Studies in chemistry of heterocyclic compounds

For investigation of substituents’ electronic impact on some steps in the mechanism of acid catalyzed indolization reaction of arylhydrazones (associate professor, doctor of chemical science, Ioseb Chikvaidze and his research group) was fulfilled indolization reaction of acetophenone and its derivatives in different condensation conditions. There was shown that the best reaction area for condensation was polyphosphoric acid and its ethylesters. The solution of concentrated sulfuric acid in ethanol and acetic acid, as well as solution of dry hydrochloride in ethanol cause the full spoilage of reaction mixture. A five-ringcontaining heterocyclic system with 4 nitrogen atoms was obtained. Two new dinitriles containing Indole ring were synthesized. Associate professor, doctor of chemical sciences, Marina Trapaidze and her research group synthesized the new bis-spirocompounds on the base of benzopyrroloindoles and studied their photochromic properties. The purpose of this work was the comparative characterisation of photochromic properties of the previously synthesized bis-spirochromes. As an object of research was chosen the bis analog of previously synthesized Fischer’s bases - 1,4,5,8-tetrahydro-1,1,8,8-tetramethy-2,7-dimethylendipyrrolo[1,2,3-d,e:3,2,1[i,j]benzo[g]quinoxaline, which further transformation led to the synthesis of new spirochromens. Dispirocompounds containing chromophore groups were obtained by condensation reaction of Fischer’s base with 5-nitro-o-vaniline and chloro-nitro-salicylic aldehyde. There was studied the influence of solvent on stereoselectivity and the yield of reaction products in Ugi’s reaction (assistant professor, doctor of chemical sciences, Elene Katsadze). For starting materials were chosen L-Alanine, as an acid component, (S)-p-methoxyphenylamine, trimethylacetaldehyde and methyl-2- isocyanoacetate. Methanol, 2,2,2-trifluoroethanol and dichloromethane were used as solvents. When reaction was carried out in dichloromethane only desired product was obtained. In methanol, along with the desired product (1), was isolated product of elimination reaction (2). However, in the case of 2,2,2-trifluoroethanol, was obtained only product 2. It was found that this reaction goes in desired direction in the case of using dichloromethane. Changing of the solvent did not have a significant impact on stereoselectivity. Shota Rustaveli National Science Foundation grant in Basic researches № FR/154 /6-420/13. Grant’s principal investigator, associate professor of academic department of chemistry of organic and natural compounds, doctor of chemical sciences, Marina Trapaidze. Title: New Derivatives of Biological Active N-Adamantyl-, N-Adamantoylaminobenzene and 2-,5(6)-Adamantylbenzimidazole: Synthesis, Reactions and Investigation“, 31.03-2014-31.03.2017. Completed project’s (IV and V periods) main theoretical and practical results: in direction of obtaining the new 5(6)–carboxy–2–(1–adamantyl)benzimidazole’s derivatives was carried out the synthesis of N-(1-adamantoyl)-p-aminobenzoic acid’s derivatives: • During the reporting period was investigated the optimal method of synthesis of adamantane-1-carboxylic acid from adamantane via Ritter reaction in sulfuric acid area. This method does not require using nitric acid and oleum. • There was studied coupling reaction of ethyl 3,4-diaminobenzoate with adamantane-1-carboxylic acid in the presence of catalyst by heating. The optimal cyclisation conditions were determined. • The reactions of synthesized carbohydrazide with aromatic aldehydes and acid chloranhydrides were studied. The proper hydrazidohydrazones and dihydrizides were synthesized. For synthesized compounds were obtained UV and IR spectra. • During the reporting period was fulfilled the virtual bioscreening of 79 compounds via internet system: http://www.way2drug.com/index.com/index.php and the results were sent to USAMRIID for discussion. Number of received grants: Shota Rustaveli National Science Foundation grants for 2016 year: • The grant for PhD students (Marina Soselia, supervisor prof. Shota Samsoniya), was received in 2016 year, for 6 months – “Researches in benzimidazole’s new derivatives” • Master research grant (Boboxidze Lia), „Synthesis and study of new potential DNA’s intercalator – 3,6-dihydropyrrolo[3,2:4’5’]indolo[2,3-b]quinoxaline”. Grant agreement № MR_2016_1_136. The scholarship grant 2016 for financing master students’ academic-research projects, period - 6 months, started from 1st January, 2017. • Master research grant (Tabatadze Tamar), „New derivatives of 2-(1-adamantyl)-1H-benzimidazol-5-carbohydrazide:Synthesis and Studies“. Grant agreement № MR_2016_1_135. The scholarship grant 2016 for financing master students’ academic-research projects, period - 6 months, started from 14th of January, 2017. • Research grants to Young Scientists 2016 - „Naphthalene, thiazole and imidazole ring containing potent biological active polycyclic compounds”. Grant’s principal investigator: TSU Head of the Laboratory of the Chemistry Department of Organic and Natural Compounds Nino Nikoleishvili, Budget 57000 Lari. Period: 01.12.2016-30.11.2018. • Basic Research Grant №FR/217996/16 “New Derivatives of Adamantane Benzimidazoles and Imidazo[4,5-e]benzoxazoles: Synthesis and Study“ Natural sciences, organic chemistry. Three years - 2016-2019, 210000 Lari. Grant’s principal investigator Zurabishvili Davit, Head of Organic Chemistry Institute’s Devision of Alicyclic Compounds.