N. G. Khusainova

Reactions of Allenylphosphonates with 2-Aminoethanol and Amines

Dialkyl 3-methyl-1,2-butadienylphosphonates take up 2-aminoethanol, butylamine, diethylamine, and morpholine in such a way that the amino nitrogen atom adds at the central carbon of the allene triad. The reactions with primary amines lead to the corresponding 1-phosphoryl-2-amino-1-butenes and isomeric 1-phosphoryl-2-iminobutanes, while secondary amines give rise to 1,2- and 2,3-enamines.

THE REACTIONS OF ALLENIC PHOSPHONYL DICHLORIDES WITH SULFENYL CHLORIDES

Abstract The structure of the product of the interaction of dichlorides of allenylphosphonic acids with sulfenyl chlorides depends on the nature of sulfenyl chlorides and substituents at the terminal carbon atom of allenic system. Arylsulfenyl chlorides and dichlorides of γ,γ-dialkylsubstituted allenylphosphonic acids form diene products. Phosphonesulfenyl chloride acts as chlorinating agent to form 4-chlorooxaphospholenes. The dichloride of propadienephosphonic acid reacts with phenylsulfenyl chloride yielding the addition product.

Reactions of allenyl- and vinylphosphonates with imidazole

Dialkyl 3-methylbuta-1,2-dienyl- and vinylphosphonates take up imidazole at the β-carbon atom in the unsaturated fragment to give the corresponding β-(1H-imidazol-1-yl)alkenyl-and alkylphosphonates.

Interaction of Vinylphosphonates with 1,2-Diaminoethane and Ethanolamine

The reaction of 1,2-diaminoethane with vinylphosphonate occurs as the addition of the amino group to the β -carbon atom of the unsaturated substrate to give 1:1 and 1:2 adducts. The nucleophilic addition of 2-aminoethanol at the β -position of the double bond of vinylphosphonates involves only the amino group and leads to the formation of hydroxy β -aminoethylphosphonates or zwitterions depending on conditions.

Synthesis of Novel Bis(aminoalkenylphosphonates) as Potential Bioactive Compounds

Abstract Mixing an excess of 3-methyl-1,2-butadienylphosphonate with 1,2-diaminoethane, 1,2-diaminopropane, or 4,7,10-trioxa-1,13-tridecandiamine leads to the formation of bis-(aminoalkenylphosphonates).

Synthesis and acid-base properties of new β-diaminophosphoryl compounds

The stable interest to development of preparation methods of new aminophosphoryl compounds is due to the wide range of their practical applications as biologically active compounds, complexing agents, membrane transport mediators. The most completely examined are the acid-base and membrane transport properties of α-aminophosphoryl derivatives, in particular, of α-bisphosphoryldiamines [1], α,ω-diphosphorylated azapodands [2], and some β-aminophosphonates [3, 4].

Reaction of 3-methylbuta-1,2-dien-1-ylphosphonates with benzimidazole and 2-aminobenzimidazole

