SYNTHESIS OF NON-CYCLIC COMPOUNDS WITH A FRAGMENT OF 1,3-THIAZOLE
Abstract
In this work, the synthesis and properties of non-cyclic two- and three-link products are discussed. The products are obtained by the interaction of the corresponding phthalonitrile, which was converted under the action of nartium methoxide in methanol into the corresponding 1,1-dimethoxy-3-iminoisoindolines, and input in the reaction with 2,4-diamino 1,3-thiazole hydrochloride. To obtain the latter, we have improved the proposed method. It is known that most of the substituted thiazoles are obtained by the interaction of the corresponding derivatives of thiourea with chloroacetaldehyde in the presence of triethylamine. We have tested this technique, which showed the acceptability of this method for the synthesis of 2,4-diamino-1,3-thiazole hydrochloride, which was previously obtained from thiourea and chloroacetonitrile by heating in alcohol. The use of 2,4-diamino-1,3-thiazole hydrochloride as a starting product in the synthesis of non-cyclic two- and three-link compounds is justified, because 2,4-diamino-1,3-thiazole is an unstable compound and it is easily oxidized. It was found that the presence of atmospheric oxygen promotes the formation of diketones (2,4-bis (isoindol-1-ylideneamino-3-one) -1,3-thiazole). For the targeted (direct) synthesis of 2,4-bis (3-iminoisoindolin-1-ylideneamino) -1,3-thiazole, was used an argon “pad”. As a result, the target compound was obtained, which was isolated (singled out) from the reaction mass by distilling off the solvent, the target compound was washed with organic solvents. The transition to substituted phthalonitrile has showed completely different results. A mixture of two products was obtained, the presence of which was established on the basis of mass spectrometry data and electronic absorption spectra. In contrast to the previous three-link products, the reaction proceeded in the direction of the formation of a three-link product, which contains two thiazole and one tert-butyl-substituted isoindole fragments. It turned out to be difficult to carry out chromatographic separation of the products due to the instability of the obtained compounds. The structure of the synthesized substances was established on the basis of modern research methods: electronic, IR, 1H NMR spectroscopy, mass spectrometry. Using the TDDFT/B3LYP/6-31G method, we calculated the theoretical absorption spectrum of an optimized 2,4-bis (3-iminoisoindolin-1-ylideneamino) -1,3-thiazole molecule.
References
Chemical Processes with Participation of Biological and Re-lated Compounds. Ed. by T.N. Lomova and G.E. Zaikov. Leiden-Boston: BRILL. 2008. P. 219-270.
Islyaikin M.K., Danilova E.A. Sructural analogs of tetrapyrrole macrocycles and their biological properties. Russ. Chem. Bull. 2007. V. 56. N 4. P. 689-706. DOI: 10.1007/s11172-007-0107-z.
Trukhina O.N., Rodríguez-Morgade M.S., Wolfrum S., Caballero E., Snejko N., Danilova E.A., Gutiérrez-Puebla E., Islyaikin M.K., Guldi D.M., Torres T. Scruti-nizing the Chemical Nature and Photophysics of an Expanded Hemiporphyrazine: The Special Case of [30]Trithia-2,3,5,10,12,13,15,20,22,23,25,30-dodecaazahexaphyrin. J. Am. Chem. Soc. 2010. V. 132. P. 12991–12999. DOI: 10.1021/ja104577d.
Danilova E.A., Islyaikin M.K., Shtrygol S.Yu. Synthesis of trinuclear CuII-complex with tris(4-triphenylmethylphenoxy) substituted hemihexaphyrazine and radioprotective properties of its watersoluble form. Izv. AN. Ser. Khim.. 2015. V. 64. N 7. P. 1610 -1615 (in Russian). DOI: 10.1007/s11172-015-1049-5.
Matis M.E., Shmyrova A.A., Malykh U.V., Podshivalova I.M., Ageeva T.A. Coordination interaction of metallopor-phyrins with nitrogen-containing ligands as a method for regulating the formation of metal isoporphyrinates. Chem-ChemTech [Izv. Vyssh. Uchebn. Zaved. Khim. Khim. Tekhnol.]. 2021.
V. 64. N 10. P. 132138. DOI: 10.6060/ivkkt.20216410.6489.
Trukhina O.N., Zhabanov Yu.A., Krasnov A.V., Danilova E.A., Islyaikin M.K. Synthesis and thermal behaviour of of unsubstituted [30]trithia-2,3,5,10,12,13,15,20,22,23,25,30-dodecaazahexaphyrin. J. Porph. Phthal. 2011. V. 15. P. 1287-1291. DOI: 10.1142/S108842461100418X.
Koifman O.I., Ageeva T.A., Beletskaya I.P., Averin A.D., Yakushev A.A., Tomilova L.G., Dubinina T.V., Tsivadze A.Yu, Gorbunova Yu.G., Martynov A.G., Konarev D.V., Khasanov S.S., Lyubovskaya R.N., Lomova T.N., Korolev V.V., Zenkevich E.I., Blaudeck T., von Borczyskowski Ch., Zahn D.R.T., Mironov A.F., Bragina N.A., Ezhov A.V., Zhdanova K.A., Stuzhin P.A., Pakhomov G.L., Rusakova N.V., Semenishyn N.N., Smola S.S., Parfenyuk V.I., Vashurin A.S., Makarov S.V., Dereven’kov I.A., Mamardashvili N.Zh., Kurtiky-an T.S., Martirosyan G.G., Burmistrov V.А., Aleksan-driiskii V.V., Novikov I.V., Pritmov D.A., Grin M.A., Suvorov N.V., Tsigankov A.A., Fedorov A.Yu., Kuzmina N.S., Nyuchev A.V., Otvagin V.F., Kustov A.V., Belykh D.V., Berezin D.B., Solovieva A.B., Timashev P.S., Milaeva E.R., Gracheva Yu.A., Dodokhova M.A., Safronenko A.V., Shpakovsky D.B., Syrbu S.A., Gubarev Yu.A., Kiselev A.N., Koifman M.O., Lebedeva N.Sh., Yurina E.S. Macroheterocyclic Compounds – a Key Build-ing Block in New Functional Materials and Molecular Devices. Macroheterocycles. 2020. V. 13 (4). P. 311 – 467. DOI: 10.6060/mhc200814k.
