Laboratory of Intermediate Products (LIP)

Head -  Cand. Sci. Dmitry G. Mazhukin

Phone: (383) 330-68-52
internal phone: 2-56
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Laboratory was organized in 1989 from scientific research group with the basic research on polycyclic aromatic compounds. This group was founded in 1983

The main scientific directions

• bimolecular nucleophilic reactions in solution: changes of activation parameters and mechanisms.
• elaboration of synthetic methods of nitrogen-containing and different heterocyclic compounds for special applying including biological active substances, perspective ligands and others.

The main scientific results

• Method for the quantitative evaluation of the basicity of aryl-containing anions as the nucleophiles in the reactions of aromatic nucleophilic substitution has been developed.
• The original approach has been found for the prediction of the mechanism change for the reactions of aromatic nucleophilic substitution from SNAr to SET based on the dependence of the oxidation potentials of nucleophiles from the reaction internal barrier.
• It was established that the relative mobility and selectivity in the substitution reactions of nitro group and fluorine in the benzene derivatives depend on the nature of the nucleophile and substrate and are controlled by the entropy of activation especially for a soft nucleophiles; the latter gives an opportunity to govern the selectivity in the SNAr reactions.
• Variation of the activation parameters in the SN2, acyl-transfer, SNAr, SNV и AdN reactions gives a useful probe for the mechanistic features of these reactions in solution.
• The one-pot synthesis of 1-hydroxyimidazole derivatives has been developed by the interaction of 1,2-hydroxylaminoxime with aromatic and heteroaromatic aldehydes.
• The synthetic method for 4-oxodihydropyridines containing carboxyamide group in the side chain of the heterocycle separated by the 4 or 5 methylene groups has been elaborated with using of the Beckman rearrangement.
• It was shown that the interaction of ethanolamine with benzofurozanes leads to quinoxalines and opens the way to the synthesis of the practically useful substances.
 

List of the priority directions in frameworks which the current investigations are realized

• Theoretical chemistry and development of the methods of organic and inorganic synthesis, novel methods of physico-chemical investigations.
• Fundamental basis of chemistry.

List of the current projects

• Mechanisms of ionic, radical-ion and radical organic reactions. Experimental and theoretical investigation of the structure and reactivity of intermediates.
• Elaboration of the synthetic methods of heteroatomic organic substances for the biomedical investigations and for the creation of the novel materials.
• Creation of the novel effective methods for the synthesis of compounds with the target functional properties on the base of aromatic and heterocyclic compounds including polyfluorinated derivatives.

A list of the most important publications

1. V. M. Vlasov, Effects of substituents on activation parameters in the reactions of carboxylic acid derivatives with anionic and neutral nucleophiles. New J. Chem., 2009, 33(3), 501 – 506.
2. S. A. Amitina, A. Ya. Tikhonov, I. A. Grigor’ev, Yu. V. Gatilov, B. A. Selivanov. Synthesis of 2-aroyl-1-hydroxy-4,5-dimethylimidazoles by interaction of 3-hydroxyamino-2-butanone oxime with arylglyoxales. Chemistry of Heterocyclic Compounds, 2009, 45 (6), 691 - 697.
3. V. M. Vlasov, Effects of substituents on activation parameters in SN2 reactions at aliphatic carbon in solution. J. Phys. Org. Chem., 2010, 23 (5), 468 – 476.
4. V. M. Vlasov, Substituent effects in substrates on activation parameters in the bimolecular nucleophilic reactions in solution. New J. Chem., 2010, 34 (12), 2962 – 2970.
5. I.А.Os’kina, Yu.V. Gatilov, A.Ya.Tikhonov. Synthesis of 3-Hydroxy-2-hydroxy(phenyl)methyl-3-methyl-2,3-dihydro-4H-furo[3,2-c]chromen-4-one from 4-Hydroxycoumarin. Russian J.Org.Chem., 2011, 47 (9), 1441 – 1443.
6. V.A.Samsonov, I.Yu.Bagryanskaya, Yu.V.Gatilov, V.F.Savel’ev. Thermal transformations of 2H-benzimidazole 1,3-dioxides. Russ. Chem. Bull., International Ed., 2011, 60 (8), 1723 – 1728.
7. B.A.Selivanov, E.F.Belanov, N.I.Bormotov, S.M.Balakhnin, O.A.Serova, V.A.Svyatchenko, N.N.Kiselev, E.I.Kazachinskaya, V.B.Loktev, A.Ya.Tikhonov. Tricyclo[3.2.2.02,4]non-8-en-6,7-dicarbonic Acid Derivatives Efficiently Inhibits the Replication of Different Orthopoxvirus Species. Doklady Biological Sciences, 2011, 441, 400 – 404.
8. V. M. Vlasov, Towards mechanisms of bimolecular nucleophilic reactions in solution probing the variation of the activation parameters in the reactions of aromatic сompounds. J. Phys. Org. Chem., 2012, 25 (4), 296 - 308.
9. V.A.Samsonov, Yu.V.Gatilov, L.B.Volodarsky. Synthesis of 1,6-dihydro-1,6-dihydroxybenzo [1,2-d:3,4-d']bistriazole, 4- и 5-nitro-1,6-dihydro-1,6-dihydroxybenzo[1,2-d:3,4-d'] bistriazole, and 4,7-dihydro-1,4,7-trihydroxy-1H-benzo[1,2-d:3,4-d':5,6-d”]tris[1,2,3]triazole. Russ. Chem. Bull., International Ed., 2012 (9), ??? - ???.