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

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.

A 31P NMR study show that diisopropyl phosphite and benzalaniline do not react with each other as individual components. Adduct formation is made possible by partial hydrolysis of the dialkyl phosphite.

The structure of a great number of methylenephosphine oxides 1-11 and cyanophosphines and their oxides 12-18 was studied by semiempirical PM3 and ab initio RHF/6-31G** calculations. Obtained results are in good agreement with experimental data (dipole moments, Kerr effect, IR spectroscopy). In 12-18 the contribution of interactions of CN group or Ph ring with lone pair of electrons (LPE) of the P atom, d-orbitals of the P atom, or P=O group is absent.

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.

For a series of phenyl-substituted N-isopropylbenzalimines, the effect of substituent on their capability to add dimethyl hydrogen phosphite was studied qualitatively in the condensed phase (DTA) and quantitatively (with determination of the kinetic and activation parameters) in 2-propanol solutions with spectrophotometric monitoring of the reaction. A reaction mechanism was proposed, involving formation of a highly organized four-membered transition state.

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.

Trichloro(o-phenylenedioxy)phosphorane reacts with 1,2-alkadienylphosphonates with selective replacement of the alkoxy group in the phosphinoyl moiety, yielding the corresponding 1,2-alkadienylchloro- phosphonates and o-phenylene chlorophosphate.

Bis(chloromethyl)phosphinic chloride reacts with trimethylsilyl methylcarbamate in benzene in the presence of a base to give trimethylsilyl bis(chloromethyl)phosphinate. The same reaction performed without a solvent and in the absence of a base yields trimethylsilyl bis(chloromethyl)phosphinate and bis(chloromethyl)phosphinic anhydride. Reaction of bis(chloromethyl)phosphinic chloride with trimethylsilyl diethylcarbamate yields N,N-diethylbis(chloromethyl)phosphinic amide. The reaction of bis(chloromethyl)phosphinic (-phosphinothioic) chlorides with trimethylsilyl N-trimethylsilylacetimidoate was studied.

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.

Reaction of equimolar amounts of (bromomethyl)phosphonic dichloride and phenol gives phenyl (bromomethyl)chlorophosphonate. Its reactions with heptamethyldisilazane, N,O-bis(trimethylsilyl)acetamide, and potassium thiocyanate, leading respectively to a silylamidophosphonate, a silyl phosphonate, and an isothiocyanatophosphonate, were studied. (Bromomethyl)(chloromethyl)phosphinoyl isocyanate was synthesized. Chemical properties of the prepared functionalyzed (bromomethyl)phosphonates were investigated.

The reactions of homologues of Davy's reagent 1 and Lawesson's reagent 9 with trimethylalkylthiosilanes 2, trimethylsilyl enol ether 4, trimethyl(diethylamino)silane 7, trialkylalkoxystannanes 14, and trialkylalkylthiostannane 15 were studied. On the basis of these studies, novel advantageous methods of synthesizing S-trialkylsilyl and stannyl esters of tetrathio-, trithio-, and amidotrithiophosphoric acids 3, 5, 6, and 4-methoxyphenyldithio- and trithiophosphonic acids 10–13 were developed

The phosphorylation reactions of the oxygen- and nitrogen-containing halocyclenes--3,4-dichloro-5-hydroxyfuranone, 3,4-dichloro-5-substi- tuted pyrrolinon-2-ones and N-phenyl-4,5 dichloropyridazin-2-one by † 3 -phosphorus compounds--trialkylphoshphites, triphenylphosphine, and some P-functionalized derivatives of the trivalent phosphorus are studied. The reactions' mechanisms are discussed; the possible and preferable reactions' routes and the relative thermodynamic stabilities of the products and intermediates are estimated via the quantum-chemical methods.

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.

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.

The reactions of tetraphosphorus decasulfide and 2,4-bis(4-alkylthio)-2,4-dithioxo-1,3,2λ5, 4λ5-dithiadiphosphetanes with disulfides and thioacetals were studied. The reactions were found to give some novel organothiophosphorus compounds.

S-Trialkylstannyl dialkyldithiophosphates 3 and tetrathiophosphates 6 were easily obtained in the reaction of tetraphosphorus decasulfide 1 with trialkylalkoxystannanes 2 or alkylthiostannanes 5 under mild conditions. Tetraphosphorus decasulfide 1 and hexaalkyl distannylsulfides 4 produce tris(trialkylstannyl) tetrathiophosphates 9.

S-Trimethylsilyl esters of dithio-and tetrathiophosphoric acids were obtained in the reaction of tetraphosphorus decasulfide with alkoxy-and alkylthiotrimethylsilanes, trimethylsilyl enol ethers and bis(trimethylsiloxy)alkylenes and phenylene.

N,N'-Dimethyl-N,N'-bis(trimethylsilyl)methylphosphonic diamide reacts with chloral to form 1,2,3-trimethyl-4,4-dichloro-5-trimethylsiloxy-1,3,2-diazaphospholidine 2-oxide and with chloromethyldi- methylchlorosilane to form 1,2,3,4,4-pentamethyl-1,3-diaza-2-phospha-4-silacyclopentane 2-oxide.

The progress attained in the field of onecoordinated phosphorus compounds was summerised recently in review (Usp. Chim., 1985, v. 54, p. 418). Formerly we have been analysed (Izv.Akad.Nauk USSR, Ser.chim., 1984, p. 415) the polarity of P°C triple bond in phosphaalkynes on the grounds of literary date on dipole moments defined by microwave spectroscopy. In this work the dipole moment of 3,3-dimethyl-1-phosphabutyne (I) was determined in cyclohexane solution:μ exp.=1,24±0,05D, α=1,250, γ=0,078, Po=31,876 cm3. Analysis of all known up to date experimental date on polarity of phosphaalkynes brings us to the conclusion about small polarity of P°C triple bond and slight sensitivity of this value (0,7±0,2D towards carbon atom) to vareing of substituent at Csp-atom. We can only note slight tendency of the increasing m(P≡C) in the phosphaalkynes RC=P (R=H, CH3, F, CH=CH2, CN, tBu) with the growth of -I - effect of substituent R.

Dialkyl trimethylsilyl dithiophosphites react with sulfenamides either through involvement of the trimethylsilyl group and the formation of trialkyl trithiophosphates or by isomerization of the starting silylphosphites to give S-alkyl O-trimethylsilyl alkyldithiophosphonates. The direction of the reaction depends on the nature of the substituents at the sulfur atoms of the silylphosphite and sulfenamide.

It was found that dibromo-2,2,3,3-tetrafluoropropoxydifluorophosphorane, obtained from 2,2,3,3-tetrafluoropropyl difluorophosphite and bromine, adds two moles of chloral or bromal with the formation of stable 2,2,3,3-tetrafluoropropoxybis(1-bromo-2,2,2-trihaloethoxy)difluorophosphoranes, the structure of which was confirmed by NMR data.