Bazı o-Hidroxsi Enaminon Türevlerinin ve Siklohekzadienin Tetrachloro-1,4-benzoquinone (TCB) Ortamında Tandem Oxidative-Reaksiyonu ile Sentezi

Abstract

Bu çalışmada 7 adet orjinal o-hidroksi aril enaminon ile siklohekzadienin türevleri TCB ortamında tandem reaksiyonu ile sentezlenip, yapıları 1H NMR, 13C NMR ve HR-MS spektroskopisi aydınlatılmıştır. Ayrıca, bu reaksiyon oxidatif birleşme ve molekül içi halkalaşma tepkimesini içermektedir. Kromonlar, doğal olarak oluşan bileşiklerden meydana gelen bir gruptur. Doğada, özellikle bitkilerin bileşenleri içerisinde bulunur. Halkalı kromonların yaygın olarak doğal biyolojik aktif özelliklere sahip olmasından dolayı, literatüre giren her kromon türevlerinin sentezi literatüre önemli katkı yapacağı düşünülmektedir. Bu çalışmada sentezlenen söz konusu bileşiklerin yüzdesel verimleri oldukça yüksek değerlere sahip olup, oda sıcaklığında ılımlı şartlarda gerçekleştirilmiştir.

Keywords

• TCB
• Oksidasyon
• Tandem halkalaşması

Supporting Institution

Tekirdağ Namık Kemal Üniversitesi tarafından desteklenmiştir

Project Number

(Proje no: NKUBAP.00.10.AR.12.15).

Thanks

Tekirdağ Namık Kemal Üniversitesi

Synthesis of some o-Hidroksi Enaminone Derivatives and Cyclohexadiene by Tandem Oxidative-Reaction in Tetrachloro-1,4-benzoquinone (TCB) Medium

Abstract

In this study, 7 original o-hydroxy aryl enaminone and cyclohexadiene derivatives were synthesized by tandem reaction in TCB medium and their structures were elucidated by 1H NMR, 13C NMR and HR-MS spectroscopy. Also, this reaction includes oxidative coupling and intramolecular cyclization reaction. Chromones are a group of naturally occurring compounds. It is ubiquitous in nature, especially in plants. Since cyclic chromones have common natural biologically active properties, it is thought that the synthesis of each chromone derivative that enters the literature will make an important contribution to the literature. The percent yields of the synthesized compounds were quite high and occurred under mild conditions at room temperature.

Keywords

• TCB
• Oxidation
• Tandem annulation

Project Number

(Proje no: NKUBAP.00.10.AR.12.15).

References

1. [1]C. F. M. Silva, D. C. G. A. Pinto and A. M. S. Silva “Chromones: A Promising Ring System for New Anti-inflammatory Drugs,” ChemMedChem,, vol. 11, pp. 2252-2260, 2016.
2. [2]K. M. Khan, N. Ambreen, U. R. Mughai, S. Perveen and M. I. Choudhary, “3-Formylchromones: Potential antiinflammatory agents,” European Journal of Medicinal Chemistry, vol. 45, pp. 4058-4064, 2010.
3. [3]D.‐R, Zhang, L. ‐P. Hu, C. ‐Y. Y. X. Li, M.‐Y. Teng, B. Liu and G.‐L. Huang, “Tetramethylammonium Iodide (TMAI)‐Promoted Sulfenylation/Annulation of Enaminones with Thiosulfonates,” Asian Journal of Organic Chemistry, vol. 11, pp. e202100694, 2022.
4. [4]G. J. Atwell, G.W. Rewcastle, B.C. Baguley and W.A. Denny, “Potential antitumor agents. 60. Relationships between structure and in vivo colon 38 activity for 5-substituted 9-oxoxanthene-4-acetic acids,” Journal of Medicinal Chemistry, vol. 33, pp. 1375–1379, 1990.
5. [5]S. H. Han, S. Kim, U. De, N. K. Mishra, J. Park, S. Sharma, J. H. Kwak, S. Han. H. S. Kim, and I. S. Kim, “Synthesis of Succinimide-Containing Chromones, Naphthoquinones, and Xanthones under Rh(III) Catalysis: Evaluation of Anticancer Activity,” Journal of Organic Chemistry, vol. 81, pp. 12416-12425, 2026.
6. [6]M. Kuroda, S. Uchida, K. Watanabe and Y. Mimaki, “Chromones from the tubers of Eranthis cilicica and their antioxidant activity, ”Phytochemistry, vol. 70, pp. 288-293, 2009.
7. [7]E. Fernandes and J. L. F. C. Lima, “ Synthesis and antioxidant properties of new chromone derivatives,” Bioorganic and Medicinal Chemistry, vol. 17, pp. 7218-7226, 2009.
8. [8]F. Cagide, T. Silva, J. Reis, A. Gaspar, F. Borges, L. R. Gomes and J. N. Low, “Discovery of two new classes of potent monoamine oxidase-B inhibitors by tricky chemistry,” Chemical Communication, vol. 51, pp. 2832–2835, 2015.

