Exothermic or Endothermic Decomposition of Disubstituted Tetrazoles Tuned by Substitution Fashion and Substituents

Abstract

Nitrogen-rich compounds such as tetrazoles are widely used as candidates in gas-generating agents. However, the details of the differentiation of the two isomers of disubstituted tetrazoles are rarely studied, which is very important information for designing advanced materials based on tetrazoles. In this article, pairs of 2,5- and 1,5-disubstituted tetrazoles were carefully designed and prepared for study on their thermal decomposition behavior. Also, the substitution fashion of 2,5- and 1,5- and the substituents at C-5 position were found to affect the endothermic or exothermic properties. This is for the first time to the best of our knowledge that the thermal decomposition properties of different tetrazoles could be tuned by substitution ways and substitute groups, which could be used as a useful platform to design advanced materials for temperature-dependent rockets. The aza-Claisen rearrangement was proposed to understand the endothermic decomposition behavior.

Intensified Continuous Flow Synthesis and Workup of 1,5-Disubstituted Tetrazoles Enhanced by Real-Time Process Analytics

“…A significant quantity of the chlorinated product 1 was also observed, likely due to displacement of the bromide by chloride, which is present in excess in the reaction medium. Alternatively, this brominated analogue or the iodide equivalent can be synthesized using a Finkelstein reaction …”

“…Alternatively, this brominated analogue or the iodide equivalent can be synthesized using a Finkelstein reaction. 25 A phenoxy group at the same position showed excellent compatibility, with quantitative yield achieved in both batch and flow (6). Aryl amides, however, were not well tolerated (products 7, 8, and 9) despite the complete conversion of the starting material.…”

Integrating Allyl Electrophiles into Nickel-Catalyzed Conjunctive Cross-Coupling

“…Compounds 1a, 1 1b, 2 1d, 3 1e, 4 S1, 5 S2, 6 S3, 7 S4, 1 5a-b, [8][9] and 5g-r [10][11][12][13][14][15][16][17][18][19] were synthesized according to literature precedents.…”

“…Two-component allylations, including the Tsuji-Trost reaction [1][2][3][4][5] and crosscoupling with organometallic nucleophiles, [6][7][8][9][10][11][12][13][14][15][16][17][18][19] are well-established and viewed as essential components of the modern synthetic repertoire.…”