Anatoly D. Sinitsa

Peculiarities of structure and properties of phosphorus-containing cations with two intramolecular donor-acceptor bonds N→P. Synthesis of the first 5-coordinated P-cation with PN bond

cations 1a,b display dual reactivity, and they interact both with electrophilic and nucleophilic reagents. Reaction with chloramine B or benzenesulphonylazide leads to the formation of first representative of 5-coordinated P-cations with PN bond.

P…N Interaction and its Effect on the Structure and Properties of Phosphorylated α-Aminoketones Derivatives

Abstract Reactions of α-aminoketones with P-chlorides in a basic medium are reported. Methods for the synthesis of Δ4-1,3,2-oxazahospholines and s-amino of phosphorus from N to O and enamin-imine isomerization are discussed for the phosphorylated aminoketones. Nucleophylic and electrophylic reactivity of cationes XV and XVI was studied.

Boron trifluoride etherate - an effective catalyst of 1,3-Phosphorotropic migration in CNC triad

A facile BF3·Et2O promoted 1,3-transfer of a diphenylphosphinoyl group in a 2-azaallylic system has been found. The isomerization was shown to proceed by an intramolecular mechanism in the complex formed with participation of a phosphorylated imine PO group.

PHOSPHORYLATED 2-AZAALLYLIC SYSTEMS. SYNTHESIS, PROPERTIES, AND REARRANGEMENTS

Abstract The methods for synthesis of mono- and bisphosphorylated 2-azaallylic compounds were developed. The relevant proto- and phosphorotropic rearrangements in the C=N-C triad were studied.

Phosphorylation of Imino Analogs of α -Halocarbonyl Compounds

Phosphorylation of the α-haloimines leads mainly to C- or N-phosphorylated compounds as the final products, and selectivity being dependent on the type of halogen, substituents at the imine carbon and nitrogen atoms, and on the nature of phosphorus regeant. Variety of transformations is connected with rearrangements accompanied by umpolung of C- and N-center of imine function, possible participation of C═N bond, halogen atoms or N-substituents, in ractions involving the Hal-C─C═N skeleton.

α—Iminotrifluoroethyl Phosphonates: The First Representatives of C-Phosphorylated N-H Imines

A convenient synthetic approach for previously unknown N-H imidoylphosphonates, based on addition of dialkyl phospites to trifluoroacetonitrile, was developed. Synthetic potentialities of imines 1 existing as equilibrium mixture of E/Z isomers, were demonstrated.

FORMATION OF PHOSPHORUS-CONTAINING SPIRO CATIONS, STABILIZED BY THREE-CENTERED N → P ← N BOND, IN THE SERIES OF PHOSPHORYLATED α-AMINOKETONES

Abstract Spiro cation stabilized by three-centered bond N → P ← N, is formed in the reaction of phosphorus trichloride with two molecules of t-BuCOCH2NMe2. According to X-ray analysis data, the structure of the compound obtained is close to a trigonal bipyramid with nitrogen atoms in axial positions (P-N 2.05 A), and two oxygen atoms and lone electron pair of phosphorus in equatorial positions.

CCDC 1444368: Experimental Crystal Structure Determination

Related Article: Alexander A. Shalimov , Tetyana I. Chudakova, Yurii G. Vlasenko, Anatoly D. Sinitsa, Petro P. Onys’ko|2016|Chemistry of Heterocyclic Compounds|52|267|doi:10.1007/s10593-016-1873-z

CCDC 1444371: Experimental Crystal Structure Determination

Related Article: Alexander A. Shalimov , Tetyana I. Chudakova, Yurii G. Vlasenko, Anatoly D. Sinitsa, Petro P. Onys’ko|2016|Chemistry of Heterocyclic Compounds|52|267|doi:10.1007/s10593-016-1873-z

Heterocyclization of N-(chlorosulfonyl)imidoyl chlorides with anilines, a new method of synthesis of 1,2,4-benzothiadiazine 1,1-dioxides

N-(Chlorosulfonyl)imidoyl chlorides react regioselectively with anilines, 2-aminomethylnaphthaline, or 1,2,3,4-tetrahydroquinoline leading to derivatives of 1,2,4-benzothiadiazine 1,1-dioxide. Heterocyclization occurs at the sterically less hindered C-6 atom in the case of 3-methoxy- and 3,4-dimethoxyaniline, while the reaction with 3-methylaniline leads to a mixture of cyclization products at the C-2 and C-6 atoms of aniline.