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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.

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.

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.

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 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.

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.

It has been established that S,S-dialkyltrimethylsilyldithiophosphites react with acyl halides in two directions, depending on the nature of the halogen in the acyl halide and on the reaction conditions, thus giving as the main reaction products either dialkyldithiohalophosphites or dialkyldithioacylphosphonates. The latter compounds react with acyl halides in accordance with a retro-Arbuzov reaction scheme, giving dialkyldithiohalophosphites.

Reactions of phenyl isothiocyanato(di)chloro-methyl(thio)phosphonates (1) with thiols in the presence of a base give rise to 2-alkylthio-4,5-dihydro-4-oxo(thioxo)-4-phenoxy-1,3,4-thiazaphospholes (5). Some of these compounds can also be obtained by alkylation of 2,4-dithioxo-4-phenoxy-1,3,4-thiazaphospholidine (4), which is formed in the reaction of phenyl isothiocyanatochloromethylthiophosphonate (1a) with sodium hydrosulfide. The interaction of 1a with H2Se and triethylamine results in the formation of 2,4-dithioxo-4-phenoxy-1,3,4-selenazaphospholidine (8), which when alkylated affords 2-alkylthio-4,5-dihydro-4-phenoxy-4-thioxo-1,3,4-selenazaphospholes (9) Diisothiocyanatodichloromethyl(thio)-phosphonates (11) react with α-toluenethiol in the presence of a base, giving rise to 3,7-bis(benzylthio)-1-oxo(thioxo)bicyclo[3.3.0]-4,6-dithia-2,8-diaza-1-phosphocta-2, 7-dienes (13). By the interaction of phenyl isothiocyanatotrichlorome-thylthiophosphonate (14) with ethanethiol and Et3N, S-ethyl-N-(O-phenyl(trichloromethyl)thiophosphonyl)dithiocarbamate triethylammonium salt (15) has been formed. The molecular structures of some P,N,S,Se-containing heterocycles that we have synthesized have been studied by X-ray diffraction.

The compounds O,O-diethyl- and O,O-diisopropyl-S-benzylthiophosphite, 2-benzyl-thio-4,5-benzo-1,3,2-dioxaphospholane, diphenyl-S-benzylthiophosphinite, and S,S-dibenzylphenyldithiophosphonite were obtained. It was found that the thiophosphites enter into isomerization initiated by oxygen in the air; substitution together with isomerization is thereby observed in the case of thioesters of P(III) with the P-C bond. The interaction of thioesters of P(III) with oxygen is inhibited by spin traps.

The reactions of tetraphosphorus trisulfide with thioacetals, aminals, sulfenamides and disulfides were studied. The reactions were found to give organothiophosphorus compounds and to be facilitated by organic amines and benzoyl peroxide.

Sodium salts of 2, 2-dimethyl-4-mercapto-5-oxo-1,3-thiazoline and 2-oxo-3-mercapto-1-thia-4-azaspiro[4.5]dec-3-ene, obtained from a solvate of sodium cyanodithioformate with three molecules of dimethylformamide, acetone, or cyclohexanone in the presence of morpholine, react with chlorothioformic dimethylamide with the formation of 2,2-dimethyl-5-oxo-4-(dimethylaminothiocarbonylthio)-1,3-thiazoline and 2-oxo-3-(dimethylaminothiocarbonylthio)-1-thia-4-azaspiro[4.5]dec-3-ene, respectively, and during acidolysis by hydrochloric acid they are converted to 2,2-dimethyl-5-oxo-4-thiono-1,3-thiazolidine and 2-oxo-3-thiono-1-thia-4-azaspiro[4.5]decane. The latter compounds are facilely phosphorylated by dialkyl chlorophosphonates at the nitrogen atom. The reaction of the solvate of sodium cyanodithioformate with three molecules of dimethylformamide with chloroacetone in the presence of morpho-line occurs anomalously with the formation of cyanothioformic morpholide.

The addition of morpholino-, piperidino-, and N,N-diethyldithiocarbamate anions to 1,2-propadiene- and 1,2-butadienephosphonates proceeds on the electrophilic 1,2-double bond of the allene system with the formation of linear dithioesters. 1-Vinylallenylphosphonates add dithiocarbamate anions on the 1,3-conjugated system of multiple bonds, forming a mixture of stereoisomeric dithioesters with a diene structure.

Dialkyl phosphonates bind to the C=N bond of bis(benzylideneimino)toluene, with formation of dialkyl (benzylideneimino)benzylaminobenzyl phosphonates. The complicated character of IR spectra of these compounds is connected with the possibility of formation of dimeric cyclic associates and intramolecular hydrogen bonding. Phosphinic acid reacts with bis(benzylidenimino)toluene in a 2: 1 ratio to affordN,N′-benzylidenebis(α-amino-benzytphosphonic) acid.

