Кафедра фармації та технології органічних речовин (ФтаТОР)

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ENG: Department of Pharmacy and Technology of Organic Substances

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An Efficient Synthetic Route to Substituted Xanthene Analogues
(Ukrainian State University of Science and Technologies, Dnipro, 2025) Varenichenko, S. A.; Kovtun, A.V.; Farat, V. K.; Farat, O. K.
ENG: The reactions of N-[(9-chloro-1,2-dihydrocyclopenta[b]chromen-3-yl)methylene]-Nmethylmethanaminium and N-[(11-chloro-7,8,9,10-tetrahydrocyclohepta[b]chromen-6- yl)methylene]-N-methylmethanaminium perchlorates with (1- phenylethylidene)malononitrile were studied in boiling acetonitrile in the presence of piperidine. These reactions led to the formation of new organic dyes, [(2E)-1-phenyl-3- (9-piperidin-1-yl-1,2-dihydrocyclopenta[b]chromen-3-yl)prop-2-en-1- ylidene]malononitrile and [(2E)-1-phenyl-3-(11-piperidin-1-yl-7,8,9,10- tetrahydrocyclohepta[b]chromen-6-yl)prop-2-en-1-ylidene]malononitrile, obtained in high yields. The structures of the products were confirmed by 1H NMR spectroscopy, mass spectrometry, and elemental analysis. The observed spin-spin coupling constants indicated that the products adopted the E-configurations of the double bonds. The reaction mechanism was determined to proceed via a Knoevenagel condensation followed by nucleophilic substitution of chlorine with a piperidine fragment. Spectroscopic investigations of the dyes were performed in organic solvents, in particular acetonitrile and chloroform. For [(2E)-1-phenyl-3-(9-piperidin-1-yl-1,2-dihydrocyclopenta[b]chromen3-yl)prop-2-en-1-ylidene]malononitrile, the absorption maximum was ~605 nm, and the emission maximum was ~685 nm, with a quantum yield of 34.62% in acetonitrile and 16.84% in chloroform. In contrast, [(2E)-1-phenyl-3-(11-piperidin-1-yl-7,8,9,10- tetrahydrocyclohepta[b]chromen-6-yl)prop-2-en-1-ylidene]malononitrile exhibited an absorption maximum at 607 nm with negligible fluorescence. The synthesized dyes may be of interest to researchers in the field of dye chemistry and related areas.
Interaction of Labile N-Alkoxy-N-Chloro-N’-Arylureas and N-Acetoxy-Nalkoxyureas With Trimethyl Phosphite
(Oles Honchar Dnipro National University, Dnipro, 2025) Shtamburg, Vasiliy G.; Klots, Evgeniy A.; Anishchenko, Andrey A.; Shtamburg, Victor V.; Shishkina, Svitlana V.; Mazepa, Alexander V.; Kravchenko, Svetlana V.
ENG: The freshly synthesized N-alkoxy-N-chloro-N’-4-bromophenylureas undergo reaction with trimethyl phosphite in diethyl ether at room temperature yielding respectively dimethyl N-alkoxy-N-(N’-4- bromophenylcarbamoyl)phosphoroamidates with high yields. The unstable N-alkoxy-N-chloro-N’-phenylureas, freshly synthesized at -30°C, interact with trimethyl phosphite in diethyl ether at this low temperature to produce previously unknown dimethyl N-alkoxy-N-(N’-phenylcarbamoyl)phosphoroamidates. This reaction is the first example of the nucleofilic substitution at the nitrogen atom for unstable N-alkoxy-N-chloro-N’-phenylureas. Careful conditions selection and precise control made it possible to pevent premature destruction of the starting N-alkoxyN-chloro-N’-4-bromophenylureas and N-alkoxy-N-chloro-N’-phenylureas. In contrast, N-acetoxy-N-alkoxyureas do not react with trimethyl phosphite under the same conditions. The structures of the resulting dimethyl N-alkoxy-N- (N’-4-bromophenylcarbamoyl)phosphoroamidates and dimethyl N-alkoxy-N-(N’- phenylcarbamoyl)phosphoroamidates were confirmed by ¹H, ³¹P, and ¹³C NMR spectroscopy, as well as mass spectrometry. A comparative analysis of ¹H, ³¹P and ¹³C NMR spectra of these dimethyl N-alkoxy-N-(N’- arylcarbamoyl)phosphoroamidates with those of dialkyl N-alkoxy-N-(N’-4- nitrophenylcarbamoyl)phosphoroamidates revealed numerous shared features and general structural characteristics of N-alkoxy-N-(N’-arylcarbamoyl)phosphoroamidates
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.
Synthesis of N,N'-(((Hydrazine-1,2- Dicarbonothioyl)Bis(Azanediyl))Bis(2,2,2-Trichloroethane-1,1- Diyl)) Carboxamides and Their Cyclisation Into N,N'-(((1,3,4-Thiadiazole-2,5- Diyl)Bis(Azanediyl))Bis(2,2,2-Trichloroethane-1,1-Diyl))Carboxamides
(Oles Honchar Dnipro National University, Dnipro, 2025) Pavlova, Valeriia V.; Zadorozhnii, Pavlo V.; Kiselev, Vadym V.; Romanenko, Pavlo V.; Okhtina, Oxana V.; Kharchenko, Aleksandr V.
ENG: 1,3,4-Thiadiazole derivatives are widely used in science and technology as biologically active compounds, components of polymer and rubber compositions, dyes and varnishes, catalysts, as well as materials for microelectronics and nanotechnology. This work presents the synthesis of new bis-amidoalkylated derivatives of 2,5-diamino-1,3,4-thiadiazole. The preparation of these compounds is based on the reaction of oxidative dehydrosulfonation of N,N'-(((hydrazine-1,2-dicarbonothioyl)bis(azanediyl))bis(2,2,2-trichloroethane-1,1- diyl))carboxamides using a mixture of iodine and triethylamine in DMF. The reaction was carried out at room temperature for two hours. This method yields target products in the range of 63–92 %. The advantage of the method is the absence of the need for expensive or hard-to-find reagents. NMR ¹H and ¹³C spectroscopy confirmed the structure of the synthesized compounds. The 1H NMR spectra of synthesized 1,3,4-thiadiazoles are distinguished by the presence of doublet signals corresponding to two NH protons observed in the 9.53–6.69 ppm range, along with a doublet of doublets assigned to the CH proton of the alkylamide fragment appearing at 6.77– 6.69 ppm. The 13C NMR spectra exhibit characteristic resonances of the C=O carbon at 168.8–164.7 ppm and the C=N carbon of the thiadiazole ring at 158.9–158.6 ppm. Furthermore, characteristics signals attributed to the CCl3_ moiety and the CH carbon of the alkylamide fragment are observed at 101.5–101.2 and 70.0–69.4 ppm respectively.