Revisiting ring-degenerate rearrangements of 1-substituted-4-imino-1,2,3-triazoles
| Autor: | Eric M. Villa, Joseph A. Christensen, James T. Fletcher, Matthew D Hanson |
|---|---|
| Jazyk: | angličtina |
| Rok vydání: | 2018 |
| Předmět: |
Steric effects
1 2 3-Triazole Imine imine exchange rearrangement Substituent 010402 general chemistry 01 natural sciences Full Research Paper Coordination complex lcsh:QD241-441 chemistry.chemical_compound lcsh:Organic chemistry Computational chemistry lcsh:Science colorimetric assay Dynamic equilibrium chemistry.chemical_classification 010405 organic chemistry Condensation Organic Chemistry Condensation reaction 3. Good health 0104 chemical sciences Chemistry condensation chemistry lcsh:Q 1 2 3-triazole |
| Zdroj: | Beilstein Journal of Organic Chemistry, Vol 14, Iss 1, Pp 2098-2105 (2018) Beilstein Journal of Organic Chemistry |
| ISSN: | 1860-5397 |
| Popis: | The 1-substituted-4-imino-1,2,3-triazole motif is an established component of coordination compounds and bioactive molecules, but depending on the substituent identity, it can be inherently unstable due to Dimroth rearrangements. This study examined parameters governing the ring-degenerate rearrangement reactions of 1-substituted-4-imino-1,2,3-triazoles, expanding on trends first observed by L’abbé et al. The efficiency of condensation between 4-formyltriazole and amine reactants as well as the propensity of imine products towards rearrangement was each strongly influenced by the substituent identity. It was observed that unsymmetrical condensation reactions conducted at 70 °C produced up to four imine products via a dynamic equilibrium of condensation, rearrangement and hydrolysis steps. Kinetic studies utilizing 1-(4-nitrophenyl)-1H-1,2,3-triazole-4-carbaldehyde with varying amines showed rearrangement rates sensitive to both steric and electronic factors. Such measurements were facilitated by a high throughput colorimetric assay to directly monitor the generation of a 4-nitroaniline byproduct. |
| Databáze: | OpenAIRE |
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