Title:Synthesis and Characterization of Polyacetyltetrazine from Hydrazonoyl via [3+3] Self-Polycycloaddition
Volume: 22
Issue: 8
Author(s): Abdelwahed R. Sayed*, Olivia D. McNair, Yasair S. Al-Faiyz and Jeffrey S. Wiggins
Affiliation:
- Department of Chemistry, Faculty of Science, Beni-Suef University, Beni-Suef 62514, Egypt
Keywords:
Hydrazonoyl, cycloaddition, tetrazine, bisnitrilimine.
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 via 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] selfcycloaddition
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.
