Synthesis of Novel (bis‐)1,5‐Disubstituted‐1H‐tetrazole‐Decorated Monomers and Their Respective Polymers via Thiol‐ene Polymerization

Abstract

Over the years, nitrogen-rich functional groups like tetrazole and its derivatives have received increasing interest in the chemistry of small molecules. There is a continuously growing interest in polymers decorated with nitrogen for potential biomedical applications because of their broad range of biological properties, such as being antibacterial, anticarcinogenic, and anti-inflammatory. On this premise, a new synthesis route is reported for nitrogen-decorated polymers via the combination of Ugi-azide four-multicomponent reaction (UA-4MCR) and thiol-ene polymerization. Accordingly, 𝜶,𝝎-diene monomers decorated with (bis-)1,5-disubstituted-1H-tetrazoles (bis-1,5-DS-Ts) are synthesized by using the UA-4MCR. Subsequently, the light-induced thiol-ene polymerization facilitates the efficient synthesis of novel tetrazole-decorated polymers with apparent number average molecular mass (M n ) up to 62 000 g mol −1 , which are characterized for their chemical, thermal, and optical properties. The comprehensive characterization of the synthesized polymers is paving the way toward a wealth of opportunities, ranging from biomaterials to energy storage−relevant materials.

Main Chain 1,5-Disubstituted-1H-Tetrazole-Based Polymers via Ugi-Azide-Four-Multicomponent Polymerization (UA-4MCP)

“…In this vein, UA-4MCPs were performed by adopting a recently established procedure reported in our previous study. 21 Briefly, 1,6-diisocyanide (1 equiv), N,N-dimethyl-1,6-hexanediamine (1 equiv), trimethylsilyl azide (TMSN 3 ) (2 equiv), and corresponding aldehyde derivatives (2 equiv) were reacted in the presence of the catalyst 1,8-diazabicyclo(5.4.0)undec-7-ene (DBU) under an inert atmosphere at 50 °C (Scheme 1b, S2, Supporting Information 2). On the one side, a solvent optimization procedure was conducted for synthesizing P1 via UA-4MCP.…”

“…Indeed, it has been observed that the majority of currently available 1,5-DS-T containing polymers are predominantly composed of a carbon−carbon backbone with tetrazole side chains, rather than the main chain. 21 For instance, the initial demonstration of polymers with a pendant 1,5-DS-T units involved the in situ formation of tetrazole on polyacrylonitrile polymers through a [2 + 3] cycloaddition reaction with azide derivatives. 22,23 Subsequently, the 1,5-DS-T moiety found practical applications in alkaline anion exchange membranes where the tetrazole moiety tethered onto poly(2,6dimethyl-1,4-phenylene oxide) with a quaternary ammonium (QA) linkage.…”

“…The advancement of organic synthesis techniques has had a significant influence on the design and synthesis of innovative structures incorporating spirocyclic, polycyclic, and heterocyclic groups. − The importance of these groups in the field of polymer chemistry has also arisen as an exceptionally promising domain due to the desirable qualities of them, such as enhanced mechanical strength, thermal stability, and electrical conductivity. − One particular class of the heterocyclic compounds, known as tetrazoles, specifically nitrogenous heterocyclic 1,5-disubstituted-1 H -tetrazoles (1,5-DS-Ts), has been gaining significant attention due to its effectiveness in applications such as energy systems, − nanomaterials, − metal–organic frameworks, and medicinal compounds. , Despite the existence of diverse and complex libraries of 1,5-DS-Ts as small compounds, − integrating them into polymer chemistry remains a challenging issue to be addressed. Indeed, it has been observed that the majority of currently available 1,5-DS-T containing polymers are predominantly composed of a carbon–carbon backbone with tetrazole side chains, rather than the main chain . For instance, the initial demonstration of polymers with a pendant 1,5-DS-T units involved the in situ formation of tetrazole on polyacrylonitrile polymers through a [2 + 3] cycloaddition reaction with azide derivatives. , Subsequently, the 1,5-DS-T moiety found practical applications in alkaline anion exchange membranes where the tetrazole moiety tethered onto poly­(2,6-dimethyl-1,4-phenylene oxide) with a quaternary ammonium (QA) linkage .…”

“…For instance, the initial demonstration of polymers with a pendant 1,5-DS-T units involved the in situ formation of tetrazole on polyacrylonitrile polymers through a [2 + 3] cycloaddition reaction with azide derivatives. , Subsequently, the 1,5-DS-T moiety found practical applications in alkaline anion exchange membranes where the tetrazole moiety tethered onto poly­(2,6-dimethyl-1,4-phenylene oxide) with a quaternary ammonium (QA) linkage . Lastly, 1,5-DS-T-containing polymers were synthesized through radical or thiol-ene polymerization by using tetrazole-containing monomers (i.e., 1-(1-vinyl-1 H -tetrazol-5-yl)­hydrazine, 1-methyl-1-(1-vinyl-1 H -tetrazol-5-yl) hydrazine, alkyl-bridged bis-(1-methyl-tetrazolylhydrazines), and (bis-)­1,5-disubstituted-1 H -tetrazoles) for studying their energetic and optical properties, respectively. Nevertheless, a very limited number of literature examples have been found for the main chain 1,5-DS-T-based polymers.…”

Synthesis, characterization and Theoretical study of some 2-Oxopyridine Carbonitrile derivatives that contain tetrazole ring and evaluation of their Biological activity

“…Tetrazole moiety has a significant group of nitrogen-rich heterocyclic compounds with numerous practical uses in a variety of industries, including high-energy materials, agriculture, medicine, and photography. [3][4][5]. It has a wide use in medicinal chemistry as anti-hyperglycemic [4], antiinflammatory [5][6], antiviral [7][8], anticancer [9], antioxidants [10].…”