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image of Synthesis and Characterization of Polyacetyltetrazine from Hydrazonoyl via [3+3] Self-Polycycloaddition

Abstract

Background

Over the past decade, tetrazines have emerged as key molecules in metal complexation, anion binding, and molecular recognition. However, limited research has focused on combining tetrazine rings into the polymer backbones.

Methods

This research aimed to focus on synthesizing novel 1,2,4,5-polyacetyl-tetrazines through 1,3-dipolar self-cycloaddition. In this process, bis-α-keto-hydrazonoyl compounds, in the presence of a base, were rapidly converted into bisnitrilimine intermediates. These intermediates then underwent head-to-tail self-polymerization 1,3-dipolar cycloaddition, resulting in the formation of poly(1,2,4,5-polyacetyltetrazines). The polymers were found to be soluble in various organic solvents, resistant to oxidative degradation, and thermally stable. Characterization of these compounds was performed using techniques, such as proton and carbon nuclear magnetic resonance (NMR) spectroscopy and thermogravimetric analysis (TGA).

Results

In this study, polyacetyl-tetrazines were synthesized by employing a [3+3] self-cycloaddition mechanism, involving the reaction of hydrazonoyl compounds to form six-membered tetrazine rings within the polymer backbone.

Conclusion

The synthesis of new polyacetyltetrazines validated the effectiveness of this method. This method will be useful due to its low cost, mild reaction conditions, and the commercial availability of the chemicals. It could potentially offer a novel pathway for synthesizing tetrazine-based polymers with unique properties.

