M. A. Pudovik

Reactions of P(III) thiobenzyl esters with methyl iodide

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.

Interaction of thioesters of P(III) with oxygen

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.

Phosphorylation of Dialkylaminomethylated Calix[4]-Resorcinarenes with Some P(III) and P(IV) Derivatives

Abstract The phosphorylation of dialkylaminomethylated calix[4]resorcinarenes with P(m)-amides and P(TV)chlorides under various conditions results in the formation of different structures with phosphorus containing fragments fixed on the cavity rim. Hydrophosphoryl compounds based on dialkylaminomethylated calix[4]resorcinarenes have been synthesized and some of their properties investigated.

Reactions of dialkyl phosphonates and phosphonates with bis(benzylideneimino)toluene

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.

Reaction of ethylN,N-(p-methoxybenzal)-p-aminobenzoate with dialkyl phosphonates

AbstactInteraction 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.

Synthesis of phosphorus (silicon, tin)-containing derivatives of mercaptoketenes and some of their properties

Some newS-phosphorylated,S-silylated, andS-stannylated derivatives of α-mercaptoketones were obtained. The reactions of some of these compounds induced by the temperature and by molecular oxygen as well as the phosphorylation of the Si- and Sn-containing derivatives were studied.

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.

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.

On the Reaction of Bis( N -methyl- N -trimethylsilylamido)methylphosphonate with Bis(chloromethyl)chlorophosphinate, Chloromethyldimethylchlorosilane, and Chloral

The interaction of bis(N-methyl-N-trimethylsilylamido)methylphosphonate 1 with bis(chloromethyl)chlorophosphinate results in the formation of N-methyl-N-trimethylsilylbis(chloromethyl)phosphinate. This result may be explained by the decomposition of intermediately formed diphosphorylated methylamine. The reaction of 1 with chloromethyldimethylchlorosilane gives rise to the new type of cyclic product 1,3-diaza-2-phospha-4-silolidine 2.

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.