Факультет фармації та біотехнології (Ф та БТ)

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ENG: Faculty of Organic Substances and Biotechnology

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Dialkyl-N-Alkoxy-N-(4-Toluenesulfonyl) Phosphoramidates: Synthesis and Structure
(Ukrainian State University of Science and Technologies, Dnipro, 2025) Shtamburg Vasiliy G.; Klots E. A.; Shtamburg V. V.; Anishchenko A. A.; Shishkina S. V.; Kravchenko S. V.; Mazepa A. V.
ENG: This study investigates the reaction between N-alkoxy-N-chloro-4-toluenesulfonamides and N-chloro-N-(methoxy)methanesulfonamide with trialkyl phosphites, resulting in the formation of dialkyl N-alkoxy-N-(4-toluenesulfonyl)phosphoroamidates and dialkyl N-methoxy-N-methanesulfonylphosphoroamidates, respectively. The resulting dialkyl Nalkoxy-N-(4-toluenesulfonyl)phosphoramidates and N-alkoxy-Nmethanesulfonylphosphoramidates are identified as products of nucleophilic substitution at the amide nitrogen atom. The structures of these compounds have been confirmed by H, P and C NMR spectroscopy, mass spectrometry, and an XRD study. The XRD study of dimethyl N-methoxy-N-(4-toluenesulfonyl)phosphoroamidate and dimethyl N-ethoxy-N-(4-toluenesulfonyl)-phosphoroamidate reveals a pyramidal configuration at the amide nitrogen atom, along with the shortening of the N–O(Alk) bond and the elongation of the N–P and N–S bonds. In the asymmetric part of the unit cell, dimethyl N-ethoxy-N-(4-toluenesulfonyl)phosphoramidate exists in the form of two independent molecules that differ in the degree of pyramidality of the nitrogen atom and the lengths of its bonds.
Interaction of N-Alkoxy-N-Chloro-N’-Arylureas With Trialkyl Phosphites AS a Route to Dialkyl N-Alkoxy-N-(N’’- Arylcarbamoyl) Phosphoramidates. Synthesis
(Ukrainian State University of Science and Technologies, Dnipro, 2025) Shtamburg, Vasiliy G.; Klots, Evgeniy A.; Anishchenko, Andrey A.; Shishkina, Svitlana V.; Mazepa, Alexander V.; Kravchenko S. V.
ENG: This article is dedicated to the study of the interaction of some kinds of N-alkoxy-Nchloroureas, such as N-alkoxy-N-chloro-N’-(4-nitrophenyl)ureas, N-ethoxy-N-chloroN’-(2-nitrophenyl)urea, N-methoxy-N-chloro-N’-(4-chlorophenyl)urea, and N-alkoxyN-chloro-N’-alkylureas, with trialkyl phosphites. The stable N-alkoxy-N-chloro-N’-(4- nitrophenyl)ureas interact with trialkyl phosphites in diethyl ether at room temperature with preferential formation of dialkyl N-alkoxy-N-(N’-4- nitrophenylcarbamoyl)phosphoramidates. N-Ethoxy-N-chloro-N’-(2-nitrophenyl)urea reacts with trimethyl phosphite in diethyl ether at room temperature giving dimethyl Nethoxy-N-(N’-2-nitrophenylcarbamoyl)phosphoramidate. The interaction of unstable Nmethoxy-N-chloro-N’-(4-chlorophenyl)urea with trialkyl phosphites in diethyl ether gives dialkyl N-methoxy-N-(N’-4-chlorophenylcarbamoyl)phosphoramidates with good yields. N-Alkoxy-N-chloro-N’-alkylureas react with trimethyl phosphite under the same conditions with selective formation of dimethyl N-alkoxy-N-(N’-alkylcarbamoyl)phosphoramidates with excellent yields. In all these cases, the nucleophilic substitution at the nitrogen atom is accompanied by a further Michaelis-Arbuzov rearrangement. The original method of creating molecules containing a P–N bond is proposed. The structures of dialkyl Nalkoxy-N-(N’-arylcarbamoyl)phosphoramidates and dimethyl N-alkoxy-N-(N’- alkylcarbamoyl)phosphoramidates have been confirmed by 1H, 31P, and 13C NMR spectroscopy, and mass spectrometry. The synthesized dialkyl N-alkoxy-N-(N’- arylcarbamoyl)phosphoramidates and dimethyl N-alkoxy-N-(N’- arylcarbamoyl)phosphoramidates simultaneously possess structural features of both phosphoramidates and ureas, and may be regarded as potential biologically active substances.