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2025-08-04
2025-12-16

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References

  1. Huisgen R. 1,3‐Dipolar Cycloadditions. Past and future. Angew. Chem. Int. Ed. Engl. 1963 2 10 565 598 10.1002/anie.196305651
    [Google Scholar]
  2. Sayed A. Synthesis of bis-thiazoles, bis-pyrazoles, bis-hydrazonates, and bis-triazolothiadiazoles based on bis-hydrazonoyl and bis-hydrazones. Turk. J. Chem. 2015 39 3 600 609 10.3906/kim‑1412‑77
    [Google Scholar]
  3. Sayed A.R. Synthesis of novel bis-thiadiazoles, bis-triazoles and polypyrazole derivatives based on hydrazonoyl halides. Tetrahedron 2013 69 26 5293 5298 10.1016/j.tet.2013.04.137
    [Google Scholar]
  4. Sayed R. Synthesis of polytetrazines, pyrazoles and polypyrazoles based on 1, 3-dipolar cycloaddition. Curr. Org. Synth. 2017 14 4 572 577 10.2174/1570179413666160909102554
    [Google Scholar]
  5. Sayed A.R. Synthesis of 1,3,4-thiadiazines, bis-1,3,4-thiadiazoles, [1,2,4]triazino[3,4-b][1,3,4]thiadiazine, thiazolines from carbonothioic dihydrazide. Tetrahedron 2012 68 13 2784 2789 10.1016/j.tet.2012.02.011
    [Google Scholar]
  6. Sayed A.R. Synthesis of novel thiadiazoles and bis-thiadiazoles from carbonothioic dihydrazide. Tetrahedron Lett. 2010 51 34 4490 4493 10.1016/j.tetlet.2010.06.060
    [Google Scholar]
  7. Sayed A.R. Wiggins J.S. Synthesis and characterization of novel polyurethanes, polypyridazine, and polyamide based on s ‐1,2,4,5‐tetrazine. J. Heterocycl. Chem. 2024 61 1 118 126 10.1002/jhet.4748
    [Google Scholar]
  8. Ali S.H. Sayed A.R. Review of the synthesis and biological activity of thiazoles. Synth. Commun. 2021 51 5 670 700 10.1080/00397911.2020.1854787
    [Google Scholar]
  9. Sayed A. Al-Faiyz Y. Convenient methods for the synthesis of novel thiadiazoles and polythiadiazoles. Heterocycles 2020 100 6 955 963 10.3987/COM‑20‑14254
    [Google Scholar]
  10. Sayed A. Zaki Y. Aish E. A convenient route for the synthesis of new thiadiazoles. Turk. J. Chem. 2016 40 1 184 191 10.3906/kim‑1505‑13
    [Google Scholar]
  11. Sayed A.R. Wiggins J.S. Synthesis of high metal‐complexation linear elastomers containing sym‐ 1,2,4,5‐tetrazine rings. J. Appl. Polym. Sci. 2009 114 6 3915 3922 10.1002/app.30931
    [Google Scholar]
  12. Sayed A.R. Wiggins J.S. 1,3-Dipolar cycloaddition polymerization reactions of novel macromolecules containing sym-tetrazine rings. Polymer 2008 49 9 2253 2259 10.1016/j.polymer.2008.02.038
    [Google Scholar]
  13. Abdelhamid A.O. Sayed A.R. Reaction of hydrazonoyl halides 52: Synthesis and antimicrobial activity of some new pyrazolines and 1,3,4-thiadiazolines. Phosphorus Sulfur Silicon Relat. Elem. 2007 182 8 1767 1777 10.1080/10426500701313938
    [Google Scholar]
  14. Sami Shawali A. Sayed A.R. A new convenient synthesis of alditol C-glycosides of 1,2,4-triazolo[3,4-b][1,3,4]thiadiazole. J. Sulfur Chem. 2007 28 1 23 29 10.1080/17415990601101020
    [Google Scholar]
  15. Shawali A.S. Sayed A.R. Tandem regioselective 1,5-electrocyclizations of bis -nitrilimines—a new convenient synthesis of 1,2,4-triazolo[3,4-b][1,3,4]thiadiazoles. J. Sulfur Chem. 2006 27 3 233 244 10.1080/17415990600649193
    [Google Scholar]
  16. Shawali A.S. Sayed A.R. A convenient one-pot synthesis of 3-arylazo derivatives of azino[b][1,2,4,5]tetrazines. J. Chem. Res. 2004 2004 6 399 401 10.3184/0308234041423718
    [Google Scholar]
  17. Sayed A.R. Wiggins J.S. Alternating copolymer of pyridine and 1,4‐diphenyl‐1,2,4,5‐tetrazine from bis ‐1,3‐dipolar cycloaddition polymerization. J. Appl. Polym. Sci. 2011 120 2 623 630 10.1002/app.33147
    [Google Scholar]
  18. Negm A. Al-Faiyz Y.S. Riyadh S. Sayed A.R. Synthesis, DPPH radical scavenging, cytotoxic activity, and apoptosis induction efficacy of novel thiazoles and bis-thiazoles. Curr. Org. Synth. 2023 21 8 1081 1090 10.2174/0115701794264504231017113027 37936471
    [Google Scholar]