We previously showed that reactions of allenyland vinylphosphonates with imidazole involve addition of the imidazole nitrogen atom to the β-carbon atom of the unsaturated substrate with formation of alkenyland alkylphosphonates functionalized with nitrogencontaining pharmacophoric fragment [1]. The addition products were found to exhibit a strong bactericidal activity against such pathogenic microorganisms as Escherichia coli, Staphylococcus aureus, and Pseudomonas aeruginosa. While continuing studies in this line we examined the reaction of diethyl and diisopropyl 3-methylbuta1,2-dien-1-ylphosphonates with benzimidazole and 2-aminobenzimidazole with a view to obtaining new biologically active compounds. An equimolar mixture of diethyl 3-methylbuta-1,2-dien-1-ylphosphonate and benzimidazole was heated for 15 h at 70–75°C, and the upper oily layer was separated and repeatedly washed with hexane until constant nD value. We thus isolated compound 1 as a yellow thick oily material. The minor bottom layer was washed in succession with hexane and diethyl ether to isolate unreacted benzimidazole as colorless crystals with mp 169–170°C (published data [2]: mp 171–173°C). The P NMR spectrum of 1 contained only one signal at δP 24.6 ppm, indicating formation of a single addition product. The following signals were observed in the H NMR spectrum of 1, δ, ppm: 1.07 t (3H, CH3CH2O, JHH = 6.9 Hz), 1.31 t (3H, CH3CH2O, JHH = 7.0 Hz), 1.49 d (3H, CH3C=, JPH = 6.0 Hz), 2.00 d (3H, CH3C=, JPH = 4.5 Hz), 2.98 d.d (1H, PCH2, JPH = 20.7, JHH = 15.7 Hz), 3.18 d.d (1H, PCH2, JPH = 20.7, JHH = 15.7 Hz), 3.98 m (4H, OCH2), 7.30–7.98 m (4H, Harom). The presence in the H NMR spectrum of doublets of doublets at δ 2.98 and 3.18 ppm with a H–P coupling constant JPH of 20.7 Hz, which are typical of methylene group attached to phosphorus, indicated that the benzimidazole nitrogen atom added to the β-carbon atom of 3-methylbuta-1,2-dienylphosphonate with formation of diethyl 2-(1H-benzimidazol-1-yl)-3methylbut-2-en-1-ylphosphonate (1). Yield 67%, nD = 1.5292. Found, %: C 60.01; H 6.97. C16H23N2O3P. Calculated, %: C 59.62; H 7.14. Theoretically possible isomerization of adduct 1 into diethyl 2-(1H-benz-

Theoretical investigation of interaction of hydrogen dithiophosphate with 2-phenyl-2H-1,2,3-diazaphosphole

We showed previously that the cyclic two-coordinate phosphorus derivative—5-methyl-2-acetyl(phenyl)-2H-1,2,3-diazaphosphole— takes up O,O′-dialkyl hydrogen phosphorothioand dithioates across the σ 2λ3P C bond; the anionic moiety of the thio and dithio acid was directed toward the two-coordinate phosphorus atom.1 In the 31P NMR spectra of the resulting 3-(dialkoxyphosphinoyldithio)-2-phenyl1,2,3-diazaphospholines 1 the chemical shifts of the three and four— coordinate phosphorus atoms were equivalent owing to intramolecular interaction of the P(III) atom with the thione sulfur atom in the adduct. As a continuation of these studies, the electron and molecular structure of adduct of hydrogen dimethyl dithiophosphate with 2phenyl-5methyl-2H-1,2,3-diazaphosphole, containing P C bond, have been studied by the methods of quantum chemical calculations (MNDO, PM3, ab initio) with the usage of the photoelectron spectrosopy. It has been shown, that the equality of the shifts of P(III) and P (IV) in 31P NMR spectra of the adduct 1 probably takes place in the results of the real of the structure with nearly equal lengths of four P S bonds.

Functionalization of Cyclic Derivatives of Two-Coordinated Phosphorus

The phosphorus containing heterocycles are of interest as bioactive substances with the various properties. We have studied of the interaction of the cyclic derivatives of the two-coordinated phosphorus, containing P C bond—2H-1,2,3-diazaphospholes—with hydrogen thioand dithiophosphates, dialkylphosphone sulfenylchlorides, and silyldithiophosphates. It is found, that the direction and the pathway of the processes of the Pand C-functionalization of diazaphospholes depend on the nature of the element at the thiolic sulfur atom of the phosphates (RO)2P(X)SR (X O, S; R H, Cl, SiMe3). The interaction of the 3-ethoxy-1,2,3-diazaphospholene 2 with α-halogen-methylenephosphonate proceeds with the formation of the new P-substituted 3-oxa-1,2,3-diazaphospholenes 3 according to the Arbuzov reaction scheme.

Reaction of Diethyl Vinylphosphonate with Benzimidazole and 2-Aminobenzimidazole

Benzimidazole reacted with diethyl vinylphosphonate to give diethyl 2-(1H-benzimidazol-1-yl)- ethylphosphonate. The addition of 2-aminobenzimidazole to vinylphosphonate involved the endocyclic nitrogen atom with formation of diethyl 2-(2-imino-2,3-dihydro-1H-benzimidazol-1-yl)ethylphosphonate.