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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.

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.

Addition of phosphoric (phosphonic) acids amides to chloromethyliso(thio)cyanatophosphonates (-phosphinates) gave rise to diphosphorylated ureas or thioureas that under effect of bases underwent cyclization into 1,3,4-oxaza(thiaza)phospholines.

New 1,3,2-thiazaphospholines were prepared, and their steric and electronic structures were examined. The steric and electronic structure of N-[(O-methyl)chloromethylthiophosphoryl]thiourea and the pathways of their intramolecular cyclization and rearrangement were studied by ab initio and semiempirical methods. The influence exerted by the conformational factors in thiourea and in the anion formed from it under the conditions of base catalysis on the direction of the reactions involving these species was revealed, and the structure of intermediate complexes and the final products was determined.

(Chloromethyl)isocyanatophosphonates(-phosphinates) take up phenol to form carbamates whose β-cleavage gives rise to phenyl (chloromethyl)phosphonates(-phosphinates). (Chloromethyl)(thio)phosphinic-(phosphonic) isothiocyanates react with phenol at 20°C in the absence of catalyst to afford phenyl phosphinates(-phosphonates). (Alkylsulfanyl)carbamates formed by addition of thiols to (chloromethyl)iso(thio)cyanastophosphonates(-phosphinates) under the action of an equimolar amount of triethylamine undergo cyclization into 1,3,4-oxaza(thiaza)phospholines.

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

The stability of phosphorylated ureas and thioureas containing various substituents at the P and N atoms and the stability of their cyclization products, the corresponding diazaphospholidines and/or oxaza(thiaza)phospholines, was evaluated by PM3, MNDO, and DFT calculations. The thermal effects of cyclizations involving phosphorylated ureas (or thioureas) and of separate steps of their synthesis were calculated. According to the calculations, diazaphospholidine structures are preferably formed from substituted ureas and thiazaphospholine structures, from their thio analogs; formation of five-membered heterorings with the P-N bond is thermodynamically preferable as compared to their six-membered analogs.

Phenyl α-aminoalkylphosphonates add to phenyl iso(thio)cyanates to give saturated heterocycles, 1,3,4-diazaphospholidin-2-(thi)ones. The reaction of diphenyl (α-methylamino)benzylphosphonate with diethyl isothiocyanatophosphate involves initial formation of 1,3,4-tiazaphospholidine-2-thiones containing exo- and endocyclic phosphorus atoms. These products are readily hydrolyzed in air, yielding diethyl isothio- cyanatophosphate and phenyl hydrogen (α-methylamino)benzylphosphonate. The final products of the reaction of chloromethyl isocyanatophosphonates with aminoalkylphosphonates are 1,3,4-oxazaphospholines. Phenyl aminoalkylphosphonates react with chloromethyl isocyanatophosphonates to give saturated heterocycles, 1,3,4-diazaphospholidines, whereas with chloromethyl isothiocyanatophosphonates 1,3,4-thiazaphospholines are formed.

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.

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 nucleophil...

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

Both enantiomers of the major diastereomer of 2-(1-­phenyl)ethylamino-4-thioxo-4-phenoxy-1,3,4-thiazaphosphol-2-ine were obtained in optically pure form by the reaction of O-­phenyl(chloromethyl)isothiophosphonate with (R)-(+)- and (S)-(-)-(1-phenyl)ethylamine.

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.

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.

Alkyl chlorides and 6-alkoxy-2,4-bis(diethylamino)-6-oxo-1,3,4,2,6-oxathiazadiphosphorines are the products of the reaction of tetraethyldiamidochlorophosphite with dialkylisothiocyanatophosphates. The structure of the oxathiazadiphosphorines was demonstrated by IR,1H,13C,31P NMR, and mass spectroscopy and it was found that they are formed as a mixture of two geometric isomers.

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.

Recently we showed that diphenyl (α-methylamino) benzylphosphonate easily added to phenyl isocyanate or phenyl isothiocyanate in the presence of a catalytic amount of triethylamine affording N,N'-substituted (thio)ureas; cyclization of the latter led to the formation of 1,3,4-diazaphospholidines [1]. Now we studied reaction of bis(chloromethyl)isocyanatophosphinate (I) with optically active diphenyl(α-methylamino)benzylphosphonate (II). Noteworthy that the formation of the latter compound was registered recently in the reaction of catalytic addition of diphenyl hydrogen phosphite to the optically active (S)-(–)-benzal(1-phenyl)ethylamine (catalyst BF3) by Р NMR spectroscopy as a mixture of stereoisomers which was not separated [2]. We obtained optically active aminophosphonate II in the same reaction using sodium phenolate as a catalyst: DOI: 10.1134/S1070363208120190

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.

The reactions ofO-phenyl chloromethylphosphonochloridate and bis(chloromethyl)phosphinous chloride with sodium acetate afford the corresponding acyloxyphosphonates and acyloxyphosphinates, which are readily transformed due to disproportionation into pyrophosphonates and pyrophosphinates.

The product of the reaction of 0-phenylisothiocyanatodichloromethylthiophosphonate with diethylamine in the presence of Et3N is 4,5-dihydro-2-diethyl-amino-4-thioxo-4-phenoxy-5-chloro-1,3,4-thiazaphosphole. 3,7-Bis(diisopropyl-amino)-1-thioxobicyclo-[3.3.0]-4,6-dithia-2,8-diaza-1-phosphaocta-2,7-diene was obtained as the result of the reaction of diisothiocyanatodichloromethylthiophosphonate with diisopropylamine and triethylamine. IR, PMR, and31P NMR spectroscopy was used to demonstrate the structures of the products synthesized.

1. The assignment of the bands and the lines in the vibrational (IR, Raman) spectra of vinyldichlorophosphine oxide (VDCPO) was refined by normal-coordinate analysis. 2. The conformational nonuniformity of VDCPO was established on the basis of an analysis of the dependence of the spectra on the phase state, the temperature, the polarity of the solvent, and the concentration of the solutions. In the liquid and in the gas VDCPO exists in an equilibrium between two forms, of which at least one is unsymmetrical. In the more stable and less polar conformer (which remains in the crystal) the C=C and P=0 double bond are close to eclipsing, while in the other they are opened up. 3. In addition to the conformational nonuniformity, the signs of intermolecular effects appear in the spectra of the liquid and the solutions.