  19. Meng X. Chen H. Xu S. Ma Y. Metal-free 1,3-dipolar cycloaddition polymerization via prearrangement of azide and alkyne in the solid state. CrystEngComm 2014 16 43 9983 9986 10.1039/C4CE01690D
    [Google Scholar]
  20. Li M.M. Huang H. Tian W. Pu Y. Zhang C. Yang J. Ren Q. Tao F. Deng Y. Lu J. Construction of multi-substituted pyrazoles via potassium carbonate-mediated [3 + 2] cycloaddition of in situ generated nitrile imines with cinnamic aldehydes. RSC Advances 2022 12 21 13087 13092 10.1039/D2RA00331G 35497007
    [Google Scholar]
  21. Baldwin M.G. Johnson K.E. Lovinger J.A. Parker C.O. 1,3‐Dipolar cycloaddition polymerization of compounds containing both azido and acetylene groups. J. Polym. Sci. B 1967 5 9 803 806 10.1002/pol.1967.110050913
    [Google Scholar]
  22. Rybakiewicz-Sekita R. Toman P. Ganczarczyk R. Drapala J. Ledwon P. Banasiewicz M. Skorka L. Matyjasiak A. Zagorska M. Pron A. D-A-D compounds combining dithienopyrrole donors and acceptors of increasing electron-withdrawing capability: Synthesis, spectroscopy, electropolymerization, and electrochromism. J. Phys. Chem. B 2022 126 22 4089 4105 10.1021/acs.jpcb.2c01772 35616402
    [Google Scholar]
  23. Wu Z.C. Houk K.N. Boger D.L. Svatunek D. Mechanistic Insights into the Reaction of Amidines with 1,2,3-Triazines and 1,2,3,5-Tetrazines. J. Am. Chem. Soc. 2022 144 24 10921 10928 10.1021/jacs.2c03726 35666564
    [Google Scholar]
  24. Amirkhanov V.M. Vishnevsky D.G. Ovdenko V.N. Chuprina N.G. Mokrinskaya E.V. Zozulya V.A. Shatrava Y.O. Ovchinnikov V.A. Sliva T.Y. Mel’nik A.K. Davidenko I.I. Davidenko N.A. Photovoltaic properties of polymer composites doped with binuclear lanthanide complexes derived from 3,6-Dipyridin-2-YL-1,2,4,5-tetrazine with carbacylamidophosphate ligands. J. Appl. Spectrosc. 2021 87 6 1135 1140 10.1007/s10812‑021‑01121‑7
    [Google Scholar]
  25. Babaryk A.A. Haouas M. Khaynakova O. Elkaïm E. Horcajada P. Bis-3,5-Diamino-1,2,4-Triazolyl-1,2,4,5-Tetrazine: From insensitive high energy density materials to small molecule organic semiconductors. Cryst. Growth Des. 2020 20 10 6510 6518 10.1021/acs.cgd.0c00698
    [Google Scholar]
  26. Ourahmoun O. Trigaud T. Ratier B. Belkaid M.S. Galmiche L. Audebert P. An efficient tetrazine photoluminescent layer used for organic solar cells down shifting. Synth. Met. 2017 234 106 110 10.1016/j.synthmet.2017.09.004
    [Google Scholar]
  27. Bleehen N.M. Newlands E.S. Lee S.M. Thatcher N. Selby P. Calvert A.H. Rustin G.J. Brampton M. Stevens M.F. Cancer Research Campaign phase II trial of temozolomide in metastatic melanoma. J. Clin. Oncol. 1995 13 4 910 913 10.1200/JCO.1995.13.4.910 7707118
    [Google Scholar]
  28. Gao H. Wang R. Twamley B. Hiskey M.A. Shreeve J.M. 3-Amino-6-nitroamino-tetrazine (ANAT)-based energetic salts. Chem. Commun. 2006 38 4007 4009 10.1039/b608214a 17003881
    [Google Scholar]
  29. Kaim W. The coordination chemistry of 1,2,4,5-tetrazines. Coord. Chem. Rev. 2002 230 1-2 127 139 10.1016/S0010‑8545(02)00044‑9
    [Google Scholar]
  30. Joshi S. Raj K.A. Rao M.R. Ghosh R. An electronic biosensor based on semiconducting tetrazine polymer immobilizing matrix coated on rGO for carcinoembryonic antigen. Sci. Rep. 2022 12 1 3006 10.1038/s41598‑022‑06976‑0 35194116
    [Google Scholar]
/content/journals/cos/10.2174/0115701794396021250713164054
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Synthesis and Characterization of Polyacetyltetrazine from Hydrazonoyl via [3+3] Self-Polycycloaddition
Bentham Science Publishers ; https://doi.org/10.2174/0115701794396021250713164054
/content/journals/cos/10.2174/0115701794396021250713164054
/content/journals/cos/10.2174/0115701794396021250713164054
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  • Article Type:     Research Article
Keywords: Hydrazonoyl ; tetrazine ; cycloaddition ; bisnitrilimine

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