphorylated oximes with sulfinyl chloride proceeds with rearrangement and leads to synthetically prospective N-sulfonylimidoylphosphonates. By the method of ¹⁹F NMR are revealed values of σ-constants of N-hydroxy- and N-acyloxy substituted imidoylphosphonate groups.     

Reactions of <Emphasis Type="Italic">N</Emphasis>-aroxycarbonyltrichloroacetimidates with nucleophilic phosphorus derivatives

Aryl N-aroxycarbonyltrichloroacetimidates (Ar = Ph, 4-FC₆H₄) react with diphenylphosphinite according to the scheme of the aza-Perkow reaction to give the corresponding aryl N-(1-aroxy-2,2-dichloro-vinyl)-N-diphenylphosphinoylcarbamates. The structure of one of these compounds was confirmed by single crystal X-ray diffraction analysis. In the case of electron-accepting substituents (Ar = 4-O₂N₆H₄), the primary product undergoes mild -elimination to give nitrophenyl diphenylphosphinate and 1-nitrophenoxy-2,2-dichlorovinyl isocyanate. The reaction of trichloroacetimidates with triethyl phosphite yields a mixture of O- and N-phosphorylation products.Translated from Zhurnal Obshchei Khimii, Vol. 74, No. 11, 2004, pp. 1797–1803.Original Russian Text Copyright © 2004 by Rassukanaya, Onysko, Sinitsa, Bolbut, Chernega.This revised version was published online in April 2005 with a corrected cover date.     

Trichloropyruvate N-acylimines. Reactions with phosphorus nucleophiles

Reactions of N-aroyltrichloroethaneimines CCl₃C(R)=NCOAr (II, R = COOMe, CN) with phosphorus nucleophiles were studied. The reaction of imines II with o-phenylenediethylamidophosphite proceeded as [4+1]-cycloaddition leading to formation of stable spirocyclic phosphoranes. The structure of one of them was proved by the XRD analysis. The reaction of imine II with acyclic P(III) derivatives [Ph₃P, Ph₂POEt, (PhO)₃P] also includes the formation of labile monocyclic phosphoranes which eliminate phosphine oxide and undergo chlorotropic transfer leading to trichloroazadienes CCl₂=C(R)N=C(Cl)Ar. The reaction of imines II with (EtO)₂POH in the presence of triethylamine leads to the formation of (EtO)₂P(O)Cl and the corresponding dichlorovinylamides CCl₂=C(R)NHCOAr.