9. [9]J. Reis, A. Gaspar, N. Milhazes and F. Borges, “Chromone as a Privileged Scaffold in Drug Discovery: Recent Advances,” Journal of Medicinal Chemistry, vol. 60, pp. 7941–7957, 2017.
10. [10]A. Gaspar, M. J. Matos, J. Garrido, E. Uriarte and F. Borges, “Chromone: A Valid Scaffold in Medicinal Chemistry,” Chemical Review, vol. 114, pp. 4960–4992, 2014.
11. [11]D.I.S.P. Resende, F. Durães, M. Maia, E. Sousa and M.M.M. Pinto, “Recent advances in the synthesis of xanthones and azaxanthones,” Organic Chemistry Frontiers, vol. 7, pp. 3027–3066, 2020.
12. [12]D. Sanglard, “Emerging threats in antifungal-resistant fungal pathogens,” Frontiers in Medicine. Vol.3, pp. 1-10, 2016.
13. [13]K. Navjeet, “Synthesis of five-membered heterocycles containing nitrogen heteroatom under ultrasonic irradiation,”, Journal of Organic Chemistry, Vol.16, pp. 481–503, 2019.
14. [14]G. Serdaroglu, and N. Uludag, “Structural, electronic, and spectroscopic study on 1, 5-methanoazocino [4, 3-b] indole synthesized by TFB-based route,” Chemical Papers, vol. 75, pp. 4549-4564, 2021.
15. [15]N. Uludag, “A New Approach to the Total Synthesıs of (±)-Nordasycarpıdone by Rıng-closure wıth Tetrachloro-1, 4-benzoquınone, Macedonian Journal of Chemistry and Chemical Engineering, vol. 39, pp. 11-16, 2020.
16. [16]N. Uludag, “An Effective Approach to the Strychnos Alkaloids: Total Synthesis of tubifolidine,” Chemistry of Natural Compounds, vol. 57, pp. 491-496, 2021.
17. [17]C.-Y. Yang, D.-R. Zhang, L.-P. Hu, X. Li, S.-C. Yang, B. Liu and G. Huang, “Visible-light-induced sulfonylation of Baylis–Hillman acetates under metal- and oxidant-free conditions,” New Journal of Chemistry, vol. 45, pp. 22243–22248, 2021.
18. [18]R. J. Reddy, A. H. Kumari, J. J. Kumar and J. B. Nanubolu, “Cs2CO3-mediated vicinal Thiosulfonylation of 1,1-dibromo-1-Alkenes with thiosulfonates: An xxpedient synthesis of (E)-1,2-thiosulfonylethenes,” Advanced Synthesis and Catalysis, vol. 361, pp.1587-1591, 2019.
19. [19]P. Mampuys, C. R. McElroy, J. H. Clark, R. V. A. Orru and B. U. W. Maes, “Thiosulfonates as Emerging Reactants: Synthesis and Applications,” Advanced Synthesis and Catalysis. Vol. 362, pp. 3-64, 2020.
20. [20]M. Y. Kornev, D. S. Tishin, D. L. Obydennov, V. Y. Sosnovskikh, “ Reactions of 3-Functionalized Chromones with Triacetic Acid Lactone,” Mendeleev Communications,Vol. 30, pp. 233-235, 2020.
21. [21]M. N. Elinson, Y. E. Ryzhkova, F. V. Ryzhkov, “Multicomponent Design of Chromeno[2,3-b]pyridine Systems,” Russian Chemical Reviews, Vol. 90, pp. 94-115, 2021.
22. [22]M. A. Ibrahim, Y. A. Alnamer, “Synthetic Approaches for Construction of Novel 3-Heteroarylchromeno[2,3-b]pyridines and Annulated Chromenopyridopyrazolopyrimidines,” Heterocycles, Vol. 102, pp. 2138-2152, 2021.