N. A. Khailova

Reaction of 1,2-borylphosphinoethene with phenyl isothiocyanate and carbodiimides

The reaction of 1-butyl-1-dibutylboryl-2-phenyl-2-diphenylphosphinoethene with phenyl isothiocyanate is a [4 + 2]-cycloadditon that involves the C=N segment of the heterocumulene; it gives 2,2,3-tributyl-6-thioxo-1,4,5,5-tetraphenyl-1-aza-5-phosphine-2-boratacyclohex-3-ene. Similarly products of the reaction of 1,2-borylphosphinoethene with diphenyl- and dicyclohexylcarbodiimides rearrange via the 1,2-B → anionotropic C shift of the butyl fragment; the products are the respective 1,6,6-tributyl-3-imino-4,4,5-triphenyl-2-aza-4-phosphine-1-bora-tabicyclo[3.1.0]hexanes.

The Interaction of Bis(chloromethyl) isocyanatophosphinate with Chiral α-Aminoalkylphosphonates: Stereoselective Synthesis of 2,4-Dioxo-5-phenyl-1-phenylethylamino-4-phenoxy-1,3,4-diazaphospholidine

O,O-Diphenyl-(α -phenylethylamino)benzylphosphonate 6 was synthesized in racemic and enantiopure forms. Its interaction with bis(chloromethyl)isocyanatophosphinate 7 results in the formation of 2,4-dioxo-5-phenyl-1-phenylethylamino-4-phenoxy-1,3,4-diazaphospholidine 10 .

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.

Synthesis and structure of 1,3,4-oxaza(thiaza)phospholines

Bis(chloromethyl)phosphinic (-phosphinothioic) iso(thio)cyanates add secondary amines to form N-phosphorylated (thio)ureas, which cyclize in the presence of a base to 1,3,4λ5-oxaza(thiaza)phospholines. Phosphorylated ureas obtained by addition of ammonia and primary amines to chloromethylphosphonic (-phosphinic) isocyanates cyclize to give 1,4,2-diazaphospholidines or 1,3,4-oxazaphospholines. Prototropic transformations in the series of 1,3,4λ5-oxazaphospholines were revealed; the electronic and steric structures of the tautomers were studied. Chloromethylphosphonothioic (-phosphinothioic) isothiocyanates add primary amines to give 1,3,4λ5-thiazaphospholines.

Synthesis of 1,3,4-oxazaphospholines based on phosphorylated carbamates

Addition of alcohols to bis(chloromethyl)phosphinoyl isocyanate, as well as the reaction of bis(chloromethyl)phosphinoyl chloride with urethanes or their silylated derivatives, gave the corresponding phosphorylated carbamates which undergo cyclization into 1,3,4-oxazaphospholines under the action of Et3N.

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.

Reaction of (chloromethyl)phosphonic(-phosphinic) iso(thio)cyanates with alcohols and (α-hydroxyalkyl)phosphonates

Alcohols and α-hydroxyphosphonates undergo the addition to (chloromethyl)phosphonic(-phosphinic) iso(thio)cyanates, yielding phosphorylated (thio)urethanes. The latter undergo cyclization to form, depending on their structure, saturated or unsaturated five-membered P,N,O,S-containing heterocycles.

Synthesis of substituted 1-thia-3-aza-λ5-phosphacyclohex-2-ene

The addition of dimethylamine to O-phenyl 2-chloropropylisothiocyanatophosphonate afforded the six-membered cyclic product, viz., 1-thia-3-aza-4λ5-phosphacyclohex-2-ene.

Phosphorylation of Ethyl Urethane, Urea, and Acetamide with Bis(chloromethyl)phosphinic Chloride in the Presence of Potassium Carbonate

Bis(chloromethyl)phosphinic chloride reacts with urethane to give phosphorylated urethane, whereas with urea and acetamide the final reaction product is bis(chloromethyl)phosphinic anhydride.

Synthesis of Azaphosphacyclanes on the Basis of Reactions of α-Aminoalkylphosphonates with Bis(chloromethyl)isocyanatophosphinate

Phosphorylated ureas 3, obtained as the result of addition of aminoalkylphosphonates 1 to bis(chloromethyl)isocyanatophosphinate 2 may be cyclized in two ways: a) with the elimination of phenol molecule and formation of diazaphospholidine 4; the latter under the action of phenol molecule is converted into diazaphospholidine 5; and b) in the presence of a base intramolecular alkylation of oxygen(sulfur) atoms of (thio)carbonyl fragmen by chloromethyl group takes place with the formation of 1,3,4-(thiaza)oxazaphosphol-2-ines 6.