Interaction of ethylN,N-(p-methoxybenzal)-p-aminobenzoate with dialkyl phosphonates results in dialkyl (N-p-ethoxycarbonylphenylamino)-p-methoxybenzal phosphonates. In the resulting compounds hydrogen bonds are observed by IR spectroscopy.

The reaction of dialkyl H-phosphonates with pyridine-3-carbaldehyde gives alkyl (3-pyridyl)hydroxymethylphosphonates. In liquid systems, the hydrogen atom is localized at the oxygen atom of the hydroxyl group; in crystals, the existence of a zwitter-ionic form could not be excluded. In CHCl3 solutions, isolated molecules and cyclic dimeric H-complexes exist in an equilibrium.

The reaction of 2-substituted 4-oxo-5, 6-benzo-1, 3, 2-dioxaphosphorinanes with ethyl pyruvate affords ring-expansion products, i.e., diastereomeric 2-substituted 2, 5-dioxo-6, 7benzo-1, 3, 2-dioxaphosphepanes.

Tris(hexafluoroisopropoxy)-bis(1-halo-2,2,2-trichloroethoxy)phosphoranes were obtained by addition of chloral to tris(hexafluoroisopropoxy)dibromo- and dichlorophosphoranes. The intermediate tris(1,1,1,3,3,3-hexafluoroisopropoxy)-1,2,2,2-tetrachloroethoxychlorophosphorane was also isolated in this reaction.

The reaction of pyrocatechol chlorophosphite with N-trimethylsilylacetamide gave 2-acetamido-4,5-benzo-1,3,2-dioxaphospholane. The reaction of this product with hexamethyldisilazane leads to 2-trimethylsiloxy-4,5-benzo-1,3,2-dioxaphospholane, while its reactions with diethylamine, trimethylsilyldiethylamine, and bis(dimethylamino)methane give 2-dialkylamino-4,5-benzo-1,3,2-dioxaphospholanes.

2,2-Dibromo-2-ethoxy-4,5-benzo-1,3,2-dioxaphospholane (I) adds to chloral with no change in the phosphorus coordination. In contrast to chloral, benzaldehyde is converted to dibromotoluene upon reaction with (I).

The reactions of 2-(N,N-bis(trimethylsilyl)]amino-4,5-benzo-1,3,2-dioxaphospholane with acetic acid, benzoic acid, and acetic anhydride yield 2-trimethylsiloxy-4,5-benzo-1,3,2-dioxaphospholane. Upon reaction with dialkyl phosphites, the silylamido-phosphite acts as a silylating agent.

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.

We previously showed that the reaction of chloro(chloromethyl)dimethylsilane with bis(N-methyl-N-trimethylsilylamido)methylphosphonate is accompanied by separation of 2 equiv of chlorotrimethylsilane and provides 1,2,3,4,4-pentamethyl-1,3-diaza-2-phospha4-silolidin-2-one [1]. With the purpose of investigate the possibility of formation of new silacyclanes on the basis of chloromethyl derivatives of silicon we turned to reaction of N,N -bis(trimethylsilyl)-N-methylN -phenylurea (Ia) and N,N -bis(trimethylsilyl)N-methyl-N -p-chlorophenylurea (Ib) with chloro(chloromethyl)dimethylsilane. Silylated urea Ib was prepared from heptamethyldisilazane and p-chlorophenyl isocyanate.

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.

Acetaldehyde and butyraldehyde azines and 1,2-bis(tert-butylimino)ethane add only one molecule of dialkyl H-phosphonate at room temperature to form alkyl (α-aminoalkyl)phosphonates. IR spectra of compounds obtained are discussed.

The reaction of N-butylisobutyraldimine with trimethyliodosilane obtained in situ proceeds to give N-butyl-N-isobutenylaminotrimethylsilane, which reacts with 4,5-benzo-2-chloro-1,3,2-dioxaphospholane to yield 2-(N-butyl-N-isobutenylamino)-4,5-benzo-1,3,2-dioxaphospholane.

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.

The reactions of S-benzyl diphenylthiophosphinite and 2-benzylthio-4,5-benzo-1,3-dioxaphospholane with methyl iodide have been examined. In contrast to the oxygen analogs, the reaction occurs under mild conditions, and does not give Arbuzov reaction products.

The reactions of S-acetylcyanophosphites with carbonyl compounds proceeds with the formation of the corresponding 1-acetoxycyanothiophosphonates.

The reaction of dialkylsilylphosphites with linear and cyclic secondary amines leads to the formation of acid alkoxydialkylamidophosphites and dialkyl phosphites. Aminolysis of pyrocatecholsilylphosphite was accomplished with retention of the phosphorus atom and formation of the corresponding amidophosphites.

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.