Zn(II) and Ag(I) complexes of N-allythioamides of pyrimidinyl (cyclohexenyl) carboxylic acids and products their proton- and iodocyclization
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Keywords

iodine/proton cyclization, N-allylcarbothioamides, complex formation, polydentate organic ligands, chelate metalocycles.

How to Cite

Borovyk, P., Litvinchuk, M., Bentya, A., Orysyk, S., Zborovskiy, Y., & Slyvka, N. (2019). Zn(II) and Ag(I) complexes of N-allythioamides of pyrimidinyl (cyclohexenyl) carboxylic acids and products their proton- and iodocyclization. Ukrainian Chemistry Journal, 85(3), 3-19. https://doi.org/10.33609/0041-6045.85.3.2019.3-19

Abstract

The possibility of using N-allylcarbothioamide derivatives as well as products of their iodine- and proton-initiated electrophilic heterocyclizations as chelating agents in complexation reactions with Zn(II) and Ag(I) ions is shown. Processing of the obtained experimental data showed that N-allythioamides of pyrimidinyl (cyclohexenyl) carboxylic acids H2L1 – H2L3 and their proton- and iodo-cyclization products HL4, HL5 containing four nucleophilic reaction centers (two oxygen atoms of the carbonyl and hydroxyl groups and N-, S-carbothioamide groups or N-atoms of the dihydrothiazole moiety) are polydentate ligands capable of coordinating with metal ions to form stable six-membered chelate metallocycles.

A series of new chelating mono-, bi- and polynuclear complexes Zn(II) and Ag (I) of the composition [Zn2L1,32]n, [Zn2(HL1-3)2(CH3COO)2], [Ag2(HL1,3)2]n, [Zn(HL1-3)2], [Ag(H2L3)2NO3], [Zn(HL4,5)2], K[Ag(HL4,5)2] were synthesized and isolated in solid state. Their molecular structure was established by methods of elemental chemical analysis, NMR 1H, IR and UV-Vis spectroscopy.

At a ratio of M:L 1:2, complexes were isolated in which two ligand molecules H2L1 − H2L3 are coordinated to the metal ion by the sulfur atoms of the carbothioamide group and the oxygen of the mono-deprotonated hydroxyl group. It was established that the products of the proton-/iodocyclization HL4, HL5 in the complex formation pass into the thione tautomeric form with coordination through the oxygen atoms of the deprotonated hydroxyl group and nitrogen atoms of the dihydrothiazole heterocycle. At M:L 1:1, binuclear or polynuclear coordination compounds are formed. It was shown that polymerisation in complexes [Zn2L1,32]n and [Ag2(HL1,3)2]n is due to the formation of Zn−(O2SN)−Zn and Ag−O−Ag polymer chains.

Investigation of the solubility of the resulting complexes showed that the polymer complexes are weakly soluble or insoluble in DMSO, DMF, while the mononuclear are soluble in methanol, as well as in water.

https://doi.org/10.33609/0041-6045.85.3.2019.3-19
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References

