Synthesis and prediction of the biological activity of heterocyclic n-derivatives naphthoquinone

2019;
: 69-75
1
Lviv Polytechnic National University
2
Lviv Polytechnic National University
3
Lviv Polytechnic National University
4
Lviv Polytechnic National University
5
Institute of Organic Chemistry, NAS of Ukrainе

The most urgent task of organic and pharmaceutical chemistry today is the search for new biologically active compounds, which in future can be used as promising substances for the development of new low-toxic, high-performance medicinal products. To this end, heterocyclic N-derivatives of 1,4-dichloroanotoquinone were synthesized and their drug-like characteristics were determined.

 On the basis of the literature data, we carried out the synthesis of aminopyrazole derivatives of dichloro-petroquinone. To obtain new aminopyrazole derivatives of dichloro-petroquinone, a nucleophilic substitution of a chlorine atom in a 2,3-dichloro-1,4-naphthoquinone by a pyrazole fragment was carried out (interaction of the equimolar amount of the corresponding aminopyrazole derivative with 2,3-dichloro-1,4-naphthoquinone in alcohol and with carbonate sodium as an acceptor of HCl). The following heterocyclic derivatives of dichlorofluoroquinone were obtained: 2-chloro-3 - ((1-methyl-1H-pyrazol-4-yl) amino) naphthalene-1,4-dione, 2-chloro-3 - ((1-methyl-1H 2-chloro-3 - ((3- (p-tolyl) -1H-pyrazol-5-yl) amino) naphthalene-1,4-dione and ethyl 4 - ((3-chloro-1,4-dioxo-1,4-dihydro-naphthalen-2-yl) amino) -1-phenyl-1H-pyrazole-3-carboxylate.

For synthesized substances, computer biological screening was carried out under the PASS program and calculated criteria of the appearance of the liver. The results of the predicted biological activity of aminopyrazoles with the quinone fragment showed that the synthesized compounds have pronounced antitumor activity, analgesic, antiparkinsonian, anti-neurodegenerative activity, activity against diabetic neuropathy, as well as the possibility of their use as inhibitors of many enzymes. Analyzing the obtained results of calculating the criteria for the appearance of the liver, it can be argued that heterocyclic naphthoquinone derivatives do not have any deviations from the Lipinsky's rules. And, consequently, it is advisable to carry out further experimental biological studies of synthesized compounds.

1. Phillips, R. M., Jaffar, M., Maitland, D. J., Loadman, P. M., Shnyder, S. D., Steans, G., & Stratford, I. J. (2004). Pharmacological and biological evaluation of a series of substituted 1, 4-naphthoquinone bioreductive drugs. Biochemical pharmacology, 68(11), 2107-2116.
https://doi.org/10.1016/j.bcp.2004.08.007
2. Tandon, V. K., Singh, R. V., & Yadav, D. B. (2004). Synthesis and evaluation of novel 1, 4naphthoquinone derivatives as antiviral, antifungal and anticancer agents. Bioorganic & medicinal chemistry letters, 14(11), 2901-2904.
https://doi.org/10.1016/j.bmcl.2004.03.047
3. Hassan, A. A., Mohamed, N. K., Ibrahim, Y. R., & Mourad, A. F. E. (1993). Chemical Interactions between Aminopyrazoles and 2, 3. Dicyano-1,  4-naphthoquinone. Liebigs Annalen der Chemie, 1993(6), 695-697.
https://doi.org/10.1002/jlac.1993199301112
4. Ibis, C., Tuyun, A. F., Bahar, H., Ayla, S. S., Stasevych, M. V., Musyanovych, R. Y., & Novikov, V. (2014). Nucleophilic substitution reactions of 1, 4naphthoquinone and biologic properties of novel S-, S, S-, N-, and N, S-substituted 1, 4-naphthoquinone derivatives. Medicinal Chemistry Research, 23(4), 2140-2149.
https://doi.org/10.1007/s00044-013-0806-y
5. Al-Adiwish, W. M., Tahir, M. I. M., SitiNoor-Adnalizawati, A., Hashim, S. F., Ibrahim, N., & Yaacob, W. A. (2013). Synthesis, antibacterial activity and cytotoxicity of new fused pyrazolo [1, 5-a] pyrimidine and pyrazolo [5, 1-c][1, 2, 4] triazine derivatives from new 5-aminopyrazoles. European journal of medicinal chemistry, 64, 464-476.
https://doi.org/10.1016/j.ejmech.2013.04.029
6. Nitulescu, G., Draghici, C., & Olaru, O. (2013). New potential antitumor pyrazole derivatives: Synthesis and cytotoxic evaluation. International journal of molecular sciences, 14(11), 21805-21818.
https://doi.org/10.3390/ijms141121805
7. Heravi, M. M., & Talaei, B. (2015). Ketenes as privileged synthons in the syntheses of heterocyclic compounds Part 2: Five-membered heterocycles. In Advances in heterocyclic chemistry (Vol. 114,  pp. 147-225). Academic Press.
https://doi.org/10.1016/bs.aihch.2015.02.001
8. qfb, s. d. n. f. (2014). naphthoquinones: biological properties and synthesis of lawsone and derivatives-a structured review/naftoquinonas: propiedades biológicas y s í ntesis de lawsona y derivados-una revisión estructurada. Vitae, 21(3), 248. 
9. Wellington, K. W. (2015). Understanding cancer and the anticancer activities of naphthoquinones-a review. RSC Advances, 5(26), 20309-20338.
https://doi.org/10.1039/C4RA13547D
10. El-Najjar, N., Gali-Muhtasib, H., Ketola, R. A., Vuorela, P., Urtti, A., & Vuorela, H. (2011). The chemical and biological activities of quinones: overview and implications in analytical detection. Phytochemistry Reviews, 10(3), 353.
https://doi.org/10.1007/s11101-011-9209-1
11. Liu, F. (2012). Synthesis of natural products and small molecules using quinones.
12. Ansari, A., Ali, A., & Asif, M. (2017). biologically active pyrazole derivatives. New Journal of Chemistry, 41(1), 16-41.
https://doi.org/10.1039/C6NJ03181A
13. Li, Y. R., Li, C., Liu, J. C., Guo, M.,  Zhang, T. Y., Sun, L. P., & Piao, H. R. (2015). Synthesis and biological evaluation of 1, 3-diaryl pyrazole derivatives as potential antibacterial and antiinflammatory agents. Bioorganic & medicinal chemistry letters, 25(22), 5052-5057.
https://doi.org/10.1016/j.bmcl.2015.10.028
14. Filimonov, D. A., Druzhilovskiy, D. S., Lagunin, A. A., Gloriozova, T. A., Rudik, A. V., Dmitriev, A. V., & Poroikov, V. V. (2018). Computeraided prediction of biological activity spectra for chemical compounds: opportunities and limitations. Biomedical Chemistry: Research and Methods, 1(1), e00004-e00004.
https://doi.org/10.18097/BMCRM00004
15. Lipinski, C. A., Lombardo, F., Dominy, B. W., & Feeney, P. J. (2012). Experimental and computational approaches to estimate solubility and permeability in drug discovery and development settings. Advanced drug delivery reviews, 64, 4-17. 
https://doi.org/10.1016/j.addr.2012.09.019