S. A. Terent’eva

Reaction of dibromoalkanes with silyl phosphites. Synthesis and properties of mono-and diphosphonoalkanes

Reactions of dibromoethane and dibromopropane with silyl phosphites are studied. Mono-and diphosphonoalkanes of various structures were prepared, and their chemical properties were studied.

Spirophosphorane in the reaction of hexamethyltriamidophosphite with bis(salicylal)-1,2-diaminopropane

In order to synthesize a new type of the tetradentate ligands we previously performed the phosphorylation of bis(salicylal)diaminoethane with alkylenechlorophosphites. Unexpectedly, the reaction products were found to be the framwork structures containing the hexacoordinated phosphorus atom [1–3]. In continuation of these studies we examined the reaction of bis(salicylal)-1,2-diaminopropane I with hexamethyltriamidophosphite. The cascade reaction involves the intramolecular transformations that result in the spirocyclic compound II. Since the molecule of this compound contains several chiral centers, and according to the H and P NMR spectra it is formed as a diastereomers mixture in the ratio of 50:50%, we can conclude that the process is stereoselective. One of the diastereomers was isolated in a pure form and its structure was established by the X-ray diffraction analysis. DOI: 10.1134/S1070363213010246

Synthesis of phosphorus-containing polycyclic derivatives by phosphorylation of hydroxyl-containing diimines

On studying phosphorylation of diimine I by cyclic chlorophosphites IIа–IIc it was established that the reaction products are polycyclic derivatives of hexacoordinated phosphorus atom IIIа–IIIc, which involve a transannular nitrogen–phosphorus bond. Their structure was proved by mass-spectrometry, Н, Р and IR spectroscopy, X-ray analysis, and composition by elemental analysis data. Chemical shifts of the phosphorus nuclei for compounds IIIа–IIIc are in the range of –109 to –112 ppm, that is characteristic for hexacoordinated phosphorus nuclei. We believe that primarily the phosphorylation of one of diimine I hydroxyl groups occurs to form phosphate and to release hydrogen chloride. The latter protonates one of imine nitrogen atoms to increase electrophilicity of С=N bond. The following nucleophilic attack of phosphorus P(III) atom on the activated imine-group is accompanied with Р–C bond formation. The reaction accomplished by the cyclization as a result of attack of the second phenol hydroxyl on phosphorus atom, which leads to appearance of two chiral centers in the molecule (in the reaction of DOI: 10.1134/S107036321005035X

Experimental and theoretical investigation of intramolecular transformations of silicon-containing (haloalkyl)phosphorylated ureas and acylamides

Silicon-containing chloromethylphosphorylated ureas undergo transformation involving evolution of chlorotrimethylsilane and formation of 1,3,4-oxazaphospholes. Their analogs, silicon-containing phosphorylated acylamides, transform in another way, viz. by β-cleavage to form the corresponding siloxyphosphonates. Quantum-chemical investigation of thermodynamic characteristics of these processes was carried out.

2-(2-Hydroxyphenyl)imidazolidines and their O-phosphorylated derivatives

Abstract2-(2-Hydroxyaryl)imidazolidines were synthesized by reaction of aromatic carbonyl compounds with N,N′-dialkylethylenediamines. The title compounds were also prepared using the corresponding Schiff bases instead of carbonyl compounds. Phosphorylation of 2-(2-hydroxyphenyl)imidazolidines with phosphoryl and phosphorothioyl chlorides and phosphorochloridites was accomplished. The reaction of O-phosphorylsalicylaldehyde with N,N′-dialkylethylenediamines also afforded 2-(2-hydroxyphenyl)imidazolidines.

Hexacoordinated phosphorus derivatives in the reaction of alkylenechlorophosphites with hydroxylated bisazomethines

We found previously that the reaction of equimolar amounts of hydroxylated bisazomethines with alkylenechlorophosphites in the absence of a base leads to the formation of the hexacoordinated phosphorus derivatives [1, 2]. In addition, the studied reactions were characterized by the high stereoselectivity, which allows obtaining P(VI)-derivatives in an optically pure form, with the phosphorus atom as a stereogenic center [3]. In order to study the limits of applicability of this reaction we involved diimine I derived from the 2-hydroxy-5chloroacetophenone and diaminoethane in the reaction with the hydroxylated alkylenechlorophosphites. DOI: 10.1134/S1070363212070225

Phosphorylation of salicylaldiimines with chiral alkylene chlorophosphites

The reaction of diimine Ia with chlorophosphite II proceeds readily in the methylene chloride medium to afford salt IVa as a mixture of two diastereomers, as follows from the P NMR spectrum of the reaction mixture, which contains two singlet peaks at –114.41 and –115.04 ppm in a 1:1 ratio. Compound IVa contains three chiral centers but is formed only as a mixture of two diastereomers, indicating that the process of cascade cyclization occurs with a high stereoselectivity. Salt IVa loses hydrogen chloride molecule under treating with triethylamine turning into neutral product Va (δР –102.42, –102.85 ppm). In view of the data, we introduced optically pure diimine Ib into the reaction with 2-chloro-4,5-dimethyl-1,3,2-dioxaphospholane III to isolate phosphorus-containing framework structures in optically pure form.

Salt structures in a series of hexacoordinated phosphorus polycyclic derivatives

Recently we synthesized polycyclic framework structures of new type formed via the nitrogen– phosphorus intramolecular coordination bonding [1]. The presence of a secondary amino group connected with the phosphorus atom through a carbon atom (aminoalkylphosphonate analog) determines a possibility to form a salt structure on this basis. Compounds Ia–Id were found to react with dibromoacetic and picric acids in a solvent at room temperature to afford the compounds of salt structure IIa–IId. The chemical shift of the phosphorus atom is observed in the range of –113 to –116 ppm, which is characteristic of the compounds of the hexacoordinated phosphorus atom. DOI: 10.1134/S1070363211020277