1. Saeed A., Flörke U., Erben M.F. A review on the chemistry, coordination, structure and biological properties of 1-(acyl/aroyl)-3-(substituted) thioureas. J. Sulfur Chem. 2014. 35 (3): 318−355.
2. Frija L.M.T., Pombeiro A.J.L., Kopylovich M.N. Coordination chemistry of thiazoles, isothiazoles and thiadiazoles. Coord. Chem. Rev. 2016. 308, Pt. 1: 32−55.
3. Haas K.L., Franz. K.J. Application of metal coordination chemistry to explore and manipulate cell biology. Chem. Rev. 2009. 109 (10): 4921−4960.
4. Bhasin H., Bhatt V. The state of art in coordination compounds with antifungal activity. J. Chem. and Chem. Sci. 2018. 8 (3): 595−605.
5. Chen J., Fukuzumi K., Ip B., Florence, Cid A.P. Metal Coordination chemistry in the study of biological pathway and processes: A review. // Inter. J. Pharm. Biol. Chem. Sci. 2014. 3 (3): 36−45.
6. Dilworth J.R., Hueting R. Metal complexes of thiosemicarbazones for imaging and therapy. Inorg. Chim. Acta. 2012. 389: 3−15.
7. Pelosi G. Thiosemicarbazone metal complexes: From structure to activity // The Open Crystallography Journal. 2010. 3, (2): 16−28.
8. Koch K.R. New chemistry with old ligands: N-alkyl- and N,N-dialkyl-N-acyl(aroyl)thioureas in co-ordination, analytical and process chemistry of the platinum group metals. Coord. Chem. Rev. 2001. 216–217: 473−488.
9. Singh R.B., lshii H. Analytical potentialities of thiosemicarbazones and semicarbazones. Critical Rev. Analyt. Chem. 1991. 22 (5): 381−409.
10. Orysyk S.I., Bon V.V., Zholob O.O., Pekhnyo V.I., Orysyk V.V., Zborovskii Yu.L., Vovk M.V. Novel Pd(II) coordination compounds involving 2-[(2-hydroxyphenyl)methylene]hydrazine-N-(2-propenyl)-carbothioamide as a ligand or pro-ligand: Synthesis, crystal structures and analytical application. Polyhedron. 2013. 51: 211−221.
11. Dey P., Basu S. Liquid–liquid extraction of silver(I) with 2-hydroxy-1-naphthaldehyde thiosemicarbazone into cyclohexene from nitrate medium in presence of neutral oxygen donor compounds. Internat. J. ChemTech Res. 2011. 3 (3): 1349−1358.
12. Banerjee S. Basu S. Synergistic extraction of Th(IV) by 2-hydroxy-1-naphthaldehyde thiosemicarbazone and neutral donors. Radiochim. Acta. 2003. 91 (2): 97−103.
13. Hossain Md.S., Roy P.K., Ali R., Zakaria C.M., Kudrat-E-Zahan Md. Selected pharmacological applications of 1st row transition metal complexes: A review. Clinical Med. Res. 2017. 6 (6): 177−191.
14. Zhao Y., Wang L., Guo C., Jiang B., Li X., Liu K., Shi D. Metal complexes of thiosemicarbazones as potent anticancer agents: a minireview. Med. Res. 2018. 2 (2). 20180009; doi: 10.21127/yaoyimr20180009.
15. Hossain Md.S., Zakaria C.M., Kudrat-E-Zahan Md. Metal complexes as potential antimicrobial agent: A review. Amer. J. Heterocycl. Chem. 2018. 4 (1): P. 1−21.
16. Patra M. Gasser G. Organometallic compounds: An opportunity for chemical biology? ChemBioChem. 2012. 13 (9): 1232−1252.
17. Zelenin K.N., Khorseeva L.A., Toshev M.T., Alekseev V.V., Dustov Kh.B. Zh. Obshch. Khim. 1990 (Russ.). Russ. J. Gen. Chem. 1990. 60: 2549.
18. Orysyk S.I., Bon V.V., Obolentseva O.V., Zborovskii Yu.L., Orysyk V.V., Pekhnyo V.I., Staninets V.I., Vovk M.V. Synthesis, structural and spectral characterization of Zn(II) complexes, derived from thiourea and thiosemicarbazide. Inorg. Chim. Acta. 2012. 382: 127−138.
19. Orysyk S.I., Bon V.V., Pekhnyo V.I., Zborovskii Yu.L., Orysyk V.V., Vovk M.V. Synthesis, structure and spectral characteristics of Ni(II), Pd(II) and Zn(II) complexes with N-(2-pyridinyl)morpholine-4-carbothioamide. Polyhedron. 2012. 38: Р.15–25.
20. Repich H.H. Synthesis, structure and spectral characteristics of Fe(III), Co(II), Ni(II), Cu(II), Pd(II), Pt(II), Ag(I) with thiourea, hydrazone and thiosemicarbazone derivatives. Ph.D (Chem.) Thesis. (Kyiv, 2015). С.108−120 http://www.ionc.kiev.ua/ssc/2016/GRepich_thesis.pdf
21. Klimova V.A. The main micro methods of analysis of organic compounds. (Moscow: Chemistry, 1967). 19−55, 101−107.
22. Wesolowska A., Jagodziñski T.S., Sosnicki J.G., Hansen P.E. Synthesis of the N-Allylthioamide Derivatives of Cyclic Oxo- and Dioxo- Acids and Their Cyclization to the Derivatives of 4,5-Dihydrothiazole. Polish J. Chem. 2001. 75: 387−400.
23. Hansen P.E., Duus F., Bolvig S., Jagodzinski T.S. Intramolecular hydrogen bonding of the enol forms of β-ketoamides and β-ketothioamides. Deuterium isotope effects on 13C chemical shifts. Journal of Molecular Structure. 1996. 378: 45−59.
24. Litvinchuk M.B., Bentya А.V., Slyvka N.Yu., Vovk М.V. 5-Functionalized (1,3-thiazolidine-2-ylidene)pirymidin-2,4,6-tri¬ones. Ukr. Chim. Zhurn. 2017. 83 (10): 90−99.

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