Mabkhot Y.N., Barakat A., Mohammad Al-Majid A., Alamary A.S., Al-Nahary T.T. A Novel and Expedient Approach to New Thiazoles, Thiazolo[3,2-a]pyridines, Di-hydrothiophenes, and Hydrazones Incorporating Thieno[2,3-b]thiophene Moiety. Int. J. Mol. Sci. 2012. 13. P. 5035-5047. DOI: 10.3390/ijms13045035.
Abdel Latifa N.A., Abbasb E.M.H., Farghalyc T.A., Awad H.M. Synthesis, Characterization, and Anticancer Screening of Some New Bithiazole Derivatives. Rus. J. Org. Chem. 2020. 56 (6). P. 1096–1107. DOI: 10.1134/S1070428020060202.
Alvareza N., Vellutia F., Guidalib F., Serrab G., Kramer M. G., Ellenae J., Facchina G., Scaroneb L., Torrea M.H. New BI and TRI-Thiazole copper (II) complexes in the search of new cytotoxic drugs against breast cancer cells. In-org. Chim. Acta. 2020. 508. P. 1-10. DOI: 10.1016/j.ica.2020.119622.
Stokes J.M., Yang K., Swanson K. A Deep Learning Approach to Antibiotic Discovery. Cell. 2020. V. 180. N 4. P. 688-702. DOI: 10.1016/j.cell.2020.01.021.
Danilova E.A., Melenchuk T.V., Melekhonova E.E., Tyutina M.A., Islyaikin M.K. Threeunit products of con-densation of alkylsubstituted thiadiazoles with 1,1-dimethoxy-3-iminoisoindoline. Macroheterocycles. 2009. V. 2. N 3. P. 246 – 250. DOI: 1060606/mhc2009.3-4.246.
Danilova E.A., Kudayarova T.V., Galiev R.M., Min Tkhyi Nguen, Abramov I.G., Abramova M.B. Synthesis and properties of substituted 3,5-bis(3-imino-2,3-dihydro-1H-isoindol-1-ylideneamino)-1,2,4-thiadiazoles. Russ. J. Gen. Chem. 2015. V. 85. N 3. P. 607-610. DOI: 10.1134/S1070363215030135.
Tyutina M.A., Kudayarova T. V., Danilova E.A. Synthe-sis of acyclic threeunit products with 3-alkyl-1,3,4-thiadiazoline fragments. Russ. J. Gen. Chem. 2017. V. 87. N 5. P. 969-972. DOI: 10.1134/S1070363217050139.
Catalog. Alfa Aesar. Catalog of Research Chemicals. Metals & Materials - A Johnson Matthey Company. 2006-2007. P. 1612.
Mikhalenko S.А. Synthesis and electronic absorption spectra of tetra-4-tert-butylphthalocyanines. ZhOKh. 1971. V. 41. N 12. P. 2735 – 2739 (in Russian).
Land A. H., Ziegler C., Sprague J. M. Derivatives of sulfathiazole. J. Org. Chem. 1946. 11. 5. P. 617–623. DOI: 10.1021/jo01175a027.
Davies W., Maclaren J.A., Wilkinson L.R. The synthesis and properties of 2 : 4-diaminothiazoles. J. Chem. Soc. 1950. V. 687. Р. 3491-3494. DOI: 10.1039/JR9500003491.
Anikanova S.V., Boboshko L.G., Mikhailov V.A., Zu-britskiy M. Yu., Kovalenko V.V. Reaction of aroylthiou-reas with chloroacetonitrile. Zhurn. Org. Farm. Khim. 2010. V. 8. N 1. P.71-78 (in Russian).
Gordon A., Ford R. Satellite chemist. M.: Mir. 1976. 542 р. (in Russian).
Brown B., Floyd A., Sainsbury M. Spectroscopy of organic substances. М.: Mir. 1992. 300 р. (in Russian).
Quantum-chemical calculations of the compound 1 were performed by DFT/B3LYP/6-31G(d,p)method, using the software package PC GAMESS v.7.1.E1 (Granovsky A., http://classic.chem.msu.su/gran/gamess/index.html). б) ChemCraft (Jurko G.A., www.chemcraftprog.com) was applied for preparation of input data files, as well as for ro-cessing and visualization of the computed results.
http://www.ccdc.cam.ac.uk/mercury/.
Zhilinskaya M.A., Danilova E.A., Suvorova Yu.V. Synthesis of acyclic compounds with a 1,3-thiazole fragment - precursors for the synthesis of macroheterocycles. In the collection of works. Modern problems of chemistry, technology and pharmacy. Cheboksary: Izd-vo. Chuvash. un-ta. 2020. P. 66-70.
