S. A. Terent'eva

Synthesis and Crystal and Molecular Structures of 2-Diethylaminomethyl- and 2-Chloromethyl-2,2'-spirobi[benzo-1,3,2-oxazaphospholines]

Chloromethylphosphonic dichloride reacts with o-aminophenol in the presence of triethylamine to form 2-chloromethyl-1,3,2-benzoxazaphospholine 2-oxide and 2-chloromethyl-2,2-spirodi[1,3,2-benzoxazaphospholine] in a 1 : 1 ratio. 3-Diethylaminomethyl-2-ethoxy-1,3,2-benzoxazaphospholine reacts with o-aminophenol to form 2-diethylaminomethyl-2,2-spirodi[benzo-1,3,2-oxazaphospholine]. The crystal and molecular structures of the synthesized spirophosphoranes were determined by single crystal X-ray diffraction.

Reaction of 2-Ethyl-1,3,2-bezoxaphospholine with Calix[4]resorcinarenes

By reaction of calix[4]resorcinarene with 2-ethyl-1,3,2-benzoxazaphospholine in 1:1 ratio we prepared a cavitand possessing one dioxaphosphocinic fragment on the upper circle of the molecule. Reaction of the same compounds in ether solution in 1:4 and 1:8 ratio according to the data of spectral methods leads initially to formation of addition product, the P-H phosphorane with composition 1:4. This compound is not stable and on keeping forms 2-oxo-2-ethyl-1,3,2-benzoxazaphospholine, spirophosphorane, o-aminophenol and phosphorylated calixarene. In the reaction of the aminoalkylated calixarene with 2-ethyl-1,3,2-benzoxazaphospholine we isolated a compound possessing four hydrophoshonyl fragments on the upper circle of the calixarene matrix.

Reaction of 2-diethylamino-3-diethylaminomethyl-1,3,2-benzoxazaphospholine with hydroxyl-containing compounds

The reaction of 2-diethylamino-3-diethylaminomethyl-1,3,2-benzoxazaphospholine with functionally substituted alcohols and phenols occurs with the cleavage of exocyclic P-N bond followed by N→P migration of the diethylaminomethyl group and formation of imidophosphonate dimers. A similar reaction with polyhydroxy compounds (diethylene glycol, glycerol) results in symmetrical and asymmetrical spirophosphoranes.

Reaction of amidophosphites with acrylic acid N-phenylamide

Mono- and diamides of phosphorus acid react with the arylamides ofα,β-unsaturated carboxylic acids, with involvement of the carbamido group, to give the corresponding mono- or diamido- N,N-alkylarylcarbamoylalkylphosphonates.

Reaction of neutral phosphites with N-phenylamides of acrylic acid

The reaction of neutral phosphites with acrylic acid N-arylamides took place with participation of the carbamide group and led to the formation of dialkyl esters of N,N-alkylarylcarbamoylethyl phosphonic acid.

Development of the Synthesis Methods of Polyheterophosphacyclanes with Endocyclic P-C Bond on the Basis of Functionalized Alkylphosphonates (-Phosphinates)

We developed a new approach to the synthesis of saturated and unsaturated phosphoruselementocontaining heterocycles was developed; we based it on the addition reactions of various proton nucleophiles (amines, silylamines, alcoholes, mercaptanes, aminoalkylphosphonates, phosphines, CH-acides, etc.) to the halogenmethylphosphonylated isocyanates or isothiocyanates. Intermediate compounds of these reactions (phosphorylated ureas, thioureas, urethanes, thiouretanes, acylamides, etc.) are easily transformed into phosphorus containing cyclic structures.

Polyheterophosphacyclanes with Endocyclic P-C Bonds

The methods of synthesizing of polyheterophosphacyclanes based onpolyfunctional organophosphorus compounds with chloromethyl groups and other structural fragments at the central atom were developed.

Studies of Hypervalency at Phosphorus (III) by Conformational “Sonde” Method

Abstract The compounds exhibiting hypervalent interactions of nonbonded atoms may be used as models of prereaction and transition states of nucleophilic substitution reactions. Our studies of the molecules X(CH2)2-O-PCl2 (X ˭ H (1); SCN (2); C2H5 (3); CH3O (4); Cl (5) revealed the possibility of subtle intramolecular 1–5 attractions between the sulfur (2) [I] or the oxygen (4) or the chlorine (5) and the phosphorus atoms. The attractions influenced perceptibly only the energy of the conformers with intramolecular contacts between the heteroatoms. A substantial energetical preference of the convoluted conformers (B) in the liquid state was observed in the case of 2. 4 and 5. In contrast. the molecules 1 and 3 preferred to exist in liquid in extended conformations (A). These dramatic changes cannot be explained by steric reasons or Coulomb attractions, and thus were attributed to hypervalent attractions between the heteroatoms. The relative energies of (A) and (B) conformers were used in quantitative assess...

Synthesis and Properties of Some Derivatives of Chloromethylphosphonic and Bis(Chloromethyl) Phosphinic Acids

Abstract Reactions of chloromethylchlorophosphonates with heptamethyldisilazane(1 : 1 ratio]proceed with the formation of silylamidophosphonates, while with bis(chloromethy1)phosphinate P-N-P compounds were formed.

Reaction of bicyclic amidophosphites with carboxylic acids

ConclusionsWhen bicyclic amidophosphites are reacted with carboxylic acids they undergo protonation and form acid cyclic phosphites.